JP2002205455A - Ink jet recording sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ink jet recording sheet not generating cracking or the like, excellent in surface glossiness and ink absorbability, capable of forming a high density image, good in color developability, excellent in the light fastness and water resistance of the image and suppressing the generation of blur or fading with the elapse of time after preservation. SOLUTION: The ink jet recording sheet contains a polymer (a) having at least one of units represented by formulae (1)-(5) (wherein, R1, R2, R3 and R4 are a 4 or more C organic group which may have a substituent, R5 and R6 are a hydrogen atom or a 1 or more C organic group which may have a substituent. The number of carbons of R5 and R6 is 2 or more in total. R11 is a hydrogen atom or a methyl group, R12 is COOR13, CN or CONR13R14, X is a paired anion and n is 0 or 1).

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-based ink, or a solid ink which is solid at ordinary temperature, melted and liquefied, and then subjected to printing. More specifically, the present invention relates to a recording sheet which is excellent in ink receiving performance and has little bleeding or fading of an image portion 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, a recording method and apparatus suitable for each information system have been developed and put into practical use. Among such recording methods, the ink jet recording method is capable of recording on various recording materials, that hardware is relatively inexpensive,
Due to its compactness and high quietness, it has been widely used not only in offices but also in so-called home use. Also, with the recent increase in resolution of ink jet printers, it has become possible to obtain so-called photo-like high-quality recorded materials. With the development of hardware (devices), various recording sheets for inkjet recording have been developed.

In general, the characteristics required for the recording sheet are (1) quick drying (high ink absorption speed), and (2) proper and uniform diameter of the ink dots (color blur). (3) good granularity, (4) high dot roundness, (5) high color density, (6) high saturation (no dullness) ), (7) that the printing portion has good light fastness and water fastness,
(8) No bleeding or fading occurs in the image even when stored for a long period of time, (9) High whiteness of the recording sheet, (10)
Good storage stability of the recording sheet, (11) good deformation and dimensional stability (sufficiently small curl), and (12) good hard running property. Furthermore, in the application of photo glossy paper used to obtain so-called photo-like high-quality recorded materials, in addition to the above, glossiness, surface smoothness, photographic paper-like texture similar to silver halide photography, etc. are also required. Is done.

Examples of recording sheets used for ink jet recording include, for example, JP-A-55-51583, JP-A-55-144172, and JP-A-55-15039.
No. 5, No. 56-148582, No. 56-14
Nos. 8583, 56-148584, 56
JP-A-148585, JP-A-57-14091, JP-A-57-38185, JP-A-57-129778, JP-A-57-129979, and JP-A-60-21908.
No. 4, JP-A-60-245588 and the like, in which a pigment such as silica and a water-soluble binder are coated on a support such as paper or a plastic film, are known. However, all of these proposed recording sheets have extremely low gloss and are insufficient for photo glossy paper applications.

Further, Japanese Patent Application Laid-Open No. Hei 4-223190 discloses
Is 0.1 g / m of borax or boric acid ^TwoCoat above
5-20 g / m on base paper^TwoSynthetic silica and polyvinyl chloride
A recording layer made of nyl alcohol (PVA) was provided.
Ink jet recording paper has been proposed. The above technology
Simply increases the coating strength of the recording layer with a low binder content.
It is intended to improve the gloss and is inferior in gloss.
Therefore, the use of photo glossy paper was insufficient.

Further, recording materials using various water-soluble polymers in order to obtain glossiness have been proposed. For example, JP-A-58-89391, JP-A-58-134784, JP-A-58-134786, and JP-A-60-44386.
JP-A-60-132785, JP-A-60-145
879, 60-168651, 60-
No. 171143 is known in which polyvinyl alcohol, polyvinylpyrrolidone, gelatin or the like is coated on a support such as paper or a plastic film. These recording sheets are also excellent in glossiness, but are inferior in ink quick-drying properties, and thus are insufficient for photo glossy paper applications.

On the other hand, JP-A-7-276789, JP-A-8-174992, JP-A-11-115308, and JP-A-11-192777 satisfy the above-mentioned required properties and production cost of the ink jet recording sheet. Ink jet recording sheets have been proposed. JP-A-7-276789 proposes a recording sheet in which a colorant receiving layer formed of inorganic pigment fine particles and a water-soluble resin and having a three-dimensional structure having a high porosity is provided on a support. Have been. According to this configuration,
It is described that the above-described ink absorbency is improved, color mixing 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. However, since it is necessary to reduce the amount of the binder for forming the layer so that voids can be formed, the coating layer is rapidly dried. Cracks occur and the transparency and appearance of the colorant receiving layer are impaired.

As a method for preventing the ink receiving layer from cracking, Japanese Patent Application Laid-Open No. 9-109545 proposes a method in which the viscosity of a binder in a coating solution is relatively high. There is a possibility that coating or coating unevenness may occur, and the level is not yet practically effective. Also, JP-A-7-76161, 10-
Japanese Patent No. 119423 discloses a method for preventing cracking using a coating solution composed of inorganic particles, polyvinyl alcohol (PVA), boric acid or borate. However, this method also increases the viscosity of the coating solution. There is a large decrease in workability, and there is also a problem in the stability over time of the liquid, and it has not yet reached a practically effective level.

In JP-A-10-119423 and JP-A-10-217601, a coloring material 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. Each of the above-mentioned ink jet recording sheets has excellent ink absorbency due to its constitution, has high ink receiving performance capable of forming a high-resolution image, and exhibits high gloss. However, from the viewpoint of gloss and texture, since a support having a resin coating such as polyethylene on the surface on both sides thereof is used as the support, the high boiling point solvent contained in the colorant receiving layer does not evaporate, and The solvent is not absorbed by the support. For this reason, the high boiling point solvent remains in the color material receiving layer as it is, and after printing, if stored for a long time in a high temperature and high humidity environment, the solvent diffuses together with the dye in the color material receiving layer, resulting in aging. There is a problem that image bleeding (hereinafter, sometimes referred to as “time bleeding”) occurs.

In addition, the ink jet recording sheet includes:
For the purpose of fixing the dye component in the ink, a compound having an amino group or an ammonium salt, particularly a high molecular compound having these, has been widely added. 64-7528
No. 1, JP-A-59-20696 and the like, (co) polymers of diallylammonium salt derivatives,
Allylamine salt copolymers described in 1-61887 and 61-72581, JP-A-6-340
No. 163, No. 4-288283, No. 9-30
Nos. 0810, 8-318672, 10-
No. 272830, JP-A-63-115780 and the like. ) Polymers, modified polyvinyl alcohol (PVA) described in JP-A-10-44588 and the like, JP-A-6-23426
No. 8, No. 11-277888, etc., amine / epichlorohydrin polyadduct, JP-A-10-119418
Diamine polyamine adduct described in JP-A-11-58934, polyamidine described in JP-A-11-28860 and the like, allylamine hydrochloride described in JP-A-12-71603 and the like, allylamine, diallyldimethylammonium Many compounds such as polymers such as salts are used. In the ink jet recording sheet described in the above publication, dyes are fixed by using these compounds, and bleeding is prevented.

[0011] However, the ink jet recording sheet having a color material receiving layer having a high porosity has advantages such as ink absorption and high gloss, and bleeding over time has been improved. Immediately after that, if the image is stored in a clear file or the like, or if the image is stored for a long period of time particularly under a high humidity condition, there is still a problem that image blurring 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 a polyamine substituted with hydroxyalkyl having 2 to 3 carbon atoms. However, these ink jet recording sheets still have an insufficient effect of preventing bleeding over time.

JP-A-8-267904 discloses an ink jet recording sheet containing polyamines substituted with an alkyl group, benzyl group or aryl group having 1 to 6 carbon atoms. However, in these cases, a quaternary ammonium salt is an essential component, and the introduction of these substituents (particularly, a substituent having high hydrophobicity) is not intended to improve the bleeding over time. Further, the polyamines are not formed by a polymer reaction.

In addition, for example, JP-A-6-340163, JP-A-6-340164, JP-A-7-224015, JP-A-8-142496, JP-A-8-267904 and JP-A-8-282929 disclose polyallylamine. And di-substituted polyallylammonium. However, since these derivatives are generally synthesized by polymerization of disubstituted allylamine or trisubstituted allylammonium salt having low polymerizability, there has been a problem that the suitability for production is poor. Furthermore, the introduction of these substituents is not intended to improve bleeding over time.

Japanese Patent Application Laid-Open Nos. 11-58634 and 11-20307 disclose an example of an inkjet recording sheet containing an amine having a substituent other than an alkyl group, an aryl group and an aralkyl group. An example in which the amine is substituted with COH, COMe is shown. However, this is an example as a part of the polyamidine mordant, and even if these groups are introduced, the effect of preventing bleeding over time was insufficient.

As described above, a solid, high surface gloss, good ink absorption and coloring properties, no cracks, etc. are generated, and a high-resolution, high-density image can be formed. There is no known inkjet recording sheet that has excellent light resistance and water resistance, does not cause bleeding or fading with time even when stored for a long time in a high-temperature, high-humidity environment, and has excellent manufacturing suitability.

[0017]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned conventional problems and achieve the following objects. That is, an object of the present invention is to provide an image having excellent light fastness, and even after long-term storage in a high-temperature and high-humidity environment after printing, without causing bleeding or fading over time, stably holding an image, and Another object of the present invention is to provide an excellent ink jet recording sheet. Further, an object of the present invention is to form a high-resolution, high-density image with high resolution, having high surface gloss, strong ink absorption and color development without generating cracks and the like. To provide an ink jet recording sheet having excellent water resistance.

[0018]

Means for Solving the Problems As a result of intensive studies for solving these problems, the present inventors have found that these problems can be solved by using the following ink jet recording sheet. The present application has been reached.

<1> An ink-jet recording sheet comprising a polymer (a) having at least one of the units represented by the following general formulas (1) to (5).

