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WO2013015387A1 - Agent de revêtement pour former une couche de réception d'encre pour jet d'encre, support d'enregistrement l'utilisant et matière imprimée - Google Patents

Agent de revêtement pour former une couche de réception d'encre pour jet d'encre, support d'enregistrement l'utilisant et matière imprimée Download PDF

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Publication number
WO2013015387A1
WO2013015387A1 PCT/JP2012/069049 JP2012069049W WO2013015387A1 WO 2013015387 A1 WO2013015387 A1 WO 2013015387A1 JP 2012069049 W JP2012069049 W JP 2012069049W WO 2013015387 A1 WO2013015387 A1 WO 2013015387A1
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WIPO (PCT)
Prior art keywords
ink
water
monomer
receiving layer
meth
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2012/069049
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English (en)
Japanese (ja)
Inventor
裕士 曽根田
真輔 山田
浅井　太郎
睦子 佐藤
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Artience Co Ltd
Original Assignee
Toyo Ink SC Holdings Co Ltd
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Filing date
Publication date
Priority claimed from JP2011163584A external-priority patent/JP2013027979A/ja
Priority claimed from JP2011163585A external-priority patent/JP2013027980A/ja
Application filed by Toyo Ink SC Holdings Co Ltd filed Critical Toyo Ink SC Holdings Co Ltd
Publication of WO2013015387A1 publication Critical patent/WO2013015387A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B41M5/5254—Macromolecular coatings characterised by the use of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/322—Pigment inks

Definitions

  • the present invention relates to a coating agent for forming an ink-jet ink receiving layer, a recording medium using the same, and a printed matter.
  • Inkjet printing generates little noise, enables high-speed printing and multicolor printing, and has been rapidly spreading in recent years.
  • a recording medium for receiving inkjet ink conventionally, a recording medium provided with an ink receiving layer on the surface of a substrate such as paper or plastic film has been used.
  • so-called water-based inks that do not contain an organic solvent or that contain a small amount of organic solvent have come to be used preferably.
  • the ink receiving layer is required not only to absorb and dry ink quickly, but also to have excellent ink fixability, color development, sharpness, and image gradation. Furthermore, printed matter that has been subjected to ink jet printing on a recording medium is required to have excellent image durability, particularly when water-based ink is used.
  • the ink jet printing method is a recording method in which ink droplets are ejected from very fine nozzles, and ink dots are deposited on a recording medium to obtain characters and images.
  • problems such as non-ejection of ink droplets, misalignment of ink dot position and volume, etc. cause missing dots on the recording medium (no ink dots exist where ink dots should be) was there.
  • the missing dots are a particular problem in solid printing in which the printing area is completely filled with dots, causing white spots and white streaks in the printed image and failing to obtain a high-definition image.
  • the ink dots on the surface of the substrate will not be in contact with ink dots of other colors. It is necessary to form an ink receiving layer that spreads moderately and prevents the fixed ink dots from being peeled off by water.
  • a receiving layer in which the hydrophilicity of the ink is good and spreads appropriately and the hydrophobic part that does not spread excessively and exhibits water resistance after drying is well-balanced and uniformly arranged on the substrate surface. It is necessary to form. Simply mixing a hydrophilic component and a hydrophobic component cannot provide an ink-receiving layer from which a high-definition image formed by multicolor ink dots can be obtained.
  • a pigment blended as a colorant is used.
  • the pigment dispersion resin is used to stabilize the dispersion in the solvent in order to maintain the pigment dispersion in the ink.
  • anionic resins are often used as pigment dispersion resins.
  • an ink jet ink containing an anionic pigment dispersion resin is used to form an image on a receiving layer made of a cationic compound, the pigment aggregates on the surface of the receiving layer. For this reason, it has been difficult to provide a printed image in which the ink dots are not sufficiently spread and there are few white spots and white stripes.
  • Patent Documents 1 to 4 disclose that paper surface sizing is performed in the paper making process.
  • anionic compounds such as styrene-maleic acid copolymer and carboxyl group-containing acrylic resin have been proposed. Since these have a carboxyl group that works predominately in ink wetting, absorption, and drying properties, they have the effect of spreading the ink dots. However, these have a drawback of poor water resistance.
