JP2007237549A - Manufacturing method of inkjet recording material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing an inkjet recording material by simultaneous multiple coating, which makes an ink accepting layer free from a coating failure and has a good production efficiency, in regard to the manufacturing method of the inkjet recording material excellent in ink absorbency. <P>SOLUTION: In the manufacturing method of the inkjet recording material wherein the inkjet recording material having at least two or more ink accepting layers on a substrate is manufactured by the simultaneous stratified coating, at least one of the two or more ink accepting layers is constituted mainly of inorganic particles having an average secondary particle diameter of 500 nm or less, and at least one of the two or more ink accepting layers contains polyethylene glycol nonyl phenylether or polyethylene glycol octyl phenylether. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for producing an ink jet recording material, and more particularly to a method for producing an ink jet recording material comprising two or more ink receiving layers in which no coating failure occurs in the ink receiving layer.

  As a recording material used in the ink jet recording method, a soluble or swellable ink-receiving layer mainly composed of a hydrophilic polymer or a pigment such as amorphous silica is formed on a support made of ordinary paper or film. A recording material having a porous ink-receiving layer as a main component is known.

  In the case of providing a soluble or swellable ink-receiving layer mainly composed of a hydrophilic polymer, JP-A-55-146786 uses a water-absorbing polymer for a colorant-absorbing layer provided on a support. The use of a soluble or swellable substance is proposed in Japanese Patent Publication No. 56-80489, and many polymer systems (polyvinyl alcohol (PVA), polyvinyl pyrrolidone (PVP), polyethylene oxide (PEO), carboxymethyl cellulose (CMC)) are used. Use is suggested. However, these absorbing materials utilize the permeation effect of the aqueous ink due to the hydrophilic group or dissociable group of the polymer, and therefore a sufficient ink absorption rate cannot be obtained even if the film is thickened.

  In the case of providing a porous ink-receiving layer, in recent years, ultrafine inorganic particles as a pigment, for example, inorganic ultrafine particles such as pulverized and dispersed gas phase method silica or wet method silica as a pigment component of the ink receiving layer. It has been proposed to use. For example, JP-A-3-56552, JP-A-10-119423, JP-A-2000-2111235, and JP-A-2000-309157 disclose examples of using vapor phase silica. JP-A-9-286165, JP-A-10 No. 181190 discloses a use example of pulverized sedimentation silica, and Japanese Patent Application Laid-Open No. 2001-277712 discloses a use example of crushed gel method silica. JP-A-62-174183, JP-A-2-276670, JP-A-5-32037, JP-A-6-199034 and the like disclose recording materials using alumina or alumina hydrate. Porous ink-receiving layers are known for their relatively high ink absorption rates.

  Conventionally, paper has been generally used as the recording material support described above, and the paper itself has a role as an ink absorbing layer. In recent years, photo-like recording materials have been demanded, and recording materials using a paper support have problems such as gloss, texture, water resistance, cockling after printing (wrinkles or undulations), and the like. Particularly for photographic use, resin-laminated paper or the like in which polyethylene resin or the like is laminated on both sides of paper has been used. In addition, a transparent support such as a resin film such as a polyester film is used for applications such as an overhead projector (OHP) or a film under a printing plate. However, unlike a paper support, a water-resistant support cannot absorb ink, so the ink absorbability of an ink receiving layer provided on the support is important.

  In the above-mentioned photographic use, for example, in order to obtain high absorbency and gloss, JP-A-2001-1630 proposes a multilayer coating of a vapor phase silica and an alumina ink receiving layer and a water-soluble polymer layer (patent). Reference 1). In order to obtain excellent scratch resistance, Japanese Patent Application Laid-Open No. 2003-159862 proposes a multilayer coating of an ink receiving layer containing inorganic fine particles and a layer containing colloidal silica (Patent Document 2). In order to obtain a high printing density, Japanese Patent Application Laid-Open No. 2004-237704 proposes multilayer coating containing wet silica in the uppermost ink receiving layer (Patent Document 3). In order to improve cracking and folding of the ink receiving layer, Japanese Patent Application Laid-Open No. 2005-335120 proposes an ink jet recording material having a multilayer structure containing a resin binder having inorganic particles and a keto group (Patent Document 4). ). In OHP applications, in order to improve the adhesive strength, JP 2004-25836 A describes an additional adhesion comprising a binder and a cationically modified silica between a support and an ink receiving layer. A multilayer ink jet recording material provided with an acceleration layer has been proposed (Patent Document 5).

  However, the ink jet recording material having the multi-layer structure as described above cannot be efficiently produced due to the occurrence of cracks and repellency in simultaneous multi-layer coating. In addition, since the coating liquid at the ear portion approaches the inside during application, there is also a drawback that the application width is narrowed.

An example using a surfactant has been disclosed for improving coating failure. To give an example, JP 2001-246838 A (Patent Document 6), JP 2004-98382 A (Patent Document 7), There exists Unexamined-Japanese-Patent No. 2005-28746 (patent document 8) etc. However, in the case of simultaneous multi-layer coating, the above technique cannot solve the problem.
JP 2001-1630 A JP 2003-159862 A JP 2004-237704 A JP-A-2005-335120 JP 2004-25836 A JP 2001-246838 A JP 2004-98382 A JP 2005-28746 A

  SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing a simultaneous multilayer coating of an ink jet recording material which is excellent in production efficiency and has no coating failure in an ink receiving layer in a method for producing an ink jet recording material excellent in ink absorbability.

  The above object of the present invention has been achieved by the following invention.

(1) In the method for producing an ink jet recording material, in which an ink jet recording material having at least two ink receiving layers on a support is simultaneously applied in multiple layers, at least one of the two or more ink receiving layers (A) is an average. An ink receiving layer mainly composed of inorganic fine particles having a secondary particle diameter of 500 nm or less, wherein at least one of the two or more ink receiving layers contains polyethylene glycol nonyl phenyl ether or polyethylene glycol octyl phenyl ether. A method for producing an inkjet recording material.
(2) The ink receiving layer (A2) provided at a position away from the support among the two or more ink receiving layers (A) contains polyethylene glycol nonyl phenyl ether or polyethylene glycol octyl phenyl ether. The method for producing an inkjet recording material according to claim 1.
(3) Of the ink receiving layer (A) on the support, the amount of the binder in the ink receiving layer (A1) provided at a position close to the support is 30 to 60% by mass with respect to the inorganic fine particles. The method for producing an ink jet recording material according to claim 1 or 2, wherein the binder amount of the ink receiving layer (A2) provided at a more distant position is 10 to 25 mass% with respect to the inorganic fine particles.

  According to the present invention, it is possible to efficiently and stably produce an ink jet recording material free from coating failure in the ink receiving layer during simultaneous multilayer coating.

Hereinafter, the present invention will be described in detail.
As the polyethylene glycol nonylphenyl ether or polyethylene glycol octylphenyl ether used in the present invention, for example, Nonion NS-215 and Nonion HS-210 manufactured by NOF Corporation can be obtained and used in the present invention.

  In the inkjet material produced by the production method of the present invention, at least one of the two or more ink receiving layers is composed of the ink receiving layer (A) mainly composed of inorganic fine particles having an average secondary particle diameter of 500 nm or less, and at least one of them is Contains polyethylene glycol nonyl phenyl ether or polyethylene glycol octyl phenyl ether. Preferably, it is contained in the ink receiving layer (A2) located away from the support. The content is used in the range of 0.01 to 5% by mass with respect to the inorganic fine particles, and preferably 0.05 to 1% by mass.

