JP2005035266A - Ink jet recording material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ink jet recording material wherein a photolike high gloss is provided and a retention property after printing is improved. <P>SOLUTION: The ink jet recording material which contains a hydrazine derivative and a quaternary phosphonate, is characterised by containing at least one layer of an ink receptive layer on a base material. and further, by containing a compound having a hydrazine structure and a quaternary phosphonate structure in the same molecule. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an ink jet recording material, and more particularly to an ink jet recording material having high photo-like gloss and improved storage stability after printing.

  As a recording material used in the inkjet recording method, porous ink absorption comprising a pigment such as amorphous silica or alumina and a water-soluble binder such as polyvinyl alcohol on a support called ordinary paper or inkjet recording paper Recording materials provided with layers are known.

  For example, JP-A Nos. 55-51583, 56-157, 57-107879, 57-107880, 59-230787, 62-160277, 62-184879, 62-183382 And a recording material obtained by applying a silicon-containing pigment such as silica to a paper support together with an aqueous binder has been proposed.

  JP-B-3-56552, JP-A-2-188287, 10-81064, 10-119423, 10-175365, 10-193976, 10-203006, 10-217601. No. 11, No. 11-20300, No. 11-20306, No. 11-34481, etc. disclose the use of synthetic silica fine particles by a vapor phase method (hereinafter referred to as vapor phase method silica). This gas phase method silica is an ultrafine particle having an average primary particle diameter of several nm to several tens of nm, and is characterized in that high gloss is obtained. Further, JP-A-2-276671, JP-A-3-251488, JP-A-5-16517, etc. show recording materials using alumina hydrate.

  In recent years, with the demand for photo-like recording sheets, glossiness has become increasingly important. Water resistance of polyolefin resin-coated paper (polyolefin resin such as polyethylene laminated on both sides of paper) and polyester film, etc. A recording material in which an ink receiving layer mainly composed of vapor phase silica, alumina or the like is coated on a support is advantageously used.

  However, a porous recording material using inorganic fine particles such as vapor phase silica and alumina has a problem that a printed image is likely to be discolored during storage after printing because it is porous. That is, there has been a big problem that fading easily occurs due to light and particularly a trace gas in the atmosphere. In addition, in the water-resistant support, unlike the paper support conventionally used, since the support itself has no ink absorption ability, the porosity of the porous recording layer is increased and the coating amount is increased. Therefore, it is necessary to ensure the ink absorption ability. As a result of such a design, the above-described problem of discoloration of the image has become particularly serious.

  Many proposals have been made for the purpose of suppressing such discoloration and improving the storability of a printed image. For example, JP-A-57-74193, JP-A-57-87988, and JP-A-62-261478 disclose a method using an ultraviolet absorber, and JP-A-57-74192, JP-A-57-87989, JP-A-60- No. 72785, No. 61-146591, No. 61-1554989, No. 62-170381, No. 62-61477, JP-A-3-133376, No. 7-314881, No. 7-314882, No. 8-25796. No. 9-267544, etc. describe methods using various antioxidants and anti-fading agents. However, any of these methods has an adverse effect such as insufficient discoloration prevention effect, coloring itself even when the prevention effect is present, or discoloring the recording dye immediately after printing. There were many things that came out, and it did not reach a sufficient level of practical use.

On the other hand, Japanese Patent Application Laid-Open Nos. 2002-321447 (Patent Document 1), 2002-337448 (Patent Document 2), 2003-48372 (Patent Document 3), and the like disclose semicarbazide and carbohydrazide having a specific structure. In other words, a technique using a so-called hydrazine derivative as an anti-fading agent for porous ink jet recording materials using inorganic fine particles has been disclosed, and among these, compounds having a good image storability effect have been found. JP-A-2001-10216 (Patent Document 4), JP-A-2001-88435 (Patent Document 5) and the like also describe a quaternary for the purpose of improving the water resistance of a porous inkjet recording material using inorganic fine particles. A technique of incorporating a phosphonium salt in an ink receiving layer is disclosed. However, in the above prior art, there is no example in which a hydrazine derivative and a quaternary phosphonium salt are simultaneously contained in the ink receiving layer. Regarding the contribution to further improving image storage stability by coexistence of these compounds, Until now there was no knowledge at all. In addition, there has been no known example in which a compound having a hydrazine structure and a quaternary phosphonium salt structure in the same molecule is used as an anti-fading agent for porous ink jet recording materials.
JP 2002-321447 A (2-5 pages) JP 2002-337448 A (pages 3 to 6) JP2003-48372A (pages 4-7) JP 2001-10216 A (pages 3 to 6) JP 2001-88435 A (pages 3 to 6)

  An object of the present invention is to provide an ink jet recording material having a photo-like high gloss and having significantly improved storability after printing.

  The above object of the present invention is achieved by an ink jet recording material having at least one ink receiving layer on a support, wherein the ink jet recording material contains a hydrazine derivative and a quaternary phosphonium salt. It was done. Similarly, the ink jet recording material is characterized by containing a compound having a hydrazine structure and a quaternary phosphonium salt structure in the same molecule. This is particularly effective when the ink receiving layer is porous containing inorganic fine particles.

  According to the present invention, a photo-like ink jet recording material having high gloss and improved storage stability can be obtained.

  The inkjet recording material of the present invention has at least one ink receiving layer, and the ink receiving layer mainly contains a water-soluble polymer even if it is a so-called void type mainly containing inorganic fine particles. It may be a swelling type. In the present invention, the former type is preferred. The above-mentioned void type is one in which ink is absorbed in the void formed in the film, and it is necessary to increase the void volume in order to exhibit high ink absorbability. For this reason, it is necessary to apply a relatively large amount of inorganic fine particles on the support, and the amount of the hydrophilic binder is preferably reduced in order to increase the porosity.