  • Patent Documents 5 to 6 an inkjet recording medium in which a surface coat layer containing an acrylic resin emulsion having a specific glass transition temperature and particle diameter is formed on a substrate, and a specific minimum film forming temperature and particle diameter are set.
  • a recording medium on which a coating layer containing water-dispersible resin particles is formed has been proposed.
  • these do not contain a carboxyl group that is superior in ink wetting, absorption, and drying properties as an essential component, and have the disadvantage that it is impossible to provide a printed image with less white spots, white streaks, and intercolor bleeding. there were.
  • JP 2009-161885 A Japanese Patent No. 3854165 JP 2001-232932 A JP 2003-227098 A Japanese Patent No. 3721651 Japanese Patent No. 3950688
  • the embodiment of the present invention includes a monomer (A) having two or more ethylenically unsaturated groups, a monomer (B) having a carboxyl group and one ethylenically unsaturated group, and one carbon atom.
  • a water-soluble solvent (G) comprising a cross-linked vinyl emulsion obtained by emulsion polymerization of a monomer mixture containing a monomer (C) having 12 to 12 hydrophobic groups and one ethylenically unsaturated group It is related with the coating agent for inkjet ink receiving layer formation characterized by including these.
  • the proportion of the monomer (A) is preferably 0.1 to 5% by weight in a total of 100% by weight of the monomers to be subjected to emulsion polymerization.
  • the proportion of the monomer (B) is preferably 20 to 80% by weight in a total of 100% by weight of the monomers to be subjected to emulsion polymerization.
  • the water-soluble solvent (G) preferably has a solubility parameter (SP value) of 8.0 to 16.0 (cal / cm 3 ) 1/2 .
  • the water-soluble solvent (G) preferably contains at least one of an alcohol solvent, a solvent represented by the general formula (1), a nitrogen-containing solvent, a sulfur-containing solvent, or a lactone solvent.
  • R 1 and R 3 each independently represent a hydrogen atom or an alkyl group having 1 or more carbon atoms, Z represents an integer of 1 or more, and R 2 represents an ethylene group or a propylene group.
  • an embodiment of the present invention relates to an image forming recording medium in which an inkjet ink receiving layer formed from the above-described coating agent for forming an inkjet ink receiving layer is provided on at least one surface of a substrate.
  • an embodiment of the present invention relates to a printed matter in which an image is formed by inkjet ink on the image forming recording medium of the above invention.
  • an embodiment of the present invention is to provide a printed matter in which white spots, white streaks, and bleeding between colors of an image formed with a water-based inkjet ink on an inkjet ink receiving layer are suppressed and water resistance is excellent. Is an issue.
  • the present inventors have found that the above-mentioned problems can be solved by forming an image with a water-based inkjet ink on the inkjet ink receiving layer shown below, thereby completing the present invention. It came to.
  • Embodiments of the present invention include a monomer (A) having two or more ethylenically unsaturated groups, a monomer (B) having a carboxyl group and one ethylenically unsaturated group, and 1 to 12 carbon atoms.
  • a coating agent for forming an ink-jet ink receiving layer comprising a cross-linked vinyl emulsion obtained by emulsion polymerization of a monomer mixture containing at least a monomer (C) having a hydrophobic group and one ethylenically unsaturated group,
  • a printed matter comprising: a first step of forming an ink-jet ink receiving layer using at least one surface of a substrate; and a second step of forming an image with a water-based ink-jet ink on the ink-jet ink receiving layer.
  • the proportion of the monomer (A) is 0.1 to 5% by weight and the proportion of the monomer (B) is 20 to 80% by weight in a total of 100% by weight of the monomers to be subjected to the emulsion polymerization. It is preferable that The acid value of the resin particles of the cross-linked vinyl emulsion is preferably 100 to 500 mgKOH / g.
  • the glass transition temperature of the resin particles of the cross-linked vinyl emulsion is preferably 0 to 100 ° C.
  • the water-based inkjet ink preferably contains a pigment, a water-soluble solvent (H), water, and a pigment dispersion resin.
  • the pigment dispersion resin includes a monomer (D) having an alkyl group (meth) acrylate ester having 10 to 24 carbon atoms, and a monomer (E) having styrene, ⁇ -methylstyrene or benzyl (meth) acrylate. And a copolymer (copolymer) containing the monomer (F) having (meth) acrylic acid in the copolymer composition.
