JP2003080838A - Ink-jet recording sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ink-jet recording sheet which can form an image high in resolution and density, is excellent in light resistance, stores the image stably without generating bleeding with the passage of time even when stored for a long time under high-temperature, high-humidity environment, and is excellent in production aptitude. SOLUTION: In the ink-jet recording sheet having a coloring matter accepting layer on the surface of a support, the coloring matter accepting layer contains at least fine particles of an inorganic pigment and a polymer having units expressed at least by formula (1) (R<1> is a hydrogen atom or a methyl group; R<2> and R<3> are each an alkylene group; R<4> is a hydrogen atom, a 1-18C alkyl group, an aryl group, an aralkyl group, or -OCOR'; Q is COO, CONR", or O; R' and R" are each a hydrogen atom, an alkyl group, an aralkyl group, or an aryl group; m and n are each an integer of 1 or greater) and formula (2) (A is a repeating unit having a cationic group).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a recording material suitable for ink jet recording using a liquid ink such as an aqueous ink or an oil ink, or a solid ink which is solid at room temperature and is melted and liquefied to be used for printing. More specifically, the present invention relates to an ink jet recording sheet which is excellent in ink receiving performance, has a high print density in the image area, and has little blurring or fading of the dye in the image area over time.

[0002]

2. Description of the Related Art In recent years, with the rapid development of the information industry,
Various information processing systems have been developed. Along with this, recording methods and devices suitable for each information system have been developed and put into practical use. Among these recording methods, the inkjet recording method is capable of recording on various recording materials, and is relatively inexpensive in hardware,
Due to its compactness and high quietness, it is widely used not only in offices but also in so-called home use. In addition, with the recent increase in resolution of inkjet printers, it has become possible to obtain so-called photograph-like high-quality recorded matter. With the development of hardware (device), various recording sheets for inkjet recording have been developed.

The properties required for the above-mentioned recording sheet are generally: (1) quick-drying property (high ink absorption speed), (2) proper and uniform ink dot diameter (bleeding). No), (3) good graininess, (4) high dot roundness, (5) high color density, (6) high saturation (no dullness) ), (7) The printed part has good light resistance and water resistance,
(8) No blurring or fading of the image even after long-term storage, (9) high whiteness of the recording sheet, (10)
The storage stability of the recording sheet is good, (11) the deformation and dimensional stability are good (curl is sufficiently small), and (12) the hard running property is good. Furthermore, in the application of photo glossy paper used for obtaining so-called photographic-like high-quality recorded matter, in addition to the above, gloss, surface smoothness, photographic paper-like texture similar to silver halide photography are also required. To be done.

Recording sheets used for ink jet recording are, for example, JP-A-55-51583, JP-A-55-144172, and JP-A-55-15039.
5 gazette, the same 56-148582 gazette, the same 56-14.
No. 8583, No. 56-148584, No. 56
-148585, 57-14091, 57-38185, 57-129778, 57-129979, 60-21908.
There is known one in which a pigment such as silica and a water-soluble binder are coated on a support such as paper or a plastic film, as described in JP-A No. 4 and JP-A No. 60-245588. However, all of these proposed recording sheets have very low glossiness, which is insufficient for use as a photo glossy paper.

Further, in Japanese Patent Laid-Open No. 4-223190,
Is 0.1 g / m of borax or boric acid. ²The above is applied
5-20g / m on base paper²Synthetic silica and polybi
A recording layer made of nyl alcohol (PVA) was provided.
Ink jet recording paper has been proposed. The above technology
Is simply the coating strength of the recording layer with a low binder content.
The purpose is to improve it, and it is inferior in terms of gloss.
Therefore, it has been insufficient as a use of photo glossy paper.

Further, recording materials using various water-soluble polymers for obtaining gloss have been proposed. For example, JP-A-58-89391, JP-A-58-134784, JP-A-58-134786, and JP-A-60-44386.
No. 60-132785, No. 60-145.
879, 60-168651, 60-
There is known one in which polyvinyl alcohol, polyvinylpyrrolidone, gelatin or the like described in Japanese Patent No. 171143 or the like is coated on a support such as paper or a plastic film. These recording sheets are also excellent in terms of glossiness, but inferior in terms of quick-drying ink, so that they are insufficient for use as photo glossy paper.

On the other hand, in JP-A-7-276789, JP-A-8-174992, JP-A-11-115308, JP-A-11-192777, etc., the required characteristics and manufacturing cost of the above-mentioned ink jet recording sheet are satisfied. An inkjet recording sheet is proposed. The above-mentioned JP-A-7-276789 proposes a recording sheet in which a coloring material receiving layer having a three-dimensional structure having a high porosity and formed of fine particles of an inorganic pigment and a water-soluble resin is provided on a support. Has been done. According to this configuration,
It is said that the above-mentioned ink absorbability is improved, color mixture blurring during printing is sufficiently suppressed, and an image with high resolution can be obtained. This color material receiving layer can be generally formed by containing a large amount of particles having a small particle diameter, but since the binder amount for layer formation needs to be reduced so that voids can be formed, the coating layer is rapidly dried. There is a defect that cracks occur and the transparency and appearance of the colorant receiving layer are impaired.

In Japanese Patent Laid-Open No. 11-115308, a gas phase method silica having an average primary particle diameter of 10 nm or less has a pH of 8.
In the above alkaline atmosphere, polyvinyl alcohol (P
A coating solution obtained by blending with VA) and then dispersing is applied, and after the application, a coating solution containing a curing agent for PVA and having a pH of 8 or more is further coated in a dry state, and dried to obtain a coloring material receiving layer. A method of forming the is described. However, according to this method, the print density and sharpness of the image are low, and a sufficient gloss feeling cannot be obtained.

In Japanese Patent Laid-Open No. 10-181190, a coloring material receiving layer is prepared by finely pulverizing and dispersing an aggregate pigment in a liquid containing a cationic resin and applying a coating liquid containing the pigment having a particle diameter of 500 nm or less. However, the glossy feeling is insufficient.

Further, JP-A-12-212135 describes an ink jet recording sheet containing a vapor phase method silica and a cationic polymer having a constitutional unit of a polydiallylylamine derivative, which is also an image. Print density, freshness and glossiness are low. Further, Japanese Patent Application Laid-Open No. 12-211241 describes a coating liquid for inkjet recording paper, which uses an aqueous dispersion having a pH of 1.0 to 4.5 and containing vapor-phase process silica. It is low and cracks occur on the surface of the recording sheet.

In Japanese Patent Laid-Open No. 10-119423 or 10-217601, a colorant receiving layer containing fine inorganic pigment particles and a water-soluble resin and having a high porosity is provided on a support. Inkjet recording sheets have been proposed. Due to its constitution, each of the above-mentioned inkjet recording sheets has excellent ink absorbency, has high ink absorbability capable of forming a high resolution image, and exhibits high gloss. However, from the viewpoint of texture with glossiness, since a support having a resin coating such as polyethylene on both surfaces thereof is used as the support, the high boiling point solvent remains in the colorant receiving layer as it is, and after printing, When stored in a high-temperature and high-humidity environment for a long time, the solvent diffuses together with the dye in the colorant-receptive layer, and blurring of the image over time (hereinafter,
There is a problem that "time-dependent blurring" may occur.

Further, the ink jet recording sheet contains
It has been widely practiced to add a compound having an amino group or an ammonium salt, particularly a polymer compound having such a compound, for the purpose of fixing a dye component in ink, for example, JP-A-60-83882. 64-7528
(Co) polymers of diallylammonium salt derivatives described in JP-A No. 1 and 59-20696, etc.
Allylamine salt copolymers described in JP-A No. 1-61887 and JP-A No. 61-72581, and JP-A-6-340.
No. 163, No. 4-288283, No. 9-30
No. 0810, No. 8-318672, No. 10-
No. 272830, JP-A No. 63-115780, and other vinyl (co) polymers such as (meth) acrylates having an ammonium salt, (meth) acrylamide (co) polymers, and vinylbenzyl ammonium salt (co) polymers. ) Polymer, modified polyvinyl alcohol (PVA) described in JP-A-10-44588, JP-A-6-23426
No. 8, JP-A-11-277888 and the like, amine-epichlorohydrin polyaddition products, JP-A-10-119418.
Dihalide / diamine polyaddition products described in JP-A No. 11-58934, polyamidines described in JP-A Nos. 11-58860, and allylamine hydrochloride, allylamine, diallyldimethylammonium described in JP-A No. 12-71603, etc. Many compounds such as salts and polymers are used. The ink jet recording sheet described in the above publication uses these compounds to immobilize the dye and prevent bleeding.

However, the ink jet recording sheet having the coloring material receiving layer having such a high porosity has advantages such as ink absorbency and high gloss, and although the blurring with time is being improved, the printed image is printed. Immediately after that, when it is stored in a clear file or the like, or particularly when it is stored for a long time under a high humidity condition, there is a problem that blurring of an image still occurs.

Further, there is known an ink jet recording sheet using a polyallylamine derivative or a polyvinylamine derivative (hereinafter sometimes referred to as "polyamines") as an ink jet recording sheet. For example, JP-A-63-280681 discloses an ink jet recording sheet using polyamines substituted with hydroxyalkyl having 2 to 3 carbon atoms. However, these ink jet recording sheets are still insufficient in the effect of preventing bleeding over time.

Japanese Unexamined Patent Publication (Kokai) No. 8-267904 discloses an ink jet recording sheet containing polyamines substituted with an alkyl group having 1 to 6 carbon atoms, a benzyl group and an aryl group. However, in these cases, the quaternary ammonium salt is an essential component, and the introduction of these substituents (substituents having particularly high hydrophobicity) is not intended to improve blurring over time. Further, the polyamines are not formed by a polymer reaction.

In addition, polyallylamine is disclosed in, for example, JP-A-6-340163, JP-A-6-340164, JP-A-7-242015, JP-A-8-142496, JP-A-8-267904, and JP-A-8-282029. And disubstituted products of polyallylammonium and trisubstituted products of polyallyl ammonium. However, since these derivatives are generally synthesized by polymerization of di-substituted allylamine or tri-substituted allyl ammonium salt, which has low polymerizability, there is a problem that the production suitability is poor. Furthermore, the introduction of these substituents is not intended to improve blurring over time.

Further, as an example of an ink jet recording sheet containing amines having a substituent other than an alkyl group, an aryl group and an aralkyl group, JP-A-11-58634 and 11-20307 disclose polyvinyl. An example is shown in which the amine is replaced by COH, COMe. However, this is an example as a part of the polyamidine mordant, and the effect of preventing bleeding over time was still insufficient even if these groups were introduced.

[0018]

SUMMARY OF THE INVENTION It is an object of the present invention to solve the above-mentioned problems of the prior art and achieve the following objects. That is, the object of the present invention is to form a high-resolution and high-density image, excellent in light resistance, and after printing, even when stored for a long time in a high-temperature and high-humidity environment, it does not cause bleeding over time, and is stable. An object of the present invention is to provide an inkjet recording sheet that holds an image and is excellent in manufacturing suitability.

[0019]

As a result of intensive studies for solving these problems, the present inventor has found that these problems can be solved by using the following ink jet recording sheet. The present invention has been reached.

Means for solving the above problems are as follows. <1> In an inkjet recording sheet having a colorant receiving layer on the surface of a support, the colorant receiving layer has a weight of at least inorganic pigment fine particles and at least units represented by the following formulas (1) and (2). An ink jet recording sheet, characterized in that it comprises a united body (a).

[0021]

[Chemical 5] [Equation (1), in (2), R ¹ represents a hydrogen atom or a methyl group, R ^2, R ³ represents an alkylene group, R ² and R ³ may be different even in the same. R ⁴ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group, an aralkyl group, or —OCOR ′, and Q represents COO or CO.
Represents either NR "or O, and R'and R" are
Each independently represents a hydrogen atom, an alkyl group, an aralkyl group, or an aryl group, and m and n each represent an integer of 1 or more. A represents a repeating unit containing a cationic group. ]

<2> The inkjet recording sheet according to <1>, wherein the unit of the formula (2) is at least one of the following formulas (3), (4), (5) and (6). is there.