  As inorganic fine particles used in the present invention, light calcium carbonate, heavy calcium carbonate, magnesium carbonate, kaolin, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulfide, zinc carbonate, satin white, aluminum silicate, Examples thereof include synthetic silica such as diatomaceous earth, calcium silicate, wet method silica, colloidal silica, and vapor phase method silica, alumina, hydrated alumina, magnesium silicate, lithopone, zeolite, and magnesium hydroxide. Among these, synthetic silica and alumina fine particles (alumina, alumina hydrate) are preferable, and vapor phase method silica and alumina fine particles are particularly preferable. These may be used alone or in combination. In particular, in the combination of vapor-phase method silica and alumina fine particles, the image density and image storability can be improved by mixing them in the same layer or using them in separate layers.

  Vapor phase silica preferably used in the present invention is also called dry silica, and is generally made by flame hydrolysis. Specifically, a method of making silicon tetrachloride by burning with hydrogen and oxygen is generally known. Vapor phase method silica is commercially available as Aerosil from Nippon Aerosil Co., Ltd. and QS type from Tokuyama Co., Ltd., and can be obtained. In general, vapor phase silica is agglomerated to form secondary particles having appropriate voids, and is used with an ultrasonic, high-pressure homogenizer, counter-impact type jet crusher, etc. until secondary particles of about 50 to 300 nm are obtained. A pulverized and dispersed product is preferable because of good ink absorbability and glossiness.

The alumina fine particles (alumina and hydrated alumina) preferably used in the present invention are aluminum oxide and its hydrate, and may be crystalline or amorphous, and have an amorphous shape, a spherical shape, a plate shape, or the like. What you are using is used. As the alumina, γ-alumina which is a γ-type crystal of aluminum oxide is preferable. Although γ-alumina can reduce the primary particles to about 10 nm, usually, secondary particles of several thousand to several tens of thousands of nanometers are mixed with ultrasonic waves, high-pressure homogenizers, counter-impact type jet crushers, etc. What grind | pulverized to about 300 nm can be used preferably. Alumina hydrate is represented by a constitutive formula of Al ₂ O ₃ .nH ₂ O (n = 1 to 3). The case where n is 1 represents an alumina hydrate having a boehmite structure, and the case where n is greater than 1 and less than 3 represents an alumina hydrate having a pseudo boehmite structure. It can be obtained by a known production method such as hydrolysis of an aluminum alkoxide such as aluminum isopropoxide, neutralization of an aluminum salt with an alkali, or hydrolysis of an aluminate.

  The average particle diameter of the primary particles of the vapor-phase method silica, alumina, and alumina hydrate of the present invention is the projection of each of the 100 primary particles existing in a certain area by observation with an electron microscope of the dispersed secondary particles. The diameter of the circle equal to the area was determined as the particle size of the particles. The average particle diameter of the primary particles of the vapor phase silica used in the present invention is 5 to 50 nm, preferably 5 to 30 nm. The average particle size of the primary particles of the alumina and alumina hydrate of the present invention is 10 to 50 nm, preferably 10 to 30 nm.

In the present invention, the amount of the inorganic fine particles used in the recording layer is preferably 8 g / m ² or more, the range of 10 to 30 g / m ² is more preferable. If the amount is less than this range, the ink absorbability is inferior. If the amount is more than this range, the strength of the ink receiving layer is lowered, which tends to cause a problem during production or use.

  In the present invention, the inorganic fine particles contain 50% by mass or more, preferably 60% by mass or more, more preferably 65% by mass or more of the inorganic fine particles with respect to the main ratio in the ink receiving layer, that is, the total solid content of the ink receiving layer. It is preferable.

  In the present invention, as the hydrophilic binder used together with the inorganic fine particles, various known binders can be used, and a hydrophilic binder that is highly transparent and can obtain higher ink permeability is preferably used. When using a hydrophilic binder, it is important that the hydrophilic binder does not swell during the initial penetration of the ink and block the voids. From this point of view, a hydrophilic binder having a relatively low swellability around room temperature is preferable. Used. Particularly preferred hydrophilic binders are fully or partially saponified polyvinyl alcohol or cation-modified polyvinyl alcohol.

  Particularly preferred among the polyvinyl alcohols are those having a saponification degree of 80 or more or those having been completely saponified. Those having an average degree of polymerization of 200 to 5000 are preferred.

  The cation-modified polyvinyl alcohol has a primary to tertiary amino group or a quaternary ammonium group in the main chain or side chain of the polyvinyl alcohol as described in, for example, JP-A-61-10383. Polyvinyl alcohol.

  In the present invention, it is preferable to use a crosslinking agent (hardener) together with the hydrophilic binder. Specific examples of the crosslinking agent include aldehyde compounds such as formaldehyde and glutaraldehyde, ketone compounds such as diacetyl and chloropentanedione, bis (2-chloroethylurea), 2-hydroxy-4,6-dichloro-1, 3,5-triazine, a compound having a reactive halogen as described in US Pat. No. 3,288,775, divinyl sulfone, a compound having a reactive olefin as described in US Pat. No. 3,635,718, N-methylol compounds as described in Japanese Patent No. 2,732,316, isocyanates as described in US Pat. No. 3,103,437, US Pat. Nos. 3,017,280 and 2,983,611 described Aziridine compounds such as US Pat. No. 3,100,704, carbodiimide compounds, US There are epoxy compounds as described in Perm 3,091,537, halogen carboxaldehydes such as mucochloric acid, dioxane derivatives such as dihydroxydioxane, chromium alum, zirconium sulfate, boric acid and inorganic cross-linking agents such as borate, etc. These can be used alone or in combination of two or more. Among these, boric acid or borate is particularly preferable.

  According to a preferred embodiment of the present invention, the hydrazine derivative of the present invention is applied to an ink jet recording material having an ink receiving layer having a film surface pH 3 to 6, preferably pH 3 to 5.5 containing inorganic fine particles on a water-resistant support. And by containing a quaternary phosphonium salt, the storage stability after printing can be remarkably improved. Similarly, the preservability after printing can be remarkably improved by incorporating a compound having a hydrazine structure and a quaternary phosphonium salt structure in the same molecule of the present invention.

