JP4171506B2 - Inkjet recording sheet - Google Patents

Description

The present invention is suitable for inkjet recording using liquid inks such as water-based inks (using dyes or pigments as coloring materials) and oil-based inks, and solid inks that are solid at room temperature and melted and liquefied for printing. More particularly, the present invention relates to an ink jet recording sheet having excellent ink receiving performance and improved light resistance and ozone resistance of a recorded image.

In recent years, with the rapid development of the information technology (IT) industry, various information processing systems have been developed, and recording methods and recording apparatuses suitable for the information processing systems have been developed and put into practical use.
Among these recording methods, the inkjet recording method is capable of recording on a variety of recording materials, the hardware (device) is relatively inexpensive and compact, and has excellent quietness. It has also been widely used for so-called home use.

In addition, with the recent increase in resolution of inkjet printers, it has become possible to obtain so-called photographic-like high-quality recorded matter. With the progress of such hardware (devices), recording for inkjet recording has become possible. Various seats have been developed.
The characteristics required for this recording sheet for ink jet recording are generally (1) fast drying (high ink absorption speed), and (2) ink dot diameter is appropriate and uniform. (No blurring), (3) good graininess, (4) high dot roundness, (5) high color density, (6) high chroma (dullness) (7) The water resistance, light resistance, and ozone resistance of the print portion are good, (8) the whiteness of the recording sheet is high, and (9) the storage stability of the recording sheet is good ( (10) it is hard to deform and has good dimensional stability (curl is sufficiently small), and (11) good hard running performance.
Furthermore, in the use of photo glossy paper used for the purpose of obtaining so-called photographic-like high-quality recorded matter, in addition to the above properties, gloss, surface smoothness, photographic paper-like texture similar to silver salt photography, etc. Is also required.

  In recent years, an ink jet recording sheet having a porous structure in a colorant receiving layer has been developed and put into practical use for the purpose of improving the various properties described above. Such an ink jet recording sheet has a porous structure, and thus has excellent ink receptivity (fast drying property) and high gloss.

For example, in Japanese Patent Application Laid-Open Nos. 10-119423 and 10-217601, etc., an inkjet recording containing fine inorganic pigment particles and a water-soluble resin and having a colorant receiving layer having a high porosity is provided on a support. Sheets have been proposed.
These recording sheets, particularly ink jet recording sheets provided with a colorant-receiving layer having a porous structure using silica as inorganic pigment fine particles, are excellent in ink absorptivity due to their configuration, and form high-resolution images. It has a high ink receiving performance and can exhibit high gloss.

  However, trace gases in the air, particularly ozone, cause discoloration of recorded images over time. Since the recording material composed of the colorant-receiving layer having the porous structure described above has many voids, the recorded image is easily faded by ozone gas in the air. For this reason, resistance to ozone in the air (ozone resistance) is a very important characteristic for the recording material having the color material receiving layer having the porous structure.

  In order to prevent the fading due to ozone, Japanese Patent Application Laid-Open No. 2001-260519 proposes an ink jet recording material containing a sulfinic acid compound, a thiosulfonic acid compound, or a thiosulfinic acid compound. EP 1,138,509 proposes an ink jet recording material containing a thioether compound having a hydrophilic group. All of these are effective in ozone resistance, but the effect does not last long and there is a problem that sufficient ozone resistance cannot be imparted.

  JP-A-7-314882 discloses a porous ink containing one or more compounds selected from the group consisting of dithiocarbamates, thiuram salts, thiocyanates, thiocyanates, and hindered amine compounds. A recording sheet having a layer is disclosed. Specific examples of the hindered amine compound include those having a structure in which all hydrogens on the carbons at the 2-position and the 6-position of piperidine are substituted with methyl groups. By containing more than seeds, there is an effect of preventing fading for about 30 days indoors, but there is a problem that sufficient long-term ozone resistance cannot be imparted.

As described above, the colorant receiving layer has a good ink absorbability and can form a high-resolution image, and the formed image has ink receiving performance that is excellent in light resistance, water resistance, aging, glossiness, At present, an ink jet recording sheet having sufficiently long ozone resistance has not yet been provided.
An object of the present invention is to provide an ink jet recording sheet having particularly improved ozone resistance.

Means of the present invention for solving the above-mentioned problems are as follows.
<1> An ink jet recording sheet having a color material receiving layer on a support, wherein the color material receiving layer contains a compound represented by the following general formula (II).


[In General Formula (II), R ²¹ and R ²² are each independently a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, —COR ⁵³ , —COOR ⁵⁴ , —SO ₂ —R ⁵⁵ , —N (R ⁵⁶ ) R ⁵⁷ is represented. Here, R ⁵³ and R ⁵⁵ each independently represent a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, or —N (R ⁵⁸ ) R ⁵⁹ , and R ⁵⁴ represents a hydrogen atom, an aliphatic group or an aromatic group. R ^{56 to} R ⁵⁹ are each independently a hydrogen atom, aliphatic group, aromatic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, aryl. Represents a sulfonyl group or a sulfamoyl group. R ²¹ and R ²² may be connected to each other to form a ring. R ²³ represents an aliphatic group, an aromatic group, a heterocyclic group, —COR ⁷¹ , —COOR ⁷² , —N (R ⁷³ ) R ⁷⁴ , and R ^{24 to} R ²⁶ each independently represent a hydrogen atom or an aliphatic group. , Aromatic group, heterocyclic group, —COR ⁷¹ , —COOR ⁷² , —N (R ⁷³ ) R ⁷⁴ . Here, R ⁷¹ represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, a ^{-N (R 58) R 59,} R 72 is a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic R ⁷³ and R ⁷⁴ each independently represents a hydrogen atom, aliphatic group, aromatic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group, sulfamoyl group. To express. ]
<2> The inkjet recording sheet according to <1>, wherein the colorant-receiving layer contains at least one compound represented by the general formula (II), fine particles, and a water-soluble resin.
< 3 > The inkjet according to <2>, wherein the fine particles are silica fine particles having an average primary particle size of 20 nm or less, alumina fine particles having an average primary particle size of 20 nm or less, or pseudoboehmite having an average pore radius of 2 to 15 nm. Recording sheet.
<4> The inkjet recording sheet according to <2> or <3>, wherein the water-soluble resin is polyvinyl alcohol or a derivative thereof.
<5> The inkjet recording sheet according to any one of <2> to <4> , wherein the colorant-receiving layer further contains a crosslinking agent capable of crosslinking the water-soluble resin.
<6> The inkjet recording sheet according to <5> , wherein the crosslinking agent is a boron compound.
<7> The ink jet recording sheet according to any one of <1> to <6> , wherein the color material receiving layer further contains a mordant.
<8> The mordant is a polyallylamine having a weight average molecular weight of 300,000 or less as an organic mordant or a derivative thereof, an aluminum-containing compound, a zirconium-containing compound, a titanium-containing compound as an inorganic mordant, a Group IIIB series metal of the periodic table The ink jet recording sheet according to the above <7> , comprising at least one kind of compound.
<9> The inkjet recording sheet according to any one of <1> to <8> , wherein the colorant-receiving layer further contains at least one acidic compound.
<10> A step of applying a first coating liquid containing at least fine particles and a water-soluble resin to the surface of the support, (1) simultaneously with the coating, and (2) during the drying of the coating layer formed by the coating. Then, before the coating layer exhibits a reduced rate of drying, or (3) after forming the coating film by drying the first coating solution, a second coating solution containing at least a mordant is applied. A process for producing an ink jet recording sheet, wherein at least one of the compounds represented by formula (II) is contained in at least one of the first coating liquid and the second coating liquid .

  According to the present invention, it retains good ink receiving performance, is strong without occurrence of cracks and the like, suppresses the occurrence of aging blur, can form a high-resolution image, and is excellent in ozone resistance and light resistance. In addition, an inkjet recording sheet can be provided.

In the inkjet recording sheet of the invention, the colorant receiving layer provided on the support contains an alicyclic amine compound having a specific structure. By containing this specific amine compound, the ozone resistance of the ink jet recording sheet is remarkably improved, and the light resistance (particularly magenta coloring) is also improved. In addition, the color material receiving layer preferably has a porous structure in order to have both ink absorptivity (fast drying property) and glossiness.
JP-A-7-1832, JP-A-7-257018, JP-A-8-238839 and the like are known as examples in which a certain kind of alicyclic amine is contained in the ink jet recording sheet. It is added as a water-peeling property, curl property, and optical density improver for inkjet recording sheets, and nothing is said about improvement of ozone resistance. Furthermore, these are used for swelling type ink jet recording sheets, and sufficient glossiness and ink absorption speed are not obtained.

(Compound represented by formula (I))
The first ink jet recording sheet in the present specification is characterized in that the colorant receiving layer provided on the support contains a compound represented by the following general formula (I).

In the above general formula (I), R ¹ and R ² are each independently a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, —COR ³ , —COOR ⁴ , —SO ₂ —R ⁵ , —N (R ⁶ ) R ⁷ is represented. Here, R ³ and R ⁵ each independently represent a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, or —N (R ⁸ ) R ⁹ , and R ⁴ represents a hydrogen atom, an aliphatic group or an aromatic group. An aromatic group, a heterocyclic group, and R ^{6 to} R ⁹ are each independently a hydrogen atom, aliphatic group, aromatic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, aryl Represents a sulfonyl group or a sulfamoyl group. R ¹ and R ² may be connected to each other to form a ring. R ¹⁰ to R ¹⁴ each independently represent a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, -COR ^31, -COOR ^32, represents a -N (R ³³⁾ R ^34. Here, R ³¹ represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, or —N (R ⁸ ) R ⁹ , and R ³² represents a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group. R ³³ and R ³⁴ each independently represent a hydrogen atom, aliphatic group, aromatic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group, sulfamoyl group. To express.

When R ¹ and R ² , R ³ and R ⁵ , R ⁴ , R ^{6 to} R ⁹ , R ^{10 to} R ¹⁴ , R ³¹ and R ³² , R ³³ and R ³⁴ represent an aliphatic group, the aliphatic group Examples of the group include an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, and the like, and these groups may further have a substituent. Among these, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aralkyl group, and a substituted aralkyl group are preferable, and an alkyl group and a substituted alkyl group are particularly preferable.
The aliphatic group may be a chain aliphatic group or a cyclic aliphatic group, and the chain aliphatic group may further have a branch.

Examples of the alkyl group include linear, branched and cyclic alkyl groups, and the number of carbon atoms of the alkyl group is preferably 1 to 30, and more preferably 1 to 20. The above range is also preferable for the number of carbon atoms in the alkyl portion of the substituted alkyl group.
Specific examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, 2-ethylhexyl group, t-octyl group, decyl group, dodecyl group, octadecyl group, cyclohexyl group. Group, cyclopentyl group, neopentyl group, isopropyl group, isobutyl group and the like.

  Examples of the substituent of the substituted alkyl group include a carboxyl group, a sulfo group, a cyano group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom), a hydroxy group, and an alkoxycarbonyl group having 30 or less carbon atoms (for example, methoxycarbonyl). Group, ethoxycarbonyl group, benzyloxycarbonyl group), aryloxycarbonyl group having 30 or less carbon atoms (for example, phenoxycarbonyl group), alkylsulfonylaminocarbonyl group having 30 or less carbon atoms (for example, methylsulfonylaminocarbonyl group, octylsulfonyl) Aminocarbonyl group), arylsulfonylaminocarbonyl group (for example, toluenesulfonylaminocarbonyl group), acylaminosulfonyl group having 30 or less carbon atoms (for example, benzoylaminosulfonyl group, acetylaminosulfo group) Group, pivaloylaminosulfonyl group), C30 or less alkoxy group (for example, methoxy group, ethoxy group, benzyloxy group, phenoxyethoxy group, phenethyloxy group, etc.), C30 or less arylthio group, alkylthio Group (for example, phenylthio group, methylthio group, ethylthio group, dodecylthio group, etc.), aryloxy group having 30 or less carbon atoms (for example, phenoxy group, p-tolyloxy group, 1-naphthoxy group, 2-naphthoxy group, etc.), nitro Group, alkyl group having 30 or less carbon atoms, alkoxycarbonyloxy group (for example, methoxycarbonyloxy group, stearyloxycarbonyloxy group, phenoxyethoxycarbonyloxy group), aryloxycarbonyloxy group (for example, phenoxycarbonyloxy group, chloropheno group) Aryloxycarbonyl group);

  Acyloxy group having 30 or less carbon atoms (for example, acetyloxy group, propionyloxy group, etc.), Acyl group having 30 or less carbon atoms (for example, acetyl group, propionyl group, benzoyl group, etc.), carbamoyl group (for example, carbamoyl group, N , N-dimethylcarbamoyl group, morpholinocarbonyl group, piperidinocarbonyl group, etc.), sulfamoyl group (for example, sulfamoyl group, N, N-dimethylsulfamoyl group, morpholinosulfonyl group, piperidinosulfonyl group, etc.), carbon An alkylsulfonyl group having a number of 30 or less (for example, methylsulfonyl group, trifluoromethylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, dodecylsulfonyl group), arylsulfonyl group (for example, benzenesulfonyl group, toluenesulfonyl group, naphthalenesulfo group) Group, pyridinesulfonyl group, quinolinesulfonyl group), aryl group having 30 or less carbon atoms (for example, phenyl group, dichlorophenyl group, toluyl group, methoxyphenyl group, diethylaminophenyl group, acetylaminophenyl group, methoxycarbonylphenyl group, hydroxyphenyl) Group, t-octylphenyl group, naphthyl group), substituted amino group (for example, amino group, alkylamino group, dialkylamino group, arylamino group, diarylamino group, acylamino group, etc.), substituted phosphono group (for example, phosphono group) , Diethylphosphono group, diphenylphosphono group), heterocyclic group (eg, pyridyl group, quinolyl group, furyl group, thienyl group, tetrahydrofurfuryl group, pyrazolyl group, isoxazolyl group, isothiazolyl group, imidazolyl group, oxalyl group) Ryl, thiazolyl, pyridazyl, pyrimidyl, pyrazyl, triazolyl, tetrazolyl, benzoxazolyl, benzimidazolyl, isoquinolyl, thiadiazolyl, morpholino, piperidino, piperazino, indolyl, isoindolyl Thiomorpholino group), ureido group (eg methylureido group, dimethylureido group, phenylureido group etc.), sulfamoylamino group (eg dipropylsulfamoylamino group etc.), alkoxycarbonylamino group (eg ethoxy) Carbonylamino group etc.), aryloxycarbonylamino group (eg phenyloxycarbonylamino group), alkylsulfinyl group (eg methylsulfinyl group etc.), arylsulfinyl group (eg phenylsyl group) And a silyl group (for example, trimethoxysilyl group, triethoxysilyl group), a silyloxy group (for example, trimethylsilyloxy group) and the like.

The carboxyl group, sulfo group, hydroxy group, and phosphono group may form a salt. In this case, as a cation forming a salt, an organic cationic compound, a transition metal coordination complex cation (a compound described in Japanese Patent No. 2791143) or a metal cation (for example, Na ⁺ , K ⁺ , Li ⁺ , Ag ⁺⁾ Fe ²⁺ , Fe ³⁺ , Cu ⁺ , Cu ²⁺ , Zn ²⁺ , Al ³⁺ , 1 / 2Ca ^2+, etc.) are preferred.
Examples of the organic cationic compound include a quaternary ammonium cation, a quaternary pyridinium cation, a quaternary quinolinium cation, a phosphonium cation, an iodonium cation, a sulfonium cation, and a dye cation.