[0023]

[Chemical 6] [In the formulas (3), (4), (5) and (6), R^Five, R^TenIs
Represents a hydrogen atom or a methyl group, R⁶Represents an alkylene group
And R⁷, R⁸, R⁹, R¹¹, R¹², R¹³, R¹⁴, R ¹⁵,
R¹⁶, And R¹⁷Are each independently a hydrogen atom,
Represents an alkyl group, an aralkyl group, or an aryl group, and W
Represents -COO-, -CONH-, or -O-,
X¹, X², X³Represents a counter anion, and l represents 0 or 1.
Represent ]

<3> The coloring material receiving layer contains at least the inorganic pigment fine particles and at least the following formulas (1) and (2).
An inkjet recording sheet characterized by being coated with an inorganic fine particle dispersion liquid comprising a polymer having a unit consisting of

[0025]

[Chemical 7] [Equation (1), in (2), R ¹ represents a hydrogen atom or a methyl group, R ^2, R ³ represents an alkylene group, R ² and R ³ may be different even in the same. R ⁴ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group, an aralkyl group, or —OCOR ′, and Q represents COO or CO.
Represents either NR "or O, and R'and R" are
Each independently represents a hydrogen atom, an alkyl group, an aralkyl group, or an aryl group, and m and n each represent an integer of 1 or more. A represents a repeating unit containing a cationic group. ]

<4> In the above inorganic fine particle dispersion,
The unit of the formula (2) is at least the following formula (3),
The inkjet recording sheet according to <3>, which comprises a polymer having any of the units (4), (5), and (6).

[0027]

[Chemical 8] [In the formulas (3), (4), (5) and (6), R^Five, R^TenIs
Represents a hydrogen atom or a methyl group, R⁶Represents an alkylene group
And R⁷, R⁸, R⁹, R¹¹, R¹², R¹³, R¹⁴, R ¹⁵,
R¹⁶, And R¹⁷Are each independently a hydrogen atom,
Represents an alkyl group, an aralkyl group, or an aryl group, and W
Represents -COO-, -CONH-, or -O-,
X¹, X², X³Represents a counter anion, and l represents 0 or 1.
Represent ]

<5> The inkjet recording sheet according to <3> or <4>, wherein the inorganic fine particle dispersion further contains a water-soluble resin. <6> The inorganic pigment fine particles have an average primary particle diameter of 20.
Silica fine particles of nm or less, or the average pore radius is 1 to
<10, which is pseudo-boehmite
The inkjet recording sheet according to any one of 1> to <5>. <7> The inkjet recording sheet according to <5> or <6>, wherein the water-soluble resin is polyvinyl alcohol or a derivative thereof. <8> The inkjet recording sheet according to any one of <5> to <7>, wherein the color material receiving layer further contains a crosslinking agent capable of crosslinking the water-soluble resin. <9> The inkjet recording sheet according to <8>, wherein the crosslinking agent is a boron compound. <10> The color material receiving layer further contains an organic mordant capable of fixing an anionic dye.
The inkjet recording sheet according to any one of 1> to <9>. <11> The inkjet recording sheet according to <10>, wherein the organic mordant is polyallylamine or a derivative thereof. <12> The coloring material receiving layer has a three-dimensional network structure with a porosity of 50 to 80%, and the mass ratio (i: p) of the inorganic pigment fine particles (i) and the water-soluble resin (p) is 1.5: 1 to 1
<1> to <11>, which is 0: 1
The inkjet recording sheet according to any one of 1. <13> The coloring material receiving layer applies a first coating liquid containing the inorganic fine particle dispersion liquid onto the surface of the support,
(1) at the same time as the coating, (2) during the drying of the coating layer formed by the coating and before the coating layer shows a rate-decreasing drying, or (3) drying the coating layer to form a coating film. After the formation, the second coating liquid containing the organic mordant is applied to any of the above <1> to <1>.
12> The inkjet recording sheet according to any one of <12>. <14> The coloring material receiving layer is provided by adding the crosslinking agent to at least one of the first coating liquid and the second coating liquid, or the first coating liquid and the second coating liquid. The inkjet recording sheet according to any one of <1> to <13>, which is formed by applying a coating liquid containing the crosslinking agent.

[0029]

DETAILED DESCRIPTION OF THE INVENTION The contents of the present invention will be described in detail below. The inkjet recording sheet of the present invention is an inkjet recording sheet having a coloring material receiving layer on the surface of a support, wherein the coloring material receiving layer contains at least inorganic fine particles and at least the following formulas (1) and (2). And a polymer having a unit represented by: Hereinafter, the color material receiving layer will be described first.

<Coloring Material Receiving Layer> (Polymer According to the Invention) The polymer (hereinafter sometimes referred to as polymer (a)) is a cationic polymer containing at least a polyalkylene oxide structure, that is, It is a polymer having units represented by the following formulas (1) and (2). The polymer has not only a function as a mordant but also a function of preventing aggregation of inorganic fine particles.

[0031]

[Chemical 9]

[0032] Equation (1), R ¹ represents a hydrogen atom or a methyl group, R ^2, R ³ represents an alkylene group, R ² and R ³ may be different even in the same. R ⁴ is a hydrogen atom,
Represents any of an alkyl group having 1 to 18 carbon atoms, an aryl group, an aralkyl group, and -OCOR ', and Q represents COO, CO
Represents either NR "or O, and R'and R" are
Each independently represents a hydrogen atom, an alkyl group, an aralkyl group, or an aryl group, and m and n each represent an integer of 1 or more. A represents a repeating unit containing a cationic group.

The alkylene group represented by R ² and R ³ is
Specific examples include an ethylene group, an n-propylene group, an n-butylene group, an n-pentylene group, an n-hexylene group, an isopropylene group, an isobutylene group and a 2-hydroxypropylene group, and an ethylene group, an n-propylene group. Group, n-
Butylene group is preferred.

Examples of the alkyl group represented by R ⁴ are methyl group, ethyl group, n-propyl group, isopropyl group, n
-Butyl group, isobutyl group, t-butyl group, n-pentyl group, n-hexyl group, 2-ethylhexyl group, n-octyl group, n-nonyl group, n-decyl group, n-dodecyl group, n-octadecyl group Groups and the like.

The aryl group represented by R ⁴ is a phenyl group, an alkylphenyl group (eg, methylphenyl group, ethylphenyl group, n-propylphenyl group, n-
Butylphenyl group, n-hexylphenyl group, n-nonylphenyl group, etc.), naphthyl group, chlorophenyl group, dichlorophenyl group, trichlorophenyl group, bromophenyl group, hydroxyphenyl group, methoxyphenyl group,
An acetoxyphenyl group, a cyanophenyl group, etc. are mentioned, Preferably, a phenyl group and an alkylphenyl group are mentioned, A nonylphenyl group is especially preferable.

Examples of the aralkyl group represented by R ⁴ include a benzyl group, a phenylethyl group, a vinylbenzyl group and a hydroxyphenylmethyl group, and a benzyl group is preferable.

The alkyl group represented by R ′ and R ″ may be linear, branched or cyclic,
For example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-hexyl group, cyclohexyl group, n-octyl group, and the like, among them, methyl A group, an ethyl group, an isopropyl group and a t-butyl group are particularly preferable.

The aralkyl group represented by R'and R '' is, for example, benzyl group, diphenylmethyl group, cinnamyl group, phenethyl group, styryl group, trityl group,
And the like, and a benzyl group is particularly preferable.

Examples of the aryl group represented by R ′ and R ″ include a phenyl group, a cumenyl group, a mesityl group,
Examples thereof include a xylyl group and the like, and a phenyl group is particularly preferable.

Specific examples of the monomer giving the unit of the formula (1) include polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polyethylene glycol-polypropylene glycol mono (meth) acrylate, poly (ethylene). Glycol-tetramethylene glycol) mono (meth) acrylate, poly (propylene glycol-tetramethylene glycol) mono (meth) acrylate, methoxy polyethylene glycol mono (meth) acrylate, octoxy polyethylene glycol mono (meth) acrylate, lauroxy polyethylene glycol Mono (meth) acrylate, stearoxy polyethylene glycol mono (meth) acrylate, stearoxy polypropylene glycol mono (meth Acrylate, nonyl phenoxy polyethylene glycol mono (meth) acrylate, nonylphenoxy polyethylene glycol - polypropylene glycol mono (meth) acrylate, nonylphenoxy polypropylene glycol - polyethylene glycol mono (meth) acrylate.

The unit represented by the formula (2) is a unit derived from a cationic group-containing monomer having an ethylenically unsaturated group, and more specifically the following formulas (3), (4),
Either of the units represented by (5) and (6) is preferable.

[0042]

[Chemical 10]

R in the formulas (3), (4), (5) and (6)
⁵ , R ¹⁰ represents a hydrogen atom or a methyl group, R ⁶ represents an alkylene group, and R ⁷ , R ⁸ , R ⁹ , R ¹¹ , R ¹² , R ¹³ , R ^13
14 , R ¹⁵ , R ¹⁶ , and R ¹⁷ each independently represent a hydrogen atom, an alkyl group, an aralkyl group, or an aryl group, and W represents —COO—, —CONH—, or —O—. , X ¹ , X ² and X ³ represent a counter anion, and l represents 0 or 1.

Examples of the alkylene group represented by R ⁶ include a methylene group, an ethylene group, an n-propylene group, an isopropylene group, an n-butylene group, an isobutylene group and an n-hexylene group. Of these, a methylene group , Ethylene group and propylene group are preferred.

R ^{7 to} R ⁹ may be the same or different and may have a substituent. R ⁷ ~
Examples of the alkyl group represented by R ⁹ include a methyl group, an ethyl group,
n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, n-hexyl group, 2-ethylhexyl group, n-octyl group, n-nonyl group, n-decyl group , N-dodecyl group, n-octadecyl group, hydroxyethyl group, 1-hydroxypropyl group and the like.

The aryl group represented by R ^{7 to} R ⁹ is a phenyl group, an alkylphenyl group (eg, methylphenyl group, ethylphenyl group, n-propylphenyl group, n-
Butylphenyl group, n-hexylphenyl group, n-nonylphenyl group, etc.), naphthyl group, chlorophenyl group, dichlorophenyl group, trichlorophenyl group, bromophenyl group, hydroxyphenyl group, methoxyphenyl group,
An acetoxyphenyl group, a cyanophenyl group, etc. are mentioned.

Examples of the aralkyl group represented by R ^{7 to} R ⁹ include a benzyl group, a phenylethyl group, a vinylbenzyl group and a hydroxyphenylmethyl group.

[0048] (X ^{1) -} is not particularly limited to a counter anion, and halogens (Cl, Br, I, F ) HSO
_{^{4 -, AcO -, NO 3}} -, TsO -, MsO -, MeOSO 3
^-, and the like.

Specific examples of the monomer giving the unit of the formula (3) include methacryloyloxymethyltrimethylammonium chloride, methacryloyloxyethyltrimethylammonium chloride, methacryloyloxyethyltrimethylammonium bromide, methacryloyloxyethyltrimethylammonium acetate and methacryloyloxy. Ethyl trimethyl ammonium tosylate, methacryloyloxyethyl dimethyl benzyl ammonium chloride, methacryloyl oxyethyl-N, N-dimethyl benzyl ammonium bromide,
Methacryloyloxyethyl-N, N-dimethyl-n-
Hexylammonium chloride, methacryloyloxyethyl-N, N-dimethyl-n-hexylammonium bromide, methacryloyloxypropyltrimethylammonium chloride, acryloyloxyethyltrimethylammonium chloride, acryloyloxyethyl-N, N-dimethylbenzylammonium chloride and the like can be mentioned. .

In the formula (4), R ^{11 to} R ¹³ may be the same or different, and these may have a substituent.
The alkyl group represented by R ^{11 to} R ¹³ is a methyl group,
Ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group,
Cyclopentyl group, n-hexyl group, cyclohexyl group, 2-ethylhexyl group, n-octyl group, n-nonyl group, n-decyl group, n-dodecyl group, n-octadecyl group, hydroxyethyl group, 1-hydroxypropyl group Etc.

The aryl group represented by R ^{11 to} R ¹³ is a phenyl group, an alkylphenyl group (eg, methylphenyl group, ethylphenyl group, n-propylphenyl group, n
-Butylphenyl group, n-hexylphenyl group, n-nonylphenyl group, etc.), naphthyl group, chlorophenyl group,
Examples thereof include a dichlorophenyl group, a trichlorophenyl group, a bromophenyl group, a hydroxyphenyl group, a methoxyphenyl group, an acetoxyphenyl group and a cyanophenyl group.