  According to another preferred embodiment of the present invention, there is provided an ink jet recording material in which a cationic compound is contained in an ink receiving layer having a pH of 3 to 6, preferably 3 to 5.5, containing vapor phase silica or alumina fine particles. By containing the hydrazine derivative of the present invention and the quaternary phosphonium salt, the storage stability after printing can be remarkably improved. Similarly, the preservability after printing can be remarkably improved by incorporating a compound having a hydrazine structure and a quaternary phosphonium salt structure in the same molecule of the present invention.

The hydrazine derivative of the present invention will be described below. The hydrazine derivative of the present invention may be a compound having one or more hydrazine structures in the same molecule, or a polymer having the same structure in the molecular main chain or side chain. Specific examples thereof include compounds described in JP-A Nos. 2002-321447, 2002-337448, and 2003-48372. Among them, preferred compounds include those represented by the following chemical formula 1. In the formula, each of R ₁ , R ₂ and R ₃ independently represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, and other substitutable groups. R ₁ and R ₂ may combine with each other to form a heterocyclic ring. R ₄ represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an amino group, a hydrazino group, and OR ₅ . R ₅ represents a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group. L ₁ represents a divalent linking group. n represents 0 or 1.

Specifically, R _{1 to} R ₃ are each independently a hydrogen atom, an alkyl group such as a methyl group, an ethyl group, a propyl group, a hexyl group, a cyclohexyl group, a chloroethyl group, a hydroxyethyl group, a benzyl group, or an allyl group. Alkenyl group such as 3-butenyl group, alkynyl group such as 2-propynyl group (above aliphatic group), phenyl group, naphthyl group, 4-methylphenyl group, 3-aminophenyl group, 2-bromophenyl group, 4 -Aromatic groups such as hydroxyphenyl group, heterocyclic groups such as pyridin-4-yl group, piperidin-4-yl group, and other substitutable groups such as acetyl group, propionyl group, hexanoyl group, benzoyl group, etc. Acyl group, methylcarbamoyl group, dimethylcarbamoyl group, carbamoyl group such as ethylcarbamoyl group, Boniru represents groups, oxycarbonyl groups such as ethoxycarbonyl group, methylsulfamoyl group, a sulfamoyl group such as dimethylsulfamoyl group, and alkanesulfonyl groups such as methanesulfonyl group. Preferred for R _{1 to} R ₃ are a hydrogen atom and an alkyl group having 4 or less carbon atoms. Examples of the heterocyclic ring formed by combining R ₁ and R ₂ with each other include a pyrrolidine ring, a piperidine ring, a piperazine ring, a morpholine ring, and a 1,2,4-triazole ring. Of these, preferred are a piperidine ring and a morpholine ring. Moreover, these R < ₁ > -R < ₃ > may have a further well-known substituent.

R ₄ represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an amino group which may have a known substituent, a hydrazino group, and OR ₅ as described in R _{1 to} R ₃ . R ₅ represents a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group as described for R _{1 to} R ₃ . The preferred R ₄ is an amino group and a hydrazino group which are unsubstituted or substituted with one or two alkyl groups having 4 or less carbon atoms, and one hydroxy group or one alkoxy group having 4 or less carbon atoms. A substituted amino group. L ₁ represents a divalent linking group such as an alkylene group, an arylene group, a carbonyl group, a thiocarbonyl group, an oxalyl group, a sulfinyl group, a sulfonyl group, or a phosphoryl group. Of these, preferred are a carbonyl group and a thiocarbonyl group. n represents 0 or 1, but preferably n = 1.

Of the above, R ₁ and R ₂ are particularly preferably methyl groups or bonded to each other to form a piperidine ring, and R ₃ is particularly preferably a hydrogen atom. And for R _4, particularly preferably 1 or 2 substituted amino group and a hydrazino group and a hydroxy group or an amino group substituted by one methoxy group, an alkyl group having not more than a few 4 carbon atoms, also L ₁ Is particularly preferably a carbonyl group.

  Although the typical compound of the hydrazine derivative used for this invention below is illustrated, of course, this invention is not limited to these.

  These compounds can be synthesized by a known method for synthesizing hydrazine derivatives or a method described in JP-A-2003-48372. Moreover, about some compounds, the chemical products marketed can also be used.

Next, the quaternary phosphonium salt of the present invention will be described. The quaternary phosphonium salt of the present invention may be a compound having one or more phosphonium salt structures in the same molecule, or a polymer having the same structure in the molecular main chain or side chain. Specific examples thereof include compounds described in JP-A Nos. 2001-10216 and 2001-88435. Among them, preferred compounds include those represented by the following chemical formula 6. In the formula, R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ each independently represents an aliphatic group, an aromatic group or a heterocyclic group. X represents a counter ion necessary for neutralizing the electric charge.

Specifically, R _{11 to} R ₁₄ are each independently an alkyl group such as a methyl group, an ethyl group, a propyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a chloroethyl group, a hydroxyethyl group, or a benzyl group. , Alkenyl groups such as allyl group and 3-butenyl group, alkynyl groups such as 2-propynyl group (above aliphatic groups), phenyl group, naphthyl group, 4-methylphenyl group, 3-aminophenyl group, 2-bromophenyl Group, an aromatic group such as 4-hydroxyphenyl group, a heterocyclic group such as 2-furyl group, 4-tetrahydropyranyl group and the like. Of these, an alkyl group having 6 or less carbon atoms and a phenyl group are preferable. Further, these R _{11 to} R ₁₄ may further have a known substituent. X represents a counter ion necessary for neutralizing the electric charge. Specific examples thereof include halogen atom ions such as chloride and bromide, and sulfonate ions such as methanesulfonate and p-toluenesulfonate.