  The production method of the present invention can also contain a surfactant other than polyethylene glycol nonylphenyl ether or polyethylene glycol octylphenyl ether. For example, cationic, anionic, nonionic, amphoteric, fluorine, and silicon surfactants can be used.

  Examples of the inorganic fine particles having an average secondary particle size of 500 nm or less used in the ink receiving layer in the invention include various known fine particles such as amorphous synthetic silica, alumina, alumina hydrate, calcium carbonate, magnesium carbonate, titanium dioxide and the like. In view of ink absorbability and productivity, amorphous synthetic silica, alumina or alumina hydrate is preferable.

  Amorphous synthetic silica can be roughly classified into wet method silica, gas phase method silica, and others depending on the production method. Wet method silica is further classified into precipitation method silica, gel method silica, and sol method silica according to the production method. Precipitated silica is produced by reacting sodium silicate and sulfuric acid under alkaline conditions, and the silica particles that have grown are agglomerated and settled, and are then commercialized through the steps of filtration, washing, drying, pulverization and classification. Precipitated silica is commercially available, for example, from Tosoh Silica Co., Ltd. as a nip seal and from Tokuyama Co., Ltd. as a Toxeal. Gel silica is produced by reacting sodium silicate and sulfuric acid under acidic conditions. During aging, the microparticles dissolve and reprecipitate so as to bind the other primary particles, so that the distinct primary particles disappear and form relatively hard aggregated particles having an internal void structure. For example, commercially available as a silo jet from Tosoh Silica Co., Ltd. as a nip gel, from Grace Japan Co., Ltd. as a syloid. The sol method silica is also called colloidal silica, which is obtained by heating and aging a silica sol obtained through metathesis of sodium silicate acid or through an ion exchange resin layer, and is commercially available, for example, as Snow Tech from Nissan Chemical Industries, Ltd. .

  Vapor phase silica is also called a dry method as opposed to a wet method, and is generally made by a flame hydrolysis method. Specifically, a method of making silicon tetrachloride by burning with hydrogen and oxygen is generally known, but methyltrichlorosilane and trichlorosilanes are also used alone or mixed with silicon tetrachloride instead of silicon tetrachloride. Can be used in the state. Vapor phase silica is commercially available as Aerosil from Nippon Aerosil Co., Ltd. and QS type from Tokuyama Co., Ltd.

The average primary particle diameter of the vapor phase silica used in the present invention is preferably 30 nm or less, and preferably 15 nm or less in order to obtain higher gloss. More preferably, an average primary particle diameter of 3 to 15 nm (particularly 3 to 10 nm) and a specific surface area by the BET method of 200 m ² / g or more (preferably 250 to 500 m ² / g) are used. The average primary particle diameter as used in the present invention is an average particle diameter obtained by measuring the diameter of a circle equal to the projected area of each of the 100 primary particles existing within a certain area by observation with an electron microscope. The BET method referred to in the present invention is one of the powder surface area measurement methods by the vapor phase adsorption method, and is a method for obtaining the total surface area, that is, the specific surface area of a 1 g sample from the adsorption isotherm. Usually, as the adsorbed gas, a large amount of nitrogen gas is used, and the most frequently used method is to measure the amount of adsorption from the pressure or volume change of the gas to be adsorbed. The most prominent expression for expressing the isotherm of multimolecular adsorption is the Brunauer, Emmett, and Teller formula, called the BET formula, which is widely used for determining the surface area. The adsorption amount is obtained based on the BET equation, and the surface area is obtained by multiplying the area occupied by one adsorbed molecule on the surface.

  Vapor phase silica is preferably dispersed in the presence of a cationic compound. The average secondary particle diameter of the dispersed vapor phase method silica is 500 nm or less, preferably 10 to 300 nm, more preferably 20 to 200 nm. As a dispersion method, premixed gas phase method silica and dispersion medium by ordinary propeller stirring, turbine type stirring, homomixer type stirring, etc., then, media mill such as ball mill, bead mill, sand grinder, high pressure homogenizer, ultra high pressure It is preferable to perform dispersion using a pressure disperser such as a homogenizer, an ultrasonic disperser, a thin film swirl disperser, or the like. The average secondary particle diameter as used in the present invention refers to an average value of the particle diameters of the dispersed aggregated particles observed by observing the ink receiving layer of the obtained recording material with an electron microscope. It is.

  In the present invention, wet process silica pulverized to an average secondary particle diameter of 500 nm or less can also be preferably used. The wet process silica particles used in the present invention preferably have an average primary particle diameter of 50 nm or less, more preferably 3 to 40 nm. It is preferable to use wet method silica fine particles obtained by finely pulverizing this in the presence of a cationic compound to an average secondary particle diameter of 500 nm or less, preferably about 20 to 200 nm.

  Since the wet process silica produced by a normal method has an average aggregate particle diameter of 1 μm or more, it is used after being finely pulverized. As a pulverization method, a wet dispersion method in which silica dispersed in an aqueous medium is mechanically pulverized can be preferably used. At this time, the increase in the initial viscosity of the dispersion is suppressed, high concentration dispersion is possible, and the pulverization / dispersion efficiency is increased so that the particles can be further pulverized. Therefore, the oil absorption is 210 ml / 100 g or less, the average aggregated particle diameter It is preferable to use precipitated silica of 5 μm or more. By using a high-concentration dispersion, the productivity of recording paper is also improved. The oil absorption is measured based on the description of JIS K-5101.

  A specific method for obtaining wet process silica fine particles having an average secondary particle diameter of 500 nm or less in the present invention will be described. First, silica particles and a cationic compound are mixed in a dispersion medium mainly composed of water, and at least one dispersion device such as a sawtooth blade type dispersion machine, a propeller blade type dispersion machine, or a rotor stator type dispersion machine is used. Used to obtain a preliminary dispersion. If necessary, an appropriate low boiling point solvent or the like may be added to the aqueous dispersion medium. The higher the solid content concentration of the silica pre-dispersion liquid, the more preferable, but when the concentration is too high, it becomes impossible to disperse, so the preferable range is 15 to 40% by mass, and more preferably 20 to 35% by mass. Next, the silica particles are pulverized by applying the silica pre-dispersion to mechanical means having a stronger shearing force to obtain a wet process silica fine particle dispersion having an average secondary particle size of 500 nm or less. As the mechanical means, a known method can be adopted, for example, a media mill such as a ball mill, a bead mill, a sand grinder, a high pressure homogenizer, a pressure disperser such as an ultra high pressure homogenizer, an ultrasonic disperser, a thin film swirl disperser, etc. Can be used.

  As the cationic compound used for the dispersion of the gas phase method silica and the wet method silica, a cationic polymer can be preferably used. As the cationic polymer, polyethyleneimine, polydiallylamine, polyallylamine, alkylamine polymer, JP-A-59-20696, JP-A-59-33176, JP-A-59-33177, JP-A-59-155088, Sho 60-11389, Sho 60-49990, Sho 60-83882, Sho 60-109894, Sho 62-198493, Sho 63-49478, Sho 63-115780, Shosho 63-280681, No. 1-40371, No. 6-234268, No. 7-125411, No. 10-193976, etc. The polymer having is preferably used. In particular, diallylamine derivatives are preferably used as the cationic polymer. In terms of dispersibility and dispersion viscosity, the molecular weight of these cationic polymers is preferably about 2,000 to 100,000, and particularly preferably about 2,000 to 30,000.

  As the alumina used in the present invention, γ-alumina which is a γ-type crystal of aluminum oxide is preferable, and among them, a δ group crystal is preferable. γ-alumina can make primary particles as small as about 10 nm. Usually, secondary particles of thousands to tens of thousands of nanometers are averaged by ultrasonic, high-pressure homogenizer, counter collision type jet crusher, etc. What grind | pulverized the particle diameter to 500 nm or less, Preferably about 20-300 nm can be used.