The aralkyl group represented by R ^{11 to} R ¹³ is benzyl group, phenylethyl group, vinylbenzyl group,
Examples thereof include a hydroxyphenylmethyl group.

[0053] (X ^{2) -} is not particularly limited to a counter anion, and halogens (Cl, Br, I, F ) HSO
_{^{4 -, AcO -, NO 3}} -, TsO -, MsO -, MeOSO 3
^-, and the like.

Specific examples of the monomer giving the unit of the formula (4) include trimethyl-p-vinylbenzylammonium chloride, triethyl-p-vinylbenzylammonium chloride, triethyl-m-vinylbenzylammonium chloride and triethyl-p. -Vinylbenzylammonium bromide, triethyl-m-vinylbenzylammonium bromide, tri-n-propyl-p
-Vinylbenzyl ammonium chloride, tri-n-
Propyl-m-vinylbenzylammonium chloride, tri-n-butyl-p-vinylbenzylammonium chloride, tri-n-hexyl-p-vinylbenzylammonium chloride, N, N-dimethylcyclohexyl-p-vinylbenzylammonium chloride,
N, N-dimethylcyclohexyl-m-vinylbenzylammonium chloride, N, N-diethylcyclohexyl-p-vinylbenzylammonium chloride,
N, N-diethylcyclohexyl-m-vinylbenzylammonium chloride, triisopropyl-p-vinylbenzylammonium chloride, triisopropyl-m-vinylbenzylammonium chloride, triisobutyl-p-vinylbenzylammonium chloride, triisobutyl-m-vinyl Examples thereof include benzylammonium chloride, triethyl-p-vinylbenzylammonium acetate, triethyl-m-vinylbenzylammonium tosylate and the like.

In the formula (5), even if R ¹⁴ and R ¹⁵ are the same,
They may be different, and these may have a substituent. Examples of the alkyl group represented by R ¹⁴ and R ¹⁵ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group,
n-butyl group, isobutyl group, t-butyl group, n-pentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, 2-ethylhexyl group, n-octyl group, n
-Nonyl group, n-decyl group, n-dodecyl group, n-octadecyl group, hydroxyethyl group, 1-hydroxypropyl group and the like can be mentioned.

The aryl group represented by R ¹⁴ and R ¹⁵ is a phenyl group, an alkylphenyl group (eg, methylphenyl group, ethylphenyl group, n-propylphenyl group, n-butylphenyl group, n-hexylphenyl group,
n-nonylphenyl group), naphthyl group, chlorophenyl group, dichlorophenyl group, trichlorophenyl group, bromophenyl group, hydroxyphenyl group, methoxyphenyl group, acetoxyphenyl group, cyanophenyl group, and the like.

Examples of the aralkyl group represented by R ¹⁴ and R ¹⁵ include a benzyl group, a phenylethyl group, a vinylbenzyl group and a hydroxyphenylmethyl group.

[0058] (X ^{3) -} is not particularly limited to a counter anion, and halogens (Cl, Br, I, F ) HSO
_{^{4 -, AcO -, NO 3}} -, TsO -, MsO -, MeOSO 3
^-, and the like.

Specific examples of the monomer giving the unit of the formula (5) include diallyl ammonium chloride, monomethyl diallyl ammonium chloride, dimethyl diallyl ammonium chloride, monoethyl diallyl ammonium chloride, diethyl diallyl ammonium chloride and mono-n-propyl. Diallyl ammonium chloride, isobutyl diallyl ammonium chloride, n-
Examples thereof include butyl diallyl ammonium chloride, n-hexyl diallyl ammonium chloride, benzyl diallyl ammonium chloride, methyl diallyl ammonium acetate, and dimethyl diallyl ammonium acetate.

In the formula (6), R ^{16 to} R ¹⁸ may be the same or different, and these may have a substituent.
The alkyl group represented by R ^{16 to} R ¹⁸ is a methyl group,
Ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group,
Cyclopentyl group, n-hexyl group, cyclohexyl group, 2-ethylhexyl group, n-octyl group, n-nonyl group, n-decyl group, n-dodecyl group, n-octadecyl group, hydroxyethyl group, 1-hydroxypropyl group Etc.

The aryl group represented by R ^{16 to} R ¹⁸ is a phenyl group or an alkylphenyl group (eg, methylphenyl group, ethylphenyl group, n-propylphenyl group, n
-Butylphenyl group, n-hexylphenyl group, n-nonylphenyl group, etc.), naphthyl group, chlorophenyl group,
Examples thereof include a dichlorophenyl group, a trichlorophenyl group, a bromophenyl group, a hydroxyphenyl group, a methoxyphenyl group, an acetoxyphenyl group and a cyanophenyl group.

The aralkyl group represented by R ^{16 to} R ¹⁸ is a benzyl group, a phenylethyl group, a vinylbenzyl group,
Examples thereof include a hydroxyphenylmethyl group.

[0063] (X ^{4) -} are not particularly limited to a counter anion, and halogens (Cl, Br, I, F ) HSO
_{^{4 -, AcO -, NO 3}} -, TsO -, MsO -, MeOSO 3
^-, and the like.

Specific examples of the monomer giving the unit of the formula (6) include vinylamine hydrochloride, allylamine hydrochloride, allylamine bromate, allylamine acetate, monomethylallylammonium chloride, dimethylallylammonium chloride and trimethylallylammonium. Examples thereof include chloride, monoethylallylammonium chloride, diethylallylammonium chloride, triethylallylammonium chloride, monobenzylallylammonium chloride, N-methylallylammonium chloride and N, N-dimethylbenzylallylammonium chloride.

In the polymer (a) in the present invention, the content of the unit represented by the above formula (1) is preferably 1 to 90 mol%, more preferably 2 to 70 mol%, and 5 to 50 m.
ol% is particularly preferred. The above content is less than 1 mol%,
Alternatively, if it exceeds 90 mol%, the inorganic fine particles may aggregate. Further, the content of the unit represented by the above formula (2) in the polymer (a) is 10 to 90 mol%.
Is preferable, 15 to 85 mol% is more preferable, and 20
-80 mol% is especially preferable. The above content is 10mo
If it is less than 1% or more than 90 mol%, the inorganic fine particles may aggregate.

In addition to the units represented by the formulas (1) and (2), the polymer (a) may be combined with other copolymerizable monomers within a range not impairing the performance as an inorganic fine particle aggregation inhibitor. May be a copolymer of Examples of the unit copolymerizable with these units include (meth) acrylic acid alkyl ester [eg, (meth) acrylic acid methyl ester,
Ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, (meth) acrylic Hexyl acid, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate,
(Meth) acrylic acid C1-18 alkyl ester such as stearyl (meth) acrylate], (meth) acrylic acid cycloalkyl ester [cyclohexyl (meth) acrylate], (meth) acrylic acid aryl ester [(meth)] Phenyl acrylate, etc.], aralkyl ester [benzyl (meth) acrylate, etc.], substituted (meth) acrylic acid alkyl ester [eg, 2-hydroxyethyl (meth) acrylate], (meth) acrylamides [eg, ( (Meth) acrylamide, dimethyl (meth) acrylamide, etc.], aromatic vinyls [styrene, vinyltoluene, α-methylstyrene, etc.], vinyl esters [vinyl acetate, vinyl propionate, vinyl versatate, etc.], allyl esters [ Allyl acetate, etc.], halogen Containing monomers [vinylidene chloride, vinyl chloride], vinyl cyanide [(meth) acrylonitrile, etc.], olefins [ethylene, propylene etc.] nonionic monomers, and the like. Further, in particular, a polymer having a unit represented by the formula (2) is usually obtained by hydrolyzing a polymer such as N-vinylformamide or N-vinylacetamide, not by polymerization of vinylamine. May remain.

It is also possible to use a monomer having an ionic or basic unit. For example, diallyldimethylammonium chloride, methacryloyloxyethyl-β
-Hydroxyethyldimethylammonium chloride,
Vinylbenzyltrialkylammonium salt, (meth)
Acryloylethyltrialkylammonium salt, (meth) acryloylpropyltrialkylammonium salt, (meth) acrylamidoethyltrialkylammonium salt, (meth) acrylamidopropyltrialkylammonium salt, [trialkyl and triethyl as the trialkyl group shown in these , Tripropyl, triisopropyl, tributyl, trihexyl, dimethylbenzyl, etc.], dialkylaminoethyl (meth) acrylate, dialkylaminopropyl (meth)
Examples thereof include acrylate, dialkylaminoethyl (meth) acrylamide, dialkylaminopropyl (meth) acrylamide [as the dialkyl group shown therein, dimethyl, diethyl, dibutyl, methylbenzyl and the like] and the like. These copolymerizable components may be used alone or in combination of two or more.

When a copolymer is used, the content of the repeating unit represented by the formula (1) and / or (2) in the copolymer is preferably 10 mol% or more, and 20 mol%
The above is more preferable, and 30 mol% or more is particularly preferable. If the amount is less than 10 mol%, the inorganic fine particles agglomerate. The molecular weight of the polymer having a unit represented by the formula (1) and / or (2) is 1000 as a weight average molecular weight.
〜500,000 is preferable, 2,000-40,000
0 is more preferable. If the molecular weight is less than 1000, the water resistance tends to be insufficient, and if it is 500000 or more, the viscosity becomes high, resulting in poor handling suitability.
The dispersibility decreases due to the formation of crosslinks between the inorganic particles.

The ink jet recording sheet of the present invention comprises
The polymer (a) according to the present invention can be used alone on the surface of the support, but a colorant receiving layer containing fine inorganic pigment particles and a water-soluble resin may be further formed and used. Another preferred embodiment of the present invention is an inkjet recording sheet having a coloring material receiving layer containing, on a support, inorganic pigment fine particles, a water-soluble resin, and the polymer (a) of the present invention. To be Further, if necessary, an undercoat layer may be provided on the surface of the support, or a back layer may be provided on the back surface of the support on which the coloring material receiving layer is provided. In this case, the content of the polymer (a) in the present invention is preferably 0.5 to 25.0% by mass, and 1.0 to 20.0% by mass based on the total solid content of the colorant receiving layer. More preferable.
When the content is in the range of 0.5 to 25.0% by mass, the water resistance and the effect of preventing bleeding over time are further improved, and the deterioration of ink absorbency can be prevented.

(Inorganic pigment fine particles) Examples of the inorganic pigment fine particles include silica fine particles, colloidal silica, titanium dioxide, barium sulfate, calcium silicate, zeolite,
Kaolinite, halloysite, mica, talc, calcium carbonate, magnesium carbonate, calcium sulfate, boehmite, pseudo-boehmite and the like can be mentioned. Among them, silica fine particles and pseudo-boehmite are particularly preferable.

Since the above-mentioned silica fine particles have a particularly large specific surface area, they have high ink absorption and retention efficiency, and also have a low refractive index. Therefore, if they are dispersed to an appropriate particle size, they are transparent to the color material receiving layer. Is provided, and high color density and good color developability are obtained. The fact that the colorant receiving layer is transparent is not only for applications requiring transparency such as OHP, but also for obtaining high color density and good colorability when applied to recording sheets such as photo glossy paper. Is important in.

The average primary particle diameter of the inorganic pigment fine particles is preferably 20 nm or less, more preferably 10 nm or less, particularly preferably 3 to 10 nm.

The silica fine particles have silanol groups on the surface thereof, and particles are likely to adhere to each other due to hydrogen bonds due to the silanol groups. The structure can be formed. Thereby, the ink absorption characteristics can be effectively improved.

The silica fine particles are roughly classified into wet method particles and dry method particles according to the manufacturing method. In the above wet method, activated silica is generated by acid decomposition of silicate,
The mainstream method is to obtain water-containing silica by appropriately polymerizing this and coagulating and precipitating it. On the other hand, the dry method is a method by high-temperature gas phase hydrolysis of silicon halide (flame hydrolysis method) or a method in which silica sand and coke are heated and reduced and vaporized by an arc in an electric furnace, and this is oxidized by air. The main method is to obtain anhydrous silica by the (arc method).