Particularly preferred among the above are R _{11 to} R ₁₄ which are an alkyl group having 3 or less carbon atoms and an unsubstituted phenyl group, and X is a halogen atom ion. Although the typical compound of the quaternary phosphonium salt used for this invention below is illustrated, of course, this invention is not limited to these.

  These compounds can be easily synthesized by known synthesis methods. Moreover, about some compounds, the chemical products marketed can also be used.

Furthermore, the compound which has the hydrazine structure and the quaternary phosphonium salt structure in the same molecule in this invention is demonstrated. This compound is a compound having a hydrazine moiety and a quaternary phosphonium salt moiety having the basic structures of the above-described chemical formulas 1 and 6 in the same molecule, respectively, and having these structures in the molecular main chain or side chain. It may be a polymer. Among them, preferred compounds include those represented by the following chemical formula 9. In the formula, R ₃₁ , R ₃₂ and R ₃₃ each independently represent a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, or other substitutable groups. R ₃₁ and R ₃₂ may combine with each other to form a heterocyclic ring. R ₃₄ , R ₃₅ and R ₃₆ each independently represents an aliphatic group, an aromatic group or a heterocyclic group. L ₃₁ represents a divalent linking group. Y represents a counter ion necessary for neutralizing the electric charge.

Specifically, R _{31 to} R ₃₃ are synonymous with R _{1 to} R ₃ in Chemical Formula 1 described above, and R _{34 to} R ₃₆ are synonymous with R _{11 to} R ₁₄ in Chemical Formula 6 described above. is there. L ₃₁ represents a divalent linking group represented by the following chemical formula 10 or chemical formula 11. In these chemical formulas 10 and 11, L ₃₂ and L ₃₄ represent a carbonyl group, a thiocarbonyl group, an oxalyl group, a sulfinyl group, a sulfonyl group, a phosphoryl group, or the like. Of these, preferred are a carbonyl group and a thiocarbonyl group. L ₃₃ and L ₃₅ represent an alkylene group, an arylene group, or the like. Of these, an alkylene group is preferred. R ₃₇ represents a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group. Of these, a hydrogen atom is preferred. Y is synonymous with X in Chemical Formula 6.

Of the foregoing, R ₃₁ and R ₃₂ are particularly preferably a methyl group or those bonded to each other to form a piperidine ring, and R ₃₃ is particularly preferably a hydrogen atom. R _{34 to} R ₃₆ are particularly preferably an unsubstituted phenyl group. L ₃₁ is particularly preferably a combination of the above-mentioned chemical formula 10 wherein L ₃₂ is carbonyl, R ₃₇ is a hydrogen atom, and L ₃₃ is an alkylene group having 2 to 4 carbon atoms, and Y is particularly preferably a halogen atom ion. preferable. In the following, representative compounds are exemplified for the compounds having a hydrazine structure and a quaternary phosphonium salt structure in the same molecule of the present invention, but the present invention is of course not limited thereto.

  The above compound can be easily synthesized by a known synthesis method. A typical synthesis example is shown below.

Synthesis of HP2 (3-aminopropyl) triphenylphosphonium bromide 4.0 g, N, N-dimethyl-N′-phenoxycarbonylhydrazine 2.2 g, and acetonitrile 20 ml were mixed and heated under reflux for 3 hours. Next, 80 ml of methanol and 4 g of activated carbon were added and stirred at room temperature for 30 minutes. Next, the insoluble material was filtered off, the solvent was evaporated, 50 ml of ethyl acetate was added to the residue, and the mixture was stirred at room temperature for 1 hour. The precipitated solid was collected by filtration, washed with ethyl acetate and dried to obtain 2.1 g of the desired product (melting point 211 to 213 ° C.).

The content of Compound 1 and Compound 6 used in the present invention in the inkjet recording material is preferably 0.1 to 50 mmol / m ^{2 and} more preferably 0.2 to 20 mmol / m ² . Regarding also compounds of 9, the amount contained in the inkjet recording material is preferably from 0.1 to 50 mmol / m ^2, more preferably 0.2 to 20 mmol / m ^2. The compounds 1, 6 and 9 of the present invention can be contained in a support, an ink receiving layer, an intermediate layer, an undercoat layer, a protective layer, etc. constituting an ink jet recording material, but preferably an ink. It is contained in the receiving layer. Further, when there are a plurality of ink receiving layers, they may be contained in any one layer or in a plurality of layers.

  Examples of the cationic compound used in the present invention include a cationic polymer and a water-soluble metal compound. As the cationic polymer, polyethyleneimine, polydiallylamine, polyallylamine, alkylamine polymer, JP-A-59-20696, 59-33176, 59-33177, 59-155888, 60-11389 No. 60-49990, No. 60-83882, No. 60-109894, No. 62-198493, No. 63-49478, No. 63-115780, No. 63-280681, JP-A-1-40371. No. 6-234268, No. 7-125411, No. 10-193376, and the like, and polymers having a primary to tertiary amino group and a quaternary ammonium base are preferably used. The molecular weight of these cationic polymers is preferably 5,000 or more, and more preferably about 5,000 to 100,000.

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

  Examples of the water-soluble metal compound used in the present invention include water-soluble polyvalent metal salts. Examples include water-soluble salts of metals selected from calcium, barium, manganese, copper, cobalt, nickel, aluminum, iron, zinc, zirconium, chromium, magnesium, tungsten, and molybdenum. Specifically, for example, calcium acetate, calcium chloride, calcium formate, calcium sulfate, barium acetate, barium sulfate, barium phosphate, manganese chloride, manganese acetate, manganese formate dihydrate, manganese ammonium sulfate hexahydrate, chloride chloride Dicopper, ammonium 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 sulfite, aluminum thiosulfate, polyaluminum chloride, aluminum nitrate nonahydrate, aluminum chloride hexahydrate, ferrous bromide, ferric chloride Ferrous, ferric chloride, ferrous sulfate, ferric sulfate, zinc bromide, zinc chloride, zinc nitrate six Japanese, Zinc sulfate, Zirconium acetate, Zirconium chloride, Zirconium chloride octahydrate, Hydroxy zirconium chloride, Chromium acetate, Chromium sulfate, Magnesium sulfate, Magnesium chloride hexahydrate, Magnesium citrate nonahydrate, Phosphorus tungsten Sodium tungstate, sodium tungsten citrate, 12 tungstophosphoric acid n hydrate, 12 tungstosilicic acid 26 hydrate, molybdenum chloride, 12 molybdophosphoric acid n hydrate, and the like.