The alumina hydrate of the present invention 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 secondary particle diameter of the alumina hydrate used in the present invention is 500 nm or less, preferably 20 to 300 nm.

  The above-mentioned alumina and alumina hydrate used in the present invention are dispersed by a known dispersing agent such as acetic acid, lactic acid, formic acid, nitric acid, etc., such as an ultrasonic dispersing machine, a sand mill, a static mixer, and a high-pressure dispersing machine. A dispersion liquid dispersed using, for example, can also be used.

  In the present invention, at least one layer of the ink receiving layer (A) is an ink receiving layer mainly composed of inorganic fine particles having an average secondary particle diameter of 500 nm or less. The inclusion of inorganic fine particles having an average secondary particle diameter of 500 nm or less. It means that the amount is 50% by mass or more with respect to the total solid content of the ink receiving layer, preferably 60% by mass or more, and more preferably in the range of 65 to 90% by mass.

  In the present invention, the ink receiving layer preferably contains an organic binder in order to maintain the properties as a film. As the organic binder, various water-soluble polymers or polymer latexes are preferably used. Examples of the water-soluble polymer include polyvinyl alcohol, polyethylene glycol, starch, dextrin, carboxymethyl cellulose, polyvinyl pyrrolidone, polyacrylate ester and derivatives thereof, lime-treated gelatin, acid-treated gelatin, enzyme-treated gelatin, gelatin derivatives, such as Various gelatins such as gelatin reacted with dibasic acid anhydrides such as phthalic acid, maleic acid, and fumaric acid are used. Particularly preferred organic binders are completely or partially saponified polyvinyl alcohol or cation-modified polyvinyl alcohol. is there.

  Particularly preferred among the polyvinyl alcohols are those having a degree of saponification of 80% or more or those completely saponified. Polyvinyl alcohol having an average degree of polymerization of 500 to 5000 is 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.

  Examples of the polymer latex used as the organic binder include acrylic latexes such as alkyl ester, aryl group, aralkyl group, hydroxyalkyl group, and other acrylic or methacrylic esters, acrylonitrile, acrylamide, acrylic acid, and the like. Homopolymers or copolymers such as methacrylic acid, or the above monomers and styrene sulfonic acid, vinyl sulfonic acid, itaconic acid, maleic acid, fumaric acid, maleic anhydride, vinyl isocyanate, allyl isocyanate, vinyl methyl ether, vinyl acetate And copolymers with styrene, divinylbenzene and the like. As the olefin latex, a polymer comprising a copolymer of a vinyl monomer and a diolefin is preferable. As the vinyl monomer, styrene, acrylonitrile, methacrylonitrile, methyl acrylate, methyl methacrylate, vinyl acetate, or the like is preferably used. Examples include butadiene, isoprene, chloroprene and the like.

  In the present invention, the ink receiving layer preferably contains a hardener together with an organic binder. Specific examples of the hardener 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 Aziridines such as carbodiimide compounds as described in US Pat. No. 3,100,704, No. 3,091,537, epoxy compounds, halogen carboxaldehydes such as mucochloric acid, dioxane derivatives such as dihydroxydioxane, chromium alum, zirconium sulfate, boric acid and inorganic hardeners 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.

  The present invention can also be used in a method for producing an ink jet recording material using a resin having a keto group as a binder for inorganic fine particles. The resin binder having a keto group can be synthesized by a method of copolymerizing a monomer having a keto group and another monomer. Specific examples of the monomer having a keto group include acrolein, diacetone acrylamide, diacetone methacrylate, acetoacetoxyethyl methacrylate, 4-vinylacetoacetanilide, acetoacetylallylamide and the like. Further, a keto group may be introduced by a polymer reaction. For example, an acetoacetyl group can be introduced by a reaction of a hydroxy group or an amino group with a diketene. Specific examples of the resin binder having a keto group include acetoacetyl-modified polyvinyl alcohol, acetoacetyl-modified cellulose derivatives, acetoacetyl-modified starch, diacetone acrylamide-modified polyvinyl alcohol, and resin binders described in JP-A-10-157283. Can be mentioned.

  In the present invention, in addition to the resin binder having a keto group, another known resin binder may be used in combination. For example, cellulose derivatives such as carboxymethyl cellulose and hydroxypropyl cellulose, starch and various modified starches, gelatin and various modified gelatins, chitosan, carrageenan, casein, soy protein, polyvinyl alcohol, various modified polyvinyl alcohols, polyvinylpyrrolidone, polyacrylamide, etc. are required It can be used together depending on the situation. Furthermore, various latexes may be used in combination as the binder resin.

  Examples of the cation-modified polyvinyl alcohol include polyvinyl alcohol having a primary to tertiary amino group or a quaternary ammonium group in the main chain or side chain of polyvinyl alcohol as described in JP-A-61-110483. It is.

  In the present invention, examples of the crosslinking agent for the resin binder having a keto group include the following compounds.

(1) Polyamines Aliphatic polyamines;
Alkylene diamines (for example, ethylene diamine, propylene diamine, trimethylene diamine, tetramethylene diamine, hexamethylene diamine, etc.).
-Polyalkylene polyamines (for example, diethylenetriamine, iminobis (propylamine), bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, etc.).
-These alkyl or hydroxyalkyl substituents (for example, aminoethylethanolamine, methyliminobis (propylamine), etc.).
-Alicyclic or heterocyclic-containing aliphatic polyamines such as 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5,5] undecane.
-Aromatic ring-containing aliphatic amines (for example, xylylenediamine, tetrachloro-p-xylylenediamine, etc.).

C4-C15 alicyclic polyamines;
For example, 1,3-diaminocyclohexane, isophorone diamine, menthane diamine, 4,4′-methylene dicyclohexane diamine (hydrogenated methylene dianiline) and the like.

A C4-C15 heterocyclic polyamine;
For example, piperazine, N-aminoethylpiperazine, 1,4-diaminopiperazine and the like.

C6-C20 aromatic polyamines;
Unsubstituted aromatic polyamines (eg 1,2-, 1,3- and 1,4-phenylenediamine, 2,4'- and 4,4'-diphenylmethanediamine, polyphenylpolymethylenepolyamine, diaminodiphenylsulfone, benzidine , Thiodianiline, bis (3,4-diaminophenyl) sulfone, 2,6-diaminopyridine, m-aminobenzylamine, triphenylmethane-4,4 ′, 4 ″ -triamine, naphthylenediamine and the like.
Aromatic polyamines (eg 2,4- and 2,6-tolylenediamine, crude tolylenediamine, diethyltolylenediamine, 4,4′-) having a nucleus-substituted alkyl group (for example, a C1-C4 alkyl group) Diamino-3,3′-dimethyldiphenylmethane, 4,4′-bis (o-toluidine), dianisidine, diaminoditolylsulfone, 1,3-dimethyl-2,4-diaminobenzene, 1,3-diethyl-2, 4-diaminobenzene, 1,3-dimethyl-2,6-diaminobenzene, 1,4-diethyl-2,5-diaminobenzene, 1,4-diisopropyl-2,5-diaminobenzene, 1,4-dibutyl- 2,5-diaminobenzene, 2,4-diaminomesitylene, 1,3,5-triethyl-2,4-diaminobenzene, 1,3,5- Riisopropyl-2,4-diaminobenzene, 1-methyl-3,5-diethyl-2,4-diaminobenzene, 1-methyl-3,5-diethyl-2,6-diaminobenzene, 2,3-dimethyl- 1,4-diaminonaphthalene, 2,6-dimethyl-1,5-diaminonaphthalene, 2,6-diisopropyl-1,5-diaminonaphthalene, 2,6-dibutyl-1,5-diaminonaphthalene, 3,3 ′ , 5,5′-tetramethylbenzidine, 3,3 ′, 5,5′-tetraisopropylbenzidine, 3,3 ′, 5,5′-tetramethyl-4,4′-diaminodiphenylmethane, 3,3 ′, 5,5′-tetraethyl-4,4′-diaminodiphenylmethane, 3,3 ′, 5,5′-tetraisopropyl-4,4′-diaminodiphenylmethane, 3,3 ′, 5,5′- Trabutyl-4,4′-diaminodiphenylmethane, 3,5-diethyl-3′-methyl-2 ′, 4-diaminodiphenylmethane, 3,5-diisopropyl-3′-methyl-2 ′, 4-diaminodiphenylmethane, 3, 3'-diethyl-2,2'-diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 3,3 ', 5,5'-tetraethyl-4,4'-diaminobenzophenone, 3, 3 ', 5,5'-tetraisopropyl-4,4'-diaminobenzophenone, 3,3', 5,5'-tetraethyl-4,4'-diaminodiphenyl ether, 3,3 ', 5,5'-tetra Isopropyl-4,4'-diaminodiphenylsulfone).