  • the pigment-dispersed resin preferably has an acid value of 50 to 400 mgKOH / g or less.
  • the water-soluble solvent (H) is preferably at least one selected from glycol ethers and diols.
  • the cross-linked vinyl emulsion includes a monomer (A) having two or more ethylenically unsaturated groups, a monomer (B) having a carboxyl group and one ethylenically unsaturated group, and 1 to 12 carbon atoms.
  • the monomer mixture containing the monomer (C) having a hydrophobic group and one ethylenically unsaturated group is produced by emulsion polymerization.
  • the monomer (A) is mainly referred to as a so-called vinyl compound having an ⁇ , ⁇ -unsaturated double bond, and is a (meth) acrylic acid ester monomer having a (meth) acryloyl group or (meta ) It contains an allyl group or another monomer having a vinyl group.
  • (meth) acrylic acid In the present specification, the terms “(meth) acrylic acid”, “(meth) acrylate”, “(meth) allyl”, and “(meth) acryloyl” respectively represent “acrylic acid and / or methacrylic acid”. "Acid”, “acrylate and / or methacrylate”, “allyl and / or methallyl” and “acryloyl and / or methacryloyl” shall be indicated.
  • Monomer (A) introduces a crosslinked structure inside resin particles of a vinyl emulsion obtained by an emulsion polymerization method.
  • the monomer (A) is not limited to the following examples.
  • ethylene oxide modified phosphoric acid poly ethylene oxide modified phosphoric acid di (meth) acrylate or ethylene oxide modified phosphoric acid tri (meth) acrylate
  • (Meth) acrylates Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tri Propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, poly (ethylene glycol-propylene glycol) di (meth) acrylate, poly (ethylene glycol-tetramethylene glycol) di (meth) acrylate, poly (propylene glycol- Tetramethylene glycol) di (meth) acrylate, polyte
  • the content of the monomer (A) is preferably 0.1 to 5% by weight out of a total of 100% by weight of the monomers to be subjected to emulsion polymerization, from the viewpoint of water resistance and stability of the resin particles of the emulsion. 0.1 to 4% by weight is more preferable.
  • the monomer (B) is used for the purpose of increasing the wettability between the ink receiving layer and the ink, absorbing the ink quickly, and drying the substrate surface.
  • the ink dot appropriately spreads and is quickly absorbed and dried, whereby ink dots having a preferable dot diameter and color density can be formed.
  • the above effects are remarkably improved.
  • the electrical affinity of the functional groups of the pigment dispersion resin and additives contained in the ink-jet ink and the carboxyl group of the emulsion resin particles contained in the ink-receiving layer, and the ink-jet ink An ink dot having a preferable dot diameter and color density can be formed by a combination with the hydrophilic solvent contained.
  • the monomer (B) are not limited to the following examples.
  • the content of the monomer (B) is preferably 20 to 80% by weight out of a total of 100% by weight of the monomers to be subjected to emulsion polymerization, from the viewpoint of spreading of ink dots on the ink receiving layer and water resistance. More preferred is ⁇ 80% by weight. If it is 20% by weight or more, the ink wettability and the ink absorption / drying property are excellent, and the ink dots are sufficiently spread on the ink receiving layer, and no whitening or white stripes are generated. In the case of multicolor printing, there is no problem that ink droplets of different colors come into contact with each other and bleeding between colors occurs. On the other hand, if it is 80% by weight or less, the water resistance is sufficient.
  • the monomer (C) has a hydrophobic group having 1 to 12 carbon atoms and one ethylenically unsaturated group for the purpose of improving the water resistance of the ink receiving layer and the prevention of intercolor bleeding of the ink. Used.
  • a monomer having one ethylenically unsaturated group, a carboxyl group, and a hydrophobic group having 1 to 12 carbon atoms is handled as the monomer (B).
  • hydrophobic group here refers to a hydrocarbon group having 1 to 12 carbon atoms that has low polarity and is not easily compatible with water.
  • the monomer (C) are not limited to the following examples.
  • aromatic monomers are preferable from the viewpoint of water resistance, and ⁇ -methylstyrene and styrene are more preferable.