  In the present invention, a water-soluble aluminum compound or a water-soluble compound containing a Group 4A element of the periodic table is particularly preferable. As the water-soluble aluminum compound, for example, aluminum chloride or its hydrate, aluminum sulfate or its hydrate, ammonium alum and the like are known as inorganic salts. Furthermore, there is a basic polyaluminum hydroxide compound which is an inorganic aluminum-containing cationic polymer. In particular, a basic polyaluminum hydroxide compound is preferable.

The basic polyaluminum hydroxide compound has a main component represented by the following formula 1, 2, or 3, for example, [Al ₆ (OH) ₁₅ ] ³⁺ , [Al ₈ (OH) ₂₀ ] ⁴⁺ , [ It is a water-soluble polyaluminum hydroxide that stably contains a basic and high-molecular polynuclear condensed ion such as Al ₁₃ (OH) ₃₄ ] ⁵⁺ , [Al ₂₁ (OH) ₆₀ ] ³⁺ , and the like.

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

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

  The water-soluble compound containing a Group 4A element of the periodic table used in the present invention is not particularly limited as long as it is water-soluble, but a water-soluble compound containing titanium or zirconium is preferable. For example, water-soluble compounds containing titanium include titanium chloride and titanium sulfate, and water-soluble compounds containing zirconium include zirconium acetate, zirconium chloride, zirconium oxychloride, hydroxy zirconium chloride, zirconium nitrate, basic zirconium carbonate, zirconium hydroxide, Zirconium carbonate / ammonium, zirconium carbonate / potassium, zirconium sulfate, zirconium fluoride compounds and the like are known. Some of these compounds have an inappropriately low pH. In that case, the pH can be appropriately adjusted and used. In the present invention, the term “water-soluble” means that 1% by mass or more dissolves in water at room temperature and normal pressure.

  In the present invention, the content of the water-soluble metal compound in the ink receiving layer is preferably from 0.1 to 10% by mass, more preferably from 1 to 5% by mass, based on the inorganic fine particles.

  Two or more of the above cationic compounds can be used in combination. For example, it is preferable to use a cationic polymer and a water-soluble metal compound in combination.

  In the present invention, it is also preferable to use a thioether compound in combination with the aforementioned hydrazine derivative and quaternary phosphonium salt, or a compound having a hydrazine structure and a quaternary phosphonium salt structure in the same molecule.

Examples of the thioether compound used in the present invention include the compounds described in JP-A-2002-337448. Preferred examples thereof include those having the structure shown by the following chemical formula (14). In the formula, R ₂₁ and R ₂₂ each independently represent a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group. R ₂₃ represents an alkylene group. m represents an integer of 0 to 10.

Among them, R ₂₁ and R ₂₂ are preferably at least one hydroxy group and an alkyl group having 6 or less carbon atoms substituted with a tertiary amino group, and R ₂₃ is an alkylene group having 4 or less carbon atoms. . Further, m is preferably 1. Among them, particularly preferred is a compound having an alkyl group having 3 or less carbon atoms in which R ₂₁ and R ₂₂ are substituted with at least one hydroxy group. Although the typical compound of the thioether compound used for this invention below is illustrated, of course, this invention is not limited to these.

Compounds used in the present invention, the content in the inkjet recording material of the formula 14 is preferably 0.1 to 50 mmol / m ^2, respectively, and more preferably 0.2 to 20 mmol / m ^2. This chemical formula 14 can be contained in the support, the ink receiving layer, the intermediate layer, the undercoat layer, the protective layer, etc. constituting the ink jet recording material as in the case of the chemical formula 1, chemical formula 6, and chemical formula 9. However, it is preferably contained in the ink receiving layer. Further, when there are a plurality of ink receiving layers, they may be contained in any one layer or in a plurality of layers.

  In the present invention, the film surface pH of the ink receiving layer is determined according to J.P. Surface pH measured after 30 seconds using distilled water according to the method described in TAPPI paper pulp test method N0.49.

  The pH of the ink receiving layer is preferably adjusted at the coating liquid stage, but the pH of the coating liquid does not necessarily match the film surface pH in the coated and dried state, so the relationship between the coating liquid and the film surface pH. Is previously determined by experiments or the like in order to obtain a predetermined film surface pH. The pH of the ink receiving layer coating solution is determined by appropriately combining acid or alkali. As the acid, inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid and phosphoric acid, and organic acids such as acetic acid, citric acid and succinic acid are used. As the alkali, sodium hydroxide, aqueous ammonia, potassium carbonate and trisodium phosphate are used. Alternatively, an alkali metal salt of a weak acid such as sodium acetate is used as the weak alkali.

  The ink receiving layer of the present invention can further contain various oil droplets in order to improve the brittleness of the film. Such oil droplets include hydrophobic high-boiling organic solvents (for example, liquid paraffin, dioctyl phthalate, tricresyl phosphate, silicone oil, etc.) having a solubility in water at room temperature of 0.01% by mass or less, and polymer particles ( For example, particles obtained by polymerizing one or more polymerizable monomers such as styrene, butyl acrylate, divinylbenzene, butyl methacrylate, and hydroxyethyl methacrylate) can be contained. Such oil droplets can be preferably used in the range of 10 to 50% by mass relative to the hydrophilic binder.