Polyamide polyamines;
For example, low molecular weight (for example, molecular weight 200 to 5000) obtained by condensation of dicarboxylic acid (such as dimer acid) and excess (more than 2 moles per mole of acid) polyamines: (such as alkylenediamine, polyalkylenepolyamine, etc.) Polyamide polyamine).

Polyether polyamines;
For example, a hydride of a cyanoethylated product of a polyether polyol (such as a polyalkylene glycol) having a molecular weight of 100 to 5,000.

(2) Dicyandiamide derivative;
Dicyandiamide, dicyandiamide / formalin polycondensate, dicyandiamide / diethylenetriamine polycondensate, etc.

(3) a hydrazine compound;
Inorganic salts of hydrazine, monoalkyl hydrazine, hydrazine (eg, inorganic salts such as hydrochloric acid, sulfuric acid, nitric acid, nitrous acid, phosphoric acid, thiocyanic acid, carbonic acid), organic salts of hydrazine (eg, organic salts such as formic acid, oxalic acid, etc.) ).

(4) polyhydrazide compounds (dihydrazide, trihydrazide);
Carbohydrazide, succinic acid dihydrazide, adipic acid dihydrazide, citric acid trihydrazide, sebacic acid dihydrazide, isophthalic acid dihydrazide, terephthalic acid dihydrazide and the like.

(5) Aldehydes;
Monoaldehyde such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, crotonaldehyde, benzaldehyde, glyoxal, malondialdehyde, succindialdehyde, glutardialdehyde, maleindialdehyde, 1,8-octane dial, phthalaldehyde, isophthalaldehyde , Terephthalaldehyde, dialdehydes such as aldehyde-terminated PVA, side chain aldehyde-containing copolymer obtained by saponifying arylidene acetate vinyl diacetate copolymer, dialdehyde starch, polyacrolein and the like.

(6) methylol compounds;
Methylolphosphine, dimethylolurea, dimethylolmelamine, trimethylolmelamine, urea resin initial polymer, melamine resin initial polymer, and the like.

(7) an activated vinyl compound;
Divinyl sulfone compounds, β-hydroxyethyl sulfone compounds, and the like.

(8) epoxy compound;
Epichlorohydrin, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin di or triglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, diglycidyl aniline, diglycidyl amine, polyepoxy compounds, etc. .

(9) Isocyanate compounds;
Tolylene diisocyanate, hydrogenated tolylene diisocyanate, trimethylolpropane-tolylene diisocyanate adduct, triphenylmethane triisocyanate, methylenebis-4-phenylmethane triisocyanate, isophorone diisocyanate, and their ketoxime block or phenol block, poly An isocyanate etc. are mentioned.

(10) phenolic compounds;
Phenol resin initial condensate, resorcinol resin, etc.

(11) a polyvalent metal salt;
Zirconium salt (zirconium nitrate, basic zirconium carbonate, zirconium acetate, zirconium sulfate, zirconium oxychloride, zirconium chloride, zirconium zirconium chloride, zirconium carbonate, zirconium carbonate / ammonium, zirconium carbonate / potassium, zirconium fluoride compound, etc.).
-Titanium salts (titanium tetrachloride, titanium lactate, tetraisopropyl titanate, etc.).
-Aluminum salt (aluminum chloride, aluminum sulfate, aluminum lactate, etc.).
・ Calcium salts (calcium chloride, calcium sulfate, calcium acetate, calcium propionate, etc.).
-Magnesium salts (magnesium chloride, magnesium sulfate, etc.).
・ Zinc salts (zinc chloride, zinc sulfate, zinc acetate, etc.).

  As a structure of the inkjet material which can utilize the manufacturing method of this invention, although the structure described in the following gazettes can be mentioned, for example, it is not limited to these in particular.

  The upper layer described in JP-A-2001-1630 is an ink receiving layer containing vapor-phase method silica and vapor-phase method alumina, and the lower layer is a water-soluble polymer layer.

  The structure described in JP-A No. 2003-159862 is a configuration in which the upper layer is a colloidal silica layer and the lower layer is an ink receiving layer containing vapor phase method silica.

  The structure described in JP-A-2004-237704, wherein the upper layer is a wet silica layer having an average particle diameter of 170 nm and the lower layer is a wet silica layer having an average particle diameter of 200 nm

  An upper layer described in JP-A-2004-335120 is an upper coating layer containing a hardener, and a lower layer is an ink receiving layer containing a vapor phase silica and a binder containing a keto group.

  In particular, the production method of the present invention preferably has a structure described in JP-A No. 2004-25836 in which an adhesion promoting layer containing a binder and silica is provided between the support and the ink receiving layer. This will be described below.

  In the ink receiving layer (A) of the ink jet recording material, the organic binder is preferably used in the range of 30 to 60% by mass, particularly preferably 40 to 50% by mass in the ink receiving layer (A1) with respect to the inorganic fine particles. Range. By setting it in the above range, the adhesive strength between the ink receiving layer and the support can be obtained. The ink receiving layer (A2) is preferably used in the range of 10 to 25% by mass. By setting it in the above range, high ink absorbability can be obtained.

  The ink receiving layer (A2) preferably contains a cationic compound together with inorganic fine particles. By containing a cationic compound in the ink receiving layer, cracking of the ink receiving layer can be prevented and water resistance can be improved. Further, by providing a layer containing colloidal silica and a cationic compound on the ink receiving layer containing the cationic compound, the scratch resistance, water resistance and ink absorbability are further improved. Aggregation at the interface is prevented, and as a result, coating unevenness and gloss unevenness can be improved. When alumina or alumina hydrate is contained as the inorganic fine particles of the ink receiving layer, sufficient cracking and water resistance can be obtained without necessarily using a cationic compound.

  As the cationic compound used in the present invention, a cationic polymer or a water-soluble polyvalent metal compound is preferably used. These cationic compounds and water-soluble polyvalent metal compounds can be used alone or in combination.

  Examples of the cationic polymer include water-soluble cationic polymers having a quaternary ammonium group, a phosphonium group, or an acid adduct of a primary to tertiary amine. For example, polyethylenimine, polydialkyldiallylamine, polyallylamine, allylamine epichlorohydrin polycondensate, JP-A-59-20696, 59-33176, 59-33177, 59-155888, 60-11389 60-49990, 60-83882, 60-109894, 62-198493, 63-49478, 63-115780, 63-280681, JP-A-1-40371, Examples thereof include cationic polymers described in JP-A-6-234268, JP-A-7-125411, JP-A-10-193976, and the like. The weight average molecular weight of the cationic polymer used in the present invention is preferably 100,000 or less, more preferably 50,000 or less, and the lower limit is about 2,000.