  Specific examples of the quaternary ammonium cation include a tetraalkylammonium cation (for example, tetramethylammonium cation, tetrabutylammonium cation), a tetraarylammonium cation (for example, tetraphenylammonium cation), and the like. Examples of the quaternary pyridinium cation include an N-alkylpyridinium cation (for example, N-methylpyridinium cation), an N-arylpyridinium cation (for example, N-phenylpyridinium cation), and an N-alkoxypyridinium cation (for example, 4-phenyl-cation). N-methoxy-pyridinium cation) and N-benzoylpyridinium cation. Examples of the quaternary quinolinium cation include an N-alkylquinolinium cation (for example, an N-methylquinolinium cation), an N-arylquinolinium cation (for example, an N-phenylquinolinium cation), and the like. It is done. Examples of the phosphonium cation include a tetraarylphosphonium cation (for example, a tetraphenylphosphonium cation). Examples of the iodonium cation include a diaryl iodonium cation (for example, a diphenyl iodonium cation). Examples of the sulfonium cation include a triarylsulfonium cation (for example, a triphenylsulfonium cation).

  Further, examples of the cation forming the salt include compounds described in paragraphs [0020] to [0038] of JP-A-9-188686.

Examples of the alkenyl group include linear, branched, and cyclic alkenyl groups, and the number of carbon atoms of the alkenyl group is preferably 2 to 30, and more preferably 2 to 20. The above range is also preferable for the number of carbon atoms in the alkenyl part of the substituted alkenyl group.
Specific examples of the alkenyl group include, for example, vinyl group, allyl group, prenyl group, geranyl group, oleyl group, and cycloalkenyl group (for example, 2-cyclopenten-1-yl group, 2-cyclohexen-1-yl group). Bicyclo [2,2,1] hept-2-en-1-yl, bicyclo [2,2,2] oct-2-en-4-yl, and the like.
Specific examples of the substituent of the substituted alkenyl group include the same substituents as in the case of the substituted alkyl group.

Examples of the alkynyl group include linear, branched, and cyclic alkynyl groups, and the number of carbon atoms of the alkynyl group is preferably 2 to 30, and more preferably 2 to 20. The above range is also preferable for the number of carbon atoms in the alkynyl part of the substituted alkynyl group.
Specific examples of the alkynyl group include ethynyl group, propargyl group, trimethylsilylethynyl group and the like.
Specific examples of the substituent of the substituted alkynyl group include the same substituents as those of the substituted alkyl group.

Examples of the aralkyl group include linear, branched, and cyclic aralkyl groups. The number of carbon atoms in the aralkyl group is preferably 7 to 35, and more preferably 7 to 25. The above range is also preferred for the number of carbon atoms in the aralkyl portion of the substituted aralkyl group.
Specific examples of the aralkyl group include, for example, benzyl group, methylbenzyl group, octylbenzyl group, dodecylbenzyl group, hexadecylbenzyl group, dimethylbenzyl group, octyloxybenzyl group, octadecylaminocarbonylbenzyl group, chlorobenzyl group and the like. Is mentioned.
Specific examples of the substituent for the substituted aralkyl group include the same substituents as those for the substituted alkyl group.

When R ¹ and R ² , R ³ and R ⁵ , R ⁴ , R ^{6 to} R ⁹ , R ^{10 to} R ¹⁴ , R ³¹ and R ³² , R ³³ and R ³⁴ represent an aromatic group, Examples of the aromatic group include an aryl group and a substituted aryl group. As a carbon atom number of this aryl group, 6-30 are preferable and 6-20 are more preferable. The above range is also preferred for the number of carbon atoms in the aryl moiety of the substituted aryl group.
Specific examples of the aryl group include a phenyl group, an α-naphthyl group, and a β-naphthyl group.
These aromatic groups may have a substituent. Examples of the substituent of the substituted aromatic group include the same substituents as those of the substituted alkyl group.

When R ¹ and R ² , R ³ and R ⁵ , R ⁴ , R ^{10 to} R ¹⁴ , R ³¹ and R ³² represent a heterocyclic group, the heterocyclic group includes a nitrogen atom, oxygen Heterocyclic groups containing atoms and sulfur atoms, such as furyl, thienyl, pyridyl, pyrazolyl, isoxazolyl, isothiazolyl, imidazolyl, oxazolyl, thiazolyl, pyridazyl, pyrimidyl, pyrazyl, triazolyl Group, tetrazolyl group, quinolyl group, benzothiazolyl group, benzoxazolyl group, benzimidazolyl group, isoquinolyl group, thiadiazolyl group, morpholino group, piperidino group, thiomorpholino group, tetrahydrofurfuryl group, piperazino group, indolyl group, isoindolyl group, etc. Is mentioned.
These heterocyclic groups may have a substituent. Examples of the substituent of the substituted heterocyclic group include the same substituents as those of the substituted alkyl group.

Moreover, when said R < ⁶ > -R < ⁹ >, R < ³³ > and R < ³⁴ > represent an acyl group, as this acyl group, an aliphatic acyl group, an aromatic acyl group, a heterocyclic acyl group etc. are mentioned, for example. The number of carbon atoms of the acyl group is preferably 1-30, and more preferably 1-20. The above range is also preferable for the number of carbon atoms in the acyl moiety of the substituted acyl group.
Specific examples of the acyl group include, for example, acetyl group, propionyl group, pivaloyl group, chloroacetyl group, trifluoroacetyl group, 1-methylcyclopropylcarbonyl group, 1-ethylcyclopropylcarbonyl group, 1-benzylcyclopropyl. Examples include carbonyl group, benzoyl group, 4-methoxybenzoyl group, pyridylcarbonyl group, and thenoyl group.
These acyl groups may have a substituent. Examples of the substituent of the substituted acyl group include the same substituents as in the case of the substituted alkyl group.

When R ^{6 to} R ⁹ , R ³³ and R ³⁴ represent an alkoxycarbonyl group, examples of the alkoxycarbonyl group include a substituted alkoxycarbonyl group and an unsubstituted alkoxycarbonyl group. The number of carbon atoms of the alkoxycarbonyl group is preferably 2-20.
Specific examples of the alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, allyloxycarbonyl group, methoxyethylcarbonyl group, octyloxycarbonyl group and the like. Examples of the substituent of the alkoxycarbonyl group having a substituent include the same substituents as in the case of the substituted alkyl group.

When R ^{6 to} R ⁹ , R ³³ and R ³⁴ represent an aryloxycarbonyl group, examples of the aryloxycarbonyl group include a substituted aryloxycarbonyl group and an unsubstituted aryloxycarbonyl group. The number of carbon atoms of the aryloxycarbonyl group is preferably 7-30.
Specific examples of the aryloxycarbonyl group include a phenoxycarbonyl group and a naphthoxycarbonyl group. Examples of the substituent of the aryloxycarbonyl group having a substituent include the same substituents as in the case of the substituted alkyl group.

When R ^{6 to} R ⁹ , R ³³ and R ³⁴ represent a carbamoyl group, examples of the carbamoyl group include a carbamoyl group having a substituent and an unsubstituted carbamoyl group. The number of carbon atoms in the carbamoyl group is preferably 1-20.
Specific examples of the carbamoyl group include a carbamoyl group, a methylcarbamoyl group, a dimethylcarbamoyl group, and the like. Examples of the substituent of the carbamoyl group having a substituent include the same substituents as those in the case of the substituted alkyl group.

When R ^{6 to} R ⁹ , R ³³ and R ³⁴ represent an alkylsulfonyl group, examples of the alkylsulfonyl group include an alkylsulfonyl group having a substituent and an unsubstituted alkylsulfonyl group. The number of carbon atoms of the alkylsulfonyl group is preferably 1-20.
Specific examples of the alkylsulfonyl group include a methylsulfonyl group, an ethylsulfonyl group, a dodecylsulfonyl group, a trifluoromethylsulfonyl group, and the like. Examples of the substituent of the alkylsulfonyl group having a substituent include the same substituents as in the case of the substituted alkyl group.

When R ^{6 to} R ⁹ , R ³³ and R ³⁴ represent an arylsulfonyl group, examples of the arylsulfonyl group include an arylsulfonyl group having a substituent and an unsubstituted arylsulfonyl group. The number of carbon atoms of the arylsulfonyl group is preferably 6-30.
Specific examples of the arylsulfonyl group include a phenylsulfonyl group, a toluenesulfonyl group, a chlorophenylsulfonyl group, a methoxyphenylsulfonyl group, an acetylaminophenylsulfonyl group, and a naphthylsulfonyl group. Examples of the substituent of the arylsulfonyl group having a substituent include the same substituents as in the case of the substituted alkyl group.

When R ^{6 to} R ⁹ , R ³³ and R ³⁴ represent a sulfamoyl group, examples of the sulfamoyl group include a sulfamoyl group having a substituent and an unsubstituted sulfamoyl group.
Specific examples of the sulfamoyl group include a sulfamoyl group, a dimethylsulfamoyl group, and a di (hydroxyethyl) sulfamoyl group. Examples of the substituent of the sulfamoyl group having a substituent include the same substituents as in the case of the substituted alkyl group.

When R ¹ and R ² are connected to each other to form a ring, the linking group is preferably an alkylene group having 2 to 4 carbon atoms, and examples thereof include an ethylene group, a propylene group, and a butylene group.

Among the compounds represented by the general formula (I) of the present invention, R ¹ and R ² are preferably a hydrogen atom, an aliphatic group, —COR ³ , —COOR ⁴ , —SO ₂ —R ⁵ , —N. (R ⁶ ) R ⁷ , particularly preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkyl group substituted with an optionally substituted hydroxy group or amino group,- COR ^3, -COOR ^4, a -N (R ⁶⁾ R ^7.
Specific examples thereof include hydrogen atom, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, dodecyl group, octadecyl group, hydroxyethyl group, hydroxypropyl group, hydroxyethoxyethyl group, hydroxybutyl group. , hydroxy octyl group, aminoethyl group, aminopropyl _{group, - (CH 2) 2 NH} (CH 2) 2 NH 2, phenoxyethyl group, phenoxypropyl group, diethylaminoethyl group, N- methyl -N- benzylamino ethyl , Phenyl group, tolyl group, methoxyphenyl group, chlorophenyl group, acetylphenyl group, biphenyl group, naphthyl group, pyridyl group, morpholino group, piperazino group, pyrrolidino group, furfuryl group, acetyl group, carbamoyl group, N, N-diethyl Carbamoyl group, benzoyl group, Toxicarbonyl group, butylaminocarbonyl group, phenylaminocarbonyl group, phenoxycarbonyl group, methylsulfonyl group, phenylsulfonyl group, toluenesulfonyl group, acetaminophenylsulfonyl group, chlorophenylsulfonyl group, amino group, dimethylamino group, methylamino group And acetylamino group.

Among the compounds represented by the general formula (I) of the present invention, R ^{10 to} R ¹⁴ are preferably a hydrogen atom, an aliphatic group, —COOR ³² , —N (R ³³ ) R ³⁴ , and particularly preferable. Are hydrogen atom, aliphatic group having 1 to 12 carbon atoms, and —COOR ³² and —N (R ³³ ) R ³⁴ having 20 or less carbon atoms.

  Specific examples of the compound represented by the general formula (I) of the present invention are shown below, but the present invention is not limited to these compounds.

(Compound represented by formula (II))
The ink jet recording sheet according to the second aspect of the present invention is characterized in that the colorant receiving layer provided on the support contains a compound represented by the following general formula (II).

In the general formula (II), R ²¹ and R ²² are each independently a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, —COR ⁵³ , —COOR ⁵⁴ , —SO ₂ —R ⁵⁵ , —N (R ⁵⁶ ) R ⁵⁷ is represented. Here, R ⁵³ and R ⁵⁵ each independently represent a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, or —N (R ⁵⁸ ) R ⁵⁹ , and R ⁵⁴ represents a hydrogen atom, an aliphatic group or an aromatic group. R ^{56 to} R ⁵⁹ are each independently a hydrogen atom, aliphatic group, aromatic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, aryl. Represents a sulfonyl group or a sulfamoyl group. R ²¹ and R ²² may be connected to each other to form a ring. R ²³ represents an aliphatic group, an aromatic group, a heterocyclic group, —COR ⁷¹ , —COOR ⁷² , —N (R ⁷³ ) R ⁷⁴ , and R ^{24 to} R ²⁶ each independently represent a hydrogen atom or an aliphatic group. , Aromatic group, heterocyclic group, —COR ⁷¹ , —COOR ⁷² , —N (R ⁷³ ) R ⁷⁴ . Here, R ⁷¹ represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, a ^{-N (R 58) R 59,} R 72 is a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic R ⁷³ and R ⁷⁴ each independently represents a hydrogen atom, aliphatic group, aromatic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group, sulfamoyl group. To express.

When R ²¹ and R ²² , R ⁵³ and R ⁵⁵ , R ⁵⁴ , R ^{56 to} R ⁵⁹ , R ²³ , R ^{24 to} R ²⁶ , R ⁷¹ and R ⁷² , R ⁷³ and R ⁷⁴ represent an aliphatic group, Examples of the aliphatic group has the same meaning as the aliphatic group represented by R ¹ and R ² or the like in the above general formula (I), a preferred range of number of carbon atoms, and preferred examples substituent similar.

When R ²¹ and R ²² , R ⁵³ and R ⁵⁵ , R ⁵⁴ , R ^{56 to} R ⁵⁹ , R ²³ , R ^{24 to} R ²⁶ , R ⁷¹ and R ⁷² , R ⁷³ and R ⁷⁴ represent an aromatic group, the aromatic group has the same meaning as the aromatic group represented by R ¹ and R ² or the like in the above general formula (I), a preferred range of number of carbon atoms, and preferred examples aromatic groups as well.

When R ²¹ and R ²² , R ⁵³ and R ⁵⁵ , R ⁵⁴ , R ²³ , R ^{24 to} R ²⁶ , R ⁷¹ and R ⁷² represent a heterocyclic group, the heterocyclic group includes the above-mentioned general groups. It is synonymous with the heterocyclic group which R < ¹ >, R < ² > etc. in Formula (I) represent, The range of a preferable carbon atom number, and a preferable example heterocyclic group are the same.

When R ^{56 to} R ⁵⁹ , R ⁷³ and R ⁷⁴ represent an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, the acyl group, an alkoxycarbonyl group, As the aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group, sulfamoyl group, acyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, carbamoyl represented by R ^{6 to} R ⁹ etc. in the aforementioned general formula (I) Group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfamoyl group, and a preferred range of the number of carbon atoms, and preferred examples of acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group The arylsulfonyl group and sulfamoyl group are the same.

When the R ²¹ and R ²² are bonded to each other to form a ring, examples of the linking group has the same meaning as the linking group represented by R ¹ and R ² in the above general formula (I), preferable number of carbon atoms The range and preferred exemplary linking groups are the same.

  Of the compounds represented by the above general formula (II), the compounds represented by the following general formula (V) are preferred from the viewpoints of ozone resistance and deodorization.