[0020]

Embedded image[Wherein, R¹, R^Two, R^ThreeAnd R^FourHas a substituent
Represents an organic group having 4 or more carbon atoms;^FiveAnd R⁶Is water
An elemental atom or an optionally substituted carbon number of 1 or more
Represents the above organic group. Where R^FiveAnd R⁶And the total number of carbon
Is 2 or more. R¹¹Represents hydrogen or a methyl group;
¹²Is COOR¹³, CN or CONR¹³R ¹⁴Represents R
¹³And R¹⁴Is a hydrogen atom or may have a substituent
Represents an alkyl, aryl, or aralkyl group
You. The alkyl group may have a branched structure or a cyclic structure.
And may have an unsaturated bond. X represents a counter anion
And n represents 0 or 1. ]

<2> The inkjet recording sheet according to <1>, wherein the polymer (a) further has a unit represented by the following general formula (6).

[0022]

Embedded image [In the formula, n represents 0 or 1. ]

<3> In the polymer (a), the total content of the units represented by the general formulas (1) to (5) is 1 mol%.
<1> or <2>, which is an ink jet recording sheet characterized by the above.

<4> The polymer (a) has a total content of the units represented by the general formulas (1) to (5) of 2 to 70 m.
<1> to <3>, which is an ink-jet recording sheet.

<5> The polymer (a) is obtained by a polymer reaction of a polymer (b) having a unit represented by the following general formula (6): <1> to <4>&Lt; Inkjet recording sheet &gt;.

[0026]

Embedded image [In the formula, n represents 0 or 1. ]

<6> The polymer (a) comprises a polymer (b) having a unit represented by the general formula (6) and a halogen-containing compound, an epoxy-containing compound, and an acid having 4 or more carbon atoms. At least one of an anhydride-containing compound, an acid halide-containing compound, an isocyanate-containing compound, an isothiocyanate-containing compound, a haloformate, an aldehyde-containing compound having 3 or more carbon atoms, and a compound represented by the following general formula (7) <5> The inkjet recording sheet according to <5>, wherein the sheet is obtained by a reaction with one kind.

[0028]

Embedded image [Wherein, R ¹¹ represents hydrogen or a methyl group, and R ¹² represents CO 2
Represents OR ¹³ , CN or CONR ¹³ R ¹⁴ . R ¹³ and R ¹⁴ represent a hydrogen atom or an optionally substituted alkyl group, aryl group or aralkyl group. The alkyl group may have a branched structure or a cyclic structure, and may have an unsaturated bond. ]

<7> The polymer (a) comprises a polymer (b) having a unit represented by the general formula (6), a benzyl halide derivative, a halomethylstyrene derivative, a glycidyl ether compound, acrylonitrile, and acrylate. And at least one of a derivative and an acrylamide derivative.
5>.

<8> The ink jet recording sheet according to any one of <5> to <7>, wherein the polymer (b) comprises substantially only the unit represented by the general formula (6). .

<9> An ink jet recording sheet having a color material receiving layer on the surface of a support, wherein the color material receiving layer comprises inorganic pigment fine particles, a water-soluble resin, and the polymer (a). <1> to <8>, which is an inkjet recording sheet.

<10> The inkjet recording sheet according to <9>, wherein the colorant receiving layer further contains a crosslinking agent capable of crosslinking the water-soluble resin.

<11> The inkjet recording sheet according to <10>, wherein the crosslinking agent is a boron compound.

<12> 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. <9> to <11> Sheet for inkjet recording.

<13> The water-soluble resin is polyvinyl alcohol or a derivative thereof.
9> to <12>, which are inkjet recording sheets.

<14> The coloring material receiving layer has a porosity of 5
It has a three-dimensional network structure of 0 to 80%, and has a mass ratio (i: p) of the inorganic pigment fine particles (i) and the water-soluble resin (p).
<1.5: 1 to 10: 1
> To <13>.

<15> The colorant receiving layer is formed by applying a first coating solution containing the inorganic pigment fine particles and the water-soluble resin to the surface of the support, and (1) simultaneously with the coating, (2) )
Either during the drying of the coating layer formed by the coating and before the coating layer exhibits a reduced rate drying rate, or (3) after the coating layer is dried to form a coating film. The inkjet recording sheet according to any one of <9> to <14>, wherein the inkjet recording sheet is obtained by applying a second coating liquid containing the combined liquid (a).

<16> The colorant receiving layer is provided by adding the crosslinking agent to at least one of the first and second coating liquids, or the crosslinking is performed separately from the first and second coating liquids. <10> to <15>, which is obtained by applying a coating liquid containing an agent.

[0039]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the contents of the present invention will be described in detail.

<< Inkjet Recording Sheet >><Polymer (a) Having Units Represented by General Formulas (1) to (5)> The inkjet recording sheet of the present invention comprises at least the following formulas (1) to (5) (Hereinafter, may be referred to as “polymer (a)”).

[0041]

Embedded image[Wherein, R¹, R^Two, R^ThreeAnd R^FourHas a substituent
Represents an organic group having 4 or more carbon atoms;^FiveAnd R⁶Is water
An elemental atom or an optionally substituted carbon number of 1 or more
Represents the above organic group. Where R^FiveAnd R⁶And the total number of carbon
Is 2 or more. R¹¹Represents hydrogen or a methyl group;
¹²Is COOR¹³, CN or CONR¹³R ¹⁴Represents R
¹³And R¹⁴Is a hydrogen atom or may have a substituent
Represents an alkyl, aryl, or aralkyl group
You. The alkyl group may have a branched structure or a cyclic structure.
And may have an unsaturated bond. X represents a counter anion
And n represents 0 or 1. ]

As used herein, the term "organic group" means a group containing at least one of a hydrocarbon site and a halogen-substituted site. The organic group may include, in addition to these sites, elements such as hydrogen, carbon, nitrogen, oxygen, sulfur, phosphorus, silicon, boron, and halogen, and a functional group including a combination thereof. Such examples include, for example, alkyl groups, aralkyl groups, aryl groups, acyl groups, sulfonyl groups, heterocycles, and the like. The above alkyl group, aralkyl group and aryl group may be substituted.

The above R ¹ , R ² , R ³ and R ⁴ are not particularly limited as long as they are organic groups having 4 or more carbon atoms. Specifically, alkyl groups (for example, n-butyl, i-butyl) , S
ec-butyl, t-butyl, n-hexyl, cyclohexyl, n-hexyl, 2-ethylhexyl, n-decyl, n-dodecyl, octadecyl, 1,3-butadienyl, 1,3-pentadienyl and the like ), Aralkyl groups (eg benzyl, phenylethyl, vinylbenzyl, 1-
Phenylvinyl, 2-phenylvinyl, etc.) and aryl groups (eg, phenyl, naphthyl, tolyl, vinylphenyl, etc.).

The organic group may have a substituent. Examples of the substituent include fluoroethyl, trifluoroethyl, methoxyethyl, phenoxyethyl, hydroxyphenylmethyl, chlorophenyl, dichlorophenyl, trichlorophenyl, bromophenyl, Iodophenyl, fluorophenyl, hydroxyphenyl, methoxyphenyl, hydroxyphenyl, acetoxyphenyl,
Cyanophenyl; Further, it may contain the following -OH group.

[0045]

Embedded image

Further, as the organic group having a substituent,
—CR ²¹ R ²² —COOR ²³ (Examples of R ²¹ , R ²² and R ²³ include a methyl group, an ethyl group, a butyl group, a benzyl group and a phenyl group, provided that the total number of carbon atoms is 4 or more. ^{), - CO-R 24 -COOH} ( as R ²⁴ is, for _{example, -CH 2 CH 2 -, -} CH 2 CH 2 CH 2 -, - C
In addition to H = CH-, the following bonding groups may be mentioned. However, the total carbon number is 4 or more. ), COR ²⁵ , -COOR ²⁶ ,
-CONHR ²⁷ , -CSNHR ²⁸ (where R ²⁵ , R ²⁶ , R ²⁷ and R ²⁸ are, for example, propyl, butyl, octadecyl, benzyl, phenyl, -CH = CH-P
h and the like. However, the total carbon number is 4 or more. ), - as the SO ₂ R ²⁹ (R ²⁹ such as butyl group,
Octadecyl group, benzyl group, phenyl group, -CH = C
H-Ph and the like. However, the total carbon number is 4 or more. ), - P (= O) (OR 30) 2 ( as R ³⁰ is, for example, methyl group, ethyl group, propyl group, butyl group, an octadecyl group, a benzyl group, a phenyl group, -CH = CH-P
h and the like. However, the total carbon number is 4 or more. )
Is mentioned.

[0047]

Embedded image

R ⁵ and R ^{6 each} represent a hydrogen atom, a carbon atom of 1
Represents the above organic groups. As an organic group having 1 or more carbon atoms,
In addition to the organic groups having 4 or more carbon atoms represented by R ^{1 to} R ⁵ , organic groups having 1 or more carbon atoms may be mentioned. For example, alkyl groups such as methyl, ethyl, n-propyl, i-propyl, and-
CR ³¹ R ³² -COOR ³³ , -COR ³⁴ , -COOR ³⁵ ,
—CONHR ³⁶ , —CSNHR ³⁷ , and —SO ₂ R ³⁸ . Examples of R ³¹ , R ³² and R ³³ include a methyl group, an ethyl group, a butyl group, a benzyl group and a phenyl group. Examples of R ³⁴ , R ³⁵ , R ³⁶ and R ³⁷ include a methyl group and an ethyl group. Further, as R ³⁸ are a methyl group, an ethyl group, a propyl group. However, in each case, the total number of carbon atoms of R ⁵ and R ⁶ is 2 or more.