  The use amount of these cationic polymers is preferably in the range of 1 to 10% by mass with respect to the inorganic fine particles.

  Examples of the polyvalent metal in the water-soluble polyvalent metal compound include calcium, barium, manganese, copper, cobalt, nickel, aluminum, iron, zinc, zirconium, titanium, chromium, magnesium, tungsten, and molybdenum. It can be used as a water-soluble metal salt. 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 products, zinc sulfate, zirconium acetate, zirconium nitrate, basic zirconium carbonate, zirconium hydroxide, zirconium carbonate / ammonium, zirconium carbonate / potassium, zirconium sulfate, zirconium fluoride, zirconium chloride, zirconium chloride octahydrate, oxychloride Zirconium, hydroxy zirconium chloride, titanium chloride, titanium sulfate, chromium acetate, chromium sulfate, magnesium sulfate, magnesium chloride hexahydrate, magnesium citrate nonahydrate, sodium phosphotungstate, sodium tungsten citrate, 12 tungstophosphoric acid n hydrate, 12 tungstosilicic acid 26 hydrate, molybdenum chloride, 12 molybdophosphoric acid n hydrate, and the like. Among these, aluminum or a water-soluble salt of a periodic table group IVa element (zirconium, titanium) is preferable. In the present invention, water-soluble means that 1% by mass or more dissolves in water at room temperature and normal pressure.

As a water-soluble aluminum compound other than the above, a basic polyaluminum hydroxide compound is preferably used. The main component of this compound is represented by the following general formula 1, 2 or 3, for example, [Al ₆ (OH) ₁₅ ] ³⁺ , [Al ₈ (OH) ₂₀ ] ⁴⁺ , [Al ₁₃ (OH) ₃₄ It is a water-soluble polyaluminum hydroxide containing a basic, high-molecular polynuclear condensed ion such as ⁵⁺ , [Al ₂₁ (OH) ₆₀ ] ³⁺ , etc. stably.

[Al ₂ (OH) _n Cl _6-n ] _m
[Al (OH) ₃ ] _n AlCl ₃ ..General formula 2
Al _n (OH) _m Cl _(3n-m) 0 <m <3n General 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. These basic polyaluminum hydroxide compounds are also described in Japanese Patent Publication Nos. 3-24907 and 3-42591.

In the present invention, the content of the water-soluble polyvalent metal compound in the ink receiving layer (A2) is 0.1 to 10 g / m ² , preferably 0.2 to 5 g / m ² .

  Various ink droplets can be contained in the ink receiving layer (A2) 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.

  The ink receiving layer (A2) further includes 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, a fluorescent whitening agent, Various known additives such as a viscosity stabilizer and a pH adjuster can also be added.

The coating amount of the ink receiving layer (A1) is a 0.6~8g / m ² in terms of solid content, preferably 1 to 5 g / m ^2, more preferably of 1.5~3.5g / m ² It is a range. The coating amount of the ink receiving layer (A2) is 5 to 40 g / m ² in terms of solid content, preferably 10 to 35 g / m ² , and more preferably 15 to 30 g / m ² .

  If the ink receiving layer (A) has a receiving layer (A1) closest to the support of the present invention in the lowermost layer and a receiving layer (A2) farthest from the support of the present invention in the uppermost layer, the ink receiving layer (A) An ink absorbing layer, an ink fixing layer, an intermediate layer, and the like may be provided. However, it is important that other properties such as adhesive strength and ink absorbency are not adversely affected.

  In the present invention, a backing layer may be provided on the surface opposite to the surface on which the ink receiving layer (A) is provided. The backcoat layer may further contain pigments, binders, antistatic agents, hardeners, surfactants, and the like for the purpose of antistatic and improved transportability.

  Next, a support for an ink jet recording material using the production method of the present invention will be described. A water resistant support is preferred as the support. As the water resistant support, a transparent support or an opaque support can be used. As the transparent support, any conventionally known one can be used, for example, a polyester resin, diacetate resin, triacetate resin, acrylic resin, polycarbonate resin, polyvinyl chloride, polyimide resin, cellophane, celluloid film or plate, and A glass plate etc. are mentioned, Among these, the film which consists of a polyethylene terephthalate is used most preferably. Such a transparent water-resistant support preferably has a thickness of about 10 to 200 μm.

  As the opaque water-resistant support, any conventionally known materials such as synthetic paper, resin-coated paper, pigmented opaque film, and foamed film can be used. Resin-coated paper and various films are more preferable in terms of gloss and smoothness, but a film made of resin-coated paper similar to a photographic support and polyethylene terephthalate with a high whiteness and strength content from a feeling of touch and luxury. Further preferably used.

  The base paper constituting the resin-coated paper as the waterproof support is not particularly limited, and generally used paper can be used. For example, a smooth base paper used for a photographic support is more 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 as a support 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. 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 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.

An undercoat layer mainly composed of a natural resin or a synthetic resin is provided on the water-resistant support. The coating amount of the undercoat layer is 2 g / m ² or less, preferably 1.5 g / m ² or less.

  In the present invention, when two or more layers are applied simultaneously, a coating device such as a slide bead coater or a curtain coater can be used.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, the content of this invention is not restricted to an Example. In the following examples, “part” and “%” are all mass converted values.

<< Creation of recording sheet 1 >>
<Water resistant support>
An undercoat layer having the following composition was provided on one side of a polyethylene terephthalate film having a thickness of 100 μm (haze value 1%) so as to have a coating amount of 1.5 g / m ² and subjected to a high-frequency corona discharge treatment.

<Composition of undercoat layer>
Latex (weight average molecular weight 42000) of vinylidene chloride: methyl acrylate: acrylic acid (90: 9: 1, mass%).

<Application of ink receiving layer (a)>
On the surface provided with the undercoat layer of the support, the following ink receiving layer (a1) coating liquid is used as a lower layer so that the solid content coating amount is 3 g / m ^2, and the following ink receiving layer (a2) coating liquid is used. The recording sheet 1 was obtained by simultaneously coating and drying with a slide bead coater so that the solid content was 20 g / m ² .

<Ink-receiving layer (a1) coating solution>
Concentration of 100 parts of vapor phase silica having an average primary particle size of 7 nm and a specific surface area of 300 m ² / g by BET method, and 4 parts of dimethyl diallyl ammonium chloride homopolymer (Charol DC902P manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) Is dispersed in water so as to be 20% by mass, and is atomized using a high-pressure homogenizer (manufactured by APV Gourin Co., Ltd., 15MR-8TA type), and a gas phase method silica dispersion having an average secondary particle size of 150 nm is obtained. Produced. To this dispersion, 6 parts of boric acid, 45 parts of polyvinyl alcohol (saponification degree 88%, average polymerization degree 3500), and 0.2 parts of polyethylene glycol nonylphenyl ether of the present invention are sequentially added to 100 parts of vapor phase silica. Finally, water was added to a concentration of 10% by mass to obtain an ink receiving layer (a1) coating solution.

<Ink-receiving layer (a2) coating solution>
3 parts of boric acid and 22 parts of polyvinyl alcohol (saponification degree 88%, average polymerization degree 3500) are sequentially added to 100 parts of vapor phase silica used in the ink receiving layer (a1) coating solution, and finally 12 masses. Water was added so that the concentration was%, and the ink receiving layer (a2) coating solution was obtained.