In the above general formula (V), R ²¹ and R ²² have the same meanings as the substituents represented by R ²¹ and R ²² in Formula (II), is the same preferred exemplified compounds. R ²⁹ represents an aliphatic group, —COOR ⁷² , —N (R ⁷³ ) R ⁷⁴ , preferably an alkyl group (eg, methyl group, ethyl group), —COOH, —CONH ₂ , —CONHNH ₂ , —NH _2. Particularly preferred is a methyl group.

(Compound represented by formula (III))
In the inkjet recording sheet of the third aspect of the invention, the colorant receiving layer provided on the support contains a compound represented by the following general formula (III), fine particles and a water-soluble resin, and the color of the fine particles The solid content in the material receiving layer is more than 60% by mass.

In the general formula (III), R ⁶¹ and R ⁶² are each independently a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, —COR ⁶³ , —COOR ⁶⁴ , —SO ₂ —R ⁶⁵ , —N (R ⁶⁶ ) R ⁶⁷ is represented. Here, R ⁶³ and R ⁶⁵ each independently represent a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, or —N (R ⁶⁸ ) R ⁶⁹ , and R ⁶⁴ represents a hydrogen atom, an aliphatic group, or an aromatic group. R ^{66 to} R ⁶⁹ each independently represents a hydrogen atom, aliphatic group, aromatic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, aryl. Represents a sulfonyl group or a sulfamoyl group. R ⁶¹ and R ⁶² may be connected to each other to form a ring.

When R ⁶¹ and R ⁶² , R ⁶³ and R ⁶⁵ , R ⁶⁴ , R ^{66 to} R ⁶⁹ represent an aliphatic group, the aliphatic group includes R ¹ and R ² in the general formula (I) described above. Are the same as the aliphatic group represented by the above formula, and the same applies to the preferable range of the number of carbon atoms and the preferable exemplified aliphatic group.

When R ⁶¹ and R ⁶² , R ⁶³ and R ⁶⁵ , R ⁶⁴ , R ^{66 to} R ⁶⁹ represent an aromatic group, the aromatic group includes R ¹ and R ² in the general formula (I) described above. Are the same as the aromatic group represented by the above formulas, and the same applies to the preferred range of the number of carbon atoms and the preferred exemplified aromatic group.

When R ⁶¹ and R ⁶² , R ⁶³ and R ⁶⁵ , R ⁶⁴ represent a heterocyclic group, the heterocyclic group includes a complex represented by R ¹ and R ² in the general formula (I) described above. It is synonymous with a cyclic group, and the range of a preferable carbon atom number and the preferable example heterocyclic group are the same.

When R ^{66 to} R ⁶⁹ represent an acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group, sulfamoyl group, the acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl As the group, alkylsulfonyl group, arylsulfonyl group, sulfamoyl group, the acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group represented by R ^{6 to} R ^{9 and the} like in the aforementioned general formula (I) Are the same as arylsulfonyl group and sulfamoyl group, and the preferred range of the number of carbon atoms and preferred examples are acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, arylsulfur group. Group, a sulfamoyl group is the same.

When R ⁶¹ and R ⁶² are linked to each other to form a ring, the linking group has the same meaning as the linking group represented by R ¹ and R ² in the general formula (I) described above, and preferably has the number of carbon atoms. The same applies to the above-mentioned ranges and preferred exemplary linking groups.

In the compound represented by the general formula (III) of the present invention, at least one of R ⁶¹ and R ⁶² is substituted with an optionally substituted hydroxy group or amino group from the viewpoint of ozone resistance and deodorization. And an alkyl group, —COR ⁶³ , —COOR ⁶⁴ , —SO ₂ —R ⁶⁵ , and —N (R ⁶⁶ ) R ⁶⁷ are preferred.

  The compound represented by the general formula (III) of the present invention is particularly preferably a compound represented by the following general formulas (VI) and (VII) from the viewpoint of ozone resistance.

In the general formula (VI), R ³⁵ and R ³⁶ are each independently a hydrogen atom, aliphatic group, aromatic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group. Represents a sulfamoyl group. Y represents a linear or branched alkylene group having 2 to 4 carbon atoms, m represents an integer of 0 to 10, and n represents an integer of 1 to 10.

In the general formula (VII), R ³⁷ and R ⁴⁰ are each independently a hydrogen atom, aliphatic group, aromatic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group. Represents a sulfamoyl group, and R ³⁸ and R ³⁹ each independently represent a hydrogen atom or an aliphatic group. Z represents a linear or branched alkylene group having 2 to 4 carbon atoms, m ′ represents an integer of 0 to 10, and n ′ represents an integer of 1 to 10.
Of the compounds represented by the above general formulas (VI) and (VII), the compound represented by the general formula (VII) is particularly preferable from the viewpoint of the effect of improving ozone resistance.

(Compound represented by formula (IV))
In the ink jet recording sheet of the fourth aspect of the invention, the color material receiving layer provided on the support contains a compound represented by the following general formula (IV), fine particles and a water-soluble resin, and the color of the fine particles The solid content in the material receiving layer is more than 60% by mass.

In the general formula (IV), R ⁴¹ represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, —COR ⁴³ , —COOR ⁴⁴ , —SO ₂ —R ⁴⁵ , —N (R ⁴⁶ ) R ^47. Represents. Here, R ⁴³ and R ⁴⁵ each independently represent a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, or —N (R ⁴⁸ ) R ⁴⁹ , and R ⁴⁴ represents a hydrogen atom, an aliphatic group or an aromatic group. R ^{46 to} R ⁴⁹ each independently represents a hydrogen atom, aliphatic group, aromatic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, aryl Represents a sulfonyl group or a sulfamoyl group. X represents an atomic group necessary for forming a 5- to 7-membered ring of a saturated hydrocarbon which may contain an oxygen atom, a sulfur atom, SO or SO ₂ . The atomic groups represented by R ⁴¹ and X may be connected to each other to form a ring.

When R ⁴¹ , R ⁴³ and R ⁴⁵ , R ⁴⁴ , R ^{46 to} R ⁴⁹ represent an aliphatic group, the aliphatic group is represented by R ¹ and R ² in the general formula (I) described above. It is synonymous with an aliphatic group, the range of a preferable carbon atom number, and the preferable example aliphatic group are also the same.

When R ⁴¹ , R ⁴³ and R ⁴⁵ , R ⁴⁴ , R ^{46 to} R ⁴⁹ represent an aromatic group, examples of the aromatic group include R ¹ and R ² in the general formula (I) described above. It is synonymous with an aromatic group, the range of a preferable carbon atom number, and the preferable illustration aromatic group are also the same.

When R ⁴¹ , R ⁴³ and R ⁴⁵ , R ⁴⁴ represent a heterocyclic group, the heterocyclic group includes a heterocyclic group represented by R ^1, R ^2, etc. in the general formula (I) described above. The same applies to the preferred range of the number of carbon atoms and preferred exemplified heterocyclic groups.

When R ^{46 to} R ⁴⁹ represent an acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group, sulfamoyl group, the acyl group, alkoxycarbonyl group, aryloxycarbonyl group , A carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfamoyl group include an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkyl represented by R ^{6 to} R ⁹ in the general formula (I) described above. Synonymous with sulfonyl group, arylsulfonyl group, sulfamoyl group, and a preferred range of the number of carbon atoms, and preferred examples of acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, aryl Sulfonyl group, sulfamoyl group is the same.

In the compound represented by the general formula (IV) of the present invention, R ⁴¹ is preferably an aliphatic group, —COR ⁴³ , —COOR ⁴⁴ , —N (R ⁴⁶ ) R ⁴⁷ . Further, from the viewpoint of further improving the ozone resistance, R ⁴¹ is preferably — (— Y—O—) _n —R ⁴⁸ or — (— Z—NR ⁴⁹ —) _n ′ —R ⁵⁰ , particularly — (— _{^{Z-NR 49 -) n '}} -R 50 are preferred. Here, R ⁴⁸ represents a hydrogen atom, aliphatic group, aromatic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group, sulfamoyl group, R ⁴⁹ and R ⁵⁰ Represents a hydrogen atom, aliphatic group, aromatic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group, sulfamoyl group.

EP 1,138,509 exemplifies a compound containing a thioether bond as an alkyl group substituted with N as an analog of the general formula (IV) of the present invention. This thioether bond In the examples, the above compound example (36) has the same gas resistance (ozone resistance) as the compound example (7) having no alicyclic amino group. It only shows. Therefore, when R ^{41 in} the general formula (IV) of the present invention represents an alkyl group, it represents one not containing a thioether bond.

X represents an atomic group necessary for forming a 5- to 7-membered ring of a saturated hydrocarbon which may contain an oxygen atom, a sulfur atom, SO or SO ₂ . Among these, as a connection ring of general formula (IV), the 5-7 membered ring shown below is preferable.

Here, the 5- to 7-membered ring may have a substituent represented by R ¹⁰ in the general formula (I).

  Specific examples of the compounds represented by the general formulas (II) to (IV) of the present invention are shown below, but the present invention is not limited to these compounds.

  The compounds represented by the general formulas (I) to (IV) may be water-soluble or oil-soluble, but using a water-soluble compound is suitable for the production of an ink jet recording sheet and imparting resistance. This is preferable because it is advantageous. The solubility in water is preferably 0.1 g or more, particularly preferably 0.5 g or more with respect to 100 g of water at a temperature of 25 ° C.

  When the colorant receiving layer contains the compounds represented by the general formulas (I) to (IV), a water-soluble organic solvent such as an alcohol compound (methanol, ethanol, isopropyl alcohol, ethylene glycol, diethylene glycol, diethylene glycol monobutyl ether) , Polyethylene glycol, polypropylene glycol, glycerin, diglycerin, trimethylolpropane, trimethylolbutane, etc.), ether compounds (tetrahydrofuran, dioxane, etc.), amide compounds (dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc.), ketone compounds ( Acetone or the like) may be mixed and added in a state of increasing the affinity for water.

  When the compounds represented by the general formulas (I) to (IV) do not have sufficient water solubility, hydrophobic organic solvents such as ester compounds (ethyl acrylate, dioctyl adipate, butyl phthalate, methyl stearate) , Tricresyl phosphate, etc.), ether compounds (anisole, hydroxyethoxybenzene, hydroquinone dibutyl ether, etc.), hydrocarbon compounds (toluene, xylene, diisopropylnaphthalene, etc.), amide compounds (N-butylbenzenesulfonamide, stearic acid) Amide, etc.), alcohol compounds (2-ethylhexyl alcohol, benzyl alcohol, phenethyl alcohol, etc.), ketone compounds (hydroxyacetophenone, benzophenone, cyclohexane, etc.), or the above water-soluble organic solvents, etc. It may be. The form when added may be oil droplets, latex, solid dispersion, polymer dispersion or the like.

The compounds represented by the general formulas (I) to (IV) may form an oligomer or polymer having a partial skeleton of the alicyclic amine in the general formulas (I) to (IV). In this case, when a reactive group exists in the general formulas (I) to (IV), the oligomer is obtained by reacting with a bifunctional or higher functional halogen compound, tosylate compound, isocyanate compound, epoxy compound, acid halide compound, etc. It is possible to produce a polymer.
These may be homopolymerized or may be copolymerized with another polymerization or a reactive agent. Alternatively, a polymer having a polymerizable group such as a methacryl group, an acryl group, an epoxy group, a reactive cyclic ether group, or a vinyl group in the general formulas (I) to (IV) may be homopolymerized or co-polymerized with another monomer. It may be polymerized.

When using low molecular weight compounds of general formulas (I) to (IV), the molecular weight is 1000 or less, preferably 500 or less. When using an oligomer and a polymer body, the molecular weight is 1200 or more, preferably 2000 or more.
The ink jet recording sheet of the present invention may contain at least one of the compounds represented by the general formulas (I) to (IV) described above in the colorant receiving layer.
The content of the colorant-receiving layer of the general formula (I) ~ the compounds represented by (IV) ^{are, 0.01g / m 2 ~5g / m} 2 are ^{preferred, 0.05g / m 2 ~3g / m} 2 Is more preferable.

(Fine particles)
In the inkjet recording sheets of the third and fourth aspects of the present invention, the colorant receiving layer provided on the support has fine particles and a compound described later together with the compound represented by the general formula (III) or the general formula (IV). It contains a water-soluble resin, and the solid content in the colorant-receiving layer of the fine particles exceeds 60% by mass. Also, in the first and second ink jet recording sheets, the colorant-receiving layer contains fine particles and a water-soluble resin together with the compound represented by the general formula (I) or the general formula (II). preferable.
A porous structure is obtained by containing fine particles in the color material receiving layer, thereby improving the ink absorption performance. In particular, when the solid content of the fine particles in the colorant-receiving layer is 60% by mass or more, more preferably more than 65% by mass, it becomes possible to form a more favorable porous structure, and sufficient ink absorption. This is preferable because an ink jet recording sheet having the properties can be obtained. Here, the solid content in the colorant receiving layer of fine particles is a content calculated based on components other than water in the composition constituting the colorant receiving layer.
As the fine particles of the present invention, organic fine particles and inorganic fine particles can be used, but it is preferable to contain inorganic fine particles from the viewpoint of ink absorbability and image stability.

  The organic fine particles are preferably polymer fine particles obtained by, for example, emulsion polymerization, microemulsion polymerization, soap-free polymerization, seed polymerization, dispersion polymerization, suspension polymerization, and the like. Polyethylene, polypropylene, polystyrene, polyacrylate, polyamide, silicon resin , Phenol resin, natural polymer powder, latex or emulsion polymer fine particles, and the like.

Examples of the inorganic fine particles include silica fine particles, colloidal silica, titanium dioxide, barium sulfate, calcium silicate, zeolite, kaolinite, halloysite, mica, talc, calcium carbonate, magnesium carbonate, calcium sulfate, pseudoboehmite, zinc oxide, water. Examples thereof include zinc oxide, alumina, aluminum silicate, calcium silicate, magnesium silicate, zirconium oxide, zirconium hydroxide, cerium oxide, lanthanum oxide, and yttrium oxide. Among these, silica fine particles, colloidal silica, alumina fine particles, or pseudoboehmite is preferable from the viewpoint of forming a good porous structure. The fine particles may be used as primary particles or in a state where secondary particles are formed. The average primary particle size of these fine particles is preferably 2 μm or less, and more preferably 200 nm or less.
Further, silica fine particles having an average primary particle size of 20 nm or less, alumina fine particles having an average primary particle size of 20 nm or less, or pseudoboehmite having an average pore radius of 2 to 15 nm are more preferable, and silica particles are particularly preferable.

  Silica fine particles are generally roughly classified into wet method particles and dry method (gas phase method) particles according to the production method. In the above wet method, a method is mainly used in which activated silica is produced by acid decomposition of a silicate, and this is appropriately polymerized and agglomerated and precipitated to obtain hydrous silica. On the other hand, the gas phase method is a method by high-temperature gas phase hydrolysis of silicon halide (flame hydrolysis method), 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 the (arc method) is the mainstream, and “gas phase method silica” means anhydrous silica fine particles obtained by the gas phase method. As the silica fine particles used in the present invention, gas phase method silica fine particles are particularly preferable.