R ¹¹ represents hydrogen or a methyl group.
R ¹² is COOR ¹³ , CN, CONR ¹³ R ¹⁴
And R ¹³ and R ¹⁴ represent a hydrogen atom or an alkyl group, an aryl group or an aralkyl group which may have a substituent. The alkyl group may have a branched structure or a cyclic structure, and may have an unsaturated bond. R ¹³
And R ¹⁴ include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a sec-butyl group, a t-butyl group,
n-hexyl group, cyclohexyl group, n-hexyl group,
2-ethylhexyl, n-decyl, n-dodecyl, octadecyl, allyl, benzyl, phenyl, naphthyl, biphenyl, 1,1,1-trifluoroethyl, 2-hydroxy-3- Chloropropyl group and the like.

The upper limit of the number of carbon atoms of these organic groups is not particularly limited, but the obtained polymer (a) is preferably soluble in a water-soluble or water-miscible organic solvent. The upper limit of the number of carbon atoms is preferably up to about 20.

It represents a counter anion ^- [0051] The X. Specific examples of the counter anion include a halogen ion (Cl ⁻ , Br ⁻ ,
I ^-), sulfonate ion, alkyl sulfonate ion, aryl sulfonate ion, alkyl carboxylic acid ion, aryl carboxylate ion, and the like.
Of these, halogen ions are preferred.

The polymer of the present invention has, in addition to at least one selected from the units represented by formulas (1) to (5), a unit represented by the following formula (6) in the polymer. May be.

[0053]

Embedded image [In the formula, n represents 0 or 1. ]

In the polymer (a), the total content of the units represented by the general formulas (1) to (5) is preferably at least 1 mol%,
Specifically, 1 to 100 mol% is preferable, and 2 mol%
７０70 mol% is more preferable, and 3 mol% ５０50 m
ol% is particularly preferred. If the total content is less than 1 mol%, the effect of preventing temporal bleeding may be insufficient.
When the polymer (a) is directly applied to the surface of the support, the coating amount of the polymer (a) is 0.1 to 6 g of the polymer (a).
/ M ² , preferably 0.2 to 5 g / m ² .

The polymer (a) having these units can be obtained by polymerization of a monomer corresponding to the units represented by the general formulas (1) to (5). Can be obtained by a polymer reaction of a polymer having a repeating unit (hereinafter, may be referred to as “polymer (b)”). In addition, (1) generally, allyl-based monomers are not sufficiently polymerizable, and (2) in the case of polyvinylamine, since there is no monomer corresponding to vinylamine, its precursor (for example, N-vinylformamide, N-vinylacetamide) needs to be hydrolyzed after polymerization. Therefore, considering the suitability for production and the degree of freedom in synthesis, the weight of the present invention having units represented by the general formulas (1) to (5) is considered. The union (a) is preferably obtained by a polymer reaction of the polymer (b) rather than the polymerization of a monomer.

As the above-mentioned polymer reaction, the polymer (b) having a repeating unit represented by the general formula (6) is
For example, a halogen-containing compound, an epoxy-containing compound, an acid anhydride-containing compound, an acid halide-containing compound, an isocyanate-containing compound, an isothiocyanate-containing compound, a haloformate having 4 or more carbon atoms, or an aldehyde-containing compound having 3 or more carbon atoms And a method of reacting a compound represented by the following general formula (7).

[0057]

Embedded image [Wherein, R ¹¹ represents hydrogen or a methyl group, and R ¹² represents CO 2
Represents OR ¹³ , CN or CONR ¹³ R ¹⁴ . R ¹³ and R ¹⁴ represent a hydrogen atom or an optionally substituted alkyl group, aryl group or aralkyl group. The alkyl group may have a branched structure or a cyclic structure, and may have an unsaturated bond. ]

Specific examples of the compound which reacts with the polymer (b) include the following. Examples of the halogen-containing compound having 4 or more carbon atoms include benzyl bromide,
Benzyl halide derivatives such as benzyl chloride and halomethylstyrene derivatives such as chloromethylstyrene may be used. Examples thereof include propyl chloroformate, butyl chloroformate, phenyl chloroformate, chloromethylstyrene, and bromomethylstyrene. By reacting the halogen-containing compound with the polymer (b), the compounds represented by the general formulas (1) to (1)
A polymer (a) having a unit represented by (3) can be obtained. The epoxy-containing compound having 4 or more carbon atoms may be a glycidyl ether compound such as phenyl glycidyl ether or allyl glycidyl ether, and specifically, butylene oxide, methyl glycidyl ether, phenyl glycidyl ether, allyl glycidyl ether, Cyclohexene oxide, styrene oxide and the like. By reacting the epoxy-containing compound with the polymer (b), a polymer (a) having a unit represented by the general formula (3) can be obtained.

Examples of the acid anhydride-containing compounds having 4 or more carbon atoms include succinic anhydride, maleic anhydride, glutaric anhydride, phthalic anhydride, cyclohexanedicarboxylic anhydride, cyclohexenedicarboxylic anhydride, and the like. Is mentioned. By reacting the acid anhydride-containing compound with the polymer (b), a polymer (a) having a unit represented by the general formula (3) can be obtained. Examples of the acid halide-containing compound having 4 or more carbon atoms include sorbic acid chloride, benzoic acid chloride, cinnamic acid chloride, and the like.
Valeric acid chloride, oleic acid chloride and the like can be mentioned. By reacting the acid halide-containing compound with the polymer (b), a polymer (a) having a unit represented by the general formula (3) can be obtained.

Examples of the isocyanate-containing compound having 4 or more carbon atoms include butyl isocyanate, cyclohexyl isocyanate, and phenyl isocyanate. By reacting the isocyanate-containing compound with the polymer (b), a polymer (a) having a unit represented by the general formula (3) can be obtained. Examples of the isothiocyanate-containing compound having 4 or more carbon atoms include butyl isothiocyanate, cyclohexyl isothiocyanate, and phenyl isothiocyanate. By reacting the isothiocyanate-containing compound with the polymer (b), a polymer (a) having a unit represented by the general formula (3) can be obtained.

Examples of the haloformate compound having 4 or more carbon atoms include propyl chloroformate, butyl chloroformate, phenyl chloroformate and the like. The polymer (a) having the units represented by the general formulas (1) to (3) can be obtained by reacting the haloformate-containing compound with the polymer (b). Examples of the aldehyde-containing compound having 3 or more carbon atoms include, for example,
Examples include butyraldehyde, benzaldehyde, salicylaldehyde, and cinnamaldehyde. By reacting the aldehyde-containing compound with the polymer (b), a polymer (a) having a unit represented by the general formula (4) can be obtained.

In the general formula (7), R ^{11 to} R ¹⁴ are the same as those described above. Examples of the compound represented by the general formula (7) include acrylates (butyl acrylate,
An acrylate derivative such as benzyl acrylate may be used. Specifically, methyl acrylate, ethyl acrylate, butyl acrylate, hexyl acrylate, 2
-Ethylhexyl acrylate, cyclohexyl acrylate, benzyl acrylate, phenyl acrylate, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminopropyl acrylate, diethylaminopropyl acrylate amide, etc.), methacrylates (for example, methyl methacrylate, ethyl methacrylate, butyl methacrylate, hexyl) Methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, phenyl methacrylate, etc.), acrylonitrile, methacrylonitrile, acrylamides (acrylamide, dimethylacrylamide, acrylamide derivatives such as dimethylaminopropyl acrylamide may be, specifically, Acrylamide, dimethylacrylamide, i-propylacrylamide, t-butylacrylamide, phenylacrylamide, dimethylaminopropylacrylamide, diethylaminopropylacrylamide, etc., methacrylamides (for example, methacrylamide, dimethylmethacrylamide, i-propylmethacrylamide, t- Butyl methacrylamide,
Phenylmethacrylamide, etc.). The polymer (a) having the unit represented by the general formula (5) can be obtained by reacting the compound represented by the general formula (7) with the polymer (b).

Other than these, there is no particular limitation as long as they are compounds having reactivity with an amino group. Other than the above-mentioned compounds, ketones such as methyl ethyl ketone, sulfonic acid halides such as benzene sulfonic acid chloride, etc.
And carbonates such as ethylene carbonate and propylene carbonate.

Among the compounds which react with the polymer (b), benzyl halide derivatives (benzyl bromide, benzyl chloride, etc.), halomethyl styrene derivatives (chloromethyl styrene, etc.), glycidyl ether compounds (phenyl glycidyl ether, allyl glycidyl ether) Acrylonitrile, acrylate derivatives (butyl acrylate, benzyl acrylate, etc.),
It is particularly preferable to use an acrylamide derivative (eg, acrylamide, dimethylacrylamide, dimethylaminopropylacrylamide, etc.).

The polymer (b) having a repeating unit represented by the general formula (6) used as a raw material for the polymer reaction includes, for example, substantially the repeating unit represented by the general formula (6). (A content of the unit represented by the general formula (6) is 90% or more, preferably 95%
And the above polymers). Since a polymer substantially consisting only of the repeating unit represented by the general formula (6) can be easily obtained as polyallylamine or polyvinylamine, it is preferable to use these compounds as starting materials from the viewpoint of production suitability. preferable. Polyallylamine can be obtained by subjecting a polymer of allylamine or a salt thereof to a desalting treatment. Further, polyvinylamine can be obtained by polymerizing a precursor of vinylamine (for example, N-vinylformamide, N-vinylacetamide, etc.) as a monomer, and then hydrolyzing it.

The polymers (a) and (b) are
In addition to the units represented by the general formulas (1) to (6), copolymers with other copolymerizable monomers may be used as long as the performance as an inkjet recording sheet is not impaired.
Examples of the copolymerizable unit include alkyl (meth) acrylates [eg, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, ( N-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, (meth)
(Meth) such as 2-ethylhexyl acrylate, lauryl (meth) acrylate, and stearyl (meth) acrylate
C1-18 alkyl acrylate], cycloalkyl (meth) acrylate [cyclohexyl (meth) acrylate], aryl (meth) acrylate [phenyl methacrylate], aralkyl ester [ Benzyl (meth) acrylate and the like, substituted alkyl (meth) acrylate [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, versatic] Vinyl acetate, etc.], allyl esters [allyl acetate, etc.], halogen-containing monomers [vinylidene chloride, vinyl chloride, etc.], vinyl cyanide [(meth) acrylonitrile, etc.], olefins [ethylene, propylene, etc.] Ionic monomers. Particularly, the general formulas (1) to (6) [n = 0]
The polymer having the unit represented by is usually obtained by hydrolysis of a polymer such as N-vinylformamide and N-vinylacetamide rather than the polymerization of vinylamine, so even if these units remain good.