<< Creation of recording sheet 2 >>
0.2 part of the polyethylene glycol nonylphenyl ether of the present invention is extracted from the ink receiving layer (a1) of the recording sheet 1 and 0.2 part of the polyethylene glycol nonylphenyl ether of the present invention is added to the ink receiving layer (a2). Sheet 2 was obtained.

<< Creation of recording sheet 3 >>
The recording sheet 3 was obtained by removing 0.2 part of the polyethylene glycol nonylphenyl ether of the present invention from the ink receiving layer (a1) of the recording sheet 1 and adding 0.2 part of the polyethylene glycol octylphenyl ether of the present invention.

<< Creation of recording sheet 4 >>
0.2 part of the polyethylene glycol octylphenyl ether of the present invention is extracted from the ink receiving layer (a1) of the recording sheet 4 and 0.2 part of the polyethylene glycol octylphenyl ether of the present invention is added to the ink receiving layer (a2). Sheet 4 was obtained.

<< Creation of recording sheet 5 >>
A recording sheet 5 was obtained in the same manner except that the polyethylene glycol octylphenyl ether of the present invention was removed from the recording sheet 4.

<< Creation of recording sheet 6 >>
<Application of ink receiving layer (b)>
On the support, the following water-soluble polymer layer (b1) coating solution was used as the lower layer, and the ink receiving layer (b2) coating solution was used as the upper layer, and simultaneous multilayer coating was performed with a slide bead coater to obtain a recording sheet 7. The coating amount of the vapor phase silica of the ink receiving layer (b2) was 7 g / m ² in terms of solid content. The coating amount of the water-soluble polymer layer (b1) was 10 g / m ² in terms of solid content.

<Water-soluble polymer layer (b1) coating solution>
Polyvinyl alcohol (saponification degree 83%, average polymerization degree 1800, cationic modification) 7 g / m ² , polyvinyl pyrrolidone 3 g / m ² , surfactant (trade name: AM-2150, manufactured by Nippon Surfactant) 10 mg / m ² , book 0.2 part of polyethylene glycol nonylphenyl ether of the invention was sequentially added to obtain a water-soluble polymer layer (b1) coating solution.

<Ink-receiving layer (b2) coating solution>
Gas phase method silica (average primary particle diameter 7 mm, specific surface area 300 m ² / g) 100 parts, polyvinyl alcohol (PVA: saponification degree 88%, average polymerization degree 3500) 20 parts, cationic polymer (trade name: Polyfix P601) , Showa Polymer Co., Ltd., modified polyamine 10 parts, surfactant (trade name: AM-2150, manufactured by Nippon Surfactant) 1 part, hardener (glyoxal) vs. PVA 5 weight, gas phase method alumina fine particles (product) Name: Aluminum oxide C, 10 parts by Degussa Huls, average primary particle size of 13 nm) were sequentially added to form an ink receiving layer (b2) coating solution.

<< Creation of recording sheet 7 >>
0.2 part of polyethylene glycol nonylphenyl ether of the present invention is extracted from the water-soluble polymer layer (b1) of the recording sheet 6 and 0.2 part of polyethylene glycol nonylphenyl ether of the present invention is added to the ink receiving layer (b2). A recording sheet 7 was obtained.

<< Creation of recording sheet 8 >>
From the water-soluble polymer layer (b1) of the recording sheet 6, 0.2 part of the polyethylene glycol nonyl phenyl ether of the present invention was extracted, and 0.2 part of the polyethylene glycol octyl phenyl ether of the present invention was added to obtain a recording sheet 8.

<< Creation of recording sheet 9 >>
0.2 part of polyethylene glycol octylphenyl ether of the present invention is extracted from the water-soluble polymer layer (b1) of the recording sheet 8, and 0.2 part of polyethylene glycol octylphenyl ether of the present invention is added to the ink receiving layer (b2). A recording sheet 9 was obtained.

<< Creation of recording sheet 10 >>
A recording sheet 10 was obtained in the same manner except that the polyethylene glycol octylphenyl ether of the present invention was removed from the recording sheet 8.

<< Creation of recording sheet 11 >>
<Application of ink receiving layer (c)>
On the support, the following ink-receiving layer (c1) coating solution was used as the lower layer, and the colloidal silica layer (c2) coating solution was used as the upper layer, and simultaneous multilayer coating was performed with a slide beat coater to obtain a recording sheet 13. The solid phase coating amount of the vapor phase method silica in the ink receiving layer (c1) was adjusted to 18 g / m ² . The solid content in the colloidal silica layer (c2) coating solution was adjusted to 1 g / m ² .

<Ink-receiving layer (c1) coating solution>
Gas phase method silica (average primary particle size 7 nm, specific surface area by BET method 300 m ² / g) 100 parts, boric acid 3 parts, polyvinyl alcohol (saponification degree 88%, average polymerization degree 3500) 22 parts, basic polyhydration Aluminum (trade name: Purachem WT, manufactured by Riken Green Co., Ltd.) 3 parts, surfactant (betaine; manufactured by Nippon Surfactant, Swanol AM) 0.3 part, polyethylene glycol nonylphenyl ether of the present invention 0.2 part Were sequentially added to prepare an ink receiving layer (c1) coating solution.

<Colloidal silica layer (c2) coating solution>
Colloidal silica (anionic spherical colloidal silica; Snowtex ST-OL40 average primary particle size 40-50 nm, manufactured by Nissan Chemical Industries, Ltd.) 100 parts, (anionic spherical colloidal silica; Nissan Chemical Industries, Ltd.) Snowtex ST-OL40, cationic polymer; 1 part of Polyfix 601 (Showa Polymer Co., Ltd., specially modified polyamine), 4 parts of polyvinyl alcohol (saponification degree 88%, average polymerization degree 3500), surfactant ( Betaine type; 0.3 part of Nippon Surfactant, Swanol AM) was sequentially added, and the pH of the coating solution was adjusted to 3.5 to obtain a colloidal silica layer (c2) coating solution.

<< Creation of recording sheet 12 >>
Recording sheet 11 0.2 part of polyethylene glycol nonylphenyl ether of the present invention is extracted from the ink receiving layer (c1), and 0.2 part of polyethylene glycol nonylphenyl ether of the present invention is added to the colloidal silica layer (c2). 12 was obtained.

<< Creation of recording sheet 13 >>
The recording sheet 13 was obtained by removing 0.2 part of the polyethylene glycol nonylphenyl ether of the present invention from the ink receiving layer (c1) of the recording sheet 11 and adding 0.2 part of the polyethylene glycol octylphenyl ether of the present invention.

<< Creation of recording sheet 14 >>
0.2 part of the polyethylene glycol octylphenyl ether of the present invention is extracted from the ink receiving layer (c1) of the recording sheet 13, and 0.2 part of the polyethylene glycol octylphenyl ether of the present invention is added to the colloidal silica layer (c2). Sheet 14 was obtained.

<< Creation of recording sheet 15 >>
A recording sheet 15 was obtained in the same manner except that the polyethylene glycol octylphenyl ether of the present invention was removed from the recording sheet 13.

<< Creation of recording sheet 16 >>
<Application of ink receiving layer (d)>
On the support, a recording sheet 16 was obtained by simultaneous multilayer coating with the ink-receiving layer (d1) coating solution as the lower layer and the overcoat layer (d2) coating solution as the upper layer. The coating amount of the ink receiving layer (d1) was set so that the solid content concentration was 25% by mass, and the coating amount of the topcoat layer (d2) was 0.2 g / m ^{2 in} terms of adipic acid dihydrazide.