The gas phase method silica is different from hydrous silica in terms of the density of silanol groups on the surface, presence or absence of vacancies, and the like, and shows different properties, but is suitable for forming a three-dimensional structure having a high porosity. The reason for this is not clear, but in the case of hydrous silica, the density of silanol groups on the surface of the fine particles is large at 5 to 8 / nm ² , and the silica fine particles tend to aggregate closely (aggregate). In the case of the method silica, the density of silanol groups on the surface of the fine particles is as small as ² to 3 / nm ² , so that it is sparse soft agglomeration (flocculate), resulting in a structure with a high porosity. Is done.

  The above-mentioned vapor phase silica has a particularly large specific surface area, so the ink absorption and retention efficiency is high, and the refractive index is low. Therefore, if the dispersion is made to an appropriate particle size, transparency can be imparted to the receiving layer. It is characterized by high color density and good color development. The transparency of the receiving layer is not only for applications that require transparency such as OHP, but also in terms of obtaining high color density and good color development gloss even when applied to recording sheets such as photo glossy paper. is important.

  The average primary particle diameter of the vapor phase silica is preferably 30 nm or less, more preferably 20 nm or less, particularly preferably 10 nm or less, and most preferably 3 to 10 nm. Since the vapor phase silica is easily adhered to each other by hydrogen bonding with a silanol group, a structure having a large porosity can be formed when the average primary particle diameter is 30 nm or less, and ink absorption characteristics are effectively improved. Can be improved.

  Silica fine particles may be used in combination with the other fine particles described above. When the other fine particles and the vapor phase silica are used in combination, the content of the vapor phase silica in all the fine particles is preferably 30% by mass or more, and more preferably 50% by mass or more.

As the inorganic fine particles of the present invention, alumina, alumina hydrate, a mixture or a composite thereof is also preferable. Of these, alumina hydrate is more preferable because it absorbs and fixes ink well, and pseudoboehmite (Al ₂ O ₃ .nH ₂ O) is particularly preferable. Alumina hydrates can be used in various forms, but it is preferable to use sol boehmite as a raw material because a smooth layer can be easily obtained.

About the pore structure of pseudo boehmite, the average pore radius is preferably 1 to 30 nm, and more preferably 2 to 15 nm. The pore volume is preferably 0.3 to 2.0 cc / g, more preferably 0.5 to 1.5 cc / g. Here, the pore radius and pore volume are measured by a nitrogen adsorption / desorption method, and can be measured by, for example, a gas adsorption / desorption analyzer (for example, trade name “Omni Soap 369” manufactured by Coulter). .
Among alumina, vapor-phase process alumina fine particles are preferable because of their large specific surface area. The average primary particle size of the vapor phase alumina is preferably 30 nm or less, and more preferably 20 nm or less.

  When the above-mentioned fine particles are used in an inkjet recording sheet, for example, JP-A-10-81064, JP-A-10-119423, JP-A-10-157277, JP-A-10-217601, JP-A-11-348409, JP-A-2001-2001. 138621, 2000-43401, 2000-21235, 2000-309157, 2001-96897, 2001-138627, JP-A-11-91242, 8-2087, 8-2090 No. 8-2091, No. 8-2093, No. 8-174992, No. 11-192777, JP-A No. 2001-301314, etc. can be preferably used.

(Water-soluble resin)
In the ink jet recording sheets of the third and fourth aspects of the present invention, the colorant receiving layer contains a water-soluble resin together with the compound of the general formula (III) or the general formula (IV) and the fine particles described above. Also in the first and second inkjet recording sheets, it is preferable that the colorant-receiving layer contains fine particles and a water-soluble resin together with the compound represented by the general formula (I) or the general formula (II).

Examples of the water-soluble resin include polyvinyl alcohol (PVA), which is a resin having a hydroxy group as a hydrophilic structural unit, acetoacetyl-modified polyvinyl alcohol, cation-modified polyvinyl alcohol, anion-modified polyvinyl alcohol, silanol-modified polyvinyl alcohol, and polyvinyl acetal. , Cellulose resins [methyl cellulose (MC), ethyl cellulose (EC), hydroxyethyl cellulose (HEC), carboxymethyl cellulose (CMC), hydroxypropyl cellulose (HPC), etc.], chitins, chitosans, starch; resins having an ether bond Certain polyethylene oxide (PEO), polypropylene oxide (PPO), polyethylene glycol (PEG), polyvinyl ether (PVE); Polyacrylamide resins having a bromide group or an amide bond (PAAM), polyvinyl pyrrolidone (PVP), polyacrylic acid hydrazide, and the like.
Moreover, the polyacrylic acid salt which has a carboxyl group as a dissociable group, maleic acid resin, alginate, gelatins, etc. can be mentioned.

  Among these, polyvinyl alcohol or a derivative thereof is particularly preferable. Examples of the polyvinyl alcohol include Japanese Patent Publication No. 4-52786, Japanese Patent Publication No. 5-67432, Japanese Patent Publication No. 7-29479, Japanese Patent No. 2537827, Japanese Patent Publication No. 7-57553, Japanese Patent No. 2502998, and Japanese Patent No. 3053231. JP-A-63-176173, JP-A-2604367, JP-A-7-276787, JP-A-9-207425, JP-A-11-58941, JP-A-2000-135858, JP-A-2001-205924, JP 2001-287444, JP 62-278080, JP 9-39373, JP 2750433, JP 2000-18801, JP 2001-213045, JP 2001-328345, JP 8 -324105, JP-A-11-348417, etc. Kill.

As content of the water-soluble resin of this invention, 9-40 mass% is preferable with respect to the total solid content mass of a color material receiving layer, and 12-33 mass% is more preferable.
The fine particles and the water-soluble resin that mainly constitute the color material receiving layer of the present invention may be a single material or a mixed system of a plurality of materials.

  From the viewpoint of maintaining transparency, the type of water-soluble resin to be combined with fine particles, particularly silica fine particles, is important. When the vapor phase silica is used, the water-soluble resin is preferably polyvinyl alcohol (PVA), more preferably PVA having a saponification degree of 70 to 100%, and a saponification degree of 80 to 99.5%. PVA is particularly preferred.

The polyvinyl alcohol (PVA) has a hydroxyl group in its structural unit. Since this hydroxyl group and the surface silanol group of the silica fine particle form a hydrogen bond, the secondary particle of the silica fine particle is a three-dimensional network unit. It becomes easy to form a network structure. By forming this three-dimensional network structure, it is considered that a color material receiving layer having a porous structure having a high porosity and sufficient strength is formed.
In ink jet recording, the porous colorant receiving layer obtained as described above can absorb ink rapidly by capillary action and form dots with good roundness without ink bleeding.

  Polyvinyl acetal, cellulose resin [methyl cellulose (MC), ethyl cellulose (EC), hydroxyethyl cellulose (HEC), carboxymethyl cellulose (CMC), hydroxypropyl cellulose (HPC), etc.], chitins, chitosans, starch; ether bond Polyethylene oxide (PEO), polypropylene oxide (PPO), polyethylene glycol (PEG), polyvinyl ether (PVE) that are resins having polyamide (PAAM), polyvinyl pyrrolidone (PVP) that is a resin having an amide group or an amide bond , Polyacrylic acid hydrazide, and other water-soluble resins such as polyacrylates, maleic acid resins, alginates, gelatins having carboxy groups as dissociative groups It may be use. When the other water-soluble resin and the polyvinyl alcohol are used in combination, the content of polyvinyl alcohol in the total water-soluble resin is preferably 50% by mass or more, and more preferably 70% by mass or more.

<Content ratio of fine particles to water-soluble resin>
The mass content ratio [PB ratio (x / y)] of the fine particles (x) and the water-soluble resin (y) greatly affects the film structure and film strength of the colorant receiving layer. That is, as the mass content ratio [PB ratio] increases, the porosity, pore volume, and surface area (per unit mass) increase, but the density and strength tend to decrease.

  The colorant receiving layer of the present invention prevents the decrease in film strength and cracking during drying caused by the PB ratio being too large as the mass content ratio [PB ratio (x / y)], and When the PB ratio is too small, the voids are easily blocked by the resin, and from the viewpoint of preventing the ink absorbency from being lowered due to the decrease in the void ratio, the ratio is 1.5: 1 to 10: 1. preferable.

  Since stress may be applied to the recording sheet when passing through the conveyance system of the ink jet printer, the color material receiving layer needs to have sufficient film strength. Further, when cutting into a sheet shape, the color material receiving layer needs to have sufficient film strength in order to prevent the color material receiving layer from being cracked or peeled off. In consideration of these cases, the mass ratio (x / y) is more preferably 5: 1 or less, while it is more preferably 2: 1 or more from the viewpoint of ensuring high-speed ink absorbency in an inkjet printer. preferable.

For example, a coating solution in which gas phase method silica fine particles having an average primary particle size of 20 nm or less and a water-soluble resin are completely dispersed in an aqueous solution at a mass ratio (x / y) of 2: 1 to 5: 1 is provided on the support. When the coating layer is dried, a three-dimensional network structure in which the secondary particles of silica fine particles are network chains is formed, the average pore diameter is 30 nm or less, the porosity is 50 to 80%, the pore ratio A translucent porous film having a 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)
The colorant receiving layer of the ink jet recording sheet of the present invention includes a coating layer (porous layer) containing fine particles and a water-soluble resin, and further includes a cross-linking agent capable of cross-linking the water-soluble resin. An embodiment that is a layer cured by a crosslinking reaction with a resin is preferable.

  The application of the cross-linking agent is previously added to a coating liquid for forming a porous color material receiving layer (coating liquid for color material receiving layer; hereinafter sometimes referred to as “coating liquid (A)”). Alternatively, it is preferably performed at the same time as the coating solution is applied, or before the coating layer formed by applying the colorant-receiving layer coating solution exhibits a reduced rate of drying. By this operation, it is possible to effectively prevent cracks that occur during the drying of the coating layer. That is, a crosslinking agent is added to the coating solution in advance, or a solution containing a crosslinking agent (crosslinking agent solution before the coating solution is applied, or before the coating layer exhibits a reduced drying rate). Hereinafter referred to as “solution (B)”) penetrates into the coating layer, reacts rapidly with the water-soluble resin in the coating layer, and gels (hardens) the water-soluble resin. The film strength of the layer can be greatly improved immediately.

  In the present invention, a coating liquid (hereinafter referred to as “coating liquid (hereinafter referred to as“ coating liquid (hereinafter referred to as “coating liquid”)) ”is obtained by adding and redispersing a solution (first solution) containing at least the above water-soluble resin to an aqueous dispersion composed of the above fine particles and a dispersant. C) ”may be applied to the surface of the support, and simultaneously with the application or during the drying of the application layer formed by the application, the application layer has a reduced drying rate. Before showing, a method of forming a colorant receiving layer by applying a solution containing at least a mordant (second solution; hereinafter sometimes referred to as “solution (D)”) to the coating layer is also preferably used. be able to. When this method is used, it is preferable to add a crosslinking agent to at least one of the aqueous dispersion composed of the fine particles and the dispersant and the second solution to be applied later.

Boron compounds are preferred for the crosslinking of the water-soluble resin, particularly polyvinyl alcohol. Examples of the boron compound include borax, boric acid, borates (for example, orthoborate, InBO ₃ , ScBO ₃ , YBO ₃ , LaBO ₃ , Mg ₃ (BO ₃ ) ₂ , Co ₃ (BO ₃ ) ₂ , 2 Borate (eg, Mg ₂ B ₂ O ₅ , Co ₂ B ₂ O ₅ ), metaborate (eg, LiBO ₂ , Ca (BO ₂ ) ₂ , NaBO ₂ , KBO ₂ ), tetraborate (eg, Na _{2 B 4 O 7 · 10H 2} O), can be mentioned five borate _{(e.g., KB 5 O 8 · 4H 2} O, Ca 2 B 6 O 11 · 7H 2 O, CsB 5 O 5) or the like. Among them, Of these, borax, boric acid and borates are preferable, and boric acid is particularly preferable because a crosslinking reaction can be promptly caused.

The following compounds other than the boron compound can also be used as the crosslinking agent for the water-soluble resin.
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-1,3,5- Active halogen compounds such as triazine and 2,4-dichloro-6-S-triazine sodium salt; divinylsulfonic acid, 1,3-vinylsulfonyl-2-propanol, N, N′-ethylenebis (vinylsulfonylacetamide) ), Active vinyl compounds such as 1,3,5-triacryloyl-hexahydro-S-triazine; N-methylol compounds such as dimethylolurea and methyloldimethylhydantoin; melamine resins (for example, methylolmelamine, alkylated methylolmelamine) ;Epoxy resin;

Isocyanate compounds such as 1,6-hexamethylene diisocyanate; aziridine compounds described in US Pat. Nos. 3,017,280 and 2,983611; carboximide compounds described in US Pat. No. 3,100,704; glycerol triglycidyl Epoxy compounds such as ether; Ethyleneimino compounds such as 1,6-hexamethylene-N, N′-bisethyleneurea; Halogenated carboxaldehyde compounds such as mucochloric acid and mucophenoxycyclolic acid; 2,3-dihydroxy Dioxane-based compounds such as dioxane; metal-containing compounds such as titanium lactate, aluminum sulfate, chromium alum, potash alum, zirconyl acetate, chromium acetate, polyamine compounds such as tetraethylenepentamine, hydrazide compounds such as adipic acid dihydrazide, A low molecule or polymer containing two or more oxazoline groups.
The above crosslinking agents may be used singly or in combination of two or more.

When the crosslinking agent is applied, the solution is prepared by dissolving the crosslinking agent in water and / or an organic solvent.
As a density | concentration of the crosslinking agent in the said crosslinking agent solution, 0.05-10 mass% is preferable with respect to a crosslinking agent solution, and 0.1-7 mass% is especially preferable.
As a solvent constituting the crosslinking agent solution, water is generally used, and an aqueous mixed solvent containing an organic solvent miscible with water may be used.
As said organic solvent, if a crosslinking agent melt | dissolves, it can be used arbitrarily, For example, alcohol, such as methanol, ethanol, isopropyl alcohol, polyethyleneglycol, and glycerol; Ketone, such as acetone and methyl ethyl ketone; Methyl acetate, Examples thereof include esters such as ethyl acetate; aromatic solvents such as toluene; ethers such as tetrahydrofuran; amide solvents such as pyrrolidone.
1-50 mass% is preferable with respect to water-soluble resin, and, as for the usage-amount of a crosslinking agent, 5-40 mass% is more preferable.

(mordant)
In the present invention, a mordant is preferably contained in the colorant receiving layer in order to improve the water resistance and aging resistance of the formed image.
As the mordant, a cationic polymer (cationic mordant) or a water-soluble metal compound is preferable. When the mordant is present in the colorant receiving layer, a liquid ink having an anionic dye as a colorant interacts with each other. It acts to stabilize the coloring material and improve water resistance and aging resistance.

  A method of adding a mordant to a coating solution containing fine particles and a water-soluble resin, or a method of preparing and applying the solution as an independent separate solution can be used when there is a concern that aggregation occurs between the fine particles.

As the cationic mordant, a polymer mordant having a primary to tertiary amino group or a quaternary ammonium base as a cationic group is preferably used, but a cationic non-polymer mordant may also be used. it can.
Examples of the polymer mordant include a homopolymer of a monomer having a primary to tertiary amino group and a salt thereof, or a quaternary ammonium base (mordant monomer), and the mordant monomer and other monomers (hereinafter, What is obtained as a copolymer or condensation polymer with "non-mordant monomer") is preferred. Moreover, these polymer mordants can be used in any form of a water-soluble polymer or water-dispersible latex particles.