  • Ethyl acrylate and butyl acrylate are also preferable from the viewpoint of water resistance.
  • These monomers may use only 1 type and may use 2 or more types together.
  • the number of carbon atoms is preferably 12 or less in consideration of the wettability and copolymerizability of the ink on the ink receiving layer.
  • the content of the monomer (C) is preferably 19.9 to 79.9% by weight out of a total of 100% by weight of the monomers to be subjected to emulsion polymerization, from the viewpoint of the balance between image formability and water resistance. More preferably, it is 25 to 79.9% by weight.
  • monomers other than the monomers (A) to (C) are copolymerized as necessary. be able to.
  • Examples of such monomers include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-acrylic acid.
  • Leuoxyethyl-2-hydroxyethyl (meth) phthalate Diethylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, propylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate; Polytetramethylene glycol mono (meth) acrylate, poly (ethylene glycol-propylene glycol) mono (meth) acrylate, poly (ethylene glycol-tetramethylene glycol) mono (meth) acrylate, poly (propylene glycol-tetramethylene glycol) mono ( (Meth) acrylates having hydroxyl groups such as meth) acrylate or glycerol (meth) acrylate; 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2-meth
  • Monomers other than the monomers (A) to (C) can be used within the range not impairing the object of the present invention, and are not particularly limited, but 60% by weight in the total 100% by weight of the monomers. The following is preferable, and 0.1 to 60% by weight is more preferable.
  • the monomer to be subjected to emulsion polymerization does not contain an ethylenically unsaturated monomer having a cationic functional group.
  • an ethylenically unsaturated monomer having a cationic functional group is copolymerized, it interacts with a functional group contained in an ink pigment dispersion resin or an additive, and the ink aggregates on the surface of the ink receiving layer. In some cases, the spread of ink dots may be hindered.
  • an acid-base bond may be formed with the carboxyl group of the monomer (B), resulting in blurring during the polymerization of the emulsion or extreme thickening.
  • ethylenically unsaturated monomer having a cationic functional group examples include (meth) acrylamides such as (meth) acrylamide, N-methylol (meth) acrylamide, and N-butoxymethyl (meth) acrylamide.
  • (meth) acrylamides such as (meth) acrylamide, N-methylol (meth) acrylamide, and N-butoxymethyl (meth) acrylamide.
  • the already crosslinked vinyl emulsion is synthesized by a conventionally known emulsion polymerization method.
  • the polymerization reaction of the polymer proceeds in water or water containing a hydrophilic organic solvent. Therefore, when hydrophobic and hydrophilic monomers are copolymerized, the center of the resin particles in the emulsion is hydrophobic.
  • the surface portion of the particle has a highly hydrophilic structure. That is, the central part of the resin particles of the emulsion has high water resistance, and further, a crosslinked structure is introduced by copolymerization of the monomer (A), so that the water resistance can be further improved.
  • the already cross-linked vinyl emulsion has a hydrophobic part in which a cross-linked structure is introduced inside the resin particles of the emulsion, and has a carboxyl group that is a hydrophilic group on the surface of the resin particles of the emulsion. Therefore, when it becomes a coating film, the inside of the resin particles of the emulsion is cross-linked and the hydrophobicity becomes high. Therefore, when printed, it has a structure that hardly swells with respect to water and water-soluble solvent (H) contained in the ink, and the resin particle surface has a plurality of carboxyl groups and is associated between the resin particles.
  • H water-soluble solvent
  • the interaction with the ink is large and it works preferentially on the wettability of the ink, but the water resistance is not lowered.
  • the ink dot can be expanded moderately without impairing water resistance, and a high-definition image without blur can be provided. Since the water resistance inside the emulsion particles as a base is excellent, even if it has a hydrophilic group, the water resistance of the image is not impaired.
  • a surfactant can be used during emulsion polymerization of the emulsion.
  • Surfactants include anionic and nonionic surfactants, and conventionally known ones such as a reactive surfactant having an ethylenically unsaturated group and a non-reactive surfactant having no ethylenically unsaturated group are used. Can be used arbitrarily.