  In the present invention, a surfactant can be added to the ink receiving layer. The surfactant used may be any of anionic, cationic, nonionic, and betaine types, and may be a low-molecular or high-molecular one. One or more surfactants are added to the ink-receiving layer coating liquid. When two or more surfactants are used in combination, an anionic one and a cationic one are used in combination. That is not preferable. The addition amount of the surfactant is preferably 0.001 to 5% by mass, more preferably 0.01 to 3% by mass with respect to the binder constituting the ink receiving layer.

  In the present invention, the ink receiving layer further comprises a coloring dye, a coloring pigment, an ink dye fixing agent, an ultraviolet absorber, an antioxidant, a pigment dispersant, an antifoaming agent, a leveling agent, an antiseptic, and a fluorescent brightening agent. Various known additives such as viscosity stabilizers can also be added.

  The support used in the present invention is preferably a water resistant support. Water-resistant supports include polyester resins such as polyethylene terephthalate, diacetate resins, triacetate resins, acrylic resins, polycarbonate resins, polyvinyl chloride, polyimide resins, cellophane, cellulosic plastic resin films, and polyolefin resins on both sides of paper. And resin-coated paper laminated. The thickness of the water-resistant support used in the present invention is preferably about 50 to 300 μm.

  The base paper constituting the resin-coated paper preferably used in the present invention is not particularly limited, and generally used paper can be used. More preferably, for example, a smooth base paper used for a photographic support is used. preferable. As the pulp constituting the base paper, natural pulp, recycled pulp, synthetic pulp or the like is used alone or in combination of two or more. This base paper is blended with additives such as sizing agent, paper strength enhancer, filler, antistatic agent, fluorescent whitening agent, and dye generally used in papermaking.

  Further, a surface sizing agent, surface paper strengthening agent, fluorescent brightening agent, antistatic agent, dye, anchor agent and the like may be applied on the surface.

In addition, the thickness of the base paper is not particularly limited, but preferably has a good surface smoothness such as a paper that is compressed by applying a pressure during or after paper making using a calendar or the like, and has a basis weight of 30 to 250 g / m ² is preferred.

  As the resin of the resin-coated paper, a polyolefin resin or a resin curable with an electron beam can be used. Examples of polyolefin resins include low-density polyethylene, high-density polyethylene, polypropylene, polybutene, olefin homopolymers such as polypentene, or copolymers composed of two or more olefins such as ethylene-propylene copolymer, and mixtures thereof. Those having various densities and melt viscosity indices (melt index) can be used alone or in combination.

  In addition, in the resin of the resin-coated paper, white pigments such as titanium oxide, zinc oxide, talc and calcium carbonate, fatty acid amides such as stearic acid amide and arachidic acid amide, zinc stearate, calcium stearate, aluminum stearate, stearin Fatty acid metal salts such as magnesium acid, antioxidants such as Irganox 1010 and Irganox 1076, blue pigments and dyes such as cobalt blue, ultramarine blue, cecilian blue and phthalocyanine blue, magenta such as cobalt violet, fast violet and manganese purple It is preferable to add various additives such as pigments and dyes, fluorescent brighteners and ultraviolet absorbers in appropriate combinations.

  In the case of a polyolefin resin on a traveling base paper, the resin-coated paper that is preferably used in the present invention is produced by a so-called extrusion coating method in which a heat-melted resin is cast, and both surfaces thereof are coated with the resin. The In the case of a resin that is cured by an electron beam, the resin is applied by a commonly used coater such as a gravure coater or a blade coater, and then irradiated with an electron beam to cure and coat the resin. Moreover, it is preferable to subject the base paper to an activation treatment such as corona discharge treatment or flame treatment before coating the resin on the base paper. The surface (surface) on which the ink receiving layer of the support is applied has a glossy surface, a matte surface, etc., depending on the application, and the glossy surface is particularly preferentially used. It is not necessary to coat the back surface with a resin, but it is preferable to coat the resin from the viewpoint of curling prevention. The back surface is usually a matte surface, and an active treatment such as corona discharge treatment or flame treatment can be applied to the front surface or both the front and back surfaces as necessary. Moreover, there is no restriction | limiting in particular as thickness of a resin coating layer, Generally, it coats on the surface or both surfaces by thickness of 5-50 micrometers.

  Various back coat layers can be coated on the support in the present invention for antistatic properties, transport properties, anticurling properties, and the like. In the backcoat layer, an inorganic antistatic agent, an organic antistatic agent, a hydrophilic binder, latex, a curing agent, a pigment, a surfactant, and the like can be appropriately combined.

  In the present invention, the coating method of the ink receiving layer is not particularly limited, and a known coating method can be used. For example, there are a slide lip method, a curtain method, an extrusion method, an air knife method, a roll coating method, a rod bar coating method, and the like.

  In the present invention, the ink jet recording material may be further provided with an ink absorbing layer, an ink fixing layer, an intermediate layer, a protective layer and the like in addition to the layer containing at least one inorganic fine particle. A layer may be coated, or a swelling layer or a porous layer may be coated on the upper layer. Then, inorganic fine particles such as the above-mentioned synthetic silica and alumina fine particles may be mixed, or may be used in the form of laminated layers as separate layers. In order to obtain a photo-like high gloss, as the synthetic silica, particles obtained by pulverizing colloidal silica or wet process silica in an aqueous medium to an average secondary particle diameter of 500 nm or less can be preferably used. Examples of combinations of these laminated forms include: lower layer: wet method silica layer / upper layer: gas phase method silica layer, lower layer: gas phase method silica layer / upper layer: colloidal silica layer, lower layer: alumina fine particle layer / upper layer: colloidal silica Layer, lower layer: gas phase method silica layer / upper layer: alumina fine particle layer. Among these, an ink jet recording material having a high printing density and excellent storability is provided by providing a vapor phase silica layer as a lower layer and an alumina hydrate layer having a coating amount smaller than that of the vapor phase silica layer as an upper layer. Obtainable.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, the content of this invention is not restricted to an Example. In addition, a part means a solid content mass part.