As the copolymerizable unit, a monomer having an ionic or basic unit may be used. For example, diallyldimethylammonium chloride, methacryloyloxyethyl-β-hydroxyethyldimethylammonium chloride, vinylbenzyltrialkylammonium salt, (meth) acryloylethyltrialkylammonium salt, (meth) acryloylpropyltrialkylammonium salt, (meth) acrylamidoethyl Trialkyl ammonium salt, (meth)
Acrylamidopropyltrialkylammonium salts [the trialkyl groups shown include trimethyl group, triethyl group, tripropyl group, triisopropyl group, tributyl group, trihexyl group, dimethylbenzyl group, etc.], dialkylaminoethyl (meta )
Acrylate, dialkylaminopropyl (meth) acrylate, dialkylaminoethyl (meth) acrylamide, dialkylaminopropyl (meth) acrylamide [the dialkyl group shown in these is a dimethyl group,
A diethyl group, a dibutyl group, a methylbenzyl group, etc.]. These copolymerizable units may be used alone or in combination of two or more.

When a copolymer is used as the polymer (b), the content of the unit represented by the general formula (6) in the copolymer is preferably at least 20 mol%, more preferably at least 50 mol%. As described above, substantially the general formula (6)
It is particularly preferred that no component other than the unit represented by is contained. When the content is 20 mol% or more, it is possible to prevent insufficient fixation of the dye and insufficient resolution and prevention of bleeding over time.

When the polymer (a) is obtained by a polymer reaction of the polymer (b), a known method can be used as the polymer reaction. Examples of the known method include a method in which the polymer (b) and a reagent for causing a polymer reaction are mixed in a solvent, and the mixture is reacted with a catalyst or the like as necessary. The solvent used in the reaction is not particularly limited as long as it does not significantly inhibit the reaction,
Water, methanol, ethanol, acetone, acetonitrile, tetrahydrofuran, dimethylsulfoxide, dimethylformamide, dimethylacetamide and the like and a mixed solvent system thereof can be used. Among them, water or an organic solvent miscible with water and a mixed solvent system are preferred from the viewpoint of production suitability. However, when a compound having reactivity with water or alcohol such as isocyanate or acid halide is used, an inactive solvent (for example, acetone, acetonitrile, tetrahydrofuran, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, etc.) is used. Is preferred.

The molecular weight of the polymer (a) is preferably about 1,000 to 500,000 as a weight average molecular weight,
0 to 400,000 is more preferable. Molecular weight 1000-
When it is 500,000, sufficient water resistance can be obtained, and further, the viscosity does not increase and the handling suitability does not deteriorate.

Further, the ink jet recording sheet of the present invention can be used as long as the performance as a recording sheet is not deteriorated.
A polymer (polymeric mordant) or a low molecular compound (non-polymeric mordant) having a known quaternary ammonium salt or amine other than the polymer (a), if necessary, may be used alone or in combination of two or more. Is also good. Preferred polymeric mordants include polydiallyldimethylammonium chloride, polymethacryloyloxyethyl-β-hydroxyethyldimethylammonium chloride, polyethyleneimine, polyallylamine hydrochloride, polyamide-
Examples thereof include polyamine resin, cationized starch, dicyandiamide formalin condensate, dimethyl-2-hydroxypropylammonium salt polymer, polyamidine and the like. These compounds have a molecular weight of 1000 to 50.
It is preferably about 0000, more preferably 2,000 to 400,000. When the molecular weight is 1,000 to 500,000, sufficient water resistance can be obtained, and further, the viscosity does not increase and the handling suitability does not deteriorate. On the other hand, as the non-polymeric mordant, a compound having a quaternary ammonium base having a total of 12 or more, preferably 18 or more carbon atoms is used.

<Color material receiving layer> In the ink jet recording sheet of the present invention, the polymer (a) of the present invention can be used alone on the surface of the support. A color material receiving layer may be formed and used. In another preferred embodiment of the present invention,
An ink jet recording sheet having a coloring material receiving layer containing a fine inorganic pigment particle, a water-soluble resin, and the polymer (a) of the present invention on a support is exemplified. 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 color material receiving layer is provided. In this case, the content of the polymer (a) in the present invention is 0.5 to 2 with respect to the total solid content of the colorant receiving layer.
5.0 mass% is preferable, and 1.0 to 20.0 mass% is 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 can be further improved, and the deterioration of the 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, and the like.
Examples include kaolinite, halloysite, mica, talc, calcium carbonate, magnesium carbonate, calcium sulfate, boehmite, pseudo-boehmite and the like. Among them, silica fine particles and pseudo-boehmite are particularly preferred.

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

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

The fine silica particles have a silanol group on the surface thereof, and the particles easily adhere to each other due to the hydrogen bond by the silanol group. A structure can be formed. Thereby, the ink absorption characteristics can be effectively improved.

The silica fine particles are roughly classified into wet process particles and dry process particles according to the production method. In the wet method, activated silica is generated by acid decomposition of silicate,
The mainstream method is to polymerize the mixture appropriately and to cause coagulation and sedimentation to obtain hydrated silica. 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 by an arc in an electric furnace and oxidized with air. The method of obtaining anhydrous silica by (arc method) is the mainstream.

The hydrated silica and anhydrous silica obtained by these methods have different properties due to differences in the density of silanol groups on the surface, presence or absence of vacancies, and the like. In particular, anhydrous silica (silicic 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 large as 5 to 8 / nm ^2, and the silica fine particles are likely to be densely aggregated. 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 to 3 / nm ² , sparse soft aggregation (flocculate) is obtained. As a result, it is assumed 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 to 3 / nm.
It is preferable to use silica (silica fine particles) which is ² .

As the above-mentioned inorganic pigment fine particles, pseudo-boehmite is also preferable. Pseudo-boehmite is boehmite (composition formula A
(IOOH) is a colloidal aggregate of crystals, and preferably contains a binder. As the pore characteristics, the average pore radius is preferably from 1 to 10 nm, more preferably from 3 to 10 nm. The pore volume is 0.5-1.0 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 ink absorbency may be reduced, 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 pseudo-boehmite unnecessarily consumed, but also the strength of pseudo-boehmite may be undesirably reduced.

The composition of the pseudo-boehmite coating liquid is preferably such that the binder contains 5 to 50 parts by mass with respect to 100 parts by mass of the pseudo-boehmite solid content, and the total solid content concentration is 5 to 3 parts.
Those having 0% by mass can be suitably used. As a solvent for the coating liquid, an aqueous solvent is preferable 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, carboxymethylcellulose, hydroxymethylcellulose and polyvinylpyrrolidone can be preferably used.

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

If the content of the water-soluble resin is too small, the film strength is reduced and cracks may easily occur during drying. On the other hand, if the content is too large, the voids are easily closed by the resin. As a result, the porosity may decrease and the ink absorbency may decrease. For this reason, the content of the water-soluble resin is preferably from 9 to 40% by mass, more preferably from 16 to 33% by mass, based on the total solid mass of the colorant receiving layer.

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

From the viewpoint of transparency, the type of resin to be combined with the silica fine particles is important. When the anhydrous silica is used, the water-soluble resin is preferably polyvinyl alcohol (PVA).
9% PVA is more preferred, and PVA having a saponification degree of 70 to 90% is particularly preferred.

The PVA has a hydroxyl group in its structural unit, and the hydroxyl group and a 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. Easy to form. It is considered that the formation of the three-dimensional network structure can form a colorant receiving layer having a porous structure with a high porosity. In ink jet recording, the porous colorant receiving layer obtained as described above can rapidly absorb ink by capillary action and form dots with good roundness without ink bleeding.

-Content ratio between inorganic pigment fine particles and water-soluble resin-Content ratio between inorganic pigment fine particles (preferably silica fine particles or pseudoboehmite; i) and water-soluble resin (p) [PB ratio (i: p), Mass of inorganic pigment fine particles with respect to 1 part by mass of water-soluble resin] greatly affects the film structure of the colorant receiving layer. That is, as the PB ratio increases, the porosity, the pore volume, and the surface area (per unit mass) increase. Specifically, the PB ratio (i: p) is 1.5: 1 to 1
0: 1 is preferred. If the PB ratio exceeds 10: 1, that is, if the PB ratio is too large, the film strength decreases, and cracks may easily occur during drying.
If the ratio is less than 1, that is, if the PB ratio is too small, the voids are likely to be closed by the resin, and as a result, the porosity may decrease and the ink absorbency may decrease.

When the recording sheet passes through the transport system of the ink jet printer, stress may be applied to the recording sheet. Therefore, the color material receiving layer needs to have a sufficient film strength. Further, when the sheet is cut into a sheet shape, the color material receiving layer needs to have a sufficient film strength in order to prevent the color material receiving layer from cracking, peeling, and the like. 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 absorption by 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 are mixed with a PB ratio of 2: 1 to 5:
When a coating solution completely dispersed in an aqueous solution is coated on a support in 1 and the coating layer is dried, a three-dimensional network structure having secondary particles of silica fine particles as chain units is formed, and the average pore diameter is reduced. A light-transmitting porous film having a porosity of 30 nm or less, a porosity of 50% to 80%, a specific pore volume of 0.5 ml / g or more, and a specific surface area of 100 m ² / g or more can be easily formed.

(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 water-soluble resin in the colorant receiving layer.