  Examples of the monomer (mordant monomer) include trimethyl-p-vinylbenzylammonium chloride, trimethyl-m-vinylbenzylammonium chloride, triethyl-p-vinylbenzylammonium chloride, triethyl-m-vinylbenzylammonium chloride, N , N-dimethyl-N-ethyl-Np-vinylbenzylammonium chloride, N, N-diethyl-N-methyl-Np-vinylbenzylammonium chloride, N, N-dimethyl-Nn-propyl-N -P-vinylbenzylammonium chloride, N, N-dimethyl-Nn-octyl-Np-vinylbenzylammonium chloride, N, N-dimethyl-N-benzyl-Np-vinylbenzylammonium chloride, N, N-die Ru-N-benzyl-Np-vinylbenzylammonium chloride, N, N-dimethyl-N- (4-methyl) benzyl-Np-vinylbenzylammonium chloride, N, N-dimethyl-N-phenyl-N -P-vinylbenzylammonium chloride;

  Trimethyl-p-vinylbenzylammonium bromide, trimethyl-m-vinylbenzylammonium bromide, trimethyl-p-vinylbenzylammonium sulfonate, trimethyl-m-vinylbenzylammonium sulfonate, trimethyl-p-vinylbenzylammonium acetate, trimethyl-m-vinyl Benzylammonium acetate, N, N, N-triethyl-N-2- (4-vinylphenyl) ethylammonium chloride, N, N, N-triethyl-N-2- (3-vinylphenyl) ethylammonium chloride, N, N-diethyl-N-methyl-N-2- (4-vinylphenyl) ethylammonium chloride, N, N-diethyl-N-methyl-N-2- (4-vinylphenyl) ethylammonium chloride Tate;

  N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate, N, N- Methyl chloride, ethyl chloride, methyl bromide of dimethylaminoethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N-diethylaminopropyl (meth) acrylamide , Quaternized products of ethyl bromide, methyl iodide or ethyl iodide, or sulfonates, alkyl sulfonates, acetates or alkyl carboxylates substituted with their anions.

  Specifically, for example, monomethyl diallyl ammonium chloride, trimethyl-2- (methacryloyloxy) ethylammonium chloride, triethyl-2- (methacryloyloxy) ethylammonium chloride, trimethyl-2- (acryloyloxy) ethylammonium chloride, triethyl- 2- (acryloyloxy) ethylammonium chloride, trimethyl-3- (methacryloyloxy) propylammonium chloride, triethyl-3- (methacryloyloxy) propylammonium chloride, trimethyl-2- (methacryloylamino) ethylammonium chloride, triethyl-2- (Methacryloylamino) ethylammonium chloride, trimethyl-2- (acryloylamino) ethyl Ammonium chloride, triethyl-2- (acryloylamino) ethylammonium chloride, trimethyl-3- (methacryloylamino) propylammonium chloride, triethyl-3- (methacryloylamino) propylammonium chloride, trimethyl-3- (acryloylamino) propylammonium chloride Triethyl-3- (acryloylamino) propylammonium chloride;

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

In addition, allylamine, diallylamine, its derivatives, salts and the like can be used. Examples of such compounds include allylamine, allylamine hydrochloride, allylamine acetate, allylamine sulfate, diallylamine, diallylamine hydrochloride, diallylamine acetate, diallylamine sulfate, diallylmethylamine and salts thereof (for example, Hydrochloride, acetate, sulfate, etc.), diallylethylamine and this salt (for example, hydrochloride, acetate, sulfate, etc.), diallyldimethylammonium salt (chloride, acetic acid as counter anions of the salt) Ion sulfate ions, etc.). In addition, since these allylamines and diallylamine derivatives are inferior in polymerizability in the amine form, they are generally polymerized in the form of a salt and desalted as required.
In addition, a unit such as N-vinylacetamide, N-vinylformamide or the like, which is converted into a vinylamine unit by hydrolysis after polymerization, and a salt thereof can also be used.

The non-mordant monomer does not include a basic or cationic moiety such as a primary to tertiary amino group and a salt thereof, or a quaternary ammonium base, and does not show an interaction with a dye in an inkjet ink. Or the monomer which interaction is substantially small is said.
Examples of the non-mordant monomer include (meth) acrylic acid alkyl ester; (meth) acrylic acid cycloalkyl ester such as cyclohexyl (meth) acrylate; (meth) acrylic acid aryl ester such as phenyl (meth) acrylate; Aralkyl esters such as (meth) benzyl acrylate; Aromatic vinyls such as styrene, vinyl toluene and α-methylstyrene; Vinyl esters such as vinyl acetate, vinyl propionate and vinyl versatic acid; Allyl esters such as allyl acetate Halogen-containing monomers such as vinylidene chloride and vinyl chloride; vinyl cyanide such as (meth) acrylonitrile; olefins such as ethylene and propylene; and the like.

The (meth) acrylic acid alkyl ester is preferably a (meth) acrylic acid alkyl ester having 1 to 18 carbon atoms in the alkyl moiety, for example, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) Propyl acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, Examples include 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and the like.
Of these, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, and hydroxyethyl methacrylate are preferable.
The non-mordant monomers can also be used singly or in combination of two or more.

Further, as the polymer mordant, polydiallyldimethylammonium chloride, polymethacryloyloxyethyl-β-hydroxyethyldimethylammonium chloride, polyethyleneimine, polyallylamine and derivatives thereof, polyamide-polyamine resin, cationized starch, dicyandiamide formalin condensate, dimethyl Addition of 2-hydroxypropylammonium salt polymer, polyamidine, polyvinylamine, dicyandiamide-formalin polycondensate, dicyanamide-cachinic resin, dicyanamide-diethylenetriamine-polycondensate, polyamine-type katine resin, epichlorohydrin-dimethylamine addition polymer, dimethyldiallylammonium phosphorus chloride -SO ₂ copolymers, diallylamine salt -SO ₂ copolymer, etc. It may be mentioned as being preferred.

  Specific examples of the polymer mordant include JP-A Nos. 48-28325, 54-74430, 54-124726, 55-22766, 55-142339, 60-23850, and 60. -23851, 60-23852, 60-23853, 60-57836, 60-60643, 60-118834, 60-122940, 60-122941, 60-122294 No. 60-235134, JP-A-1-161236, U.S. Pat.Nos. 2,484,430, 2,548,564, 3,148,061, 3,309,690, 4,115,124, 4,124,386, 4,193,800, 4,273,853, JP 4282305, JP 4450224, JP-A-1-16123. 10-81064, 10-119423, 10-157277, 10-217601, 11-348409, JP-A-2001-138621, 2000-43401, 2000-212235 2000-309157, 2001-96897, 2001-138627, JP-A-11-91242, 8-2087, 8-2090, 8-2091, 8-2093, Examples described in JP-A-8-174992, JP-A-11-192777, JP-A-2001-301314, and the like. Of these, polyallylamine and derivatives thereof are particularly preferable.

  As the organic mordant in the present invention, polyallylamine having a weight average molecular weight of 100,000 or less and derivatives thereof are particularly preferable from the viewpoint of preventing bleeding with time.

<Polyallylamine or its derivative>
As the polyallylamine or derivative thereof of the present invention, various known allylamine polymers and derivatives thereof can be used. Such derivatives include salts of polyallylamine and acids (acids include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, methanesulfonic acid, toluenesulfonic acid, acetic acid, propionic acid, cinnamic acid, (meth) Organic acids such as acrylic acid, or a combination thereof, or a derivative of allylamine as a salt), a derivative of polyallylamine by a polymer reaction (for example, repeating structural units represented by the following formulas (1) to (5)) ), Polyallylamine and other copolymerizable monomers (specific examples of such monomers include (meth) acrylic acid esters, styrenes, (meth) acrylamides, acrylonitrile, vinyl). Esters) and the like.

In the above formula, R ^{81 to} R ⁸⁴ represent an organic group which may have a substituent, and R ⁸⁵ and R ⁸⁶ are synonymous with R ^{81 to} R ⁸⁴ or represent a hydrogen atom. R ⁸⁷ represents a hydrogen atom or a methyl group, and R ⁸⁸ represents —COOR ⁸⁹ , —CN, or —CONR ⁹⁰ R ⁹¹ . Here, R ^{89 to} R ⁹¹ represent a hydrogen atom, an aliphatic group, or an aromatic group. G ^- represents a counter anion.

  The organic group shown above is a group containing a hydrocarbon moiety and / or a hydrogen halide moiety, and in addition, atoms such as hydrogen, carbon, nitrogen, oxygen, sulfur, phosphorus, silicon, boron, halogen, and / or Or the functional group which consists of these combination may be included. Examples of such include (substituted) alkyl groups, (substituted) aralkyl groups, (substituted) aryl groups, (substituted) acyl groups, (substituted) sulfonyl groups, and heterocyclic rings.

Specific examples of the organic group represented by R ^{81 to} R ⁸⁴ include alkyl groups (for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, n -Hexyl, cyclohexyl, n-octyl, 2-ethylhexyl, n-decyl, n-dodecyl, octadecyl, 1,3-butadienyl, 1,3-pentadienyl, etc .; aralkyl groups (eg benzyl, phenylethyl, vinylbenzyl, 1 -Phenyl vinyl, 2-phenyl vinyl, etc.); aryl groups (for example, phenyl, naphthyl, tolyl, vinyl phenyl, etc.).

  Further, the organic group having a substituent includes fluoroethyl group, trifluoroethyl group, methoxyethyl group, phenoxyethyl group, hydroxyphenylmethyl group, chlorophenyl group, dichlorophenyl group, trichlorophenyl group, bromophenyl group, iodophenyl group, fluoro Examples thereof include a phenyl group, a hydroxyphenyl group, a methoxyphenyl group, a hydroxyphenyl group, an acetoxyphenyl group, and a cyanophenyl group.

Examples of the group having a hydroxyl group include the following groups.

Moreover, the organic group etc. which are shown next are mentioned.
-CR ¹⁰¹ R ¹⁰² -COOR ¹⁰³
[R ¹⁰¹ to R ¹⁰³ is a hydrogen atom, an aliphatic group, an aromatic group, such as methyl group, ethyl group, butyl group, benzyl group, phenyl group. ]
-CO-R ¹⁰⁴ -COOH
[R ¹⁰⁴ represents a divalent linking group, for example _{-CH 2 CH 2 -, - CH} 2 CH 2 CH 2 -, - CH = CH-,

Etc. ]
^{-COR 105, -COOR 106, -CONHR 107} , -CSNHR 108, -SO 2 R 109, -P (= O) (OR 110) 2
[R ¹⁰⁵ to R ¹¹⁰ represents a hydrogen atom, an aliphatic group, an aromatic group, such as methyl group, ethyl group, propyl group, butyl group, an octadecyl group, a benzyl group, a phenyl group, -CH = CH-Ph, etc. Is mentioned. ]

R ⁸⁷ is a hydrogen atom or a methyl group.
R ⁸⁸ is —COOR ¹¹¹ , —CN, or —CONR ¹¹² R ¹¹³ , and R ^{111 to} R ¹¹³ represent a hydrogen atom, an aliphatic group, or an aromatic group.
Specific examples of R ^{111 to} R ¹¹³ include hydrogen, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n- Hexyl, cyclohexyl, n-octyl, 2-ethylhexyl, n-decyl, n-dodecyl, octadecyl, allyl, benzyl, phenyl, naphthyl, biphenyl, 1,1,1- A trifluoroethyl group, 2-hydroxy-3-chloropropyl group, etc. are mentioned.

Specific examples of G ⁻ include halogen ions (Cl ⁻ , Br ⁻ , I ⁻ ), sulfonate ions, alkyl sulfonate ions, aryl sulfonate ions, alkyl carboxylate ions, aryl carboxylate ions, and the like.

  The structure of these polyallylamine derivatives is not particularly limited, but the obtained polymer is preferably soluble in an organic solvent that is water-soluble or miscible with water, but also in the form of water-dispersible latex particles. Can be used.

An inorganic mordant can also be used as the mordant of the present invention, and examples thereof include polyvalent water-soluble metal salts and hydrophobic metal salt compounds.
Specific examples of the inorganic mordant include, for example, magnesium, aluminum, calcium, scandium, titanium, vanadium, manganese, iron, nickel, copper, zinc, gallium, germanium, strontium, yttrium, zirconium, molybdenum, indium, barium, lanthanum, Examples thereof include salts or complexes of metals selected from cerium, praseodymium, neodymium, samarium, europium, gadolinium, dysproprosium, erbium, ytterbium, hafnium, tungsten, and bismuth.

  Specifically, for example, calcium acetate, calcium chloride, calcium formate, calcium sulfate, barium acetate, barium sulfate, barium phosphate, manganese chloride, manganese acetate, manganese formate dihydrate, manganese ammonium sulfate hexahydrate, chloride chloride Dicopper, ammonium copper (II) chloride dihydrate, copper sulfate, cobalt chloride, cobalt thiocyanate, cobalt sulfate, nickel sulfate hexahydrate, nickel chloride hexahydrate, nickel acetate tetrahydrate, nickel sulfate Ammonium hexahydrate, nickel amidosulfate tetrahydrate, aluminum sulfate, aluminum alum, basic polyaluminum hydroxide, aluminum sulfite, aluminum thiosulfate, polyaluminum chloride, aluminum nitrate nonahydrate, aluminum chloride hexahydrate Products, ferrous bromide, ferrous chloride, ferric chloride, Ferrous acid, ferric sulfate, zinc phenolsulfonate, zinc bromide, zinc chloride, zinc nitrate hexahydrate, zinc sulfate, titanium tetrachloride, tetraisopropyl titanate, titanium acetylacetonate, titanium lactate, zirconium acetyl Acetonate, zirconyl acetate, zirconyl sulfate, ammonium zirconium carbonate, zirconyl stearate, zirconyl octylate, zirconyl nitrate, zirconium oxychloride, zirconium hydroxychloride, chromium acetate, chromium sulfate, magnesium sulfate, magnesium chloride hexahydrate, citric acid Magnesium nonahydrate, sodium phosphotungstate, sodium tungsten citrate, 12 tungstophosphoric acid n hydrate, 12 tungstosilicic acid 26 hydrate, molybdenum chloride, 12 molybdophosphoric acid n hydrate, gallium nitrate Germanium nitrate, strontium nitrate, yttrium acetate, yttrium chloride, yttrium nitrate, indium nitrate, lanthanum nitrate, lanthanum chloride, lanthanum acetate, lanthanum benzoate, cerium chloride, cerium sulfate, cerium octylate, praseodymium nitrate, neodymium nitrate, nitric acid Examples include samarium, europium nitrate, gadolinium nitrate, dysprosium nitrate, erbium nitrate, ytterbium nitrate, hafnium chloride, and bismuth nitrate.

The inorganic mordant of the present invention is preferably an aluminum-containing compound, a titanium-containing compound, a zirconium-containing compound, or a metal compound (salt or complex) of Group IIIB series of the periodic table of elements.
Mordant amount contained in the colorant receiving layer in the present invention is preferably from ^{0.01g / m 2 ~5g / m 2} , 0.1g / m 2 ~3g / m 2 is more preferable.