A 1: 1 mixture of hardwood bleached kraft pulp (LBKP) and softwood bleached sulfite pulp (NBSP) was beaten to 300 ml with Canadian Standard Freeness to prepare a pulp slurry. The sizing agent is alkyl ketene dimer 0.5% by weight of pulp, the strength agent is polyacrylamide 1.0% by weight of pulp, cationized starch is 2.0% by weight of pulp, and polyamide epichlorohydrin resin. 0.5% by mass of pulp was added and diluted with water to give a 1% slurry. This slurry was made with a long paper machine to a basis weight of 170 g / m ² , dried and conditioned to obtain a polyolefin resin-coated paper base paper. A polyethylene resin composition in which 10% by mass of anatase-type titanium was uniformly dispersed with respect to 100% by mass of low density polyethylene having a density of 0.918 g / cm ³ was melted at 320 ° C. at 320 ° C. The film was extrusion coated to a thickness of 35 μm per minute, and extrusion coated using a cooling roll with a finely roughened surface. On the other side, 70 parts by mass of a high density polyethylene resin having a density of 0.962 g / cm ³ and 30 parts by mass of a low density polyethylene resin having a density of 0.918 g / m ³ were similarly melted at 320 ° C. Then, it was extrusion-coated so as to have a thickness of 30 μm, and extrusion-coated using a cooling roll having a rough surface.

The polyolefin resin-coated paper surface was subjected to high-frequency corona discharge treatment, and then the undercoat layer was applied and dried so that the gelatin content was 50 mg / m ² to prepare a support.

An aqueous solution containing gas phase method silica and Charol DC902P is dispersed with a high-pressure homogenizer, and polyvinyl alcohol or the like is added to prepare an ink receiving layer coating solution having the following composition. The amount of gas phase method silica applied is 18 g in solid content. An ink jet recording sheet was prepared by coating and drying so as to be / m ² . Each recording sheet was adjusted so that the film surface pH of the ink receiving layer was 4.0.

<Recording sheet 1>
<Ink-receiving layer composition>
Gas phase method silica (average primary particle size 7 nm, specific surface area 300 m ² / g by BET method) 100 parts dimethyldiallylammonium chloride polycondensate 3 parts (Daiichi Kogyo Seiyaku Co., Ltd., trade name Charol DC902P)
25 parts of polyvinyl alcohol (trade name: PVA235, manufactured by Kuraray Co., Ltd., saponification degree 88%, average polymerization degree 3500)
Boric acid 4 parts Basic polyaluminum hydroxide (Purechem WT manufactured by Riken Green Co., Ltd.) 2 parts Amphoteric surfactant 0.3 parts (Product name: SWAM AM-2150, manufactured by Nippon Surfactant)

<Recording sheet 2>
2 mmol / m ² of H2 was added to the ink receiving layer of the recording sheet 1.

<Recording sheet 3>
4 mmol / m ² of H2 was added to the ink receiving layer of the recording sheet 1.

<Recording sheet 4>
2 mmol / m ² of H21 was added to the ink receiving layer of the recording sheet 1.

<Recording sheet 5>
4 mmol / m ² of H21 was added to the ink receiving layer of the recording sheet 1.

<Recording sheet 6>
To the ink receiving layer of the recording sheet 1, 2 mmol / m ² of P4 was added.

<Recording sheet 7>
P4 was added to the ink receiving layer of the recording sheet 1 at 4 mmol / m ² .

<Recording sheet 8>
2 mmol / m ² of P5 was added to the ink receiving layer of the recording sheet 1.

<Recording sheet 9>
The recording sheet 1 of the ink receiving of H2 in layer 2 mmol / m ^2, P1 was added 2 mmol / m ^2.

<Recording sheet 10>
The recording sheet 1 of the ink receiving of H2 in layer 2 mmol / m ^2, P4 was added 2 mmol / m ^2.

<Recording sheet 11>
The recording sheet 1 of the ink receiving of H2 in layer 2 mmol / m ^2, P5 was added 2 mmol / m ^2.

<Recording sheet 12>
The recording sheet 1 of the ink receiving of H2 in layer 2 mmol / m ^2, P6 was added 2 mmol / m ^2.

<Recording sheet 13>
Ink-receiving layer in H21 2 mmol / m ² of the recording sheet 1, P4 was added 2 mmol / m ^2.

<Recording sheet 14>
Ink-receiving layer in H21 2 mmol / m ² of the recording sheet 1, P5 was added 2 mmol / m ^2.

<Recording sheet 15>
Ink-receiving layer in H21 2 mmol / m ² of the recording sheet 1, P6 was added 2 mmol / m ^2.

<Recording sheet 16>
It said the H21 in the ink-receiving layer of the recording sheet 1 2 mmol / m ^2, P8 was added 1 mmol / m ^2.

<Recording sheet 17>
2 mmol / m ² of HP1 was added to the ink receiving layer of the recording sheet 1.

<Recording sheet 18>
2 mmol / m ² of HP2 was added to the ink receiving layer of the recording sheet 1.

<Recording sheet 19>
2 mmol / m ² of HP6 was added to the ink receiving layer of the recording sheet 1.

  About each obtained inkjet recording sheet, the preservability after printing and glossiness were evaluated. The result is shown in (Result 1).

<Preservability>
After printing with CMYK ink using an ink jet printer (Seiko Epson PM-880C) and exposing to a sunny window (the daytime illuminance is about 6000 lux) for 2 months, the reflection density when fresh The density of about 1.0 part was measured, and the image residual ratio (post-exposure density / pre-exposure density) was determined, and the CMYK image having the lowest residual ratio was displayed.

<Glossiness>
It was measured according to the method described in JIS P-8142 (75-degree specular gloss test method for paper and paperboard).