The cross-linking agent solution is applied at the same time as when the coating solution for forming the porous color material receiving layer (coating solution for the color material receiving layer) is applied, or when the coating solution for the color material receiving layer is applied. It is preferable that the coating be performed before the coating layer formed by coating exhibits a reduced drying rate. By this operation, it is possible to effectively prevent the occurrence of cracks that occur while the coating layer dries. That is, at the same time as the application liquid is applied, or before the application layer exhibits a reduced drying rate, the cross-linking agent solution penetrates into the application layer and quickly reacts with the water-soluble resin in the application layer, By gelling (curing) the water-soluble resin, the film strength of the coating layer is immediately and greatly improved.

As the cross-linking agent capable of cross-linking the water-soluble resin, a suitable cross-linking agent may be appropriately selected in relation to the water-soluble resin used in the colorant receiving layer. Among them, a cross-linking reaction is rapid. And boron compounds are preferable, for example, borax, boric acid, and 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 (eg, 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 (eg, methylol melamine, alkylated methylol melamine), methylol urea, resole resin, polyisocyanate, epoxy resin and the like. Above all, borax, boric acid, and borate are preferable in that a cross-linking reaction is promptly caused, and it is more preferable to use the water-soluble resin in combination with polyvinyl alcohol.

When gelatin is used as the water-soluble resin, the following compounds known as hardeners for gelatin can be used as crosslinking agents. 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; divinylsulfonic acid, 1,3-vinylsulfonyl-2-propanol, N, N'-ethylenebis (vinylsulfonylamine) Active vinyl compounds such as cetamide), 1,3,5-triacryloyl-hexahydro-s-triazine; N-methylol compounds such as dimethylol urea and methylol dimethylhydantoin;

Isocyanate compounds such as 1,6-hexamethylene diisocyanate; US Patent No. 301
Nos. 7280 and 29836311; aziridine compounds; carboximide compounds described in U.S. Pat. No. 3,100,704; epoxy compounds such as glycerol triglycidyl ether; and 1,6-hexamethylene-N, N '. Ethyleneimino compounds such as bisethyleneurea; halogenated carboxaldehyde compounds such as mucochloric acid and mucophenoxycyclolic acid; dioxane compounds such as 2,3-dihydroxydioxane; chromium alum, potassium alum, zirconium sulfate; Chromium acetate and the like. The crosslinking agent 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 set at 0.1 to the mass of the cross-linking agent solution.
It is preferably from 0.05 to 10% by mass, particularly preferably from 0.1 to 7% by mass. As a solvent constituting the crosslinking agent solution, water is generally used, and an aqueous mixed solvent containing an organic solvent miscible with the water may be used. Any organic solvent can be used as long as it can dissolve the crosslinking agent. Examples thereof include alcohols such as methanol, ethanol, isopropyl alcohol, and glycerin; ketones such as acetone and methyl ethyl ketone; methyl acetate and ethyl acetate. Esters; aromatic solvents such as toluene; ethers such as tetrahydrofuran; and halogenated carbon-based solvents such as dichloromethane.

(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, it may contain various ultraviolet absorbers, antioxidants, and anti-fading agents such as singlet oxygen quencher. Examples of the ultraviolet absorber include cinnamic acid derivatives, benzophenone derivatives, and benzotriazolylphenol derivatives. For example, α-cyano-phenyl butyl cinnamate, o-
Benzotriazole phenol, o-benzotriazole-p-chlorophenol, o-benzotriazole-
Examples include 2,4-di-t-butylphenol, o-benzotriazole-2,4-di-t-octylphenol and the like. A hindered phenol compound can also be used as an ultraviolet absorber, and specifically, a phenol derivative in which at least one of the 2- and 6-positions is substituted with a branched alkyl group is preferable.

Further, a benzotriazole-based UV absorber, a salicylic acid-based UV absorber, a cyanoacrylate-based UV absorber, an oxalic acid anilide-based UV absorber, and the like can also be used. For example, JP-A-47-1053
No. 7, No. 58-111942, No. 58-21
Nos. 2844, 59-19945 and 59-
Nos. 46646, 59-109055 and 6
JP-A-3-53544, JP-B-36-10466, JP-A-42-26187, JP-A-48-30492, JP-A-48-31255, JP-A-48-41572.
JP-A-48-54965, JP-A-50-1072
No. 6, US Pat. No. 2,719,086, US Pat. No. 3,707,375, US Pat. No. 3,754,919, US Pat. No. 4,220,711, and the like. I have.

A fluorescent whitening agent can also be used as an ultraviolet absorber, and examples thereof include coumarin-based fluorescent whitening agents. Specifically, Japanese Patent Publication Nos. 45-4699 and 54-53
No. 24, and the like.

Examples of the antioxidants include EP-A-223239, EP-A-309401, JP-A-309402, JP-A-310551, and JP-A-31551.
Nos. 0552 and 594416, German Patent No. 3435443, and JP-A-54-48535.
JP-A-60-107384 and JP-A-60-107384
No. 383, No. 60-125470, No. 60-125
No. 125471, No. 60-125472, No. 60-287485, No. 60-287486, No. 60-287487, No. 60-28748.
No. 8, No. 61-160287, No. 61-18
Nos. 5483, 61-211079 and 62
-146678, 62-146680,
JP-A-62-146679, JP-A-62-282885, JP-A-62-262047, and JP-A-63-0511
Nos. 74, 63-89877 and 63-88
Nos. 380, 66-88381, 63-1
No. 13536,

JP-A-63-163351 and JP-A-63-2
03372, 63-224989, 6
JP-A-3-251282, JP-A-63-267594, JP-A-63-182484, JP-A-1-23992
No. 82, JP-A-2-262654, JP-A-2-7
No. 1262, No. 3-121449, No. 4-2
Nos. 91686, 4-291684, 5-
Nos. 61166, 5-119449, 5-
188687, 5-18886, 5
No. 110490, No. 5-1108437,
No. 5-170361, JP-B-48-43295, JP-B-48-33212, U.S. Pat.
No. 262, No. 4,980,275 and the like.

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 -Ethyl hexane, 2
-Methyl-4-methoxy-diphenylamine, 1-methyl-2-phenylindole and the like.

The anti-fading agents may be used alone or in combination of two or more. This lightfastness improver is made water-soluble, dispersed,
It may be emulsified or included in microcapsules. As the addition amount of the anti-fading agent,
The content of the coating material for the colorant receiving layer is preferably 0.01 to 10% by mass.

Further, for the purpose of enhancing the dispersibility of the inorganic pigment fine particles, various inorganic salts and acids or alkalis as pH adjusters may be contained. In addition, 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 triboelectric charging and peeling charging of the surface. It is preferable to include various matting agents for the purpose of reducing the friction characteristics of the surface.

The matting agent has a particle size of 3 μm to 30 μm.
A matting agent of μm is preferred, and a particle size of 10 μm to 30 μm is more preferred. As the above matting agent, 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 inorganic matting agents include oxides (eg, silicon dioxide, titanium oxide, magnesium oxide, aluminum oxide, etc.) and alkaline earth metal salts (eg, sulfates and carbonates, specifically, barium sulfate, carbonate Calcium, magnesium sulfate, calcium carbonate, etc.), silver halide grains which do not form an image (silver chloride, silver bromide, etc., and a small amount of iodine atom as a halogen component may be added), glass and the like.

In addition to the above matting agents, for example, West German Patent 2,529,321 and British Patent 760,77
5, No. 1,260,772, U.S. Pat. No. 1,201,905, 2,192,241
No. 3,053,662, No. 3,063
2,649, 3,257,206,
3,322,555 and 3,353,958
No. 3,370,951, No. 3,41
1,907, 3,437,484,
3,523,022, 3,615,554
No. 3,635,714, No. 3,76
9,020, 4,021,245,
Inorganic matting agents described in JP-A-4,029,504 and the like can also be used.

The matting agent may be an organic matting agent. Examples of the organic matting agent include starch, cellulose ester (eg, cellulose acetate propionate, etc.), cellulose ether (eg, ethyl cellulose, etc.), synthetic resin, etc. Is mentioned. As the synthetic resin,
Synthetic polymers that are insoluble or poorly soluble in water can be used, for example, alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, glycysilyl (meth) acrylate, (meth) acrylamide, vinyl ester (eg, vinyl acetate), acrylonitrile Olefins (eg, ethylene, etc.), styrene, benzoguanamine / formaldehyde condensate alone or in combination, or acrylic acid, methacrylic acid, α, β
A polymer having a combination of unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, sulfoalkyl (meth) acrylate, styrene sulfonic acid or the like as a monomer component can be used.

Further, as an organic matting agent, epoxy resin, nylon, polycarbonate, phenol resin,
Polyvinyl carbazole, polyvinylidene chloride and the like can also be used. In addition, British Patent 1,055,
713, U.S. Pat. Nos. 1,939,213, 2,221,873, and 2,268,6.
No. 62, No. 2,322,037, No. 2,
376,005, 2,391,181, 2,701,245, 2,992,1
No. 01, 3,079,257 and 3,
262,782, 3,443,946, 3,516,832, 3,539,3
Nos. 44, 3,591,379, 3,
754,924, 3,767,448, JP-A-49-106821, and 57-148.
The organic matting agent described in JP-A-35-35 and the like 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 resins (manufactured by Moritex) and the like can be suitably used.

As the above matting agent, an alkali-soluble matting agent can also be suitably used. Examples of the alkali-soluble matting agent include JP-A-53-7231 and JP-A-58-7231.
Alkali-soluble matting agents such as alkyl methacrylate / methacrylic acid copolymers described in JP-A-66937 and JP-A-60-8894, and alkali-soluble 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.
No. 5935, two or more kinds of fine particle powders having different Mohs' hardness are used in combination, JP-A-59-149356, two or more kinds of spherical matting agents having different average particle diameters are used in combination, and a coloring material receiving layer is used. A combination of an amorphous matting agent such as silica and a spherical matting agent such as polymethyl methacrylate for the back layer may be used.