<Ink-receiving layer (d1) coating solution>
Gas phase method silica (average primary particle diameter 7 nm, specific surface area 300 m ² / g) 100 parts, acetoacetyl-modified polyvinyl alcohol (acetoacetylation degree 3%, saponification degree 98%, average polymerization degree 2350) 20 parts, nonionic Surfactant (polyoxyethylene alkyl ether) 0.3 part and 0.2 parts of polyethylene glycol nonylphenyl ether of the present invention were sequentially added, adjusted with water so that the solid content concentration would be 9% by mass, and ink reception The layer (d1) coating solution was used.

<Topcoat layer (d2) coating solution>
2 parts of adipic acid dihydrazide, 0.1 part of nonionic surfactant (polyoxyethylene alkyl ether) and 98 parts of water were sequentially added to obtain a coating solution for the topcoat layer (d2).

<< Creation of recording sheet 17 >>
0.2 part of polyethylene glycol nonylphenyl ether of the present invention is extracted from the ink receiving layer (d1) of the recording sheet 16, and 0.2 part of polyethylene glycol nonylphenyl ether of the present invention is added to the overcoat layer (d2). 17 was obtained.

<< Creation of recording sheet 18 >>
From the ink receiving layer (d1) of the recording sheet 16, 0.2 part of the polyethylene glycol nonylphenyl ether of the present invention was extracted, and 0.2 part of the polyethylene glycol octyl phenyl ether of the present invention was added to obtain a recording sheet 18.

<< Creation of recording sheet 19 >>
0.2 parts of polyethylene glycol octylphenyl ether of the present invention is extracted from the ink receiving layer (d1) of the recording sheet 18 and 0.2 part of polyethylene glycol octylphenyl ether of the present invention is added to the overcoat layer (d2). 19 was obtained.

<< Creation of recording sheet 20 >>
A recording sheet 20 was obtained in the same manner except that the polyethylene glycol octylphenyl ether of the present invention was removed from the recording sheet 18.

<< Creation of recording sheet 21 >>
<Application of ink receiving layer (e)>
On the support, the following wet silica layer (e1) coating solution is used as the lower layer, and the wet silica layer (e2) coating solution is used as the upper layer, so that the coating amount is 8 g / m ^{2 for} each layer. The recording sheet 21 was obtained by performing simultaneous layer stacking.

<Wet silica layer (e1) coating solution>
Mass% of wet process silica (Tokuyama Co., Ltd., T-32, average particle diameter after dispersion 200 nm) is 6 times solid mass% of polyvinyl alcohol solution (10 mass%, Kuraray Co., Ltd .: PVA235). Then, 0.2 part of polyethylene glycol nonylphenyl ether of the present invention was added to prepare a coating solution for wet silica layer (e1).

<Wet silica layer (e2) coating solution>
Mass% of wet process silica (Tokuyama Co., Ltd., T-32, average particle diameter after dispersion of 170 nm) is 6 times the solid content mass% of polyvinyl alcohol solution (10 mass%, Kuraray Co., Ltd .: PVA235). It mixed so that it might become a wet silica layer (e2) coating liquid.

<< Creation of recording sheet 22 >>
0.2 parts of the polyethylene glycol nonylphenyl ether of the present invention is extracted from the recording sheet 21 wet silica layer (e1), and 0.2 part of the polyethylene glycol nonylphenyl ether of the present invention is added to the wet silica layer (e2). 22 was obtained.

<< Creation of recording sheet 23 >>
From the wet silica layer (e1) of the recording sheet 21, 0.2 part of the polyethylene glycol nonylphenyl ether of the present invention was extracted, and 0.2 part of the polyethylene glycol octyl phenyl ether of the present invention was added to obtain a recording sheet 23.

<< Creation of recording sheet 24 >>
Further, 0.2 part of the polyethylene glycol octylphenyl ether of the present invention was added to the wet silica layer (e2) to the wet silica layer (e1) of the recording sheet 23 to obtain a recording sheet 24.

<< Creation of recording sheet 25 >>
A recording sheet 25 was obtained in the same manner except that the polyethylene glycol octylphenyl ether of the present invention was removed from the recording sheet 23.

<< Creation of recording sheet 26 >>
<Application of ink receiving layer (f)>
On the support, the uppermost third layer (f3) is formed so that the first layer (f1) coating solution close to the support has a thickness of 50 μm and the second layer (f2) coating solution thereon has a thickness of 100 μm. ) The coating solution was simultaneously applied to a thickness of 50 μm to obtain a recording sheet 26.

  (Preparation of Silica Dispersion 1) 125 kg of vapor phase silica (Nippon Aerosil Kogyo Co., Ltd .: A300) having an average primary particle size of about 0.007 μm was jet stream inductor manufactured by Mitamura Riken Kogyo Co., Ltd. Using a mixer TDS, the mixture was sucked and dispersed in 620 L of pure water adjusted to pH = 2.5 with nitric acid at room temperature, and then the whole amount was finished to 69.4 L with pure water.

  (Preparation of Silica Dispersion 2) To an aqueous solution containing 1.29 kg of cationic polymer, 4.2 L of ethanol, and 1.5 L of n-propanol 1, 69.4 L of silica dispersion 1 was added with stirring. 7.0 L of an aqueous solution containing 260 g of acid and 230 g of borax was added. This mixed solution was dispersed, and the whole amount was finished to 97 L with pure water.

  (Preparation of fluorescent brightening agent dispersion) 400 g of oil-soluble fluorescent brightening agent UVITEX-OB manufactured by Ciba Geigy Co., Ltd. was dissolved in 9000 g of diisodecyl phthalate and 12 L of ethyl acetate and dissolved in 3500 g of acid-treated gelatin, cationic polymer, saponin 50 The mixture was added to and mixed with 65 L of an aqueous solution containing 6,000 ml of a% aqueous solution, emulsified and dispersed with a high-pressure homogenizer manufactured by Sanwa Kogyo Co., Ltd., and ethyl acetate was removed under reduced pressure.

  (Preparation of Titanium Oxide Dispersion) 20 kg of titanium oxide having an average particle size of about 0.25 μm (Ishihara Sangyo: W-10), 150 g of sodium tripolyphosphate with pH = 7.5, polyvinyl alcohol (manufactured by Kuraray Co., Ltd .: PVA235) 500g, cationic polymer 150g and Sannobuco Co., Ltd. Antifoaming agent · SN381 10L added to 90L of aqueous solution, dispersed with high pressure homogenizer (Sanwa Kogyo Co., Ltd.), then finished to 100L, uniform titanium oxide dispersion A liquid was obtained.

  (Preparation of matting agent dispersion) 156 g of methacrylic acid ester matting agent MX-1500H manufactured by Soken Kagaku Co., Ltd. is added to 7 L of pure water containing 3 g of PVA235, and dispersed with a high-speed homogenizer, and the total amount is 7.8 L. Finished.

<First layer (f1) coating solution>
Silica dispersion 2 600 ml, polyvinyl alcohol (Kuraray Industrial Co., Ltd .: PVA203) 10% aqueous solution 0.6 ml, polyvinyl alcohol (Kuraray Kogyo Co., Ltd .: PVA235) 5% aqueous solution 260 ml, fluorescent brightener dispersion 25 ml, 33 ml of titanium oxide dispersion, manufactured by Daiichi Kogyo Co., Ltd .: 18 ml of Latex Imulsion AE-803 and 0.2 part of polyethylene glycol nonylphenyl ether of the present invention were added and finished to 1000 ml with pure water.