The hydrous silica and anhydrous silica obtained by these methods have different properties because of the difference in the density of silanol groups on the surface, the presence or absence of pores, and the like. In particular, anhydrous silica (silicic acid anhydride) is preferable because it easily forms a three-dimensional structure having a high porosity. Although the reason for this is not clear, in the case of hydrous silica, the density of silanol groups on the surface of the fine particles is as high as 5 to 8 / nm ^2, and the silica fine particles are likely to densely aggregate (aggregate). On the other hand, in the case of anhydrous silica, since the density of silanol groups on the surface of the fine particles is as small as 2-3 / nm ^2, it causes sparse soft flocculation. As a result, it is estimated that the structure has a high porosity. Therefore, in the present invention, the density of silanol groups on the surface of the fine particles is 2-3 / nm.
It is preferable to use silica (fine silica particles) of ² .

Pseudo-boehmite is also preferable as the above-mentioned inorganic pigment fine particles. Pseudo-boehmite is boehmite (compositional formula A
10OOH) crystal colloidal aggregates, preferably containing a binder. As the pore characteristics, the average pore radius is preferably 1 to 10 nm, more preferably 3 to 10 nm. The pore volume is 0.5 to 1.0 ml /
It is preferably in the range of g. The coating amount of the pseudo-boehmite is preferably in the range of 5 to 30 g / m ² . If the coating amount is less than 5 g / m ² , the absorptivity of the ink may be lowered or the glossiness may be deteriorated due to the influence of the unevenness of the substrate, which is not preferable. Coating amount is 3
If it exceeds 0 g / m ² , not only is pseudoboehmite consumed unnecessarily, but the strength of the pseudoboehmite may be reduced, which is not preferable.

The composition of the pseudo-boehmite coating solution contains the binder in an amount of preferably 5 to 50 parts by mass based on 100 parts by mass of the pseudo-boehmite solid content, and the total solid content concentration is 5 to 3 parts.
Those of 0 mass% can be preferably used. The solvent of the coating liquid is preferably an aqueous system from the viewpoint of handleability. As the binder, an organic binder composed of a high molecular compound such as starch or a modified product thereof, polyvinyl alcohol and a modified product thereof, SBR latex, NBR latex, carboxymethyl cellulose, hydroxymethyl cellulose, polyvinylpyrrolidone can be preferably used.

(Water-soluble resin) As the above-mentioned water-soluble resin,
For example, a resin having a hydroxyl group as a hydrophilic structural unit, polyvinyl alcohol (PVA), cation-modified polyvinyl alcohol, anion-modified polyvinyl alcohol, silanol-modified polyvinyl alcohol, polyvinyl acetal, cellulose resin [methyl cellulose (MC), ethyl cellulose ( EC), hydroxyethyl cellulose (HEC), carboxymethyl cellulose (CMC), etc.], chitins, chitosans, starches; polyethylene oxide (PEO) and polypropylene oxide (PP) which are resins having an ether bond.
O), polyethylene glycol (PEG), polyvinyl ether (PVE); polyacrylamide (PAAM) which is a resin having an amide group or an amide bond, polyvinylpyrrolidone (PVP), and the like. Further, polyacrylic acid salts, maleic acid resins, alginates and gelatins having a carboxyl group as a dissociative group can be mentioned. Among the above, polyvinyl alcohols are particularly preferable.

When the content of the water-soluble resin is too low, the film strength is lowered and cracks are likely to occur during drying, and when the content is too high, the voids are easily blocked by the resin. As a result, the porosity may decrease and the ink absorbency may decrease. Therefore, the content of the water-soluble resin is preferably 9 to 40% by mass, more preferably 16 to 33% by mass, based on the total mass of the solid content of the colorant receiving layer.

The inorganic pigment fine particles and the water-soluble resin, which mainly constitute the colorant receiving layer, may be a single material or a mixture of a plurality of materials.

From the viewpoint of transparency, the type of resin combined with the silica fine particles is important. When the above anhydrous silica is used, polyvinyl alcohol (PVA) is preferable as the water-soluble resin, and the saponification degree is 70 to 9 among them.
9% PVA is more preferable, and P with a saponification degree of 90% or more is used.
VA is particularly preferred.

The PVA has a hydroxyl group in its structural unit, and the hydroxyl group and the silanol group on the surface of the silica fine particles form a hydrogen bond to form a three-dimensional network structure in which the secondary particles of the silica fine particles are chain units. Make it easier to form. It is considered that the formation of the above-mentioned three-dimensional network structure makes it possible to form a coloring material receiving layer having a porous structure with a high porosity. In inkjet recording, the porous coloring material-receiving layer obtained as described above can rapidly absorb ink by a capillary phenomenon and form dots with good circularity without ink blurring.

-Content Ratio of Inorganic Pigment Fine Particles to Water-Soluble Resin-Content ratio of inorganic pigment fine particles (preferably silica fine particles or pseudo-boehmite; i) to water-soluble resin [PB ratio (i: p), The mass of the inorganic pigment fine particles with respect to 1 part by mass of the water-soluble resin] has a great influence on the film structure of the colorant receiving layer. That is, as the PB ratio increases, the porosity, pore volume, and surface area (per unit mass) increase. But P
If the B ratio becomes too large, the film strength will decrease, and cracks will tend to occur during drying, and if the PB ratio is too small, the voids will become more likely to be blocked by the resin, resulting in a decrease in the void ratio. As a result, the ink absorbability may decrease. Therefore, the PB ratio (i: p) is 1.
5: 1 to 10: 1 is preferred.

Since the recording sheet may be stressed when passing through the transport system of the ink jet printer, it is necessary that the coloring material receiving layer has sufficient film strength. Further, in the case of cutting into a sheet shape, it is necessary that the coloring material receiving layer has sufficient film strength in order to prevent cracking or peeling of the coloring material receiving layer. In this case, the PB ratio is preferably 5: 1 or less, and is preferably 2: 1 or more from the viewpoint of ensuring high-speed ink absorbency in an inkjet printer.

For example, anhydrous silica fine particles having an average primary particle diameter of 20 nm or less and a water-soluble resin have a PB ratio of 2: 1 to 5:
When the coating solution completely dispersed in an aqueous solution in 1 was coated on a support and the coating layer was dried, a three-dimensional network structure having secondary particles of silica fine particles as chain units was formed, and the average pore diameter was It is possible to easily form a translucent porous film having a thickness of 30 nm or less, a porosity of 50% to 80%, a pore specific volume of 0.5 ml / g or more and a specific surface area of 100 m ² / g or more.

(Crosslinking Agent) In the ink jet recording sheet of the present invention, it is also preferable to use a crosslinking agent capable of crosslinking the above water-soluble resin in the above colorant receiving layer.

The above-mentioned crosslinking agent solution is applied at the same time as the coating liquid for forming the porous color material receiving layer (coating liquid for the color material receiving layer) is applied, or the coating liquid for the color material receiving layer is applied. It is preferable to be carried out before the coating layer formed by coating exhibits a decreasing rate of drying. By this operation, it is possible to effectively prevent the generation of cracks that occur during the drying of the coating layer. That is, at the same time when the coating liquid is applied, or before the coating layer shows a decreasing rate of drying, the crosslinking agent solution penetrates into the coating layer and reacts rapidly with the water-soluble resin in the coating layer, By gelling (curing) the water-soluble resin, the film strength of the coating layer is immediately and significantly improved.

As the cross-linking agent capable of cross-linking the water-soluble resin, a suitable one may be appropriately selected in relation to the water-soluble resin used in the colorant receiving layer, but among them, the cross-linking reaction is rapid. From the above, a boron compound is preferable, and examples thereof include borax, boric acid, borate (eg, orthoborate, In
_{BO 3, ScBO 3, YBO 3} , LaBO 3, Mg 3 (B
O ₃ ) ₂ , Co ₃ (BO ₃ ) ₂ , diborate (eg Mg _{2
B 2 O 5, Co 2 B} 2 O 5), metaborate (e.g., Li
_{BO 2, Ca (BO 2)} 2, NaBO 2, KBO 2), tetraborates _{(eg, Na 2 B 4 O 7 ·} 10H 2 O), pentaborate (e.g., KB ₅ O ₈ · 4H _{2 O, Ca 2 B 6 O 11} · 7H 2
O, CsB ₅ O ₅ ), glyoxal, melamine formaldehyde (for example, methylol melamine, alkylated methylol melamine), methylol urea, resole resin, polyisocyanate, epoxy resin and the like. Among them, borax, boric acid, and borate are preferable because they cause a crosslinking reaction quickly, and it is more preferable to use them in combination with polyvinyl alcohol as a water-soluble resin.

When gelatin is used as the water-soluble resin, the following compounds known as a hardening agent for gelatin can be used as a crosslinking agent. For example, aldehyde compounds such as formaldehyde, glyoxal, and glutaraldehyde; ketone compounds such as diacetyl and cyclopentanedione; bis (2-chloroethylurea) -2-hydroxy-4,6-dichloro-1,3.
Active halogen compounds such as 5-triazine and 2,4-dichloro-6-S-triazine sodium salt; divinyl sulfonic acid, 1,3-vinylsulfonyl-2-propanol, N, N'-ethylenebis (vinylsulfonyl acetate) Cetamide), active vinyl compounds such as 1,3,5-triacryloyl-hexahydro-S-triazine; N-methylol compounds such as dimethylolurea and methyloldimethylhydantoin;

Isocyanate compounds such as 1,6-hexamethylene diisocyanate; US Pat. No. 301
Nos. 7280 and 2983611; aziridine compounds; carboximide compounds described in U.S. Pat. No. 3,100,704; epoxy compounds such as glycerol triglycidyl ether; 1,6-hexamethylene-N, N '. -Ethyleneimino compounds such as bisethyleneurea; halogenated carboxaldehyde compounds such as mucochloric acid and mucophenoxycyclo acid; dioxane compounds such as 2,3-dihydroxydioxane; chromium alum, potassium alum, zirconium sulfate, Chromium acetate and the like. The cross-linking agents may be used alone or in combination of two or more.

The above crosslinking agent solution is prepared by dissolving the crosslinking agent in water and / or an organic solvent. The concentration of the cross-linking agent in the cross-linking agent solution is 0.
05-10 mass% is preferable and 0.1-7 mass% is especially preferable. Water is generally used as the solvent constituting the crosslinking agent solution, and may be an aqueous mixed solvent containing an organic solvent miscible with the water. Any organic solvent can be used as long as it can dissolve the crosslinking agent, and examples thereof include alcohols such as methanol, ethanol, isopropyl alcohol, and glycerin; ketones such as acetone and methyl ethyl ketone; methyl acetate, ethyl acetate, and the like. And the like; aromatic solvents such as toluene; ethers such as tetrahydrofuran; and halogenated carbon solvents such as dichloromethane.

(Organic mordant) In the present invention, in order to further improve the water resistance and bleeding resistance over time of the formed image,
It is preferable that the colorant receiving layer contains an organic mordant (hereinafter, may be simply referred to as “mordant”). As the mordant, a cationic polymer (cationic mordant)
It is preferable that the presence of the mordant in the colorant-receptive layer interacts with a liquid ink having an anionic dye as a colorant to stabilize the colorant and improve water resistance and blurring over time. it can.

As the cationic mordant, a polymer mordant having a primary to tertiary amino group or a quaternary ammonium salt group as a cationic group is preferably used, but a cationic non-polymer mordant is also used. can do. As the polymer mordant, first to third
A homopolymer of a monomer (mordant monomer) having a primary amino group and a salt thereof or a quaternary ammonium salt group, or a copolymerization weight of the mordant monomer and another monomer (hereinafter, referred to as "non-mordant polymer"). Those obtained as a polymer or a condensation polymer are preferable. Further, these polymer mordants can be used in the form of either a water-soluble polymer or water-dispersible latex particles.