  • anionic reactive surfactant having an ethylenically unsaturated group examples include alkyl ethers (commercially available products include, for example, Aqualon KH-05, KH-10, KH-20, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Adeka Soap SR-10N, SR-20N manufactured by ADEKA Corporation, LATEMUL PD-104 manufactured by Kao Corporation, etc.); Sulfosuccinic acid esters (for example, LATEMUL S-120, S-120A, S-180P, S-180A, Sanyo Kasei Co., Ltd.
  • alkyl ethers commercially available products include, for example, Aqualon KH-05, KH-10, KH-20, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Adeka Soap SR-10N, SR-20N manufactured by ADEKA Corporation, LATEMUL PD-104 manufactured by Kao Corporation, etc.
  • Elminol JS-2 manufactured by Kao Corporation Alkyl phenyl ethers or alkyl phenyl esters (commercially available products include, for example, Aqualon H-2855A, H-3855B, H-3855C, H-3856, HS-05, HS-10, HS, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) -20, HS-30, ADEKA Corporation ADEKA rear soap SDX-222, SDX-223, SDX-232, SDX-233, SDX-259, SE-10N, SE-20N, etc.); (Meth) acrylate sulfates (commercially available products include, for example, Antox MS-60, MS-2N manufactured by Nippon Emulsifier Co., Ltd., Eleminol RS-30 manufactured by Sanyo Chemical Industries, Ltd.); and phosphate esters (commercially available) Examples of the product include H-3330PL manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
  • Nonionic reactive surfactants include, for example, alkyl ethers (commercially available products such as Adeka Soap ER-10, ER-20, ER-30, ER-40, manufactured by ADEKA Corporation, and Kao Corporation). Laterum PD-420, PD-430, PD-450, etc.); Alkyl phenyl ethers or alkyl phenyl esters (commercially available products include, for example, Aqualon RN-10, RN-20, RN-30, RN-50, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., and ADEKA rear soap NE- manufactured by ADEKA Corporation.
  • non-reactive nonionic surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether or polyoxyethylene stearyl ether; Polyoxyethylene alkylphenyl ethers such as polyoxyethylene octylphenyl ether or polyoxyethylene nonylphenyl ether; sorbitan higher fatty acid esters such as sorbitan monolaurate, sorbitan monostearate, or sorbitan trioleate; Polyoxyethylene sorbitan higher fatty acid esters such as polyoxyethylene sorbitan monolaurate; Polyoxyethylene higher fatty acid esters such as polyoxyethylene monolaurate or polyoxyethylene monostearate; Examples include glycerol higher fatty acid esters such as oleic acid monoglyceride or stearic acid monoglyceride; and polyoxyethylene / polyoxypropylene / block copolymer or polyoxyethylene distyrenated phenyl ether.
  • non-reactive anionic surfactants include higher fatty acid salts such as sodium oleate; Alkylaryl sulfonates such as sodium dodecylbenzenesulfonate; Alkyl sulfate salts such as sodium lauryl sulfate; Polyoxyethylene alkyl ether sulfate salts such as sodium polyoxyethylene lauryl ether sulfate; Polyoxyethylene alkylaryl ether sulfate salts such as sodium polyoxyethylene nonylphenyl ether sulfate; Examples thereof include alkyl sulfosuccinic acid ester salts such as sodium monooctyl sulfosuccinate, sodium dioctyl sulfosuccinate, or sodium polyoxyethylene lauryl sulfosuccinate and derivatives thereof; and polyoxyethylene distyrenated phenyl ether sulfates.
  • surfactants may be used alone or in combination of two or more.
  • the amount of the surfactant used is not necessarily limited, and can be appropriately selected according to physical properties required when the already crosslinked vinyl emulsion is finally used as a coating agent for forming an ink receiving layer.
  • the surfactant is usually preferably 0.1 to 30 parts by weight, more preferably 0.3 to 20 parts by weight with respect to 100 parts by weight of the total of ethylenically unsaturated monomers, More preferably, it is in the range of 0.5 to 10 parts by weight.
  • the surfactant is 0.1 parts by weight or more, the polymerization stability and mechanical stability are good.
  • it is 30 parts by weight or less the water resistance of the obtained ink receiving layer is excellent.
  • a water-soluble protective colloid can be used in combination.