(Result 1)
────────────────────────
Record sheet retention (%) Remarks ────────────────────────
1 66 Comparison 2 86 Comparison 3 88 Comparison 4 84 Comparison 5 86 Comparison 6 66 Comparison 7 65 Comparison 8 66 Comparison 9 92 Invention 10 93 Invention 11 93 Invention 12 91 Invention 13 92 Invention 14 93 Invention 15 91 Present invention 16 91 Present invention 17 93 Present invention 18 93 Present invention 19 91 Present invention -------------------

  The glossiness of each recording sheet was 60 to 65%, indicating a high glossiness. As is apparent from the above results, it can be seen that the use of the compounds of Chemical Formula 1 and Chemical Formula 6 in combination improves the storage stability compared to the chemical formula 1 used alone. In addition, in the comparison between Chemical Formula 1 and Chemical Formula 9, the superiority of Chemical Formula 9 over storage stability is clear.

  The following four types of recording sheets were prepared using the support and the ink-receiving layer coating solution used in Example 1.

<Recording sheet 20>
2 mmol / m ² of S3 was added to the ink receiving layer of the recording sheet 1.

<Recording sheet 21>
S4 was added at 2 mmol / m ² to the ink receiving layer of the recording sheet 1.

<Recording sheet 22>
The recording of H2 in the ink-receiving layer of the sheet 1 2 mmol / m ^2, P4 2 mmol / m ^2, S3 was added 1 mmol / m ^2.

<Recording sheet 23>
The recording of H2 in the ink-receiving layer of the sheet 1 2 mmol / m ^2, P5 and 2 mmol / m ^2, S3 was added 1 mmol / m ^2.

<Recording sheet 24>
The recording of H2 in the ink-receiving layer of the sheet 1 2 mmol / m ^2, P5 and 2 mmol / m ^2, S4 was added 1 mmol / m ^2.

<Recording sheet 25>
Wherein the recording ink receiving layer in HP1 to 2 mmol / m ^2, S3 of the sheet 1 was added 1 mmol / m ^2.

<Recording sheet 26>
Wherein the recording ink receiving layer HP2 2 mmol / m ^2, S3 of the sheet 1 was added 1 mmol / m ^2.

  Using the obtained inkjet recording sheets 20 to 26 and the recording sheets 1, 11, and 17 used in Example 1, storage stability was evaluated under the same conditions as in Example 1. The result is shown in (Result 2).

(Result 2)
───────────────────────
Record sheet retention (%) Remarks ────────────────────────
1 65 Comparison 20 63 Comparison 21 63 Comparison 11 92 Present Invention 17 92 Present Invention 22 95 Present Invention 23 95 Present Invention 24 95 Present Invention 25 95 Present Invention 26 95 Present Invention ─────────── ──────────

  From the above results, it can be seen that when the compound of the chemical formula 1 and the chemical compound of the chemical formula 6 are further combined with the compound of the chemical formula 14 or when the compound of the chemical formula 14 is combined with the chemical compound of the chemical formula 9.

  The vapor phase silica used in Example 1 was tested in the same manner as in Example 1 except that it was replaced with flat pseudoboehmite having an average primary particle size of 15 nm and an aspect ratio of 5. As a result, almost the same results were obtained in terms of storage stability and glossiness.

  As a result of testing in the same manner as in Example 1 except that a polyester film was used as the support of Example 1, the same result as in Example 1 was obtained.

The ink receiving layers A and B coating liquids having the following two types of compositions were prepared on the support of Example 1, and simultaneously coated with a slide bead coating apparatus and dried. The lower layer ink receiving layer A and the upper layer ink receiving layer B coating solution close to the support shown below were prepared by dispersing inorganic fine particles with a high-pressure homogenizer so as to have a solid content concentration of 9% by mass. These coating liquids were coated and dried so that the ink-receiving layer A had a solid vapor-phase silica of 16 g / m ² and the pseudo-boehmite of the ink-receiving layer B was 4 g / m ² to obtain a comparative recording sheet. .

<Ink-receiving layer A composition>
Gas phase method silica 100 parts (average primary particle size 7nm)
Dimethyldiallylammonium chloride polycondensate 4 parts (Daiichi Kogyo Seiyaku Co., Ltd., trade name Charol DC902P)
Boric acid 4 parts Polyvinyl alcohol 20 parts (saponification degree 88%, average polymerization degree 3500)
Surfactant 0.3 parts Zirconium acetate 2 parts

<Ink-receiving layer B composition>
Pseudo boehmite 100 parts (flat plate shape with average primary particle size 15nm, aspect ratio 5)
Boric acid 4 parts Polyvinyl alcohol 20 parts (saponification degree 88%, average polymerization degree 3500)
Surfactant 0.3 parts Zirconium acetate 2 parts

Recording sheets prepared by adding 1 mmol / m ^{2 of} each of the compounds used in the recording sheets 9 to 19 of Example 1 to the ink receiving layer A and the ink receiving layer B were prepared and evaluated in the same manner as in Example 1. As a result, the recording sheet containing the compound of the present invention was superior in storage stability compared to the comparative recording sheet.

Claims (9)

  An inkjet recording material having at least one ink-receiving layer on a support, wherein the inkjet recording material contains a hydrazine derivative and a quaternary phosphonium salt.   An ink jet recording material having at least one ink receiving layer on a support, wherein the ink jet recording material contains a compound having a hydrazine structure and a quaternary phosphonium salt structure in the same molecule. Recording material.   The ink jet recording material according to claim 1, wherein the ink receiving layer contains inorganic fine particles.   The inkjet recording material according to claim 3, wherein the inorganic fine particles are vapor phase silica or alumina fine particles having an average primary particle diameter of 30 nm or less.   The ink jet recording material according to claim 1, wherein the ink receiving layer is crosslinked with a crosslinking agent.   The ink jet recording material according to any one of claims 1 to 5, wherein a film surface pH of the ink receiving layer is 3 to 6.   Furthermore, the inkjet recording material as described in any one of Claims 1-6 containing a cationic compound.   Furthermore, the inkjet recording material as described in any one of Claims 1-7 containing a thioether compound.   The ink jet recording material according to claim 1, wherein the support is a water resistant support.