The coloring material receiving layer and other layers in the present invention may include coating aids, antistatic, improving slipperiness, emulsifying and dispersing, preventing adhesion and improving photographic properties (for example, acceleration of development, enhancement of contrast,
For various purposes such as sensitization, various surfactants may be contained. Examples of the surfactant include saponins (steroids), alkylene oxide derivatives (eg, polyethylene glycol, polyethylene glycol / polypropylene glycol condensate, 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 silicones),
Nonionic surfactants such as glycidol derivatives (eg, alkenyl succinic acid polyglyceride, alkylphenol polyglyceride), fatty acid esters of polyhydric alcohols, etc .; alkyl carboxylate, alkyl sulfonate, alkyl benzene sulfonic acid Salts, alkyl naphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurates, sulfosuccinates, esphoalkyl polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl eico Carboxy group, sulfo group, such as sanates, etc.
Anionic surfactants containing an acidic group such as a phospho group, a sulfate group or a phosphate group;

Amphoteric surfactants such as amino acids, aminoalkylsulfonic acids, aminoalkylsulfuric acid or phosphoric acid esters, alkylbetaines and amine oxides; alkylamine salts, aliphatic or aromatic quaternary ammonium salts, pyridinium And cationic surfactants such as heterocyclic quaternary ammonium salts such as imidazolium, and phosphonium or sulfonium salts containing an aliphatic or heterocyclic ring.

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

Also, French Patent No. 2,180,465, British Patent No. 955,061 and 1,1
43,118, 1,270,578, 1,320,564, 1,320,7
No. 57, JP-A-49-5017, JP-A-51-50
JP-A-141623, JP-A-54-159221, JP-A-56-81841, Research Disclosure 1396
9, U.S. Pat. Nos. 1,263,722;
588,765, 2,739,891, 3,018,178, 3,042,5
No. 22, 3,080, 317, No. 3,
082,087, 3,121,060, 3,222,178, 3,295,9
No. 79, 3,489,567, 3,
516,832, 3,658,573, 3,679,411, 3,870,5
No. 21 can be used. An appropriate amount of the 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, especially colloidal silica, for the purpose of improving adhesion resistance, improving film strength, and improving curl balance.

<Support> As a material that can be used as the support, a transparent material such as plastic may be used.
An opaque material such as paper may be used. In the invention, in order to utilize the transparency of the colorant receiving layer, the support is preferably a transparent support or a high gloss opaque support.

As a material that can be used as the transparent support, a material that is transparent and has a property of resisting radiant heat when used in an OHP or a backlight display is preferable. Such materials include polyesters such as polyethylene terephthalate, nitrocellulose, cellulose acetate, or cellulose esters such as cellulose acetate butyrate, and polysulfone,
Examples thereof include polyphenylene oxide, polyimide, polycarbonate, and polyamide. Among these, polyesters are preferred, and polyethylene phthalate is particularly preferred. The thickness of the transparent support is not particularly limited, but a thickness of 50 to 200 μm is preferable because it is easy to handle.

The high gloss opaque support preferably has a glossiness of 40% or more on the surface on which the color material receiving layer is provided. The glossiness is JIS P-81
42 (75-degree specular gloss test method of paper and paperboard). Examples of high gloss opaque supports include art paper,
Coated paper, cast-coated paper, high gloss paper such as baryta paper used for silver salt photographic supports, polyesters such as polyethylene terephthalate (PET), nitrocellulose, cellulose acetate, cellulose acetate butyrate, etc. Cellulose esters, or polysulfone, polyphenylene oxide, polyimide,
High gloss (may be subjected to surface calendering, etc.) film made by adding a white pigment or the like to a plastic film such as polycarbonate or polyamide, or the above-mentioned various papers, the above-mentioned transparent plastic film, or a plastic containing a white pigment or the like Examples of the support include a polyolefin coating layer containing a white pigment or not containing a white pigment on the surface of the film. Furthermore, a foamed polyester film containing a white pigment (eg, a foamed PET in which voids are formed by stretching and containing polyolefin fine particles) can also be mentioned.

A polyolefin-coated paper generally used as a silver salt photographic support (eg, a paper support having a white pigment-containing polyolefin layer on its surface) or a special paper provided with a metal vapor-deposited layer is provided. Paper or the like can be suitably used. In particular, a silver salt photographic paper support provided with a white pigment-containing polyolefin layer, a polyester (preferably PE) provided with a white pigment-containing polyolefin layer
T) A film, a white pigment-containing polyester film or a white pigment-containing foamed polyester film is preferred. The thickness of the opaque support is not particularly limited.
Those having a size of 0 to 300 μm are preferred because they are easy to handle. Further, as the support, those subjected to a corona discharge treatment, a glow discharge treatment, a flame treatment, or an ultraviolet irradiation treatment in order to impart adhesion to the colorant receiving layer may be used.

<< Method of Making Ink-Jet Recording Sheet >> As a method of making an ink-jet recording sheet,
A method of applying a coating liquid prepared in the form of an aqueous solution or a mixed solution of water and an organic solvent, which contains the polymer (a) of the present invention, to the surface of the support is exemplified. However, it is particularly preferable to apply as a dissolved solution from the viewpoint of the glossiness of the obtained coating film. Examples of the method of applying the coating liquid include: (1) a method of coating on a support or the like; (2) a method of spraying a coating liquid by a method such as spraying; And the like.

(Organic solvent) Examples of the organic solvent usable for the coating include alcohols such as methanol, ethanol, n-propanol, i-propanol and methoxypropanol; ketones such as acetone and methyl ethyl ketone; tetrahydrofuran, acetonitrile; Examples include ethyl acetate and toluene.

(Method of Forming Coloring Material Receptive Layer) Next, another embodiment of the present invention, an ink jet method, wherein the coloring material receiving layer contains fine inorganic pigment particles, a water-soluble resin, and the polymer (a) of the present invention. A method for manufacturing a recording sheet will be described. First, as a method of forming the colorant receiving layer, for example, an aqueous dispersion of inorganic pigment fine particles and a water-soluble resin (an organic solvent may be used in addition to water as appropriate. Hereinafter, the case of "first coating liquid" The polymer (a) of the present invention is prepared during the drying of the coating layer formed by the coating or the like and before the coating layer exhibits a reduced drying rate. And a method of applying a coating solution prepared in the form of an aqueous solution or a mixed solution of water and an organic solvent (hereinafter, may be referred to as a “second coating solution”). Alternatively, a method of applying the second solution simultaneously with the application of the first solution, or after applying and drying the first solution to form a coating film can also be used.

In the present invention, the first material for a colorant-receiving layer containing at least inorganic pigment fine particles and a water-soluble resin.
Can be prepared, for example, as follows. That is, silica fine particles having an average primary particle diameter of 20 nm or less are added to water (for example, 10 to 20% by mass), and a high-speed rotating wet colloid mill (for example, CLEARMIX (manufactured by M Technique Co., Ltd.)) is used. , For example, 10,000 rpm
After dispersing for 20 minutes (preferably 10 to 30 minutes) under the condition of high-speed rotation (preferably 5000 to 20000 rpm), an aqueous polyvinyl alcohol solution (for example, PVA having a mass of about 1/3 of silica) is added. In addition, it can be prepared by further dispersing under the same rotation conditions as described above. The obtained coating solution is a uniform sol, and by coating this on a support by the following coating method, a porous colorant receiving layer having a three-dimensional network structure can be formed. If necessary, a surfactant, a pH adjuster, an antistatic agent and the like can be further added to the first solution.

As a method of applying the first solution,
(1) a method of coating on a support or the like, (2) a method of spraying the first solution by a method such as spraying, and (3) a method of immersing the support or the like in the liquid of the first solution. No. The application of the first solution is preferably performed by a known coating 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, and a bar coater.

The above-mentioned "before the coated layer exhibits the reduced drying rate" usually refers to a few minutes immediately after the application of the first solution. It shows the constant rate drying rate, which is a phenomenon in which the content of the solvent decreases in proportion to time. The time showing the constant rate drying rate is described in Chemical Engineering Handbook (pp. 707-712, published by Maruzen Co., Ltd., Oct. 25, 1980).

As described above, after the application of the first solution, the coated layer is dried until a reduced rate of drying is obtained. The drying is generally performed at 50 to 180 ° C. for 0.5 to 10 minutes. (Preferably 0.5 to 5 minutes). The drying time naturally varies depending on the amount of application, but the above range is appropriate.

Before the above-mentioned coating layer exhibits a reduced drying rate, an aqueous dispersion containing the polymer (a) according to the present invention,
The method of applying a coating solution (second coating solution) prepared in the form of an organic solvent solution or a mixed solution of water and an organic solvent includes the following methods. (2) a method of spraying the second coating liquid by a method such as spraying, and (3) a method of immersing the support having the coating layer formed therein in the liquid of the second coating liquid. No.

In the above method (1), the coating method for applying the second coating liquid includes, for example, a curtain flow coater, an extrusion die coater, an air doctor coater, a bread coater, a rod coater, a knife coater, a squeeze coater, and a reverse roll. Known coating methods such as a coater and 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. In addition, two or more kinds of coating solutions may be simultaneously applied in multiple layers.

The simultaneous coating (multilayer coating) can be performed by a coating method using, for example, an extrusion die coater or a curtain flow coater. After the simultaneous coating, the formed coating layer is dried. In this case, the drying is generally performed by heating the coating layer at 40 to 150 ° C for 0.5 to 1
This is done by heating for 0 minutes, preferably
It is performed by heating at 40 to 100 ° C for 0.5 to 5 minutes. For example, when using borax or boric acid as a 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.

Further, the colorant receiving layer is formed by coating the polymer (a) and the inorganic pigment fine particles in the present invention in advance and then further mixing a water-soluble resin (an aqueous dispersion or an organic solvent). (Hereinafter, may be referred to as “third solution”). As a method of applying the third solution, (1)
A method of applying the third solution on a support, (2) a method of spraying the third solution by a method such as spraying,
(3) A method in which the support is immersed in the solution of the third solution.