When the compounds of the general formulas (I) to (IV) of the present invention are contained in the colorant receiving layer, they may be used in the form of organic acid or inorganic acid salts. The acid may be previously mixed with the compounds of the general formulas (I) to (IV), or a coating solution containing the compounds of the general formulas (I) to (IV) may be applied simultaneously or at the same time and mixed. May be.
By adding an acid, the surface PH of the colorant receiving layer is adjusted to 3 to 8, preferably 5 to 7.5. This is preferable because yellowing resistance of the white background portion is improved. The surface PH is measured by the A method (coating method) of the surface PH measurement determined by Japan Paper Pulp Technology Association (J.TAPPI). For example, the measurement can be performed by using a paper PH measurement set “Type MPC” manufactured by Kyoritsu Riken Co., Ltd. corresponding to the method A.

Specific examples of acids include formic acid, acetic acid, glycolic acid, oxalic acid, propionic acid, malonic acid, succinic acid, adipic acid, maleic acid, malic acid, tartaric acid, citric acid, benzoic acid, phthalic acid, isophthalic acid , Glutaric acid, gluconic acid, lactic acid, aspartic acid, glutamic acid, salicylic acid, metal salts of salicylic acid (salts such as Zn, Al, Ca, Mg), methanesulfonic acid, itaconic acid, benzenesulfonic acid, toluenesulfonic acid, trifluoromethanesulfone Acid, styrenesulfonic acid, trifluoroacetic acid, barbituric acid, acrylic acid, methacrylic acid, cinnamic acid, 4-hydroxybenzoic acid, aminobenzoic acid, naphthalenedisulfonic acid, hydroxybenzenesulfonic acid, toluenesulfinic acid, benzenesulfinic acid, Sulfanilic acid, sulfamic acid, α-le Examples include ricinic acid, β-resorcinic acid, γ-resorcinic acid, gallic acid, phloroglicin, sulfosalicylic acid, ascorbic acid, erythorbic acid, bisphenolic acid, hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, polyphosphoric acid, boric acid, boronic acid, etc. It is done. What is necessary is just to determine the addition amount of these acids so that the surface PH of a color material receiving layer may be 3-8.
The above acids can be metal salts (eg sodium, potassium, calcium, cesium, zinc, copper, iron, aluminum, zirconium, lanthanum, yttrium, magnesium, strontium, cerium, etc.) or amine salts (eg ammonia, triethylamine, tri Butylamine, piperazine, 2-methylpiperazine, polyallylamine, etc.).

(Other ingredients)
The ink jet recording sheet of the present invention, if necessary, various other known additives such as ultraviolet absorbers, antioxidants, fluorescent brighteners, monomers, polymerization initiators, polymerization inhibitors, anti-bleeding agents, An antiseptic, a viscosity stabilizer, an antifoaming agent, a surfactant, an antistatic agent, a matting agent, an anti-curling agent, a water-proofing agent and the like can be contained.

The compounds represented by the above general formulas (I) to (IV) of the present invention are preferably used in combination with a preservability improving agent such as an ultraviolet absorber, an antioxidant, or a bleeding inhibitor.
These ultraviolet absorbers, antioxidants, and bleeding inhibitors that may be used in combination include alkylated phenol compounds (including hindered phenol compounds), alkylthiomethylphenol compounds, hydroquinone compounds, alkylated hydroquinone compounds, tocopherol compounds, thiols. Diphenyl ether compounds, compounds having two or more thioether bonds, bisphenol compounds, O-, N- and S-benzyl compounds, hydroxybenzyl compounds, triazine compounds, phosphonate compounds, acylaminophenol compounds, ester compounds, amide compounds, ascorbic acid , Amine antioxidants, 2- (2-hydroxyphenyl) benzotriazole compounds, 2-hydroxybenzophenone compounds, acrylates, water-soluble or hydrophobic metal salts, organometallic compounds , Metal complexes, hindered amine compounds (including TEMPO compounds), 2- (2-hydroxyphenyl) 1,3,5, -triazine compounds, metal deactivators, phosphite compounds, phosphonite compounds, hydroxyamine compounds, nitrone compounds , Peroxide scavenger, polyamide stabilizer, polyether compound, basic auxiliary stabilizer, nucleating agent, benzofuranone compound, indolinone compound, phosphine compound, polyamine compound, thiourea compound, urea compound, hydrazide compound, amidine compound, sugar compound , Hydroxybenzoic acid compounds, dihydroxybenzoic acid compounds, trihydroxybenzoic acid compounds and the like.

  Among these, alkylated phenol compounds, compounds having two or more thioether bonds, bisphenol compounds, ascorbic acid, amine-based antioxidants, water-soluble or hydrophobic metal salts, organometallic compounds, metal complexes, hindered amine compounds, It is preferable to use at least one of polyamine compounds, thiourea compounds, hydrazide compounds, hydroxybenzoic acid compounds, dihydroxybenzoic acid compounds and trihydroxybenzoic acid compounds in combination.

  Specific examples of the compound include JP-A-10-182621, JP-A-2001-260519, JP-B-4-34953, JP-B-4-34513, JP-A-11-170686, JP-A-2001-152237, JP 4-34512, EP 1138509, JP 60-67190, JP 7-276808, JP 2001-94829, JP 47-10537, 58-111942, 58-212844. Gazettes, 59-19945 gazettes, 59-46646 gazettes, 59-109055 gazettes, 63-53544 gazettes, 36-36466 gazettes, 42-26187 gazettes, and 48-30492 gazettes. Gazette, 48-31255, 48-41572, 48-54965, 50 10726 JP, U.S. Patent Nos. 2,719,086, 3,707,375, the 3,754,919 Pat, the 4,220,711 Pat;

  Japanese Patent Publication Nos. 45-4699, 54-5324, European Published Patent No. 223739, No. 309401, No. 309402, No. 310551, No. 310552, No. 459416, German Published Patent No. 3435443, JP-A-54-48535, JP-A-60-107384, JP-A-60-107383, JP-A-60-125470, JP-A-60-125471, JP-A-60-125472 Publication No. 60-287485, No. 60-287486, No. 60-287487, No. 60-287488, No. 61-160287, No. 61-185483, No. 61-2111079. 62-146678, 62-146680, 62-146679, 62-282858, 62-262447, 63-05174, 63-89877, 63-88380, 66-88381, 63 No. 113536 publication;

  JP-A-63-163351, JP-A-63-203372, JP-A-63-224989, JP-A-63-251282, JP-A-63-267594, JP-A-63-182484, JP-A-1-239282, JP-A-2-262654, JP-A-2-71262, JP-A-3-121449, JP-A-4-29185, JP-A-4-291684, JP-A-5-61166, JP-A-5-119449, 5-188687, 5-188686, 5-110490, 5-110437, 5-170361, JP 48-43295, 48-33212, Examples thereof include those described in U.S. Pat. Nos. 4,814,262 and 4,980,275.

The other components may be used alone or in combination of two or more. These other components may be added after being water-solubilized, dispersed, polymer-dispersed, emulsified or oil-dropped, or may be encapsulated in microcapsules. In the ink jet recording sheet of the present invention, the amount of the other ingredients, preferably 0.01 to 10 g / m ^2.

  Further, for the purpose of improving the dispersibility of the inorganic fine particles, the inorganic surface may be treated with a silane coupling agent. The silane coupling agent includes an organic functional group (for example, a vinyl group, an amino group, an epoxy group, a mercapto group, a chloro group, an alkyl group, a phenyl group, an ester group, etc.) in addition to a coupling treatment site. Those having the following are preferred.

In the present invention, the colorant-receiving layer coating liquid preferably contains a surfactant. As the surfactant, any of cationic, anionic, nonionic, amphoteric, fluorine, and silicon surfactants can be used.
Examples of the nonionic surfactant include polyoxyalkylene alkyl ethers and polyoxyalkylene alkyl phenyl ethers (for example, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene Ethylene nonylphenyl ether), oxyethylene / oxypropylene block copolymer, sorbitan fatty acid esters (for example, sorbitan monolaurate, sorbitan monooleate, sorbitan trioleate, etc.), polyoxyethylene sorbitan fatty acid esters (for example, polyoxyethylene) Sorbitan monolaurate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan Lyolate, etc.), polyoxyethylene sorbitol fatty acid esters (eg, polyoxyethylene sorbitol tetraoleate), glycerin fatty acid esters (eg, glycerol monooleate), polyoxyethylene glycerin fatty acid esters (polyoxymonostearate) Ethylene glycerin, monooleic acid polyoxyethylene glycerin, etc.), polyoxyethylene fatty acid esters (polyethylene glycol monolaurate, polyethylene glycol monooleate, etc.), polyoxyethylene alkylamine, acetylene glycols (eg, 2, 4, 7) , 9-tetramethyl-5-decyne-4,7-diol, and ethylene oxide adducts, propylene oxide adducts, etc. of the diols), and polyoxy Ruki alkylene alkyl ethers are preferable. The nonionic surfactant can be used in the first coating solution and the second coating solution. Moreover, the said nonionic surfactant may be used independently and may use 2 or more types together.

  Examples of the amphoteric surfactants include amino acid type, carboxyammonium betaine type, sulfoammonium betaine type, ammonium sulfate betaine type, imidazolium betaine type, etc., for example, U.S. Pat. No. 3,843,368, Those described in JP-A-59-49535, JP-A-63-236546, JP-A-5-303205, JP-A-8-262742, and JP-A-10-282619 can be suitably used. As the amphoteric surfactant, an amino acid type amphoteric surfactant is preferable, and as the amino acid type amphoteric surfactant, as described in JP-A-5-303205, for example, an amino acid (glycine, glutamic acid, Histidine acid etc.) and N-aminoacyl acids and salts thereof into which long chain acyl groups have been introduced. The amphoteric surfactants may be used alone or in combination of two or more.

Examples of the anionic surfactant include fatty acid salts (for example, sodium stearate, potassium oleate), alkyl sulfate esters (for example, sodium lauryl sulfate, triethanolamine lauryl sulfate), and sulfonates (for example, sodium dodecylbenzenesulfonate). Alkyl sulfosuccinate (for example, sodium dioctyl sulfosuccinate), alkyl diphenyl ether disulfonate, alkyl phosphate, and the like.
Examples of the cationic surfactant include alkylamine salts, quaternary ammonium salts, pyridinium salts, imidazolium salts, and the like.

Examples of the fluorosurfactant include compounds derived from an intermediate having a perfluoroalkyl group using a method such as electrolytic fluorination, telomerization, or oligomerization.
Examples thereof include perfluoroalkyl sulfonates, perfluoroalkyl carboxylates, perfluoroalkyl ethylene oxide adducts, perfluoroalkyl trialkyl ammonium salts, perfluoroalkyl group-containing oligomers, and perfluoroalkyl phosphate esters.

  As the silicon-based surfactant, silicon oil modified with an organic group is preferable, and a structure in which a side chain of a siloxane structure is modified with an organic group, a structure in which both ends are modified, and a structure in which one end is modified can be taken. Examples of the organic group modification include amino modification, polyether modification, epoxy modification, carboxyl modification, carbinol modification, alkyl modification, aralkyl modification, phenol modification, and fluorine modification.

  In the present invention, the content of the surfactant is preferably 0.001 to 2.0%, more preferably 0.01 to 1.0% with respect to the coating solution for the colorant receiving layer. In addition, when coating is performed using two or more liquids as the colorant receiving layer coating liquid, it is preferable to add a surfactant to each coating liquid.

(High boiling point organic solvent)
In the present invention, the colorant receiving layer preferably contains a high boiling point organic solvent for curling prevention. The high-boiling organic solvent is an organic compound having a boiling point of 150 ° C. or higher at normal pressure, and is a water-soluble or hydrophobic compound. These may be liquid or solid at room temperature, and may be low molecules or polymers.
Specifically, aromatic carboxylic acid esters (for example, dibutyl phthalate, diphenyl phthalate, phenyl benzoate, etc.), aliphatic carboxylic acid esters (for example, dioctyl adipate, dibutyl sebacate, methyl stearate, dibutyl maleate) , Dibutyl fumarate, triethyl acetyl citrate, etc.), phosphate esters (eg, trioctyl phosphate, tricresyl phosphate, etc.), epoxies (eg, epoxidized soybean oil, epoxidized fatty acid methyl, etc.), alcohols (eg, stearyl) Alcohol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, glycerol, diethylene glycol monobutyl ether (DEGMBE), triethylene glycol monobutyl ether, glycerol Methyl ether, 1,2,3-butanetriol, 1,2,4-butanetriol, 1,2,4-pentanetriol, 1,2,6-hexanetriol, thiodiglycol, triethanolamine, polyethylene glycol, etc. ), Vegetable oils (eg, soybean oil, sunflower oil, etc.) and higher aliphatic carboxylic acids (eg, linoleic acid, oleic acid, etc.).

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

The material that can be used for the transparent support is preferably a material that is transparent and can withstand radiant heat when used in an OHP or a backlight display. Examples of the material include polyesters such as polyethylene terephthalate (PET); polysulfone, polyphenylene oxide, polyimide, polycarbonate, polyamide and the like. Of these, polyesters are preferable, and polyethylene terephthalate is particularly preferable.
Although there is no restriction | limiting in particular as thickness of the said transparent support body, 50-200 micrometers is preferable at the point which is easy to handle.

  As the highly glossy opaque support, one having a glossiness of 40% or more on the surface on which the colorant receiving layer is provided is preferable. The glossiness is a value determined according to the method described in JIS P-8142 (75-degree specular gloss test method for paper and paperboard). Specifically, the following supports are mentioned.

For example, high gloss paper support such as art paper, coated paper, cast coated paper, baryta paper used for silver salt photographic support, polyester such as polyethylene terephthalate (PET), nitrocellulose, cellulose acetate , Cellulose esters such as cellulose acetate butyrate, and plastic films such as polysulfone, polyphenylene oxide, polyimide, polycarbonate, and polyamide are made opaque by adding a white pigment or the like (surface calendering may be applied). Glossy film; or a support in which a polyolefin coating layer containing or not containing a white pigment is provided on the surface of a highly glossy film containing the various paper supports, the transparent support or the white pigment. Etc.
A white pigment-containing foamed polyester film (for example, foamed PET containing polyolefin fine particles and forming voids by stretching) can also be suitably exemplified. Furthermore, resin-coated paper used for silver salt photographic printing paper is also suitable.

  Although there is no restriction | limiting in particular also about the thickness of the said opaque support body, 50-300 micrometers is preferable at the point of handleability.

  The surface of the support may be subjected to corona discharge treatment, glow discharge treatment, flame treatment, ultraviolet irradiation treatment or the like in order to improve wettability and adhesion.

Next, the base paper used for the resin-coated paper will be described in detail.
The base paper is made from wood pulp as a main raw material and, if necessary, paper using synthetic pulp such as polypropylene or synthetic fibers such as nylon or polyester in addition to wood pulp. As the above-mentioned wood pulp, any of LBKP, LBSP, NBKP, NBSP, LDP, NDP, LUKP, NUKP can be used, but more LBKP, NBSP, LBSP, NDP, LDP with more short fibers are used. preferable.
However, the ratio of LBSP and / or LDP is preferably 10% by mass or more and 70% by mass or less.

  The pulp is preferably a chemical pulp (sulfate pulp or sulfite pulp) with few impurities, and a pulp having a whiteness improved by bleaching is also useful.