<Second layer (f2) coating solution>
Silica dispersion 2 640 ml, polyvinyl alcohol (Kuraray Industrial Co., Ltd .: PVA203) 10% aqueous solution 0.6 ml, polyvinyl alcohol (Kuraray Kogyo Co., Ltd .: PVA235) 5% aqueous solution 260 ml, fluorescent whitening agent dispersion 35 ml The total amount was made up to 1000 ml with pure water.

<Third layer (f3) coating solution>
Silica dispersion 650 ml, polyvinyl alcohol (Kuraray Industrial Co., Ltd .: PVA203) 10% aqueous solution 0.6 ml, polyvinyl alcohol (Kuraray Kogyo Co., Ltd .: PVA235) 5% aqueous solution 270 ml, saponin 50% aqueous solution 4 ml, mat agent dispersion 10 ml of the liquid was added, and the whole amount was finished to 1000 ml with pure water.

<< Creation of recording sheet 27 >>
0.2 part of polyethylene glycol nonylphenyl ether of the present invention is extracted from the first layer (f1) of the recording sheet 26, 0.2 part of polyethylene glycol nonyl phenyl ether of the present invention is added to the second layer (f2), and the recording sheet 27 was obtained.

<< Creation of recording sheet 28 >>
0.2 parts of the polyethylene glycol nonylphenyl ether of the present invention is extracted from the first layer (f1) of the recording sheet 26, and 0.2 part of the polyethylene glycol nonylphenyl ether of the present invention is added to the third layer (f3). 28 was obtained.

<< Creation of recording sheet 29 >>
0.2 parts of polyethylene glycol nonylphenyl ether of the present invention is extracted from the first layer (f1) of the recording sheet 26, 0.2 parts of polyethylene glycol octyl phenyl ether of the present invention is added to the second layer (f2), and recording is performed. Sheet 29 was obtained.

<< Creation of recording sheet 30 >>
0.2 parts of polyethylene glycol octylphenyl ether of the present invention is extracted from the first layer (f1) of the recording sheet 29, 0.2 parts of polyethylene glycol octylphenyl ether of the present invention is added to the second layer (f2), and recording is performed. Sheet 31 was obtained.

<< Creation of recording sheet 31 >>
0.2 parts of polyethylene glycol octylphenyl ether of the present invention is extracted from the first layer (f1) of the recording sheet 29, 0.2 parts of polyethylene glycol octylphenyl ether of the present invention is added to the third layer (f3), and recording is performed. Sheet 31 was obtained.

<< Creation of recording sheet 32 >>
A recording sheet 32 was obtained in the same manner except that the polyethylene glycol octylphenyl ether of the present invention was removed from the recording sheet 29.
The ink jet recording material produced as described above was evaluated as follows. The results are shown in Table 1.

<Applicable surface failure>
Cracks and repellency on the coated surface of the inkjet recording material were visually evaluated.
A: No coating failure occurred.
○: There was a slight application failure, but there was virtually no problem.
Δ: Application failure occurs but there is no practical problem.
×: Application failure occurred and cannot be used.

<Ink absorbability>
Color (C, M, Y) characters were printed on the ink receiving layer of the ink jet recording material with a Seiko Epson ink jet printer, PM-880C, under conditions of 23 ° C. and 50% RH, and ink bleeding was evaluated.
○: There is no problem in recognizing characters without bleeding.
Δ: Recognizable for a while, although there is some character blurring. However, there are practical problems.
X: Characters are greatly blurred and cannot be recognized.

  The added product of the present invention (N) in the table is polyethylene glycol nonyl phenyl ether, and (O) is polyethylene glycol octyl phenyl ether.

<< Creation of recording sheet 33 >>
0.2 part of the polyethylene glycol nonylphenyl ether of the present invention is extracted from the ink receiving layer (a2) of the recording sheet 2, and an anionic fluorine-based surfactant manufactured by Dainippon Ink & Chemicals, Inc. is used as the ink receiving layer (a2). The recording sheet 33 was obtained by adding 0.2 part of MegaFuck F-120.

<< Creation of recording sheet 34 >>
0.2 part of the polyethylene glycol nonylphenyl ether of the present invention is removed from the ink receiving layer (a2) of the recording sheet 2 and the nonionic fluorine-based surfactant manufactured by Dainippon Ink & Chemicals, Inc. is used as the ink receiving layer (a2). The recording sheet 34 was obtained by adding 0.2 part of MegaFuck F-144D.

<< Creation of recording sheet 35 >>
0.2 parts of the polyethylene glycol nonylphenyl ether of the present invention is extracted from the ink receiving layer (a2) of the recording sheet 2, and a cationic fluorine-based surfactant manufactured by Dainippon Ink & Chemicals, Inc. is used as the ink receiving layer (a2). The recording sheet 35 was obtained by adding 0.2 part of MegaFuck F-150.

<< Creation of recording sheet 36 >>
0.2 parts of the polyethylene glycol nonylphenyl ether of the present invention is extracted from the ink receiving layer (a2) of the recording sheet 2 and the amphofluoric surfactant surfactant 400S manufactured by Neos Co., Ltd. is used as the ink receiving layer (a2). Two parts were added to obtain a recording sheet 36.

<< Creation of recording sheet 37 >>
0.2 part of the polyethylene glycol nonylphenyl ether of the present invention is extracted from the ink receiving layer (a2) of the recording sheet 2, and the nonionic surfactant Emulgen 109 0.2 manufactured by Kao Corporation is added to the ink receiving layer (a2). The recording sheet 37 was obtained.

<Creation of recording sheet 38>
0.2 parts of the polyethylene glycol nonylphenyl ether of the present invention was extracted from the ink receiving layer (a2) of the recording sheet 2, and 0.2 part of saponin was added to the ink receiving layer (a2) to obtain a recording sheet 38.

<Creation of recording sheet 39>
0.2 parts of the polyethylene glycol nonylphenyl ether of the present invention is extracted from the ink receiving layer (a2) of the recording sheet 2, and the alkyl betaine surfactant LD-350 manufactured by Sanyo Chemical Co., Ltd. is used as the ink receiving layer (a2). 2 parts were added to obtain a recording sheet 39.

<< Creation of recording sheet 40 >>
0.2 part of the polyethylene glycol nonylphenyl ether of the present invention is removed from the ink receiving layer (a2) of the recording sheet 2 and 0.2 part of Nippon Oil & Fats Co., Ltd. Stahome D is added to the ink receiving layer (a2). A sheet 40 was obtained.

  From the above results, according to the present invention, in the method for producing an ink jet recording material excellent in ink absorbability, it was possible to efficiently and stably produce an ink jet recording material having no coating failure in the ink receiving layer.

Claims (3)

  In the method for producing an ink jet recording material, wherein at least one layer of the two or more ink receiving layers (A) is an average secondary particle, wherein an ink jet recording material having at least two ink receiving layers on a support is simultaneously applied. An ink receiving layer mainly composed of inorganic fine particles having a diameter of 500 nm or less, wherein at least one of the two or more ink receiving layers contains polyethylene glycol nonyl phenyl ether or polyethylene glycol octyl phenyl ether. A method for producing an inkjet recording material.   Of the two or more ink receiving layers (A), the ink receiving layer (A2) provided at a position away from the support contains polyethylene glycol nonyl phenyl ether or polyethylene glycol octyl phenyl ether. The method for producing an ink jet recording material according to claim 1.   Of the ink receiving layer (A) on the support, the binder amount of the ink receiving layer (A1) provided at a position close to the support is 30 to 60% by mass with respect to the inorganic fine particles, and is separated by the support. The method for producing an ink jet recording material according to claim 1 or 2, wherein the binder amount of the ink receiving layer (A2) provided at the position is 10 to 25 mass% with respect to the inorganic fine particles.