Further, a crosslinking agent may be added to any of the above-mentioned first, second, and third solutions, and the crosslinking agent may be coated on a support or the like. The crosslinking agent may be added to two or more of the first, second, and third solutions. Alternatively, a solution containing a crosslinking agent may be prepared separately from the first, second, and third solutions described above, and the solution may be applied at any stage of the application process.

In each step of the above-mentioned coating, water, an organic solvent, or a mixed solvent thereof can be used as a solvent. 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, and toluene. Can be

After the color material receiving layer is formed on the support, the color material receiving layer is smoothed by calendering through a roll nip under heat and pressure using, for example, a super calendar or a gloss calendar. Nature, glossiness,
It is possible to improve transparency and coating film strength.
However, since the calendering process may cause a decrease in the porosity (that is, the ink absorbency may be reduced), it is necessary to set a condition under which the porosity does not decrease much.

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

In the case of an ink jet recording sheet, the layer thickness of the colorant receiving layer needs to have an absorption capacity to absorb all of the liquid droplets, and thus needs to be determined in relation to the porosity in the layer. There is. For example, if the ink amount is 8 nL / mm
² , when the porosity is 60%, the layer thickness is about 15 μm.
m or more is required. Considering this point, in the case of ink jet recording, the layer thickness of the colorant receiving layer is:
10 to 50 μm is preferred.

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

The color material receiving layer is preferably excellent in transparency. As a rule, the haze value when the color material receiving layer is formed on a transparent film support is 30%.
% Or less, and more preferably 20% or less. The above haze value is measured with a haze meter (H
GM-2DP: Suga Test Instruments Co., Ltd.).

On the support, for the purpose of enhancing the adhesiveness between the colorant receiving layer and the support and adjusting the electric resistance,
An undercoat layer may be provided. The color material receiving layer may be provided on only one side of the support, or may be provided on both sides of the support for the purpose of suppressing deformation such as curling. When used in OHP or the like and the colorant receiving layer is provided on only one surface of the support, an antireflection film can be provided on the opposite surface or both surfaces for the purpose of enhancing light transmittance. .

Further, a boric acid or boron compound is coated on the surface of the support on which the color material receiving layer is formed, and the color material receiving layer is formed on the surface, whereby the glossiness of the color material receiving layer is improved. In addition, the surface smoothness can be ensured, and blurring with time of an image after printing in a high temperature and high humidity environment can be suppressed. In addition, the colorant receiving layer has a three-dimensional network structure having a porosity of 50 to 80% containing inorganic pigment fine particles, exhibits good ink absorbency, and can form a high-resolution and high-density image. Excellent ink receiving performance such as high light resistance and high water resistance can be secured.

[0139]

Hereinafter, the present invention will be described with reference to Examples.
The present invention is not limited to these examples.
In the examples, “parts” and “%” are all “parts by mass”.
And "% by mass".

Synthesis Example 1 2.5 parts of benzyl chloride was added to 57.0 parts of a 20% aqueous solution of polyallylamine (weight average molecular weight: about 5000), and the mixture was heated and stirred at 50 ° C. for 3 hours, and water was added. Polymer 1 by adjusting the concentration
To give a 10% aqueous solution of

[Synthesis Examples 2 to 12] Synthesis Examples 1 to 12 were repeated except that 2.5 parts of benzyl chloride were changed to the compounds and addition amounts shown in Table 1 below, and the reaction conditions were changed to the conditions shown in Table 1. The reaction was carried out in the same manner as in Example 1, and the concentration was adjusted with water to obtain a 10% aqueous solution of Polymers 2 to 12.

[0142]

[Table 1]

[Synthesis Example 13] In Synthesis Example 3, 57.0 parts of a 20% aqueous solution of polyallylamine (weight average molecular weight of about 5000) was replaced with 114.0 parts of a 10% aqueous solution of polyallylamine (weight average molecular weight of about 10,000). Except for the change, a 10% aqueous solution of the polymer 13 was obtained by treating and adjusting the concentration in the same manner as in Synthesis Example 3.

[Synthesis Example 14] In Synthesis Example 1, 57.0 parts of a 20% aqueous solution of polyallylamine (weight average molecular weight of about 5000) was replaced with 71.8 parts of a 12% aqueous solution of polyvinylamine (weight average molecular weight of about 70000). A 10% aqueous solution of the polymer 14 was obtained by treating and adjusting the concentration in the same manner as in Synthesis Example 1 except for the change.

[Example 1]-Preparation of support-Wood pulp consisting of 100 parts of LBKP was subjected to Canadian Freeness 300 by a double disc refiner.
beaten to 0.5 ml, epoxidized behenamide 05 parts, anionic polyacrylamide 1.0 part, polyamide polyamine epichlorohydrin 0.1 part, cationic polyacrylamide 0.5 part, all added at absolute dry mass ratio to pulp, Base paper having a basis weight of 170 g / m ² was produced by a fourdrinier machine.

To adjust the surface size of the above atoms, a fluorescent enhancer (White) was added to a 4% aqueous solution of polyvinyl alcohol.
ex BB, manufactured by Sumitomo Chemical Co., Ltd.) was added in an amount of 0.04%, impregnated with the above atoms so that the absolute dry mass was 0.5 g / m ² , dried, and then calendered. Thus, a substrate adjusted to a density of 1.05 was obtained.

After performing corona discharge treatment on the wire surface (back surface) side of the obtained base paper, high-density polyethylene was coated to a thickness of 19 μm using a melt extruder, and a resin having a matte surface was formed. A layer was formed (hereinafter, the resin layer surface may be referred to as a “back surface”). After subjecting the resin layer on the back side to corona discharge treatment, aluminum oxide (alumina sol 100, manufactured by Nissan Chemical Industries, Ltd.) and silicon dioxide (Snowtex O,
(Nissan Chemical Industry Co., Ltd.) in water at a ratio (mass ratio) of 1: 2, and the mass after drying is 0.2 g / m ^2.
It applied so that it might become.

After the corona discharge treatment was applied to the felt side (front side) of the base paper, the anatase type titanium dioxide 10
% By mass, trace amount of ultramarine blue and 0.01% by mass of optical brightener
A low density polyethylene having an MFR (melt flow rate) of 3.8 containing (to polyethylene) was melt-extruded to a thickness of 29 μm using a melt extruder to form a thermoplastic resin layer having a glossy surface. It is formed on the base paper (hereinafter, this surface may be referred to as “front surface”).
This was used as a support.

-Preparation of Coating Solution for Colorant Receiving Layer- (1) Silica fine particles and (2) ion-exchanged water in the following composition are mixed, and a high-speed rotating colloid mill (CLEARMIX, manufactured by M Technic Co., Ltd.) Using 10,000
After dispersing at 20 rpm for 20 minutes, the following (3) 9% aqueous solution of polyvinyl alcohol was added, and the mixture was further dispersed under the same conditions as above to prepare a coating material for a colorant receiving layer. Mass ratio of silica fine particles to water-soluble resin (PB ratio)
Was 3.5: 1.

<Composition of Coloring Material Receptive Layer Coating Solution> (1) Silica Fine Particles (Inorganic Pigment Fine Particles) 9.9 Parts (Average Primary Particle Diameter 7 nm; Aerosil 300, manufactured by Nippon Aerosil Co., Ltd.) (2) Ion-exchanged water 73.1 parts (3) 9% aqueous solution of polyvinyl alcohol (water-soluble resin) 31.6 parts (PVA420, manufactured by Kuraray Co., Ltd., saponification degree 81.8%, polymerization degree 2000)

-Preparation of Ink-Jet Recording Sheet of the Present Invention- Next, the colorant-receiving layer coating solution obtained above was applied to the above-mentioned support for 200 m using an extrusion die coater.
The coating was applied at a coating amount of 1 / m ² (coating step) and dried at 80 ° C. (wind speed 3 to 8 m / sec) using a hot air drier until the solid content concentration of the coating layer became 20%. The coating layer exhibited a constant rate of drying during this period. Immediately thereafter, it was immersed in a coating solution having the following composition (a solution containing a polymer and a crosslinking agent) for 30 seconds.
20 g / m ² is adhered onto the coating layer (step of applying a solution containing a polymer and a cross-linking agent).
It dried at 10 degreeC for 10 minutes (drying process). This allows
A colorant receiving layer having a dry film thickness of 32 μm was formed on the support to prepare an ink jet recording sheet of the present invention.

<Composition of Solution Containing Polymer and Crosslinking Agent> (1) 1.8 parts of boric acid (crosslinking agent) (2) 2.4 parts of 10% aqueous solution of surfactant (F114 manufactured by Dainippon Ink and Chemicals, Inc.) (3) 85.8 parts of ion-exchanged water (4) 30.0 parts of polymer 1 (10% aqueous solution) shown in Synthesis Example 1 (polymer (a) in the present invention)

-Evaluation Method- (1-1) Ink Absorption Rate Using an inkjet printer (PM-800C, manufactured by Seiko Epson Corporation), Y (yellow), M (magenta), C (Cyan), K
(Black), B (blue), G (green), and R (red) solid images are printed, and immediately thereafter (about 10 seconds later), paper is contact-pressed on the images to transfer the ink to the paper. Was evaluated according to the following criteria. [Criterion] AA: No transfer of ink to paper was observed at all. This indicates that the ink absorption speed is good. CC: Partial transfer of ink on paper was observed.

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

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

(1-4) Time-lapse bleeding Using the same printer as in the above (1-1), a grid-like linear pattern (line width of 0. 0) in which magenta ink and black ink are arranged side by side on an ink jet recording sheet. 2
8 mm) was printed, and the visual density was measured using an X light 310TR (manufactured by X light). Furthermore, after leaving for 3 hours after printing, it was stored for 1 day in a thermo-hygrostat at 40 ° C. and 90% relative humidity, and the visual density was measured again to calculate the density difference (ΔOD). The smaller the value of the density difference (ΔOD) is, the more the occurrence of bleeding with time is suppressed.