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

  The freeness of the pulp used for papermaking is preferably 200 to 500 ml as defined by CSF, and the fiber length after beating is a 24 mesh residual mass% and a 42 mesh residual as defined in JIS P-8207. 30 to 70% of the sum with the mass% of is preferable. In addition, it is preferable that the mass% of 4 mesh remainder is 20 mass% or less.

The basis weight of the base paper is preferably 30 to 250 g, and particularly preferably 50 to 200 g. The thickness of the base paper is preferably 40 to 250 μm. The base paper can be given a high smoothness by calendering at the paper making stage or after paper making. The density of the base paper is generally 0.7 to 1.2 g / m ² (JIS P-8118).
Furthermore, the base paper stiffness is preferably 20 to 200 g under the conditions specified in JIS P-8143.

A surface sizing agent may be applied to the surface of the base paper. As the surface sizing agent, a sizing agent similar to the size that can be added to the base paper can be used.
The pH of the base paper is preferably 5 to 9 when measured by a hot water extraction method defined in JIS P-8113.

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

  In particular, the polyethylene layer on the side that forms the colorant-receiving layer is added with rutile or anatase-type titanium oxide, fluorescent whitening agent, ultramarine, and polyethylene, as is widely done in photographic paper. Those with improved transparency, whiteness and hue are preferred. Here, as a titanium oxide content, about 3-20 mass% is preferable with respect to polyethylene, and 4-13 mass% is more preferable. Although the thickness of a polyethylene layer does not have limitation in particular, 10-50 micrometers is suitable for both front and back layers. Further, an undercoat layer can be provided on the polyethylene layer in order to provide adhesion to the colorant receiving layer. As the undercoat layer, aqueous polyester, gelatin and PVA are preferable. Moreover, as thickness of this undercoat layer, 0.01-5 micrometers is preferable.

  Polyethylene-coated paper can be used as glossy paper, or when it is melt-extruded onto the surface of the base paper and coated, the matte surface or silky surface that can be obtained with ordinary photographic printing paper by so-called molding Can also be used.

A back coat layer can be provided on the support, and examples of components that can be added to the back coat layer include a white pigment, an aqueous binder, and other components.
Examples of white pigments contained in the backcoat layer include light calcium carbonate, heavy calcium carbonate, kaolin, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulfide, zinc carbonate, satin white, and aluminum silicate. , Diatomaceous earth, calcium silicate, magnesium silicate, synthetic amorphous silica, colloidal silica, colloidal alumina, pseudoboehmite, aluminum hydroxide, alumina, lithopone, zeolite, hydrous halloysite, magnesium carbonate, magnesium hydroxide, white inorganic pigment, styrene And organic pigments such as polyethylene plastic pigments, acrylic plastic pigments, polyethylene, microcapsules, urea resins, and melamine resins.

Examples of the aqueous binder used in the backcoat layer include styrene / maleate copolymer, styrene / acrylate copolymer, polyvinyl alcohol, silanol-modified polyvinyl alcohol, starch, cationized starch, casein, gelatin, carboxy Examples thereof include water-soluble polymers such as methyl cellulose, hydroxyethyl cellulose, and polyvinyl pyrrolidone, and water-dispersible polymers such as styrene butadiene latex and acrylic emulsion.
Examples of other components contained in the backcoat layer include an antifoaming agent, an antifoaming agent, a dye, a fluorescent brightening agent, a preservative, and a water-proofing agent.

(Preparation of inkjet recording sheet)
The colorant-receiving layer of the ink jet recording sheet of the present invention is, for example, a first coating liquid containing at least fine particles and a water-soluble resin on the surface of the support (hereinafter also referred to as “coating liquid (A)”). (1) At the same time as the coating, (2) before the coating layer is in the process of being dried and before the coating layer exhibits a reduced drying rate, or (3) the first coating. After the liquid is dried to form a coating film, a second coating liquid containing at least a mordant (hereinafter also referred to as “coating liquid (B)”) is applied to any of the two, and then the second coating liquid is applied. It is preferable to form by the method (Wet-on-Wet method) of bridge | crosslinking and hardening the coating layer which provided the coating liquid of. Here, at least one of the compounds represented by the general formulas (I) to (IV) of the present invention is preferably contained in at least one of the first coating liquid and the second coating liquid. Moreover, it is preferable that a crosslinking agent capable of crosslinking the water-soluble resin is also contained in at least one of the first coating solution and the second coating solution.
Providing a colorant-receiving layer that has been crosslinked and cured in this manner is preferable from the viewpoints of ink absorptivity and prevention of film cracking.

In addition, the colorant receiving layer of the ink jet recording sheet of the present invention crosslinks the first coating liquid (liquid A) containing fine particles and a water-soluble resin and the second coating liquid (liquid B) containing a mordant. It is obtained by simultaneously coating on a support with a barrier liquid composed of a component that does not react with the agent (however, at least one of a solution containing a crosslinking agent or a barrier liquid containing mordant) sandwiched and dried and cured. You can also.
This is preferable because a large amount of mordant is present near the surface of the colorant-receiving layer, so that the ink-jet colorant is sufficiently mordanted and the water resistance of characters and images after printing is improved. A part of the mordant may be contained in the coating liquid (A). In that case, the mordants of the first coating liquid (A) and the coating liquid (B) may be the same or different.

In the present invention, the colorant-receiving layer coating liquid (A liquid) containing at least fine particles (for example, vapor-phase process silica) and a water-soluble resin (for example, polyvinyl alcohol) is prepared, for example, as follows. be able to. That is,
Vapor phase silica fine particles and a dispersant are added to water (for example, silica fine particles in water are 10 to 20% by mass), and a high-speed rotating wet colloid mill (for example, “Clairemix” manufactured by M Technique Co., Ltd.) For example, at a high speed of 10,000 rpm (preferably 5000-20000 rpm), for example, for 20 minutes (preferably 10-30 minutes), and then dispersed in an aqueous polyvinyl alcohol (PVA) solution (for example, the above gas phase method). In the case where the compound of the general formulas (I) to (IV) in the present invention is further included in the coating solution for the colorant receiving layer, the compound is added. In addition, it can be prepared by dispersing under the same rotation conditions as described above. The obtained coating solution is in a uniform sol state, and a porous colorant receiving layer having a three-dimensional network structure can be formed by applying the coating solution onto a support by the following coating method and drying it. .

As the dispersion treatment method, various conventionally known dispersers such as a high-speed rotary disperser, a medium stirring disperser (ball mill, sand mill, etc.), an ultrasonic disperser, a colloid mill disperser, and a high pressure disperser are used. However, in the present invention, a colloid mill disperser or a high-pressure disperser is preferably used from the viewpoint of efficiently dispersing the formed fine particles.
In addition, a chaotic polymer can be used as the dispersant. Examples of the chaotic polymer include the above-mentioned examples of mordants.

If necessary, a surfactant, a pH adjuster, an antistatic agent, and the like can be further added to the colorant-receiving layer coating solution.
The coating material for the colorant receiving layer is applied by a known coating method such as, for example, an extrusion die coater, an air doctor coater, a bread coater, a rod coater, a knife coater, a squeeze coater, a reverse roll coater, or a bar coater. Can do.

  The coating liquid (B) is applied to the coating layer at the same time as or after the coating of the colorant-receiving layer coating liquid. The coating liquid (B) has a reduced drying rate when the coating layer after coating is applied. It may be given before it becomes shown. That is, after the coating liquid for the colorant receiving layer is applied, the mordant is preferably introduced while the coating layer exhibits a constant rate of drying.

  Here, “before the coating layer comes to exhibit a decreasing rate of drying” usually refers to a process of several minutes immediately after the coating of the coating solution for the colorant receiving layer, and during this time, the coated coating is applied. This shows the phenomenon of “constant rate drying rate” in which the content of the solvent (dispersion medium) in the layer decreases in proportion to time. About the time which shows this "constant rate drying speed", it describes in chemical engineering handbook (pages 707-712, Maruzen Co., Ltd. issue, October 25, 1980), for example.

  As described above, after the application of the first coating solution, the coating layer is dried until the coating layer exhibits a reduced rate of drying. This 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 coating amount, but the above range is usually appropriate.

  As a method of giving before the said 1st application layer comes to show a decreasing rate of drying, (1) The method of further apply | coating a coating liquid (B) on an application layer, (2) By methods, such as a spray The method of spraying, (3) The method of immersing the support body in which this coating layer was formed in a coating liquid (B), etc. are mentioned.

  In the method (1), examples of the coating method for coating the coating liquid (B) include 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 coater. A known coating method such as a bar coater can be used. However, it is preferable to use a method in which the coater does not directly contact the already formed first coating layer, such as an extrusion die coater, a curtain flow coater, a bar coater or the like.

  After the application of the mordant solution, it is generally heated at 40 to 180 ° C. for 0.5 to 30 minutes, and dried and cured. Especially, it is preferable to heat at 40-150 degreeC for 1 to 20 minutes.

  Further, when the mordant solution is applied at the same time as the color material receiving layer coating solution is applied, the color material receiving layer coating solution and the mordant solution are supported so that the color material receiving layer coating solution is in contact with the support. A colorant-receiving layer can be formed by simultaneously applying (multilayer application) on the substrate and then drying and curing.

  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 10 minutes, preferably 40 to 100. It is carried out by heating at a temperature of 0.5 to 5 minutes.

  When the above simultaneous coating (multilayer coating) is performed by, for example, an extrusion die coater, the two types of coating liquid discharged at the same time are close to the discharge port of the extrusion die coater, that is, before moving onto the support. A multilayer is formed, and in that state, the multilayer is applied on the support. Since the two-layer coating liquid layered before coating is likely to cause a cross-linking reaction at the interface between the two liquids when transferred to the support, the two liquids to be ejected are mixed in the vicinity of the discharge port of the extrusion die coater. As a result, thickening is likely to occur, which may hinder the application operation. Therefore, when applying simultaneously as described above, it is preferable to apply a triple layer coating with a barrier layer solution (intermediate layer solution) interposed between the two solutions together with the application of the colorant receiving layer coating solution and the mordant solution. .

  The barrier layer solution can be selected without particular limitation. For example, an aqueous solution containing a trace amount of water-soluble resin, water, and the like can be given. The water-soluble resin is used in consideration of coatability for the purpose of a thickener and the like, for example, hydroxypropylmethylcellulose, methylcellulose, hydroxyethylmethylcellulose, polyvinylpyrrolidone, gelatin And the like. The barrier layer solution may contain the above mordant.

  The colorant-receiving layer in the present invention is a coating obtained by adding and redispersing a solution (first solution) containing at least the polyvinyl alcohol to an aqueous dispersion composed of the vapor phase silica and a dispersant. The liquid (C) is applied to the surface of the support, and the application is performed simultaneously with the application or during the drying of the application layer formed by the application, before the application layer exhibits a reduced rate of drying. You may form by the method of hardening the said coating layer, after providing the solution (D) (2nd solution) containing the said mordant to a layer at least. Under the present circumstances, the compound of general formula (I)-(IV) in this invention should just be added to either the said coating liquid (C) and the said coating liquid (D), and may add to both. Use of this method is preferable because glossiness and print density are improved. It is preferable that a crosslinking agent capable of crosslinking the water-soluble resin is also included in at least one of the coating solution (C) and the coating solution (D).

  As the dispersant, a cationic polymer can be used. As the cationic polymer, a homopolymer of a monomer having a primary to tertiary amino group and a salt thereof, or a quaternary ammonium base, exemplified as the above-mentioned mordant, Those obtained as copolymers or condensation polymers with other monomers can be suitably used. These dispersants are preferably used in the form of a water-soluble polymer. It is also preferable to use a silane coupling agent as the dispersant.

  The molecular weight of the dispersant is preferably 1000 to 200000, more preferably 3000 to 60000 in terms of weight average molecular weight. The amount of the dispersant added to the vapor phase silica is preferably 0.1% to 30%, more preferably 1% to 10%.

In addition, the preparation of the aqueous dispersant composed of the above-mentioned vapor phase method silica and a dispersant may be performed by preparing a vapor phase method silica aqueous dispersion in advance and adding the aqueous dispersion to the aqueous dispersant solution. May be added to the vapor phase silica aqueous dispersion, or may be mixed simultaneously. Further, instead of vapor phase silica aqueous dispersion, powder vapor phase silica may be used and added to the aqueous dispersant as described above.
After mixing said vapor phase silica and a dispersing agent, the mixed liquid is refined using a disperser, whereby an aqueous dispersion having an average particle diameter of 50 to 300 nm can be obtained. As a disperser used for obtaining the aqueous dispersion, various kinds of conventionally known dispersers such as a high-speed rotary disperser, a medium agitating disperser (such as a ball mill and a sand mill), an ultrasonic disperser, a colloid mill disperser, and a high pressure disperser. Although a disperser can be used, a colloid mill disperser or a high-pressure disperser is preferable from the viewpoint of efficiently dispersing the formed fine particles.

  Moreover, water, an organic solvent, or these mixed solvents can be used as a solvent in each process. 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. It is done.

  After the colorant receiving layer is formed on the support, the colorant receiving layer is made of, for example, a super calender, a gloss calendar, etc., and subjected to a calendering process between the roll nips under heat and pressure, so that surface smoothness, gloss It is possible to improve the degree, transparency and coating strength. However, the calendar process may cause a decrease in the porosity (that is, the ink absorptivity may be decreased), so it is necessary to set conditions under which the decrease in the porosity is small.

As roll temperature in the case of performing a calendar process, 30-150 degreeC is preferable and 40-100 degreeC is more preferable.
Moreover, as a linear pressure between rolls at the time of a calendar process, 50-400 kg / cm is preferable and 100-200 kg / cm is more preferable.

The layer thickness of the colorant-receiving layer needs to be determined in relation to the porosity in the layer because it needs to have an absorption capacity sufficient to absorb all droplets in the case of inkjet recording. For example, if the ink amount is 8 nL / mm ² and the porosity is 60%, a film having a layer thickness of about 15 μm or more is required.
Considering this point, in the case of inkjet recording, the thickness of the colorant receiving layer is preferably 10 to 50 μm.

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

The color material receiving layer is preferably excellent in transparency. As a guide, the haze value when the color material receiving layer is formed on a transparent film support is 30% or less. Preferably, it is 20% or less.
The haze value can be measured using a haze meter (HGM-2DP: Suga Test Instruments Co., Ltd.).

  A polymer fine particle dispersion may be added to a constituent layer (for example, a colorant receiving layer or a back layer) of the ink jet recording sheet of the present invention. This polymer fine particle dispersion is used for the purpose of improving film properties such as dimensional stabilization, curling prevention, adhesion prevention, and film cracking prevention. The polymer fine particle dispersion is described in JP-A Nos. 62-245258, 62-1316648, and 62-110066. If a polymer fine particle dispersion having a low glass transition temperature (40 ° C. or lower) is added to the layer containing the mordant, cracking and curling of the layer can be prevented. Further, even when a polymer fine particle dispersion having a high glass transition temperature is added to the back layer, curling can be prevented.

Further, the inkjet recording sheet of the present invention is disclosed in JP-A-10-81064,
10-119423, 10-157277, 10-217601, 11-348409, JP-A-2001-138621, 2000-43401, 2000-212235, 2000-309157, Also produced by the methods described in JP-A Nos. 2001-96897, 2001-138627, JP-A Nos. 11-91242, 8-2087, 8-2090, 8-2091, and 8-2093. Is possible.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples. In the examples, “parts” and “%” represent “parts by mass” and “mass%” unless otherwise specified, and “average molecular weight” and “degree of polymerization” are “mass average molecular weight” and “mass”. It represents “average degree of polymerization”.