Examples of the above-mentioned monomer (mordanting monomer) include trimethyl-p-vinylbenzylammonium chloride, trimethyl-m-vinylbenzylammonium chloride, triethyl-p-vinylbenzylammonium chloride and triethyl-m-vinylbenzylammonium. Chloride, N, N-dimethyl-N-ethyl-N-p-vinylbenzylammonium chloride,
N, N-diethyl-N-methyl-N-p-vinylbenzylammonium chloride, N, N-dimethyl-Nn
-Propyl-N-p-vinylbenzyl ammonium chloride, N, N-dimethyl-Nn-octyl-N-p
-Vinylbenzylammonium chloride, N, N-dimethyl-N-benzyl-Np-vinylbenzylammonium chloride, N, N-diethyl-N-benzyl-
N-p-vinylbenzylammonium chloride, N,
N-dimethyl-N- (4-methyl) benzyl-Np-
Vinylbenzylammonium chloride, N, N-dimethyl-N-phenyl-Np-vinylbenzylammonium chloride,

Trimethyl-p-vinylbenzylammonium bromide, trimethyl-m-vinylbenzylammonium bromide, trimethyl-p-vinylbenzylammonium sulfonate, trimethyl-m-vinylbenzylammonium sulfonate, trimethyl-p-vinylbenzylammonium acetate, trimethyl- m
-Vinylbenzyl ammonium acetate, N, N, N
-Triethyl-N-2- (4-vinylphenyl) ethylammonium chloride, N, N, N-triethyl-N
-2- (3-vinylphenyl) ethylammonium chloride, N, N-diethyl-N-methyl-N-2- (4
-Vinylphenyl) ethylammonium chloride,
N, N-diethyl-N-methyl-N-2- (4-vinylphenyl) ethylammonium acetate,

N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth)
Acrylate, N, N-diethylaminopropyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, Methyl chloride of N-diethylaminopropyl (meth) acrylamide,
Examples thereof include ethyl chloride, methyl bromide, ethyl bromide, quaternary compounds of methyl iodide or ethyl iodide, and sulfonates, alkylsulfonates, acetates or alkylcarboxylates of which anions are substituted.

Specifically, for example, monomethyldiallylammonium chloride, trimethyl-2- (methacryloyloxy) ethylammonium chloride, triethyl-2- (methacryloyloxy) ethylammonium chloride, trimethyl-2- (acryloyloxy) ethylammonium chloride. , Triethyl-2-
(Acryloyloxy) ethylammonium chloride, trimethyl-3- (methacryloyloxy) propylammonium chloride, triethyl-3- (methacryloyloxy) propylammonium chloride, trimethyl-2- (methacryloylamino) ethylammonium chloride, triethyl-2- (methacryloyl) Amino) ethylammonium chloride, trimethyl-
2- (acryloylamino) ethylammonium chloride, triethyl-2- (acryloylamino) ethylammonium chloride, trimethyl-3- (methacryloylamino) propylammonium chloride, triethyl-3- (methacryloylamino) propylammonium chloride, trimethyl-3- (Acryloylamino) propyl ammonium chloride, triethyl-
3- (acryloylamino) propylammonium chloride,

N, N-dimethyl-N-ethyl-2- (methacryloyloxy) ethylammonium chloride,
N, N-diethyl-N-methyl-2- (methacryloyloxy) ethylammonium chloride, N, N-dimethyl-N-ethyl-3- (acryloylamino) propylammonium chloride, trimethyl-2- (methacryloyloxy) ethylammonium Bromide, trimethyl-3- (acryloylamino) propylammonium bromide, trimethyl-2- (methacryloyloxy) ethylammonium sulfonate, trimethyl-
3- (acryloylamino) propyl ammonium acetate etc. can be mentioned. In addition, examples of copolymerizable monomers include N-vinylimidazole and N-vinyl-2-methylimidazole.

The non-mordant polymer does not contain a basic or cationic moiety such as a primary to tertiary amino group and its salt, or a quaternary ammonium salt group, and interacts with the dye in the ink jet ink. A monomer that does not show or has a substantially small interaction. Examples of the non-mordanting monomer include (meth) acrylic acid alkyl ester; (meth) acrylic acid cycloalkyl ester such as cyclohexyl (meth) acrylate; (meth)
(Meth) acrylic acid aryl ester such as phenyl acrylate; aralkyl ester such as benzyl (meth) acrylate; aromatic vinyls such as styrene, vinyltoluene, α-methylstyrene; vinyl acetate, vinyl propionate, vinyl versatate And vinyl esters such as allyl acetate; halogen-containing monomers such as vinylidene chloride and vinyl chloride; vinyl cyanide such as (meth) acrylonitrile; olefins such as ethylene and propylene.

The above-mentioned (meth) acrylic acid alkyl ester has a carbon number of 1 to 18 at the alkyl moiety (meth).
Acrylic acid alkyl esters are preferable, for example, methyl (meth) acrylate, ethyl (meth) acrylate,
Propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate,
Examples include hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, and stearyl (meth) acrylate. Among them, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate and hydroxyethyl methacrylate are preferable. The non-mordant monomers can be used alone or in combination of two or more.

Further, as a polymer mordant, polydiallyldimethylammonium chloride, polymethacryloyloxyethyl-β-hydroxyethyldimethylammonium chloride, polyethylenimine, polyallylamine and its modified products, polyallylamine hydrochloride, polyamide-polyamine resin, cation Preferred examples include modified starch, dicyandiamide formalin condensate, dimethyl-2-hydroxypropylammonium salt polymer, polyamidine, and polyvinylamine.
Polyallylamine and its modified products are particularly preferred.

The modified polyallylamine is obtained by adding acrylonitrile, chloromethylstyrene, TEMPO, epoxyhexane, sorbic acid, etc. to polyallylamine in an amount of 2-5.
0 mol% added, preferably 5 to 10 mol% of acrylonitrile and chloromethylstyrene, particularly 5 to 10 mol% of polyallylamine.
Acrylonitrile adducts are preferable from the viewpoint of exerting the effect of preventing ozone fading.

The molecular weight of the mordant is preferably 5,000 to 30,000 in terms of weight average molecular weight. When the molecular weight is in the range of 5,000 to 300,000, water resistance and bleeding resistance over time can be improved.

The content of the organic mordant is preferably 0.5 to 25% by mass, more preferably 1 to 20% by mass based on the total mass of the solid content of the colorant receiving layer.

(Other Additives) The ink jet recording sheet of the present invention may further contain the following components, if necessary. For the purpose of suppressing the deterioration of the coloring material, various kinds of ultraviolet absorbers, antioxidants, and fading inhibitors such as singlet oxygen quencher may be contained. Examples of the ultraviolet absorber include cinnamic acid derivatives, benzophenone derivatives, benzotriazolylphenol derivatives and the like. For example, α-cyano-phenyl butyl cinnamate, o-
Benzotriazole phenol, o-benzotriazole-p-chlorophenol, o-benzotriazole-
2,4-di-t-butylphenol, o-benzotriazole-2,4-di-t-octylphenol and the like can be mentioned. A hindered phenol compound can also be used as an ultraviolet absorber, and specifically, a phenol derivative in which at least one of 2-position or 6-position is substituted with a branched alkyl group is preferable.

Further, benzotriazole type ultraviolet absorbers, salicylic acid type ultraviolet absorbers, cyanoacrylate type ultraviolet absorbers, oxalic acid anilide type ultraviolet absorbers and the like can also be used. For example, JP-A-47-1053
No. 7, gazette 58-111942 gazette, gazette 58-21.
No. 2844, No. 59-19945, No. 59-
46646, 59-109055, and 6
No. 3-53544, Japanese Patent Publication No. 36-10466, No. 42-26187, No. 48-30492, No. 48-31255, No. 48-41572.
JP-A-48-54965 and JP-A-50-1072.
No. 6, gazettes, US Pat. Nos. 2,719,086, 3,707,375, 3,754,919, 4,220,711, etc. There is.

A fluorescent brightening agent can also be used as an ultraviolet absorber, and examples thereof include a coumarin-based fluorescent brightening agent. Specifically, JP-B-45-4699 and 54-53.
No. 24, etc.

Examples of the above-mentioned antioxidant include European Patent Nos. 223739, 309401, 309402, 310551 and 31.
No. 0552, No. 459416, German Published Patent No. 3435443, and Japanese Patent Laid-Open No. 54-48535.
No. 60-107384 and No. 60-107.
No. 383, No. 60-125470, No. 60-
No. 125471, No. 60-125472, No. 60-287485, No. 60-287486, No. 60-287487, and No. 60-28748.
8 gazette, the same 61-160287 gazette, the same 61-18.
5483, 61-211079 and 62.
No. 146678, No. 62-146680,
62-146679, 62-282885, 62-262047, 63-0511.
74, 63-89877, 63-88.
No. 380, No. 66-88381, No. 63-1.
No. 13536,

63-163351 and 63-2.
No. 03372, No. 63-224989, No. 6
No. 3-251282, No. 63-267594, No. 63-182484, Japanese Patent Laid-Open No. 1-2392.
82, JP-A-2-262654, and 2-7.
No. 1262, No. 3-121449, and No. 4-2.
No. 91685, No. 4-291684, No. 5-
No. 61166, No. 5-119449, No. 5-
No. 188687, No. 5-188686, No. 5
-110490 gazette, the same 5-1108437 gazette,
No. 5-170361, Japanese Patent Publication No. 48-43295, No. 48-33212, and U.S. Pat. No. 4,814.
No. 262, No. 4980275, etc. are mentioned.

Specifically, 6-ethoxy-1-phenyl-2,2,4-trimethyl-1,2-dihydroquinoline, 6-ethoxy-1-octyl-2,2,4-trimethyl-1,2. -Dihydroquinoline, 6-ethoxy-1-
Phenyl-2,2,4-trimethyl-1,2,3,4-
Tetrahydroquinoline, 6-ethoxy-1-octyl-
2,2,4-trimethyl-1,2,3,4-tetrahydroquinoline, nickel cyclohexanoate, 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) -2 -Ethylhexane, 2
-Methyl-4-methoxy-diphenylamine, 1-methyl-2-phenylindole and the like can be mentioned.

The anti-fading agents may be used alone or in combination of two or more kinds. This anti-fading agent may be water-solubilized, dispersed or emulsified, or may be contained in microcapsules. The amount of the anti-fading agent added is preferably 0.01 to 10% by mass of the coating liquid for the colorant receiving layer.

Further, for the purpose of enhancing the dispersibility of the fine particles of the inorganic pigment, various inorganic salts may be contained, and an acid, an alkali or the like may be contained as a pH adjusting agent. Further, various surfactants are used for the purpose of improving coating suitability and surface quality, and surfactants having ionic conductivity and metal oxide fine particles having electronic conductivity are used for the purpose of suppressing frictional electrification and peeling electrification on the surface. It is preferable to include various matting agents for the purpose of reducing the frictional properties of the surface.

The matting agent may have a particle size of 3 μm to 30 μm.
A matting agent having a particle size of 10 μm is preferable, and a particle size of 10 μm to 30 μm is more preferable. Conventionally known matting agents can be used. Matting agents are well known in the photographic art and can be defined as discrete solid particles of an inorganic or organic material dispersible in a hydrophilic organic colloid binder. Examples of the inorganic matting agent include oxides (for example, silicon dioxide, titanium oxide, magnesium oxide, aluminum oxide, etc.), alkaline earth metal salts (for example, sulfates and carbonates, specifically, barium sulfate and carbonate). Examples thereof include calcium, magnesium sulfate, and calcium carbonate), silver halide grains that do not form an image (such as silver chloride and silver bromide, and a small amount of iodine atoms may be added as a halogen component) and glass.

In addition to the above-mentioned inorganic matting agents, for example, West German Patent No. 2,529,321 and British Patent No. 760,7.
No. 75, No. 1,260,772, US Pat. No. 1,201,905, No. 2,192,24.
1, No. 3,053,662, No. 3,0
62,649, 3,257,206, 3,322,555, 3,353,9
No. 58, No. 3,370,951 and No. 3,
411,907, 3,437,484, 3,523,022, 3,615,5
No. 54, No. 3,635,714, No. 3,
It is also possible to use the inorganic matting agents described in the specifications of No. 769,020, No. 4,021,245, No. 4,029,504 and the like.

The matting agent may be an organic matting agent, and examples of the organic matting agent include starch, cellulose ester (eg, cellulose acetate propionate), cellulose ether (eg, ethyl cellulose), synthetic resin and the like. Is mentioned. As the synthetic resin,
It is possible to use synthetic polymers that are insoluble or sparingly soluble in water, such as alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, glycysilyl (meth).
Acrylate, (meth) acrylamide, vinyl ester (eg vinyl acetate), acrylonitrile, olefin (eg ethylene), styrene, benzoguanamine / formaldehyde condensate, etc., alone or in combination,
Alternatively, it is possible to use a polymer having a monomer component of a combination of these with acrylic acid, methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, sulfoalkyl (meth) acrylate, styrenesulfonic acid, or the like. it can.

Further, as the organic matting agent, epoxy resin, nylon, polycarbonate, phenol resin,
Polyvinylcarbazole, polyvinylidene chloride, etc. can also be used. Besides this, British Patent No. 1,055
No. 713, U.S. Pat. No. 1,939,213, No. 2,221,873, No. 2,268,6.
No. 62, No. 2,322,037, No. 2,
376,005, 2,391,181, 2,701,245, 2,992,1
No. 01, No. 3,079,257, No. 3,
262,782, 3,443,946, 3,516,832, 3,539,3
No. 44, No. 3,591,379, No. 3,
754,924, 3,767,448, JP-A-49-106821, 57-148.
The organic matting agents described in JP-A-35-35 can be used.

Examples of the organic matting agent include polystyrene beads (manufactured by Moritex), nylon beads (manufactured by Moritex), AS resin beads (manufactured by Moritex),
Epoxy resin beads (manufactured by Moritex), polycarbonate resin (manufactured by Moritex) and the like can be preferably used.

Further, as the above matting agent, an alkali-soluble matting agent can be preferably used. Examples of the alkali-soluble matting agent include JP-A Nos. 53-7231 and 58-58.
Alkali-soluble matting agents such as alkyl methacrylate / methacrylic acid copolymers described in JP-A-66937 and JP-A-60-8894, and alkali-soluble matting agents having an anionic group described in JP-A-58-166341. Polymers can also be used.

Two or more of the above-mentioned matting agents may be used in combination, and examples of the combined use of matting agents include JP-A-58-14.
No. 5,935, a combination of two or more kinds of fine particle powders having different Mohs' hardness, a combination of two or more kinds of spherical matting agents having different average particle sizes as described in JP-A-59-149356, and a colorant receiving layer. A combination of an amorphous matting agent such as silica and a spherical matting agent such as polymethylmethacrylate in the back layer may be used.

The coloring material-receptive layer and other layers in the present invention include coating aids, antistatic agents, slipperiness improvement, emulsion dispersion, adhesion prevention and photographic property improvement (for example, development acceleration, high contrast,
Various surfactants may be included for various purposes such as sensitization). Examples of the surfactant include saponins (steroidal), alkylene oxide derivatives (eg, polyethylene glycol, polyethylene glycol / polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene). Glycol sorbitan esters, polyalkylene glycol alkylamines or amides, polyethylene oxide adducts of silicone),
Nonionic surfactants such as glycidol derivatives (eg, alkenyl succinic acid polyglyceride, alkylphenol polyglyceride), fatty acid esters of polyhydric alcohols, etc., alkyl carboxylates, alkyl sulfonates, alkylbenzene sulfonates Salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurates, sulfosuccinates, esphoalkyl polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl eicos Carboxy group, sulfo group, such as sun acid esters,
An anionic surfactant containing an acidic group such as a phospho group, a sulfuric acid ester group, a phosphoric acid ester group;

Amphoteric surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphoric acid esters, alkylbetaines, amine oxides; alkylamine salts, aliphatic or aromatic quaternary ammonium salts, pyridinium , Cationic surfactants such as heterocyclic quaternary ammonium salts such as imidazolium and phosphonium or sulfonium salts containing an aliphatic or heterocyclic ring can be used.

A slipping agent may be added to the color material receiving layer. Examples of the slip agent include higher alkyl sodium sulfate, higher fatty acid higher alcohol ester, carbowax, higher alkyl phosphate ester, and silicon compound. Especially US Pat. No. 2,882,15
No. 7, No. 3,121,060, No. 3,850,640, JP-A-51-14162.
The compounds described in JP-A-3, etc. are particularly effective when used alone or in combination of two or more kinds.

Also, French Patent No. 2,180,465, British Patent No. 955,061 and No. 1,1.
43,118, 1,270,578, 1,320,564, 1,320,7.
57, JP-A-49-5017 and 51-
141623, 54-159221, 56-81841, and Research Disclosure 1396.
9, US Pat. Nos. 1,263,722 and 2,
588,765, 2,739,891, 3,018,178, 3,042,5
No. 22, No. 3,080,317, No. 3,
082,087, 3,121,060, 3,222,178, 3,295,9
79, 3,489,567, 3,
516, 832, 3,658, 573, 3,679, 411, 3,870, 5
No. 21, etc. can be used. The appropriate amount of the above-mentioned sliding agent applied is about 5 to 200 mg / m ² .

Each layer of the ink jet recording sheet of the present invention may contain silica, particularly colloidal silica, for the purpose of improving adhesion resistance, film strength, curl balance and the like.

<< Method for Producing Inkjet Recording Sheet >> Next, a method for forming the colorant receiving layer will be described. The colorant receiving layer in the present invention has a pH of 5 including the polyvinyl alcohol, a nonionic or amphoteric surfactant, and the high-boiling organic solvent in a dispersion containing the vapor grown silica and the polymer (a). First obtained by adding the following solution
Solution (inorganic fine particle dispersion), (1) at the same time as the coating, (2) during the drying of the coating layer formed by the coating, and before the coating layer exhibits a rate of decrease in drying rate. ,
And (3) after drying the coating layer to form a coating film, a second solution containing an organic mordant is applied to the coating layer, and the coating layer is cured and dried. Has a porous structure. The second coating liquid contains the cross-linking agent and the nonionic surfactant, and has a pH of 8.
It is preferably adjusted to 5 or more.

According to another aspect of the colorant receiving layer in the present invention, the surface of the support is coated with the first coating liquid containing the inorganic fine particle dispersion, and (1) simultaneously with the coating,
(2) Either during the drying of the coating layer formed by the coating and before the coating layer shows a reduction rate drying, or (3) after the coating layer is dried to form a coating film. ,
It is formed by applying a second coating liquid containing an organic mordant.

As described above, in the present invention, the water resistance of the colorant receiving layer can be improved by simultaneously applying the mordant together with the crosslinking agent. That is, when the mordant is added to the coating liquid for the colorant receiving layer, the mordant may be aggregated in the coexistence with the gas phase method silica having an anionic charge on the surface because the mordant is cationic. If a method of independently preparing a second coating liquid containing a pigment and a coating liquid for a colorant receiving layer and individually coating them is used, it is not necessary to consider the aggregation of the inorganic pigment fine particles, and the selection range of the mordant can be reduced. Spreads.

In the present invention, the first coating liquid (coating liquid for the colorant receiving layer) containing vapor-phase grown silica, a cationic resin, PVA, a nonionic or amphoteric surfactant, and a high-boiling organic solvent. Can be prepared, for example, as follows. That is, vapor phase silica is added to water, a cationic resin is further added, and the mixture is dispersed with a high pressure homogenizer, a sand mill or the like, and then an aqueous polyvinyl alcohol solution (for example, about 1/3 the mass of vapor phase silica PVA), nonionic or amphoteric surfactant, and high boiling point organic solvent are added, and the mixture is stirred. The obtained coating liquid is a uniform sol, and by coating it on a support by the coating method described below,
It is possible to form a porous coloring material-receptive layer having a three-dimensional network structure.

In the present invention, the pH of the first coating liquid is
It is preferably 5 or less, more preferably 4.2 or less, still more preferably 3.7 or less.
When the pH of the first coating liquid is higher than 5, the print density, sharpness and gloss of the image may be deteriorated. First
The pH of the coating solution can be adjusted to 5 or less by appropriately selecting the type and addition amount of the cationic resin. Further, it may be adjusted by adding an inorganic acid or alkali. If necessary, a pH adjusting agent, an antistatic agent, or the like can be added to the first coating liquid (coating liquid for the color material receiving layer).

The first coating liquid can be applied by a known application method such as an extrusion die coater, an air doctor coater, a bread coater, a rod coater, a knife coater, a squeeze coater, a reverse roll coater, a bar coater and the like.

After applying the first coating solution, the second coating solution is applied to the coating layer, but the second coating solution (crosslinking agent solution) is applied to the coating layer after application at a reduced drying rate. May be given before it becomes. That is, after applying the first coating liquid,
It is preferably produced by introducing a crosslinking agent, a mordant and a nonionic surfactant while the coating layer exhibits a constant drying rate. The pH of the second coating liquid is preferably 8.5 or more, more preferably 9.0 or more,
More preferably, it is 9.2 or more. If the pH of the second coating liquid is less than 8.5, cracks may occur in the color material receiving layer.

Here, "before the coating layer starts to exhibit a decreasing rate drying rate" usually means a few minutes immediately after the coating of the coating liquid for the colorant-receptive layer, and during this period, the coating layer coated The constant drying rate, which is a phenomenon in which the content of the solvent therein decreases in proportion to time, is shown. The time indicating the constant rate of drying is described in Chemical Engineering Handbook (p. 707 to 712, published by Maruzen Co., Ltd., October 25, 1980).

As described above, after coating the first coating liquid, the coating layer is dried until it exhibits a rate of reduction drying, and the drying is generally at 50 to 180 ° C. for 0.5 to 10 minutes. (Preferably 0.5 to 5 minutes). As the drying time, it naturally depends on the coating amount, but the above range is suitable.

As the method for applying the second coating solution before the above coating layer shows the decreasing rate of drying, (1) a method of further coating the crosslinking agent solution on the coating layer, (2) spraying And the like, and (3) a method of immersing the support on which the coating layer is formed in the second coating liquid (crosslinking agent solution).

In the above method (1), the method for applying the second coating solution (crosslinking agent solution) includes, for example, curtain flow coater, extrusion die coater, air doctor coater, bread coater, rod coater, knife coater, squeeze coater. A known coating method such as a coater, a reverse roll coater or a bar coater can be used. However, it is preferable to use a method such as an extrusion die coater, a curtain flow coater, or a bar coater in which the coater does not directly contact the already-formed coating layer.

The coating amount of the second coating liquid (crosslinking agent solution) to be applied to the colorant receiving layer is 0.01 to 50 in terms of crosslinking agent.
It is generally 10 g / m ² , and preferably 0.05 to 5 g / m ² .

After the application of the crosslinking agent solution, it is generally 40 to 18
It is heated at 0 ° C. for 0.5 to 30 minutes to be dried and cured. Above all, it is preferable to heat at 40 to 150 ° C. for 1 to 20 minutes. For example, when borax or boric acid is used as the boron compound contained in the cross-linking agent solution, it is preferable to perform heating at 60 to 100 ° C for 0.5 to 15 minutes.

The second coating solution (crosslinking agent solution)
May be applied at the same time when the first coating liquid (coloring material receiving layer coating liquid) is applied. In this case, the color material-receptive layer coating solution and the cross-linking agent solution are simultaneously coated on the support so that the color material-receptive layer coating solution is in contact with the support (multi-layer coating), and then dried and cured to obtain the color. A material receiving layer can be formed.

The simultaneous coating (multilayer coating) can be carried out by a coating method using an extrusion die coater or a curtain flow coater. After the simultaneous coating, the formed coating layer is dried, and the drying in this case is generally performed by heating the coating layer at 40 to 150 ° C. for 0.5 to 10 minutes, preferably 40 to 150 ° C.
It is carried out by heating at 100 ° C. for 0.5 to 5 minutes. For example, when borax or boric acid is used as the cross-linking agent contained in the cross-linking agent solution, it is preferable to heat at 60 to 100 ° C. for 5 to 20 minutes.

When the above simultaneous coating (multilayer coating) is carried out, for example, by an extrusion die coater, the two kinds of coating liquids discharged at the same time are near the discharge port of the extrusion die coater, that is, before being transferred onto the support. Is formed in multiple layers, and in that state, multiple layers are applied on the support. Since the two-layer coating solution that has been overlaid before coating tends to cause a cross-linking reaction at the interface between the two solutions when it is transferred to the support, the two solutions to be discharged are mixed near the discharge port of the extrusion die coater. May increase the viscosity, which may hinder the coating operation. Therefore, in the case of simultaneous coating as described above, along with the coating of the colorant-receptive layer coating solution and the crosslinking agent solution containing the crosslinking agent and the mordant, a barrier layer solution (intermediate layer solution) made of a material that does not react with the crosslinking agent. It is preferable to apply (3) at the same time by interposing between the above two liquids.

The barrier layer liquid can be selected without particular limitation as long as it can form a liquid film without reacting with the boron compound. For example, an aqueous solution containing a trace amount of a water-soluble resin that does not react with a boron compound, water, and the like can be given. The above-mentioned water-soluble resin is used in consideration of coatability for the purpose of a thickener and the like, and examples thereof include hydroxypropylmethylcellulose, methylcellulose, hydroxyethylmethylcellulose, polyvinylpyrrolidone, gelatin. And the like. The mordant may be contained in the barrier layer liquid.

Further, water, an organic solvent, or a mixed solvent thereof can be used as a solvent in each step.
Examples of the organic solvent that can be used for this coating include alcohols such as methanol, ethanol, n-propanol, i-propanol and methoxypropanol, ketones such as acetone and methyl ethyl ketone, tetrahydrofuran, acetonitrile, ethyl acetate, toluene and the like. To be

After the color material receiving layer is formed on the support, the surface of the color material receiving layer is smoothed by calendering through a roll nip under heat and pressure using, for example, a super calender or a gloss calender. It is possible to improve properties, glossiness, transparency and coating film strength. However, the calendering process may cause a decrease in the porosity (that is, the ink absorbency may decrease), and therefore, it is necessary to set conditions under which the decrease in the porosity is small.

The roll temperature for calendering treatment is preferably from 30 to 150 ° C., and from 40 to 100 ° C.
C is more preferred. Further, the linear pressure between the rolls during the calendar treatment is preferably 50 to 400 kg / cm,
100 to 200 kg / cm is more preferable.

In the case of ink jet recording, the layer thickness of the color material receiving layer needs to be determined in relation to the porosity in the layer, because it is necessary to have an absorption capacity enough to absorb all the droplets. is there. For example, if the ink amount is 8 nL / mm ²
If the porosity is 60%, the layer thickness is about 15 μm.
The above film is required. Considering this point, in the case of inkjet recording, the layer thickness of the colorant receiving layer is 1
0 to 50 μm is preferable.

The pore diameter of the color material receiving layer is preferably 0.005 to 0.030 μm in terms of median diameter, and 0.01 to
0.025 μm is more preferable. The porosity and the median pore diameter can be measured using a mercury porosimeter (trade name: Boasizer 9320-PC2, manufactured by Shimadzu Corporation).

The colorant-receiving layer preferably has excellent transparency. As a guideline, the haze value when the colorant-receiving layer is formed on a transparent film support is 30.
% Or less, and more preferably 20% or less. The haze value is a haze meter (HG
M-2DP: It can be measured using Suga Test Instruments Co., Ltd.

<Support> As the support, any of a transparent support made of a transparent material such as plastic and an opaque support made of an opaque material such as paper can be used. In order to make the most of the transparency of the colorant receiving layer, it is preferable to use a transparent support or a highly glossy opaque support.

As a material that can be used for the transparent support, a material that is transparent and has a property of withstanding radiant heat when used in an OHP or a backlight display is preferable. Examples of the material include polyesters such as polyethylene terephthalate (PET); polysulfone,
Examples thereof include polyphenylene oxide, polyimide, polycarbonate and polyamide. Among them, polyesters are preferable, and polyethylene terephthalate is particularly preferable. The thickness of the transparent support is not particularly limited, but is preferably 50 to 200 μm from the viewpoint of handleability.

As the highly glossy opaque support, it is preferable that the surface on the side where the color material receiving layer is provided has a glossiness of 40% or more. The glossiness is JIS P-814.
It is a value determined according to the method described in 2 (75 degree specular gloss test method for paper and board). Specific examples include the following supports.

For example, high gloss paper supports such as art papers, coated papers, cast coated papers, and baryta papers used for silver salt photographic supports; polyesters such as polyethylene terephthalate (PET); nitrocellulose. , Cellulose acetate, cellulose acetate such as cellulose acetate butyrate, plastic film such as polysulfone, polyphenylene oxide, polyimide, polycarbonate, polyamide, etc. were made opaque by containing a white pigment etc. (may be subjected to surface calendering treatment) High-gloss film; or a high-gloss film containing the above various paper supports, the above-mentioned transparent supports, or white pigments, etc., provided with a polyolefin coating layer containing or not containing a white pigment. Support. Further, a white pigment-containing expanded polyester film (for example, expanded PET in which polyolefin fine particles are contained and voids are formed by stretching) can also be preferably mentioned.

The thickness of the opaque support is not particularly limited, but is preferably 50 to 300 μm from the viewpoint of handleability.

Further, a corona discharge treatment,
Those subjected to glow discharge treatment, flame treatment, ultraviolet irradiation treatment and the like may be used.

Next, the base paper used for the paper support will be described in detail. The base paper is made from wood pulp as a main raw material, and if necessary, synthetic paper such as polypropylene, or synthetic fiber such as nylon or polyester is used in addition to wood pulp. As the wood pulp, LBKP, LBSP, NBKP, NBSP, LD
Any of P, NDP, LUKP and NUKP can be used, but LBKP, NBSP, LB with a large amount of short fibers
It is preferable to use more SP, NDP, and LDP. However, the ratio of LBSP and / or LDP is preferably 10% by mass or more and 70% by mass or less.

As the above pulp, a chemical pulp containing few impurities (sulfate pulp or sulfite pulp) is preferably used,
Pulp that has been bleached to improve its whiteness is also useful.

In the base paper, sizing agents such as higher fatty acids and alkyl ketene dimers, white pigments such as calcium carbonate, talc and titanium oxide, paper strength enhancers such as starch, polyacrylamide and polyvinyl alcohol, fluorescent whitening agents, A water retention agent such as polyethylene glycol, a dispersant, and a softening agent such as quaternary ammonium can be appropriately added.

The freeness of the pulp used for papermaking is as follows.
According to CSF regulations, 200 to 500 ml is preferable, and
The fiber length after beating is preferably 30 to 70% of the sum of the 24 mesh residual mass% and the 42 mesh calculated mass% defined in JIS P-8207. The mass% of the 4-mesh residue is preferably 20 mass% or less.

The basis weight of the base paper is preferably 30 to 250 g, and particularly preferably 50 to 200 g. The thickness of the base paper is preferably 40 to 250 μm. The base paper can be given a high smoothness by calendering at the papermaking stage or after the papermaking. The base paper density is 0.7 to 1.2 g / m ² (J
ISP-8118) is common. Furthermore, the stiffness of the base paper is 2 under the conditions specified in JIS P-8143.
0 to 200 g is preferable.

A surface sizing agent may be applied to the surface of the base paper, and as the surface sizing agent, the same sizing agent as that which can be added to the base paper can be used. The pH of the base paper is JI
It is preferably 5 to 9 when measured by the hot water extraction method specified in SP-8113.

The polyethylene for covering the front and back surfaces of the base paper is mainly low-density polyethylene (LDPE) and / or high-density polyethylene (HDPE), but other LLDPE, polypropylene or the like can be partially used.

In particular, the polyethylene layer on the side for forming the colorant receiving layer is formed by adding rutile or anatase type titanium oxide to polyethylene, as is commonly used in photographic printing paper, to obtain opacity and whiteness. Those improved are preferable. Here, the content of titanium oxide is preferably 3 to 20 mass% with respect to polyethylene, and 4 to 13 is preferable.
Mass% is more preferable.

The polyethylene-coated paper can be used as a glossy paper, or when a polyethylene is melt-extruded on the surface of a base paper for coating, a so-called patterning treatment is performed to obtain a matte surface or a matte surface obtained by ordinary photographic printing paper. It is also possible to use those having a silk surface.

[0163]

EXAMPLES [Synthesis Example 1] Methacryloyloxyethyltrimethylammonium chloride (trade name: light ester DQ) was added as a unit represented by the formula (1) to a flask injection equipped with a stirrer, a reflux condenser and a nitrogen inlet tube. -1
00, Kyoeisha Chemical Co., Ltd.) 30 parts, as a unit represented by the formula (2), methoxy polyethylene glycol monomethacrylate (trade name: Bremmer PME-200, manufactured by NOF Corporation) 6 parts, ethanol 108 parts , 0.078 parts of 2,2′-azobis (2-amidinopropane) dihydrochloride (V-50, manufactured by Wako Pure Chemical Industries, Ltd.) was added as an initiator and reacted at 70 ° C. for 2 hours in a nitrogen atmosphere. Let After that, 0.078 parts of V-50 was added, and further 7
The mixture was heated and stirred at 0 ° C. for 4 hours. This reaction liquid was poured into a mixed solvent of 1000 parts of ethyl acetate and 1000 parts of hexane while stirring, and the resulting viscous solid was dried by heating to obtain 28 parts of a white solid of Polymer 1.

[Synthesis Examples 2 to 14] As shown in Table 1, light ester DQ-100 was used as trimethylvinylbenzylammonium chloride (trade name: QBm, manufactured by Seimi Chemical Co., Ltd.), and Bremmer PME-200 was used as polyethylene oxide. Blemmer PME-1000 having different chain lengths
Polymers 2 to 1 in the same manner as in Synthesis Example 1 except that
Got 4.

[0165]

[Table 1]

(Example 1) -Preparation of support-Art paper (OK Kinfuji; manufactured by Oji Paper Co., Ltd.) having a basis weight of 186 g / m ² was subjected to corona discharge treatment, and then a high density was obtained using a melt extruder. Polyethylene was coated to a thickness of 19 μm to form a matte surface resin layer (hereinafter, the resin layer surface is referred to as “back surface”). The resin layer on the back surface is further subjected to corona discharge treatment, and then aluminum oxide (alumina sol 100, manufactured by Nissan Chemical Industries, Ltd.) and silicon dioxide (Snowtex O, as an antistatic agent).
A dispersion liquid obtained by dispersing in a ratio of 1: 2 (manufactured by Nissan Chemical Industries, Ltd.) in water (mass ratio) was applied so that the dry mass would be 0.2 g / m ² .

Further, after the corona discharge treatment was applied to the felt surface (front surface) side where the resin layer was not provided, anatase type titanium dioxide 10%, a trace amount of ultramarine blue, and an optical brightening agent 0.01% ( To polyethylene), MFR
(Melt float) 3.8 low-density polyethylene is melt-extruded using a melt extruder to a thickness of 24 μm, and a high-gloss thermoplastic resin layer is formed on the surface side of the base paper (hereinafter referred to as “high-gloss surface”). Is referred to as "surface"), and was used as a support. The surface of the support was used after being subjected to corona discharge treatment before applying the coating liquid.

-Preparation of Inorganic Fine Particle Dispersion- (2) Ion-exchanged water in the following composition was mixed with (1) vapor-phase method silica fine particles, and (3) 10% of the polymer 1 according to the present invention was mixed.
Aqueous solution was further added, by using nanomizer LA31 (Nanomizer Co., Ltd.), after the two treatment at a pressure of 500 kg / m ^2, further subjected to stirring for 60 minutes, in the following composition (4) polyvinyl 8% alcohol aqueous solution,
(5) Emulgen 109P and (6) diethylene glycol monobutyl ether were added to prepare a coating liquid (first coating liquid) A for the colorant receiving layer. The mass ratio of the silica fine particles to the water-soluble resin (PB ratio / (1) :( 4)) is 4.5:
It was 1. [Composition of coating liquid A for colorant receiving layer] (1) Fine particles of vapor-phase method silica (inorganic pigment fine particles) 7.7 parts (QS-30, manufactured by Tokuyama Corp .; specific surface area by BET method: 300 m ² / g) , Average primary particle diameter 7 nm) (2) Ion-exchanged water 68.8 parts (3) Polymer 1 10% aqueous solution 3.85 parts (4) Polyvinyl alcohol 8% aqueous solution 21.3 parts (PVA124, Kuraray Co., Ltd.) Made, saponification degree 98.5%, degree of polymerization 2400) (5) polyoxyethylene lauryl ether 10% aqueous solution 1.0 part (Emulgen 109P, Kao Co., Ltd.) (6) diethylene glycol monobutyl ether 0.6 part

[Evaluation] (Viscosity) 300 g of the above coating solution was sampled in a 500 cc container and immersed in a high temperature bath at 30 ° C. for 10 minutes, and then the viscosity was measured using a B-type viscometer (manufactured by Tokimec) at 60 rpm. did. AA: 0.1 Pa · s (100 cp) or less, coatable and good dispersion state BB: less than 1 Pa · s (1000 cp), dispersion state CC: 1 Pa · s (1000 cp) or more , Dispersed state that cannot be applied

(Average particle size) A volume-based median particle size D50 was measured using a light scattering diffraction type particle size distribution measuring device (LA910, manufactured by Horiba Ltd.), and this value was adopted as the average particle size. did. In addition, in the measurement, the refractive index 1.10 was input as a parameter. AA: 0.2 μm or less BB: Less than 5 μm CC: 5 μm or more

(Coarse particles) In the above particle size measurement, 5 μ
The evaluation was made by the ratio of particles of m or more in the whole. AA: 2% or less BB: less than 10% CC: 10% or more

(Examples 2-9, Comparative Examples 1-5) Example 1
In the same manner as above, coating solutions for coloring material receiving layers of Examples 2 to 9 and Comparative Examples 1 to 5 were prepared, and the evaluation results are summarized in Table 2.