(1-5) Light fastness Using the same printer as in the above (1-1), a solid Y (yellow), M (magenta), C (cyan) and K (black) Print the image, X-light 3
The visual density of each color was measured by 10TR (manufactured by X-Light). After that, 365n for the printed image
m through a film that cuts ultraviolet light in the wavelength range of less than
Using a 65A (manufactured by ATLAS), the lamp was turned on for 3.8 hours under an environment condition of 25 ° C. and a relative humidity of 32%, and then, with the lamp turned off, at 20 ° C. and a relative humidity of 91%. The cycle of standing underneath for 1 hour was performed for 11 days. Thereafter, the visual density of each color was measured again, and the fading of each color was evaluated by calculating the residual rate (density change rate before and after the test).

Table 2 shows the results of these evaluations.

Examples 2 to 14 An ink jet recording sheet was prepared and evaluated in the same manner as in Example 1 except that Polymer 1 in Example 1 was changed to Polymers 2 to 14, respectively.

Comparative Example 1 Polymer 1 in Example 1 was replaced with polyallylamine (weight average molecular weight: about 5,000)
An ink jet recording sheet was prepared and evaluated in the same manner as in Example 1, except that the solution was changed to 0% solution.

Comparative Example 2 The polymer 1 in Example 1 was replaced with polyallylamine hydrochloride (weight average molecular weight: about 1000
An ink jet recording sheet was prepared and evaluated in the same manner as in Example 1 except that the solution was changed to the 10% solution of 0).

Comparative Example 3 Polymer 1 in Example 1 was replaced with polydimethylallylamine (weight average molecular weight: about 100
An ink jet recording sheet was prepared and evaluated in the same manner as in Example 1 except that the 10% solution of (00) was changed.

Comparative Example 4 An ink jet recording sheet was prepared and evaluated in the same manner as in Example 1 except that the compositions of the polymer and the solution containing a crosslinking agent in Example 1 were changed to the following compositions.

<Composition of Polymer and Crosslinking Agent-Containing Solution> (1) Boric acid (crosslinking agent) 1.8 parts (2) Surfactant 10% aqueous solution 2.4 parts (F114 manufactured by Dainippon Ink and Chemicals, Inc.) (3) 107.2 parts of ion-exchanged water

Table 2 shows the results of the evaluation.

[0166]

[Table 2]

[0167]

Table 2 shows that when the polymer (a) in the present invention was used as a mordant, the ink absorbency, cracking,
It was found that bleeding over time and light resistance can be simultaneously satisfied while maintaining basic performance such as water resistance.

[Example 15, Comparative Example 5]-Preparation of support-Wood pulp consisting of 80 parts of LBKP and 20 parts of NBKP was beaten to 430 ml of Canadian freeness with a double disc refiner, and 10 parts of kaolin and 0.4 parts of cationized starch were used. Part, polyacrylamide 0.2
Parts and 0.075 parts of a neutral rosin sizing agent were added at an absolute dry mass ratio to the pulp, and a base paper having a basis weight of 80 g / m ² was produced by a fourdrinier machine. An amount of 2 g of a 10% aqueous solution of the polymer 1 shown in Synthesis Example 1 after drying was applied to the substrate.
/ M ² to obtain a recording sheet. In addition, as Comparative Example 5, one using the substrate without performing the above-mentioned coating was used for evaluation.

(Evaluation method) (2-1) Image density inkjet printer (PM-
A solid image of K (black) was printed on the ink jet recording sheet by 800C (manufactured by Seiko Epson Corporation), and after standing for 3 hours, the reflection density of the printed surface was measured with a Macbeth reflection densitometer.

(2-2) Water resistance Using the same printer as in the above (2-1), Y (yellow), M (magenta), C (cyan), K (black), B (Blue), G (green) and R (red)
Was left for 3 hours, immersed in water for 1 minute, and the degree of outflow of the ink into water was visually observed and evaluated according to the following criteria. [Criterion] AA: No outflow of dye was observed. BB: The part where the dye had flowed out was observed, and the color density was lowered. CC: The dye has almost completely flowed into the water.

Table 3 shows the results of these evaluations.

[0173]

[Table 3]

From Table 3, it can be seen that when the polymer (a) of the present invention was directly coated on a support, the image density was higher and the occurrence of bleeding with time was significantly reduced as compared with the case where no mordant was used. I understand. In Examples 1 to 14, the colorant receiving layer containing the inorganic pigment fine particles and the water-soluble resin on the surface of the support contained the polymer (a) of the present invention. In comparison with the case where the polymer according to the present invention was directly applied on the body, Examples 1 to
The ink jet recording sheet in No. 14 was able to suppress generation of bleeding over time.

[0175]

According to the present invention, it is excellent in light fastness, and after printing, even if it is stored for a long time in a high-temperature and high-humidity environment, the image can be stably retained without causing bleeding or fading with time, An inkjet recording sheet excellent in manufacturing suitability can be provided. Further, according to the present invention, it is possible to form a high-resolution, high-density image with good ink absorption, in addition to being strong and having high surface gloss without occurrence of cracks and the like, Is good, and an ink jet recording sheet excellent in water resistance of an image portion can be provided.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Mizuki Yamamoto 200 Onakazato, Fujinomiya City, Shizuoka Prefecture Fuji Photo Film F-term (reference) 2C056 FC06 2H086 BA01 BA14 BA15 BA19 BA21 BA33 BA35 BA46

Claims (16)

[Claims] 1. A single unit represented by the following general formulas (1) to (5):
Containing a polymer (a) having at least one of the
And a sheet for inkjet recording. Embedded image[Wherein, R¹, R^Two, R^ThreeAnd R^FourHas a substituent
Represents an organic group having 4 or more carbon atoms;^FiveAnd R⁶Is water
An elemental atom or an optionally substituted carbon number of 1 or more
Represents the above organic group. Where R^FiveAnd R⁶And the total number of carbon
Is 2 or more. R¹¹Represents hydrogen or a methyl group;
¹²Is COOR¹³, CN or CONR¹³R ¹⁴Represents R
¹³And R¹⁴Is a hydrogen atom or may have a substituent
Represents an alkyl, aryl, or aralkyl group
You. The alkyl group may have a branched structure or a cyclic structure.
And may have an unsaturated bond. X represents a counter anion
And n represents 0 or 1. ] 2. The ink jet recording sheet according to claim 1, wherein the polymer (a) further has a unit represented by the following general formula (6). Embedded image [In the formula, n represents 0 or 1. ] 3. The polymer (a) has the general formula (1)
3. The inkjet recording sheet according to claim 1, wherein the total content of the units represented by (1) to (5) is 1 mol% or more. 4. The polymer (a) has the general formula (1)
The total content of the unit represented by (5) to 2 to 70 mol%
The inkjet recording sheet according to any one of claims 1 to 3, wherein: 5. The polymer (a) has the following general formula (6)
The inkjet recording sheet according to any one of claims 1 to 4, which is obtained by a polymer reaction of a polymer (b) having a unit represented by the following formula: Embedded image [In the formula, n represents 0 or 1. ] 6. The polymer (a) has the general formula (6)
A polymer (b) having a unit represented by the formula: and a halogen-containing compound, an epoxy-containing compound, an acid anhydride-containing compound, an acid halide-containing compound, an isocyanate-containing compound, an isothiocyanate-containing compound, Acid esters, aldehyde-containing compounds having 3 or more carbon atoms,
The ink jet recording sheet according to claim 5, wherein the sheet is obtained by a reaction with at least one compound selected from the compounds represented by the following general formula (7). Embedded image [Wherein, R ¹¹ represents hydrogen or a methyl group, and R ¹² represents CO 2
Represents OR ¹³ , CN or CONR ¹³ R ¹⁴ . R ¹³ and R ¹⁴ represent a hydrogen atom or an optionally substituted alkyl group, aryl group or aralkyl group. The alkyl group may have a branched structure or a cyclic structure, and may have an unsaturated bond. ] 7. The polymer (a) has the general formula (6)
Is obtained by reacting a polymer (b) having a unit represented by the following formula with at least one of a benzyl halide derivative, a halomethylstyrene derivative, a glycidyl ether compound, an acrylonitrile, an acrylate derivative, and an acrylamide derivative. The inkjet recording sheet according to claim 5, wherein: 8. The ink-jet recording sheet according to claim 5, wherein the polymer (b) is substantially composed of only a unit represented by the general formula (6). . 9. An ink jet recording sheet having a color material receiving layer on the surface of a support, wherein the color material receiving layer comprises inorganic pigment fine particles, a water-soluble resin, the polymer (a),
The inkjet recording sheet according to any one of claims 1 to 8, comprising: 10. The ink jet recording sheet according to claim 9, wherein the coloring material receiving layer further contains a crosslinking agent capable of crosslinking the water-soluble resin. 11. The sheet according to claim 10, wherein the crosslinking agent is a boron compound. 12. 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. 3. The sheet for inkjet recording according to item 1. 13. The method according to claim 9, wherein the water-soluble resin is polyvinyl alcohol or a derivative thereof.
13. The sheet for inkjet recording according to any one of to 12 above. 14. The coloring material receiving layer has a porosity of 50-8.
It has a three-dimensional network structure of 0%, and has a mass ratio (i: p) of the inorganic pigment fine particles (i) and the water-soluble resin (p).
The inkjet recording sheet according to any one of claims 9 to 13, wherein the ratio is 1.5: 1 to 10: 1. 15. The color material receiving layer according to claim 1, wherein the first surface contains the inorganic pigment fine particles and the water-soluble resin on 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 exhibits a reduced rate drying rate, or (3) the coating The method according to any one of claims 9 to 14, wherein the layer is obtained by applying a second coating liquid containing the polymer (a) to any of the layers after drying the layer to form a coating film. Sheet for inkjet recording. 16. The colorant receiving layer is provided by adding the crosslinking agent to at least one of the first and second coating liquids, or separately from the first and second coating liquids. The inkjet recording sheet according to claim 10, wherein the sheet is obtained by applying a coating solution containing: