JP2003025723A - Ink jet acceptive layer resin composition for pigment dispersed oily ink, material to be recorded, and printed matter using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ink jet acceptive layer resin composition for a pigment dispersed oily ink for obtaining an image having a high minuteness and an excellent color developability by an ink jet printer for the pigment disperse oily ink and to provide a material to be recorded and a printed matter using the same. SOLUTION: The ink jet acceptive layer resin composition for the pigment dispersed oily ink contain a polyurethane resin emulsion having a polycarbonate chain and/or a polyester chain in a molecule. A film having a thickness of 200±20 μm obtained by drying the polyurethane resin emulsion is in a range of 150 to 1,000% of an areal swelling rate of the film when the film is dipped in a methylisobutyl ketone at liquid temperature of 25 deg.C for 24 hrs. A tensile fracture strain of the film is 550% or more. The material to be recorded comprises an ink acceptive layer made of the ink jet acceptive layer resin composition on a base. The printed matter is obtained by printing an image on the material by an ink jet printer.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an inkjet receiving layer resin composition for a pigment-dispersed oil-based ink, which is applicable to inkjet printing of outdoor advertising signs and the like, a recording material, and a printed matter using the recording material.

[0002]

2. Description of the Related Art Inkjet recording methods are rapidly spreading because of their advantages such as plateless printing, low noise, high density recording, and full color compatibility. It is also widely used for business advertising. Particularly in recent years, since the pigment ink has improved light resistance as compared with the conventional dye ink, the demand for the printer for outdoor advertisement using the pigment ink has remarkably increased, and the demand for the pigment ink has also increased accordingly. .

However, since these pigment inks are those in which pigments are dispersed in water or the like, the printed image has poor water resistance, and when a printed matter is posted outdoors as an advertisement, it is usually printed. Need to be laminated with transparent film. Therefore, in recent years, a pigment-dispersed oil-based ink in which a pigment having the advantages of good water resistance of an image and no need for a lamination step is dispersed in an organic solvent, and a printer for the pigment-dispersed oil-based ink (hereinafter, pigment-dispersed oil Inkjet printer) was developed.

Usually, in an ink jet recording material, an ink receiving layer provided on a base material by a method such as coating or impregnation prevents bleeding or repellency of printing by ink and is excellent in color development and has high definition. Give a print image. Therefore, a method of applying an ink receiving layer resin composition containing an inorganic pigment such as silica, kaolin or clay and a water-soluble polymer binder such as polyvinyl alcohol, starch or polyurethane to obtain an ink jet recording material (Japanese Patent Laid-Open No. Sho 61-206). 59-185690, JP-A-4-219267
JP-A-5-294057 and JP-A-10-294057.
No. 181189, etc.) has been proposed. Since such an ink jet recording material is designed to efficiently absorb water, which is the main solvent of the ink,
It is hard to say that it efficiently absorbs the organic solvent that is the solvent of the pigment-dispersed oil-based ink, and as a result, even when the pigment-dispersed oil-based inkjet printer is used to print on the inkjet recording material, high-definition and excellent color development is achieved. There was a problem that images could not be obtained.

On the other hand, an ink jet printer for a pigment-dispersed oil-based ink is said to be capable of forming an image on a substrate without using a recording material having an ink receiving layer as described above. When printing on an untreated recording material having no layer, a high-definition image having excellent color developability cannot be obtained.

Therefore, it is desired to develop an ink jet recording material suitable for printing with an ink jet printer for pigment-dispersed oil-based inks and an ink jet receiving layer resin composition that enables the recording material. Therefore, a coating sheet having a coating layer composed of an oil-absorptive inorganic pigment such as clay, an organic pigment such as urea formalin resin, and an aqueous adhesive (Japanese Patent Application Laid-Open No. Sho 6-96).
No. 4-24785) or a coating sheet obtained by applying a composition comprising silica and an adhesive (Japanese Patent Laid-Open No. 1-25555).
No. 80) has been proposed, but these techniques are substantially the same as the conventional recording materials for water-based inkjet printers, and high-definition images can be obtained when pigment-dispersed oil-based inks are used. Absent. In addition, an oil-based ink jet recording sheet coated with a resin composition comprising a pigment and a specific thermoplastic resin (JP-A-10-250219, JP-A-10-250220, JP-A-10-264503).
JP-A-11-286166, JP-A-11-286166
No. 286167) has been proposed. However, these prior arts do not disclose an example in which a polyurethane resin emulsion is specifically used as the thermoplastic resin of the ink receiving layer, and the recording sheet is substantially for printing with an oil-soluble dye ink. However, the ink jet printer for the pigment-dispersed oil-based ink has a drawback that a high-definition image cannot be obtained.

[0007]

An object of the present invention is to provide an ink jet receiving layer resin composition for a pigment-dispersed oil-based ink, which is capable of obtaining an image with high definition and excellent color development in the ink-jet printer for a pigment-dispersed oil-based ink. It is to provide a recording material and a printed matter using the recording material.

[0008]

As a result of intensive studies to solve the above problems, the present inventors have found that a resin composition containing a specific polyurethane resin emulsion and a recording material solve the above problems. The inventors have found that a printed matter on which an image having high precision and excellent color development is printed can be obtained, and have completed the present invention.

That is, the present invention is a resin composition for an ink jet receiving layer for a pigment-dispersed oil-based ink, which comprises a polyurethane resin emulsion having a polycarbonate chain and / or a polyester chain in a molecule, and the polyurethane resin emulsion is dried. Obtained thickness 200 ± 20μ
The film of m is 2 at a liquid temperature of 25 ° C in methyl isobutyl ketone.
The area swelling ratio of the film when immersed for 4 hours is 150 to
The present invention relates to an inkjet receiving layer resin composition for a pigment-dispersed oil-based ink, which is in the range of 1000%.

Further, the present invention relates to a recording material having an ink receiving layer comprising the above-mentioned ink jet receiving layer resin composition for a pigment-dispersed oily ink on a substrate.

Further, the present invention relates to a printed matter characterized in that an image is printed on the ink jet recording material for the pigment-dispersed oily ink by an ink jet printer.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The necessary items for carrying out the present invention will be specifically described below.

First, the ink jet receiving layer resin composition for a pigment-dispersed oily ink of the present invention (hereinafter referred to as the ink jet receiving layer resin composition) will be described. The ink jet receiving layer resin composition of the present invention comprises a polyurethane resin emulsion, and the polyurethane resin constituting the polyurethane resin emulsion has a polycarbonate chain and / or a polyester chain in the molecule. By using a polyurethane resin emulsion having a polycarbonate chain and / or a polyester chain in the molecule, a high-definition image can be obtained by printing with an inkjet printer on an inkjet recording material coated with the inkjet receiving layer resin composition of the present invention. You can

The average particle size of the polyurethane resin emulsion particles is not particularly limited, but the storage stability of the polyurethane resin emulsion, the transparency of the ink receiving layer formed by applying the resin composition of the ink jet receiving layer of the present invention, and the printing glossiness. From the viewpoint of the storage stability of the polyurethane resin emulsion, it is preferably 1.0 μm or less.

In the polyurethane resin emulsion used in the resin composition for the ink jet receiving layer of the present invention, the area swelling ratio of the film having a thickness of 200 ± 20 μm obtained by drying the emulsion is in the range of 150 to 1000%. preferable. The area swelling ratio as referred to in the present invention means that after the polyurethane resin emulsion is dried to obtain a film having a thickness of 200 ± 20 μm, this film is immersed in methyl isobutyl ketone at 25 ° C. for 24 hours, before immersion. The ratio of the swelling of the coating area after immersion to the coating area of. Here, examples of the drying method include heat drying, air drying, and room temperature drying.

The numerical value of the area swelling ratio of such a film can be obtained by inserting the numerical value obtained by the measuring method described in the following examples into the following formula.

Area swelling ratio (%) = (coating area after immersion for 24 hours / coating area before immersion × 100) -100

By using a polyurethane resin emulsion having an area swelling ratio of 150% or more in the resin composition for an ink jet receiving layer, an ink receiving layer having a high swelling rate with respect to the solvent of the pigment-dispersed oil-based ink can be obtained. , A good image can be printed. Further, by using a polyurethane resin emulsion in which the area swelling rate of the film is 1000% or less, excessive swelling of the ink receiving layer with respect to the solvent of the pigment-dispersed oil-based ink is prevented,
A good image without bleeding can be obtained.

The polyurethane resin emulsion used in the resin composition of the ink jet receiving layer of the present invention preferably has a tensile breaking strain of 550% or more in the film obtained by drying the polyurethane resin emulsion.
Such a polyurethane resin emulsion has a low crystallinity and forms a high molecular weight film, and an ink receiving layer that swells more quickly with respect to the solvent of the pigment-dispersed oil-based ink is obtained. Images can be printed.

The polyisocyanate unit of the polyurethane resin constituting the polyurethane resin emulsion used in the present invention is not particularly limited, but examples thereof include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, 3,3'-dichloro -4,4'-biphenylene diisocyanate, 1,5-naphthalene diisocyanate, 1,5-tetrahydronaphthalene diisocyanate, tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate , Dodecamethylene diisocyanate, trimethylhexamethylene diisocyanate,
1,3-cyclohexylene diisocyanate, 1,4-
Cyclohexylene diisocyanate, xylylene diisocyanate, tetramethylene xylylene diisocyanate, hydrogenated xylylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, 4,4 '
-Dicyclohexylmethane diisocyanate, 3,3 '
-Dimethyl-4,4'-dicyclohexylmethane diisocyanate and the like can be mentioned. These polyisocyanates can be used alone or in combination of two or more. Among the polyisocyanate units of the polyurethane resin forming the polyurethane resin emulsion, aliphatic polyisocyanates and / or alicyclic polyisocyanates are preferable. By using an aliphatic polyisocyanate and / or an alicyclic polyisocyanate, the area swelling ratio of the film obtained by drying the polyurethane resin emulsion to methyl isobutyl ketone can be set in the range of 150 to 1000%. I can. Further, the use of an aliphatic polyisocyanate and / or an alicyclic polyisocyanate is preferable also from the viewpoint of light resistance of a recording material and a printed material using the ink jet receiving layer resin composition for a pigment-dispersed oil-based ink of the present invention. .

In the present invention, it is preferable to use a linear polyurethane resin in order to make the tensile fracture strain of the film obtained by drying the polyurethane resin emulsion 550% or more. Therefore, polyisocyanate is used. The unit is preferably diisocyanate. Incidentally, a polyisocyanate having a valence of 3 or more can be used in combination within a range not impairing the effects of the present invention.

The content of the polyisocyanate unit in the polyurethane resin used in the resin composition for the ink jet receiving layer of the present invention is preferably in the range of 10 to 30% by weight. If the content of the polyisocyanate unit is within such a range, the area swelling ratio of the above-mentioned film is 150 to 1
000% range, the tensile strain of the film is 550%
It is possible to do the above.

The polyol used in the present invention is preferably a polycarbonate polyol or a polyester polyol in order to obtain a polyurethane resin having a polycarbonate chain and / or a polyester chain in the molecule.

As the polycarbonate polyol,
Examples thereof include 1,4-butanediol, 1,6-hexanediol, glycols such as diethylene glycol, diphenyl carbonate, and compounds obtained by the reaction of phosgene. These may be used alone or in combination of two or more.

As the polyester polyol,
A polyester obtained by subjecting a low molecular weight polyol and a carboxylic acid described below to a dehydration condensation reaction, or ε
-A polyester obtained by a ring-opening polymerization reaction of a cyclic ester compound such as caprolactone and a copolyester thereof.

The low molecular weight polyol is, for example,
Ethylene glycol, propylene glycol, 1,3-
Propanediol, 1,4-butanediol, 1,5-
Pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol (molecular weight 300 to 6,000), dipropylene glycol, Tripropylene glycol, bishydroxyethoxybenzene, 1,4-cyclohexanediol, 1,
4-cyclohexanedimethanol, bisphenol A,
Examples thereof include hydrogenated bisphenol A, hydroquinone, and alkylene oxide adducts thereof. These may be used alone or in combination of two or more.

Examples of the carboxylic acid include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic anhydride, fumaric acid, 1,3-cyclopentanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid. , Terephthalic acid, isophthalic acid, phthalic acid,
1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, 1,2-bis (phenoxy) ethane-p, p'-dicarboxylic acid and these Anhydride or ester-forming derivative of dicarboxylic acid; p
-Hydroxybenzoic acid, p- (2-hydroxyethoxy) benzoic acid, and ester-forming derivatives of these hydryloxycarboxylic acids. These alone or 2
It can be used in combination of two or more species.

The above polyester polyol unit has an area swelling ratio of the coating of the present invention of 150 to 1000.
In order to set the tensile fracture strain of the coating to 550% or more in the range of 0.1%, a polyester polyol using an amorphous low molecular weight polyol is preferable. As such a low molecular weight polyol, those having an odd number of carbon atoms and those having a branched structure are preferable, and for example, propylene glycol, 3-methyl-1,5-pentanediol, neopentyl glycol, tripropylene glycol and the like. The thing using is mentioned.

The method for producing the polyurethane resin emulsion used in the present invention may be any of the methods well known in the prior art. For example, a polyurethane resin having no hydrophilic group is forced into an aqueous medium by an external emulsifier. There is also a method of dispersing in the above method, but a more preferable method is, for example, the following method.

Method: Neutralize, if necessary, an organic solvent solution or dispersion of a hydrophilic group-containing polyurethane resin obtained by reacting an active hydrogen-containing compound and a hydrophilic group-containing compound with a polyisocyanate. Method of obtaining a polyurethane resin emulsion by mixing an aqueous solution containing an agent, or

Method: A hydrophilic group-containing terminal isocyanate group-containing urethane prepolymer obtained by reacting an active hydrogen-containing compound and a hydrophilic group-containing compound with a polyisocyanate is mixed with an aqueous solution containing a neutralizing agent. Alternatively, a method of obtaining a polyurethane resin emulsion by reacting with a polyamine after adding a neutralizing agent to a prepolymer in advance, mixing water and dispersing in water, or

Method: A hydrophilic group-containing terminal isocyanate group-containing urethane prepolymer obtained by reacting an active hydrogen-containing compound and a hydrophilic group-containing compound with a polyisocyanate is mixed with an aqueous solution containing a neutralizing agent and a polyamine. Or a method in which a neutralizing agent is added to the prepolymer in advance and then mixed with an aqueous solution containing a polyamine to obtain a polyurethane resin emulsion.

In these methods, the above-mentioned polycarbonate polyol or polyester polyol can be used as the active hydrogen-containing compound.

In order to set the area swelling ratio in the range of 150 to 1000% and the tensile breaking strain to 550% or more, it is preferable that urea bond is appropriately present in the skeleton of the polyurethane resin. The amount of urea bond for that purpose is 5 to 5 in terms of an equivalent ratio of urea bond to the sum of equivalents of urethane bond and urea bond in the polyurethane resin skeleton.
It is preferably in the range of 0%. In order to obtain a polyurethane resin having such a urea bond ratio, a method or a method is particularly preferable among the above manufacturing methods.

The raw material used for introducing the hydrophilic group into the polyurethane resin emulsion used in the present invention is, for example, a salt of carboxylic acid or sulfonic acid which has at least one active hydrogen atom in the molecule. Salt, phosphoric acid salt, quaternary ammonium salt, carboxylic acid group, sulfonic acid group, phosphoric acid group, and tertiary amino group containing at least one functional group selected from the group consisting of Compounds, or nonionic compounds having at least one active hydrogen atom in the molecule and containing a group consisting of ethylene oxide repeating units and a group consisting of ethylene oxide repeating units and other alkylene oxide repeating units, etc. Is mentioned. Among these hydrophilic groups, when used in combination with a cationic compound described below, anionic groups are preferable as the hydrophilic groups from the viewpoint of improving the printability of the film, and the inkjet receiving layer resin composition of the present invention is used. In order to improve the curl property of the coated sheet obtained by coating, a sulfonate group is particularly preferable.

Examples of the hydrophilic group-containing compound include 2-oxyethanesulfonic acid, phenolsulfonic acid, sulfobenzoic acid, sulfosuccinic acid, 5-sulfoisophthalic acid, sulfanilic acid, 1,3-phenylenediamine-4,6. -Sulfonic acid-containing compounds such as disulfonic acid and 2,4-diaminotoluene-5-sulfonic acid, and derivatives thereof or polyester polyols obtained by copolymerizing these; 2,2-dimethylolpropionic acid;
2-dimethylol butyric acid, 2,2-dimethylol valeric acid,
Dioxymaleic acid, 2,6-dioxybenzoic acid, 3,
Carboxylic acid-containing compounds such as 4-diaminobenzoic acid and derivatives thereof or polyester polyols obtained by copolymerizing these; tertiary amino group-containing compounds such as methyldiethanolamine, butyldiethanolamine, alkyldiisopropanolamine and derivatives thereof Are polyester polyols or polyether polyols obtained by copolymerizing these; the above-mentioned tertiary amino group-containing compound and derivatives thereof, or polyester polyols or polyether polyols obtained by copolymerizing these, methyl chloride and bromide. Reaction products of quaternary agents such as methyl, dimethylsulfate, diethylsulfate, benzyl chloride, benzyl bromide, ethylene chlorohydrin, ethylene bromohydrin, epichlorohydrin, brombutane; repeating units of ethylene oxide Polyoxyethylene glycol or polyoxyethylene-polyoxypropylene copolymer glycol having a molecular weight of 300 to 20,000 containing at least 30% by weight or more and containing at least one active hydrogen in the polymer, polyoxyethylene-poly Oxybutylene copolymer glycol, polyoxyethylene-polyoxyalkylene copolymer glycol or a nonionic group-containing compound such as a monoalkyl ether thereof or a polyester polyether polyol obtained by copolymerizing these, and these alone, Or they are used in combination.

When this hydrophilic group is an anionic group,
In order to improve the glossiness and printability of the above film,
The amount of anionic groups in the polyurethane resin emulsion is preferably 0.005 to 0.2 equivalents, more preferably 0.01 to 0.1 equivalents per 100 parts by weight of the finally obtained polyurethane resin solids. . When the amount of anionic groups in the polyurethane resin emulsion is in such a range, the polyurethane resin emulsion is excellent in dispersion stability and stability to an epichlorohydrin polyamide resin described later.

The polyurethane resin emulsion having a polycarbonate chain and / or a polyester chain in the molecule used in the present invention is produced by using a polycarbonate polyol and / or a polyester polyol as the polyol in the above-mentioned known production method. However, the polyurethane resin emulsion produced by the above production method using a polycarbonate polyol and the polyurethane resin emulsion produced by the above production method using a polyester polyol may be mixed and used.

The above polycarbonate polyol,
In addition to the polyester polyol, a polyol other than these may be used within a range that does not impair the physical properties of the ink jet receiving layer resin composition of the present invention. Examples of polyols other than the above include polyether polyols, polyacetal polyols, polyacrylate polyols, polyesteramide polyols, polythioether polyols, polybutadiene-based polyolefin polyols, and the like. Examples of the polyether polyol that can be used in the present invention include ethylene glycol, diethylene glycol, triethylene glycol,
Propylene glycol, trimethylene glycol, 1,
3-butanediol, 1,4-butanediol, 1,6
-Hexanediol, neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane, sorbitol, sucrose, aconit sugar, trimellitic acid, hemimellitic acid, phosphoric acid, ethylenediamine, diethylenetriamine, triisopropanolamine, pyrogallol, dihydroxybenzoic acid, Ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin using one or more compounds having at least two active hydrogen atoms such as hydroxyphthalic acid and 1,2,3-propanetrithiol as an initiator. Examples thereof include those obtained by addition-polymerizing one or more monomers such as tetrahydrofuran and cyclohexylene by a conventional method.

The polyurethane resin emulsion having a polycarbonate chain and / or a polyester chain is
A polyurethane resin emulsion having neither a polycarbonate chain nor a polyester chain can be used together. In this case, the amount of the polyurethane resin emulsion having a polycarbonate chain and / or a polyester chain used is preferably 5 in terms of solid content based on the total polyurethane resin emulsion in terms of obtaining a higher definition image.
It is 0% by weight or more, more preferably 70% by weight or more.

The non-volatile content of the polyurethane resin emulsion used in the present invention is preferably 5 to 70% by weight, more preferably 10 from the viewpoint of particle size and stability of the polyurethane resin emulsion. ~ 6
It is in the range of 0% by weight. In the present invention, the non-volatile content means that the polyurethane resin emulsion has a content of 2 at 107 ° C. with respect to the initial weight of the polyurethane resin emulsion.
It means the ratio (% by weight) of the weight of the residual content after holding for a time.

It is preferable that the resin composition of the ink jet receiving layer of the present invention further contains an inorganic filler. Examples of such inorganic fillers include amorphous synthetic silica, natural silicic acid, clay, talc, calcium carbonate, diatomaceous earth, kaolin, calcined kaolin, magnesium carbonate, basic magnesium carbonate, titanium oxide, zinc oxide, silicon oxide, Examples thereof include aluminum hydroxide, calcium silicate, barium sulfate, calcium sulfate, surface-treated calcium and silica. By including these inorganic fillers, the absorbability of the pigment-dispersed oil-based ink can be improved. Among these inorganic fillers, amorphous synthetic silica is preferable from the viewpoints of quality homogeneity (particle size, pore size, etc.) and good dispersibility in an aqueous medium.

The amount of the inorganic filler used is not particularly limited, but is preferably in the range of 1 to 90% by weight, more preferably 20 to 80% by weight in terms of solid content in the ink jet receiving layer resin composition of the present invention. Is the range. By using the inorganic filler in such a range, the stability as the resin composition, the absorbability of the pigment-dispersed oil-based ink, and the strength of the ink receiving layer can be achieved with a better balance.

Furthermore, it is preferable that the ink jet receiving layer resin composition of the present invention contains an epichlorohydrin polyamide resin. Epichlorohydrin polyamide resin is obtained by adding epichlorohydrin to a polyamide polyamine obtained by condensing a polyfunctional polyamine such as diethylenetriamine and a polybasic acid such as adipic acid, and is generally known as a wet paper strengthening agent. It is what has been. This resin is a cationic water-soluble resin having a reactive azetidinium ring in its molecule, but due to its ionic nature it forms a slow aggregate with the polyurethane resin emulsion, which is an essential component, and as a result, the pigment dispersion It is possible to improve the absorbability of the oil-based ink and make the color of the printed matter clear.

Commercially available products of this epichlorohydrin polyamide resin are "WS525" manufactured by Japan PMC Co., Ltd.,
"WS535" and "WS570" (both are trade names),
Sumitomo Chemical Co., Ltd.'s "Smiley's Resin" (brand name)
Etc. The amount of the epichlorohydrin polyamide resin used is not particularly limited, but is 10 to 10 parts by weight of the resin solid content of the polyurethane resin emulsion.
A range of 500 parts by weight is preferable, and a range of 50 to 200 parts by weight is particularly preferable. By using the epichlorohydrin polyamide resin in such a range, the stability of the resin composition of the present invention and the color developability of the printed matter become more excellent.

Other additives may be added to the ink-jet receiving layer resin composition of the present invention within the range not impairing the physical properties. Examples of such additives include polyoxyethylene alkyl ether-based, polyoxyethylene fatty acid ester-based, polyoxyethylene alkylphenyl ether-based, sorbitan fatty acid ester-based, polyoxyethylene sorbitan fatty acid ester-based, polyoxyethylene alkylamine ether-based , Nonionic hydrocarbon surfactants such as fatty acid diethanolamide type and sucrose ester type, dialkyl sulfosuccinic acid ester type, polyoxyethylene alkyl ether sulfate type, higher alkyl ether sulfate ester salt, anion type phosphate ester salt, etc. Hydrocarbon-based surfactant, cation-type hydrocarbon-based surfactant such as quaternary ammonium salt-based such as alkyl trimethyl ammonium chloride, dimethyl alkyl lauryl betaine, alkyl Amphoteric hydrocarbon surfactants such as lysine and amidobetaine type, polymer type hydrocarbon surfactants such as imidazoline type polyoxyethylene polyoxypropylene block polymer, acetylene glycol type special surfactant, silicone type surfactant Agents, various leveling agents such as fluorine-based surfactants, various ultraviolet absorbers such as benzotriazole ultraviolet absorbers and hindered amine ultraviolet absorbers, and hindered phenol-based and sulfur-based antioxidants. The amount of these additives used is usually in the range of 0.01 to 5% by weight in terms of solid content in the resin composition. These may be used alone or in combination of two or more.

The ink jet receiving layer resin composition of the present invention may further contain a water-soluble resin such as polyvinyl alcohol, polyvinylpyrrolidone and a cellulose resin, an acrylic resin emulsion or a synthetic rubber emulsion. The addition amount of these is preferably in the range of 1 to 30% by weight in terms of solid content in the resin composition.

In order to further improve the strength and durability of the ink receiving layer, the ink jet receiving layer resin composition of the present invention contains a crosslinking agent such as an epoxy type crosslinking agent, an isocyanate type crosslinking agent and a melamine type crosslinking agent. You may mix.
The addition amount of these is preferably in the range of 0.1 to 10% by weight in terms of solid content in the resin composition.

The ink-jet receiving layer resin composition of the present invention further contains a water-soluble solvent such as an alcohol solvent or a ketone solvent in order to improve the processing speed when the resin composition is applied to various substrates. Can be blended. The amount of these water-soluble solvents used is preferably in the range of 0.1 to 20% by weight in the solvent in the resin composition.

The ink jet receiving layer resin composition of the present invention can be prepared by stirring the above raw materials with an appropriate stirrer, for example, a propeller type, a disper, a homogenizer, etc., and thoroughly mixing them.

Inkjet recording material for pigment-dispersed oil-based ink of the present invention (hereinafter referred to as inkjet recording material)
Is an ink-receiving layer comprising the ink-jet receiving layer resin composition obtained above on a substrate.

The ink jet recording material of the present invention can be produced, for example, by coating the above resin composition of the present invention on a substrate and then quickly drying.
The drying temperature in this case may be set in consideration of the dimensional stability of the base material, and is usually preferably 150 ° C. or lower.

Examples of the substrate include paper, paperboard, various synthetic resin films, synthetic paper, fibers, non-woven fabrics, spunbonds, and composites thereof.

As a method of coating the ink jet receiving layer resin composition of the present invention on the above-mentioned substrate, a known method can be used and is not particularly limited. Examples of the coating method include coating with an air knife, coating with a blade, coating with a roll coater, coating with a gravure coater, size press coating, and gate roll coating.

The thickness of the ink receiving layer used in the present invention is
In terms of printability of the pigment-dispersed oil-based ink, the dry coating amount is 15
It is preferably at least g / m ² . Coating amount is 15g /
If it is less than m ² , when the ink discharge amount is maximized, the ink may bleed and a high-definition image may not be obtained.

The printed matter of the present invention is obtained by printing an image on an inkjet recording material for a pigment-dispersed oil-based ink by an inkjet printer. The printed matter of the present invention becomes high-definition and excellent in color developability by using the above-mentioned ink-jet receiving layer resin composition of the present invention.

The pigment-dispersed oil-based ink used in the present invention is
It is an ink in which a pigment, which is a coloring material, is dispersed in an organic solvent.

Examples of the pigment used in the present invention include inorganic oxides such as titanium oxide, iron oxide and carbon black, and organic pigments such as insoluble azo pigments and condensed azo pigments.
Examples thereof include chelate azo pigments, phthalocyanine pigments, perylene pigments, anthraquinone pigments, quinacdrine pigments, dioxazine pigments, thioindigo pigments, dye chelates, nitro pigments, nitroso pigments, and aniline black.

Examples of the above organic solvent include petroleum naphtha type solvents, aromatic petroleum solvents, aliphatic petroleum solvents, naphthene type petroleum solvents, aliphatic or aromatic hydrocarbons, halogenated hydrocarbons, alkyls. Alcohols, ketones,
Examples include ketone alcohols, ethers, esters, plasticizers and the like.

The ink-jet receiving layer resin composition of the present invention can be applied not only to pigment-dispersed oil-based inks, but also to oil-based inks using oil-soluble dyes.

Ink jet printers are roughly classified into those of the continuous jet charging control system and those of the on-demand system. Typical of these are, for example, a charge modulation system, a diffusion system, and an electric printer. Examples include a mechanical conversion system, an electrothermal conversion system, and an electrostatic suction system. Ink jet printers have different principles of ink ejection depending on the respective methods, but the present invention can be used for printers by any method and is not particularly limited.

The ink jet recording material of the present invention can be used to obtain a printed matter by using an ink jet printer other than the ink jet printer for pigment dispersed oil-based ink.

The printed matter of the present invention can be applied to various uses such as home and business materials, but since it has excellent light resistance, it can be preferably applied to outdoor advertisements. This outdoor advertisement can also be used for corporate advertisements at department stores, timetables on station platforms, and large-scale illumination advertisements at airports.

[0064]

EXAMPLES Next, the present invention will be described more specifically by way of examples. In the following, all percentages are by weight unless otherwise specified. The present invention is not limited to these examples. The measuring method and the preparing method used in the present invention are as follows.

[Measurement Method of Area Swelling Ratio of Dry Film to Methyl Isobutyl Ketone] The polyurethane resin emulsion was dried to prepare a film having a thickness of 200 ± 20 μm, which was heated in an oven at 140 ° C. for 5 minutes.
Next, the obtained film was made into a square sample of 3 cm × 3 cm, and immersed in 50 ml of methyl isobutyl ketone at a liquid temperature of 25 ° C. The area (cm ² ) of the test piece after immersion for 24 hours was measured, and the area swelling rate (%) was calculated according to the following formula.

Area swelling ratio (%) = (area after immersion for 24 hours / 9 × 100) -100

[Measurement Method of Tensile Fracture Strain of Dry Film]
Dry the polyurethane resin emulsion to a thickness of 200 ±
A 20 μm film was prepared and heated in an oven at 140 ° C. for 5 minutes. Next, the obtained film is 4 cm
A rectangular test piece of 0.5 cm was formed, and this test piece was subjected to a tensile property test using a tensile tester Autograph AG-1 (manufactured by Shimadzu Corporation) at a test speed of 300 mm / min, and the test piece was broken. The tensile strain (%) at that time was measured. The measurement was performed according to JIS K7161 except for the conditions described.

[Evaluation method of printability of pigment-dispersed oil-based ink] The ink jet recording materials obtained in Examples and Comparative Examples were subjected to solid printing by ink jet recording to visually check the appearance of the printed image and the presence or absence of bleeding. It was confirmed and evaluated according to the following criteria. A: The image is clear and has no blur. ○: The image is clear and has some bleeding. Δ: The image is unclear and has some blurring. X: The image is unclear and has many blurs.

Example 1 Hydran HW-930 [A polyurethane resin emulsion having a polyester chain and an anion group in the molecule and using an aliphatic diisocyanate as an isocyanate component, an area swelling ratio of a dry film to methyl isobutyl ketone 170% , Tensile strain of dry film 600%, manufactured by Dainippon Ink and Chemicals, Inc.]
(A), paper strength agent WS535 [epichlorohydrin polyamide resin, manufactured by Japan PMC Ltd.] (B), Mizukasil P-78A [amorphous synthetic silica, manufactured by Mizusawa Chemical Industry Co., Ltd.]
(C) in solid content conversion weight ratio (A) / (B) / (C) =
25/25/50 and a solid content of 20% were mixed to obtain an inkjet receiving layer resin composition (Z1).

Next, the above ink jet receiving layer resin composition (Z1) was applied to an easily-adhesive-treated polyester film A-4100 (manufactured by Toyobo Co., Ltd.), and 120
By heating for 3 minutes at 0 ° C., an inkjet recording material (M1) having a coating thickness after heating of 30 μm was obtained. Next, the obtained ink jet recording material (M1) was provided with an ink jet printer for pigment-dispersed oil-based ink [Lamiless, Mutoh Industry Co., Ltd.
Inkjet recording is performed by using
1) was obtained. With respect to this printed matter (P1), the printing state such as image characteristics was evaluated. The evaluation results are shown in Table 1.

Example 2 In place of (A) used in Example 1, hydrane HW-935 [a polyurethane resin emulsion having a polycarbonate chain and an anion group in the molecule and using an aliphatic diisocyanate as an isocyanate component, Area swelling ratio of dry film to methyl isobutyl ketone 164%, tensile breaking strain of dry film 60
0%, manufactured by Dainippon Ink and Chemicals, Inc.]
The ink jet receiving layer resin composition (Z2) having the same composition as in Example 1 except that a paper strength agent WS525 [Epichlorohydrin polyamide resin, manufactured by Nippon PMC Ltd.] was used in place of (B) used in Example 1. A recording material (M2) and a printed matter (P2) were obtained and evaluated in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 1 (A) used in Example 1 above
In place of GOHSENOL GH-17R [polyvinyl alcohol, area swelling ratio of the dry film to methyl isobutyl ketone 3.3%, tensile breaking strain of the dry film 220
%, Manufactured by Nippon Synthetic Chemical Industry Co., Ltd.] (a), and this (a) and Mizukacil P-78A (C) are solid (a) / (C) = 50/50 in terms of solid content. The ink composition of the ink jet receiving layer resin composition (Z
3) was obtained, and using Z3, the same operation as in Example 1 was performed to obtain a recording material (M3) and a printed matter (P3). This printed matter (P3) was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

[0073]

[Table 1]

[0074]

INDUSTRIAL APPLICABILITY The ink jet receiving layer resin composition for a pigment-dispersed oily ink and the recording material of the present invention are high-definition and vivid by using an ink jet printer,
It is possible to obtain a printed matter having excellent color developability. Moreover, since the printed matter of the present invention is particularly excellent in light resistance and water resistance, it can be used not only indoors but also outdoors, and is useful, for example, for business advertisement applications such as signboards.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 2C056 EA04 FC06                 2H086 BA01 BA15 BA33 BA36 BA41                       BA54 BA55

Claims (9)

[Claims] 1. A resin composition for an inkjet receiving layer for a pigment-dispersed oily ink, comprising a polyurethane resin emulsion having a polycarbonate chain and / or a polyester chain in a molecule, and having a thickness obtained by drying the polyurethane resin emulsion. Inkjet reception for pigment-dispersed oil-based ink, wherein a 200 ± 20 μm film has an area swelling ratio in the range of 150 to 1000% when immersed in a liquid temperature of 25 ° C. in methyl isobutyl ketone for 24 hours. Layer resin composition. 2. The ink jet receiving layer resin composition for a pigment-dispersed oil-based ink according to claim 1, wherein a film having a thickness of 200 ± 20 μm obtained by drying the polyurethane resin emulsion has a tensile strain at break of 550% or more. 3. The pigment-dispersed oily ink according to claim 1, wherein the polyisocyanate unit of the polyurethane resin constituting the polyurethane resin emulsion is an aliphatic polyisocyanate compound and / or an alicyclic polyisocyanate compound. Inkjet receiving layer resin composition. 4. The ink jet receiving layer resin composition for a pigment-dispersed oily ink according to claim 3, wherein the content of the polyisocyanate unit in the polyurethane resin is in the range of 10 to 30% by weight. 5. The ink-jet receiving layer resin composition for a pigment-dispersed oil-based ink according to claim 1, wherein the polyurethane resin constituting the polyurethane resin emulsion has a sulfonate group in the molecule. 6. The ink-jet receiving layer resin composition for a pigment-dispersed oil-based ink according to any one of claims 1 to 5, further comprising an inorganic filler. 7. The ink-jet receiving layer resin composition for a pigment-dispersed oil-based ink according to claim 1, which further comprises an epichlorohydrin polyamide resin. 8. A recording material having an ink receiving layer comprising the ink jet receiving layer resin composition for a pigment-dispersed oil-based ink according to any one of claims 1 to 7 on a substrate. 9. A printed matter, which is obtained by printing an image on the inkjet recording material for a pigment-dispersed oil-based ink according to claim 8 by an inkjet printer.