(Production of support)
Wood pulp composed of 100 parts of LBKP is beaten to 300 ml Canadian freeness with a double disc refiner, 0.5 parts of epoxidized behenamide, 1.0 part of anionic polyacrylamide, 0.1 part of polyamide polyamine epichlorohydrin, 0.5 part of cationic polyacrylamide All parts were added at an absolutely dry mass ratio with respect to the pulp, and weighed with a long net paper machine to produce a base paper of 170 g / m ² .

In order to adjust the surface size of the base paper, 0.04% of a fluorescent whitening agent (“Whiteex BB” manufactured by Sumitomo Chemical Co., Ltd.) is added to a 4% aqueous solution of polyvinyl alcohol, and this is 0 in terms of absolute dry mass. The base paper was impregnated so as to have a density of 0.5 g / m ² , dried, and then subjected to a calendering process to obtain a base paper adjusted to a density of 1.05 g / cc.

After the corona discharge treatment was performed 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 to form a resin layer composed of a mat surface. (Hereinafter, the resin layer surface is referred to as “back surface”). The resin layer on the back side is further subjected to corona discharge treatment, and thereafter, as an antistatic agent, aluminum oxide (“Alumina sol 100” manufactured by Nissan Chemical Industries, Ltd.) and silicon dioxide (“Nissan Chemical Industry Co., Ltd.” “ Snowtex O ") and a 1: a dispersion dispersed in water at 2 weight ratio, dry mass was coated to a 0.2 g / m ^2.

  Furthermore, after the corona discharge treatment is applied to the felt surface (surface) side where the resin layer is not provided, anatase-type titanium dioxide 10%, a trace amount of ultramarine blue, and a fluorescent whitening agent 0.01% (vs. polyethylene) A low-density polyethylene containing MFR (melt flow rate) 3.8 is extruded using a melt extruder to a thickness of 29 μm, and a high gloss thermoplastic resin layer is formed on the surface side of the base paper. (Hereinafter, this high-gloss surface is referred to as a “front side”), which was used as a support.

[Example 1]
(Preparation of coating material A for colorant receiving layer)
(1) Vapor phase silica fine particles, (2) ion-exchanged water, and (3) “PAS-M-1” in the following composition are mixed, and a high-speed rotating colloid mill (“Claire” manufactured by M Technique Co., Ltd.) After mixing for 20 minutes at a rotational speed of 10,000 rpm, the following (4) polyvinyl alcohol, (5) boric acid, (6) polyoxyethylene lauryl ether, and (7) ion-exchanged water are included. The solution was added, and dispersion was performed again at a rotational speed of 10,000 rpm for 20 minutes to prepare a coating material A for a colorant receiving layer.
The mass ratio between the silica fine particles and the water-soluble resin (PB ratio = (1) :( 4)) is 4.5: 1, and the pH of the coating material A for the colorant receiving layer is 3.5 and is acidic. Indicated.

<Composition of Color Material Receiving Layer Coating Liquid A>
(1) Gas phase method silica fine particles (inorganic fine particles) 10.0 parts (“Reoseal QS30” manufactured by Tokuyama Corporation, average primary particle diameter 7 nm)
(2) Ion-exchanged water 51.7 parts (3) “PAS-M-1” (60% aqueous solution) 0.83 parts (dispersant, manufactured by Nittobo Co., Ltd.)
(4) Polyvinyl alcohol (water-soluble resin) 8% aqueous solution 27.8 parts ("PVA124" manufactured by Kuraray Co., Ltd., saponification degree 98.5%, polymerization degree 2400)
(5) Boric acid (crosslinking agent) 0.4 part (6) Polyoxyethylene lauryl ether (surfactant) 1.2 parts (“Emulgen 109P” (10% aqueous solution) manufactured by Kao Corporation, HLB value 13. 6)
(7) Ion exchange water 33.0 parts

(Preparation of inkjet recording sheet)
After the corona discharge treatment is performed on the front surface of the support, the coating solution A for the colorant receiving layer obtained above is applied at a coating amount of 200 ml / m ² using an extrusion die coater on the front surface of the support. It was coated (coating step) and dried with a hot air dryer at 80 ° C. (wind speed 3 to 8 m / sec) until the solid content concentration of the coating layer reached 20%. This coating layer exhibited a constant rate of drying during this period. Immediately after that, it was immersed in a mordant solution B having the following composition for 30 seconds to deposit 20 g / m ² on the coating layer (step of applying a mordant solution), and further dried at 80 ° C. for 10 minutes (drying step). ). This produced the inkjet recording sheet (1) of the present invention provided with a colorant receiving layer having a dry film thickness of 32 μm.

<Composition of mordant solution B>
(1) Boric acid (crosslinking agent) 0.65 parts (2) Polyallylamine “PAA-10C” 10% aqueous solution 25 parts (Mordant, manufactured by Nittobo Co., Ltd.)
(3) The following compound (a) (compound of the present invention) 2.5 parts (4) ion-exchanged water 59.7 parts (5) ammonium chloride (surface pH adjuster) 0.8 parts (6) polyoxyethylene lauryl 10 parts of ether (surfactant) (“Emulgen 109P” manufactured by Kao Corporation, 2% aqueous solution, HLB value 13.6)
(7) 2.0 parts of Megafuck “F1405” 10% aqueous solution (fluorine surfactant manufactured by Dainippon Ink & Chemicals, Inc.)

[Examples 2-3, Reference Examples 4-5, Examples 6-26]
Inkjet recording of the present invention was carried out in the same manner as in Example 1 except that the compound (a) was changed to each of the following compound (b) to the following compound (z) in <Composition of the mordant solution B> in Example 1. Sheets (2 to 26) were prepared.

[Example 27]
The ink jet recording sheet of the present invention (27) was added in the same manner as in Example 1 except that 0.4 parts of the following light fastness improver (1) was further added in <Mordant Solution B Composition> of Example 1. ) Was produced.

[Example 28]
The ink jet recording sheet of the present invention (28) was added in the same manner as in Example 1 except that 1.0 part of the following light fastness improver (2) was further added to <Composition of Mordant Solution B> in Example 1. ) Was produced.

[Example 29]
The ink jet recording sheet of the present invention (29) was added in the same manner as in Example 1 except that 0.7 parts of the following light fastness improver (3) was further added in <Mordant Solution B Composition> of Example 1. ) Was produced.

[Example 30]
In <Composition of the mordant solution B> in Example 1, the addition amount of the compound (a) was changed from 2.5 parts to 4.0 parts, and 3.0 parts of toluenesulfonic acid was further added, In the same manner as in Example 1, an inkjet recording sheet (30) of the present invention was produced.

[Example 31]
In <Mordant Solution B Composition> of Example 1, the amount of compound (a) added was changed from 2.5 parts to 1.5 parts, and 0.4 parts of the above light fastness improver (1) and guanylthiourea were added. An ink jet recording sheet (31) of the present invention was produced in the same manner as in Example 1 except that 1.5 parts was added.

[Example 32]
In <Composition of Coloring Material Receiving Layer Coating Liquid A> in Example 1, 0.83 part of “PAS-M-1” was added to dimethyldiallylammonium chloride (“Charol DC-902” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.). The ink jet recording sheet (32) of the present invention was produced in the same manner as in Example 1 except that the amount was changed to 0.6 part of 50% aqueous solution).

[Example 33]
In Example 1 <Composition of Color Material Receiving Layer Coating Solution A>, further, basic aluminum chloride (Al ₂ (OH) ₅ Cl, “PAC # 1000” manufactured by Taki Chemical Co., Ltd., 40% aqueous solution) An ink jet recording sheet (33) of the present invention was produced in the same manner as in Example 1 except that 0.63 part was added.

[Example 34]
In the ink jet recording of the present invention, the same procedure as in Example 1 was performed except that 0.6 part of zirconyl acetate (30% aqueous solution) was further added to the <Coloring material receiving layer coating solution A composition> in Example 1. A sheet (34) was produced.

[Example 35]
The ink jet recording sheet (35) of the present invention was prepared in the same manner as in Example 1 except that 0.2 part of lanthanum nitrate was further added to <Composition of Color Material Receiving Layer Coating Liquid A> in Example 1. Produced.

[Example 36]
The ink jet recording sheet of the present invention (in the same manner as in Example 1 except that 0.1 part of the compound (a) was further added to the <Composition of the colorant-receiving layer coating solution A> in Example 1 ( 36) was produced.

[Comparative Example 1]
A comparative inkjet recording sheet (1) was prepared in the same manner as in Example 1, except that 2.5 parts of the compound (a) was not used in <Mordant solution B composition> in Example 1. .

[Comparative Example 2]
Implementation was performed except that 2.5 parts of HOCH ₂ CH ₂ SCH ₂ CH ₂ SCH ₂ CH ₂ OH was used in place of 2.5 parts of compound (a) in <Mordant solution B composition> of Example 1. In the same manner as in Example 1, a comparative inkjet recording sheet (2) was produced.

[Comparative Example 3]
In the <Composition of the mordant solution B> in Example 1, the same procedure as in Example 1 was repeated except that 2.5 parts of N-methylthiourea was used instead of 2.5 parts of compound (a). An ink jet recording sheet (3) was prepared.

[Comparative Example 4]
Example 1 <Mordant solution B composition> In the same manner as in Example 1 except that 2.5 parts of CH ₃ NHCH ₂ CH ₂ OH was used instead of 2.5 parts of compound (a). A comparative ink jet recording sheet (4) was prepared.

(Evaluation test)
The following evaluation tests were performed on each of the inkjet recording sheets (1) to (36) of the present invention obtained above and the comparative inkjet recording sheets (1) to (4). The test results are shown in Table 1 below.

<Ozone resistance>
Using an inkjet printer (“PM-900C” manufactured by Seiko Epson Corporation), solid magenta and cyan images were printed on each inkjet recording sheet, and stored in an environment with an ozone concentration of 2.5 ppm for 24 hours. did. The magenta and cyan densities before and after storage were measured with a reflection densitometer (“Xrite 938” manufactured by Xrite), and the residual ratio of the magenta and cyan densities was calculated.

<Light resistance>
Using an inkjet printer (“PM-900C” manufactured by Seiko Epson Corporation), a solid magenta and cyan image is printed on each inkjet recording sheet, and then passed through a filter that cuts out ultraviolet rays in a wavelength region of 365 nm or less. Using a Xenon Weather-ometer Ci65A (ATLAS), the lamp was turned on for 3.8 hours under an environmental condition of a temperature of 25 ° C. and a relative humidity of 32%. The cycle was allowed to stand for 1 hour under 1% environmental conditions over 168 hours. Each color image density before and after this test was measured with a reflection densitometer (“Xrite 938” manufactured by Xrite), and the residual ratio of each color density was calculated.

From the results of Table 1 above, the ink jet recording sheets (Examples 1 to 3 and Examples 6 to 36) containing the compounds represented by the general formulas (II) to (IV) of the present invention have a high concentration. Even after being stored for a long time in an ozone environment, the density residual rate of the formed image was high, and it was found that the recording sheet was excellent in ozone resistance. Further, even after the xenon irradiation and high humidity standing cycle test, the density residual rate of the formed image was high, and it was found that the recording sheet had excellent light resistance, particularly magenta color development.
Moreover, it turned out that the inkjet recording sheet (Examples 27-29) of this invention which used the hindered amine type compound together is an inkjet recording sheet which was further excellent in ozone resistance and light resistance.
Further, the ink jet recording sheets of the present invention (Examples 33 to 35) combined with the metal compound further improved the bleeding of the image over time.
Further, the inkjet recording sheet of the present invention was excellent in all of glossiness, ink absorption speed, image area density, and water resistance.
On the other hand, the comparative inkjet recording sheet that does not use the compounds represented by the general formulas (II) to (IV) has a low density residual ratio of the image after the test, and has insufficient ozone resistance and light resistance. It was.

Claims (10)

An ink jet recording sheet having a color material receiving layer on a support, wherein the color material receiving layer contains a compound represented by the following general formula (II).


[In General Formula (II), R ²¹ and R ²² are each independently a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, —COR ⁵³ , —COOR ⁵⁴ , —SO ₂ —R ⁵⁵ , —N (R ⁵⁶ ) R ⁵⁷ is represented. Here, R ⁵³ and R ⁵⁵ each independently represent a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, or —N (R ⁵⁸ ) R ⁵⁹ , and R ⁵⁴ represents a hydrogen atom, an aliphatic group or an aromatic group. R ^{56 to} R ⁵⁹ are each independently a hydrogen atom, aliphatic group, aromatic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, aryl. Represents a sulfonyl group or a sulfamoyl group. R ²¹ and R ²² may be connected to each other to form a ring. R ²³ represents an aliphatic group, an aromatic group, a heterocyclic group, —COR ⁷¹ , —COOR ⁷² , —N (R ⁷³ ) R ⁷⁴ , and R ^{24 to} R ²⁶ each independently represent a hydrogen atom or an aliphatic group. , Aromatic group, heterocyclic group, —COR ⁷¹ , —COOR ⁷² , —N (R ⁷³ ) R ⁷⁴ . Here, R ⁷¹ represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, a ^{-N (R 58) R 59,} R 72 is a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic R ⁷³ and R ⁷⁴ each independently represents a hydrogen atom, aliphatic group, aromatic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group, sulfamoyl group. To express. ]   The inkjet recording sheet according to claim 1, wherein the colorant-receiving layer contains at least one compound represented by the general formula (II), fine particles, and a water-soluble resin. The inkjet recording sheet according to claim 2, wherein the fine particles are silica fine particles having an average primary particle size of 20 nm or less, alumina fine particles having an average primary particle size of 20 nm or less, or pseudoboehmite having an average pore radius of 2 to 15 nm. The inkjet recording sheet according to claim 2 or 3, wherein the water-soluble resin is polyvinyl alcohol or a derivative thereof. The inkjet recording sheet according to any one of claims 2 to 4 , wherein the colorant-receiving layer further contains a crosslinking agent capable of crosslinking the water-soluble resin. The inkjet recording sheet according to claim 5 , wherein the crosslinking agent is a boron compound. The ink jet recording sheet according to claim 1 , wherein the colorant receiving layer further contains a mordant. The mordant is a polyallylamine having a weight average molecular weight of 300,000 or less as an organic mordant or a derivative thereof, an aluminum-containing compound, a zirconium-containing compound, a titanium-containing compound as an inorganic mordant, or a group IIIB series metal-containing compound of the Periodic Table of Elements. The ink jet recording sheet according to claim 7 , comprising at least one kind. The inkjet recording sheet according to any one of claims 1 to 8 , wherein the colorant-receiving layer further contains at least one acidic compound. Applying a first coating solution containing at least fine particles and a water-soluble resin to the support surface;
(1) Simultaneously with the coating, (2) during the drying of the coating layer formed by the coating and before the coating layer exhibits a reduced rate of drying, or (3) the first coating solution is dried. And a step of applying a second coating liquid containing at least a mordant to any of the coating film,
A method for producing an ink jet recording sheet, wherein at least one of the compounds represented by the general formula (II) is contained in at least one of the first coating liquid and the second coating liquid .