[0173]

[Table 2]

From Table 2, the polymer of the present invention can suppress the aggregation of the inorganic pigments and can provide a dispersion having good fluidity. On the other hand, a cationic polymer not containing a polyethylene oxide chain has a large particle size. Further, when the anti-aggregation agent is not used, viscosity increases, aggregation of the inorganic pigments with each other, and coarse particles occur, resulting in poor fluidity.

In Table 2, an ink jet recording sheet was prepared as follows for the dispersions having a rating of BB or higher.

Example 10-Preparation of Inkjet Recording Sheet-The coating solution A for colorant-receiving layer was applied on the surface of a support at a coating amount of 200 ml / m ² using an extrusion die coater, 80 ° C with hot air dryer (wind speed 3-8m /
sec), the coating layer was dried until the solid content concentration became 20%. The coating layer showed a constant drying rate during this period. Immediately after that, the cross-linking agent solution (second coating solution) A having the following composition
20 g / m ² was adhered on the coating layer by dipping for 2 seconds, and further dried at 80 ° C. for 10 minutes. From this, an ink jet recording sheet of the present invention provided with a coloring material receiving layer having a dry film thickness of 32 μm was produced.

[0177] [Composition of Crosslinking Agent Solution A] Boric acid (crosslinking agent) 2.5 parts Ion-exchanged water 69.5 parts Polyallylamine (molecular weight 10,000) 10% aqueous solution 25 parts Polyoxyethylene lauryl ether 2 parts Ammonium chloride 1 part

(Examples 11 to 18) Ink jet recording was carried out in the same manner as in Example 10 except that the coating solution for the color material receiving layer in Example 10 was changed to the coating solution for the color material receiving layer in Examples 2 to 9, respectively. A sheet was prepared and evaluated in the same manner.

(Comparative Examples 6 to 8) The same procedure as in Example 10 was carried out except that the coating solutions for the color material receiving layers in Example 10 were changed to the coating solutions for the color material receiving layers in Comparative Examples 1, 2, and 4, respectively. An inkjet recording sheet was prepared and evaluated in the same manner.

-Evaluation Method- (1-1) Ink Absorption Rate Using an inkjet printer (PM-900C, manufactured by Seiko Epson Corp.), Y (yellow), M (magenta), and C were recorded on the inkjet recording sheet. (Cyan), K
Solid images of (black), B (blue), G (green) and R (red) are printed, and immediately (after about 10 seconds), the paper is contact-pressed on the image to transfer the ink to the paper. The presence or absence of each of these was evaluated according to the following criteria. [Standard] AA: Ink transfer onto paper was not observed at all.
It shows that the ink absorption rate is good. CC: Partial transfer of the ink onto the paper was observed.

(1-2) Occurrence of cracks The presence or absence of cracks on the surface of the ink jet recording sheet and the size thereof were visually observed and evaluated according to the following criteria. [Standard] AA: No cracks were observed on the surface. BB: A crack having a length of 1 to 2 mm was recognized. CC: A crack having a length of 3 mm or more was recognized.

(1-3) Water resistance Using the same printer as in (1-1) above, the same printing pattern was formed on the ink jet recording sheet, left for 3 hours, and then immersed in water for 1 minute to prepare the ink. The degree of outflow into water was visually observed and evaluated according to the following criteria. [Standard] AA: No dye outflow was observed. BB: A portion where the dye flowed out was recognized, and the color density was lowered. CC: The dye has run out into the water almost completely.

(1-4) Blurring with time Using the same printer as in (1-1) above, a grid-like linear pattern (line width 0. Two
8 mm) was printed, and the visual density was measured by X-light 310TR (manufactured by X-light). Furthermore, after printing for 3 hours, the product was stored in a thermo-hygrostat at 40 ° C. and a relative humidity of 90% for 1 day, and the visual density was measured again to calculate the density difference (ΔOD). The smaller the value of the density difference (ΔOD), the more the generation of bleeding with time is suppressed. AA: No bleeding over time was observed BB: Some bleeding over time was observed, but a level at which some problems occur in practical use

(1-5) Light resistance Using the same printer as in (1-1) above, solid Y (yellow), M (magenta), C (cyan) and K (black) inks are formed on an ink jet recording sheet. Print the image, X light 3
The visual density of each color was measured by 10TR (manufactured by X-Light Co., Ltd.). After that, 365n for the printed image
Xenon weather-ometer Ci through a film that blocks ultraviolet rays in the wavelength range of m or less
Using 65A (manufactured by ATLAS), the lamp was lit for 3.8 hours under the environmental conditions of 25 ° C. and relative humidity of 32%, and then the lamp was extinguished at 20 ° C. and relative humidity of 91%. A cycle of standing underneath for 1 hour was carried out for 11 days. Then, the visual density of each color was measured again, and the fading of each color was evaluated by calculating the residual rate (the rate of change in density before and after the test). AA: The level of fading is small and good (remaining rate 70% or more) BB: Level of fading is recognized but a slight problem occurs in practical use (remaining rate 70% or less)

(1-6) Printing Density Using an inkjet printer (PM-900C, manufactured by Seiko Epson Corp.), a solid K (black) image was printed on an inkjet recording sheet, and the printing was allowed to stand for 3 hours before printing. The reflection density of the surface was measured with an X-light densitometer. AA: High density, good image was obtained BB: Low density, but a level at which some problems occur in practical use

The results of evaluation of these are shown in Table 3.

[0187]

[Table 3]

From Table 3, in the ink jet recording sheet using the polymer according to the present invention, generation of bleeding with time was not observed, and the print density was excellent. In addition, good results were obtained with respect to the ink absorption rate, cracking of the recording sheet surface, water resistance, and light resistance. On the other hand, when an inorganic fine particle agglomeration inhibitor containing no polyalkylene oxide structure or having a high polyalkylene oxide content is used, it is not possible to obtain an excellent print density, and the dispersibility of the inorganic fine particles is poor. Cracks occur. In addition, none of the dispersion liquids using the known anti-agglomeration agent showed good results in bleeding with time and light resistance.

[0189]

EFFECTS OF THE INVENTION According to the present invention, not only the light fastness is good, but also after printing, even if the image is stored for a long time in a high temperature and high humidity environment, it does not cause bleeding or yellowing over time, and is stable. An ink jet recording sheet capable of holding an image can be provided. Further, according to the present invention, without the occurrence of cracks, having a strong and high surface gloss,
It is possible to provide an inkjet recording sheet having good ink absorbability, capable of forming a high-resolution and high-density image, good color developability, and excellent water resistance in the image area.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C09D 133/14 C09D 133/24 133/24 139/00 139/00 165/00 165/00 B41J 3/04 101Y F term (reference) 2C056 EA13 FC06 2H086 BA15 BA16 BA31 BA33 BA34 BA35 BA37 BA41 BA45 4J038 BA011 BA022 BA112 CC091 CE022 CE051 CE052 CE062 CG012 CG141 CG171 CG172 CH14 CK022

Claims (14)

[Claims] 1. An inkjet recording sheet having a colorant receiving layer on the surface of a support, wherein the colorant receiving layer comprises at least inorganic pigment fine particles and at least a unit represented by the following formulas (1) and (2). An ink jet recording sheet comprising the polymer (a) having [Chemical 1] [Equation (1), in (2), R ¹ represents a hydrogen atom or a methyl group, R ^2, R ³ represents an alkylene group, R ² and R ³ may be different even in the same. R ⁴ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group, an aralkyl group, or —OCOR ′, and Q represents COO or CO.
Represents either NR "or O, and R'and R" are
Each independently represents a hydrogen atom, an alkyl group, an aralkyl group, or an aryl group, and m and n each represent an integer of 1 or more. A represents a repeating unit containing a cationic group. ] 2. The unit of the formula (2) is at least the following:
A contract that is one of formulas (3), (4), (5), and (6)
The inkjet recording sheet according to claim 1. [Chemical 2] [In the formulas (3), (4), (5) and (6), R^Five, R^TenIs
Represents a hydrogen atom or a methyl group, R⁶Represents an alkylene group
And R⁷, R⁸, R⁹, R¹¹, R¹², R¹³, R¹⁴, R ¹⁵,
R¹⁶, And R¹⁷Are each independently a hydrogen atom,
Represents an alkyl group, an aralkyl group, or an aryl group, and W
Represents -COO-, -CONH-, or -O-,
X¹, X², X³Represents a counter anion, and l represents 0 or 1.
Represent ] 3. The coloring material receiving layer is formed by applying an inorganic fine particle dispersion liquid comprising at least an inorganic pigment fine particle and a polymer having at least a unit represented by the following formula (1) and formula (2). Characteristic inkjet recording sheet. [Chemical 3] [Equation (1), in (2), R ¹ represents a hydrogen atom or a methyl group, R ^2, R ³ represents an alkylene group, R ² and R ³ may be different even in the same. R ⁴ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group, an aralkyl group, or —OCOR ′, and Q represents COO or CO.
Represents either NR "or O, and R'and R" are
Each independently represents a hydrogen atom, an alkyl group, an aralkyl group, or an aryl group, and m and n each represent an integer of 1 or more. A represents a repeating unit containing a cationic group. ] 4. In the inorganic fine particle dispersion liquid, the above formula
The unit of (2) is at least the following formulas (3), (4),
Is the polymer having any of the units (5) and (6)?
The ink jet printer according to claim 3, wherein
Recording sheet. [Chemical 4] [In the formulas (3), (4), (5) and (6), R^Five, R^TenIs
Represents a hydrogen atom or a methyl group, R⁶Represents an alkylene group
And R⁷, R⁸, R⁹, R¹¹, R¹², R¹³, R¹⁴, R ¹⁵,
R¹⁶, And R¹⁷Are each independently a hydrogen atom,
Represents an alkyl group, an aralkyl group, or an aryl group, and W
Represents -COO-, -CONH-, or -O-,
X¹, X², X³Represents a counter anion, and l represents 0 or 1.
Represent ] 5. The inkjet recording sheet according to claim 3, wherein the inorganic fine particle dispersion further contains a water-soluble resin. 6. The inorganic pigment fine particles are silica fine particles having an average primary particle diameter of 20 nm or less, or pseudo-boehmite having an average pore radius of 1 to 10 nm. 2. An ink jet recording sheet according to item 1. 7. The ink jet recording sheet according to claim 5, wherein the water-soluble resin is polyvinyl alcohol or its derivative. 8. The ink jet recording sheet according to claim 5, wherein the color material receiving layer further contains a crosslinking agent capable of crosslinking the water-soluble resin. 9. The ink jet recording sheet according to claim 8, wherein the crosslinking agent is a boron compound. 10. The ink jet recording sheet according to claim 1, wherein the color material receiving layer further contains an organic mordant capable of fixing an anionic dye. 11. The ink jet recording sheet according to claim 10, wherein the organic mordant is polyallylamine or a derivative thereof. 12. The coloring material receiving layer has a porosity of 50 to 8
It has a three-dimensional network structure of 0% and the mass ratio (i: p) of the inorganic pigment fine particles (i) and the water-soluble resin (p) is 1.
The inkjet recording sheet according to any one of claims 1 to 11, wherein the ratio is 5: 1 to 10: 1. 13. The color material-receiving layer is formed by applying a first coating solution containing the inorganic fine particle dispersion on the surface of the support, and (1) simultaneously with the application and (2) the application. A second step containing an organic mordant, which is in the middle of drying the coating layer and before the coating layer shows a rate-decreasing drying, or (3) after the coating layer is dried to form a coating film. The inkjet recording sheet according to any one of claims 1 to 12, which is formed by applying a coating liquid. 14. The coloring material-receptive layer is provided by adding the crosslinking agent to at least one of the first coating liquid and the second coating liquid, or the first coating liquid and the second coating liquid. The inkjet recording sheet according to any one of claims 1 to 13, which is formed by applying a coating liquid containing the cross-linking agent, separately from the above.