  • the water-soluble protective colloid include polyvinyl alcohols such as partially saponified polyvinyl alcohol, fully saponified polyvinyl alcohol, or modified polyvinyl alcohol; Examples thereof include cellulose derivatives such as hydroxyethyl cellulose, hydroxypropyl cellulose, or carboxymethyl cellulose salt; and natural polysaccharides such as guar gum. These can be used either alone or in a combination of a plurality of types.
  • the use amount of the water-soluble protective colloid is preferably 0.1 to 5 parts by weight, more preferably 0.5 to 2 parts by weight per 100 parts by weight of the total of ethylenically unsaturated monomers.
  • a polymerization initiator can be used when obtaining a cross-linked vinyl emulsion.
  • the polymerization initiator is not particularly limited as long as it has the ability to initiate radical polymerization, and known oil-soluble polymerization initiators and water-soluble polymerization initiators can be used.
  • the oil-soluble polymerization initiator is not particularly limited, and examples thereof include benzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl hydroperoxide, tert-butyl peroxy (2-ethylhexanoate), and tert-butyl peroxide.
  • Organic peroxides such as oxy-3,5,5-trimethylhexanoate or di-tert-butyl peroxide; and 2,2′-azobisisobutyronitrile, 2,2′-azobis-2
  • azobis compounds such as 4-dimethylvaleronitrile, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) or 1,1′-azobiscyclohexane-1-carbonitrile. These may use only 1 type and may use 2 or more types together.
  • These polymerization initiators are preferably used in an amount of 0.1 to 10.0 parts by weight with respect to 100 parts by weight of the ethylenically unsaturated monomer.
  • a water-soluble polymerization initiator is preferably used.
  • ammonium persulfate, potassium persulfate, hydrogen peroxide, or 2,2′-azobis (2-methylpropionamidine) dihydrochloride is known. Can be used for
  • a reducing agent can be used in combination with a polymerization initiator as desired. Thereby, it becomes easy to accelerate the emulsion polymerization rate or to perform the emulsion polymerization at a low temperature.
  • reducing agents include reducing organic compounds such as metal salts such as ascorbic acid, ersorbic acid, tartaric acid, citric acid, glucose, or formaldehyde sulfoxylate, Reducing inorganic compounds such as sodium thiosulfate, sodium sulfite, sodium bisulfite, or sodium metabisulfite, Examples thereof include ferrous chloride, Rongalite, or thiourea dioxide.
  • reducing agents are preferably used in an amount of 0.05 to 5.0 parts by weight based on 100 parts by weight of the total of ethylenically unsaturated monomers.
  • it can superpose
  • the polymerization temperature is not less than the half-life temperature of each polymerization initiator.
  • a peroxide-based polymerization initiator it may be usually about 70 ° C.
  • the polymerization time is not particularly limited, but is usually 2 to 24 hours.
  • aqueous medium used in the emulsion polymerization examples include water, and a water-soluble solvent (G) can be used as long as the object of the present invention is not impaired.
  • the water-soluble solvent (G) will be described later.
  • a buffering agent and a chain transfer agent can be used as necessary.
  • the buffer include sodium acetate, sodium citrate, and sodium bicarbonate.
  • chain transfer agents include mercaptans such as octyl mercaptan, 2-ethylhexyl thioglycolate, octyl thioglycolate, stearyl mercaptan, lauryl mercaptan, and t-dodecyl mercaptan.
  • All or part of the acidic functional group of the monomer (B) can be neutralized with a basic compound before or after polymerization.
  • a neutralizing agent ammonia; alkylamines such as trimethylamine, triethylamine, or butylamine; alcohol amines such as 2-dimethylaminoethanol, diethanolamine, triethanolamine, or aminomethylpropanol; or a base such as morpholine is used. can do.
  • the acid value of the resin particles of the already crosslinked vinyl emulsion can be adjusted by the composition of the ethylenically unsaturated monomer used for the polymerization, but is preferably in the range of 100 mgKOH / g to 500 mgKOH / g. If it is 100 mg KOH / g or more, the ink wettability and the ink absorption / drying properties are excellent, and the ink dots are sufficiently spread on the ink receiving layer, so that white spots and white stripes are not easily generated. Further, in the case of multicolor printing, ink droplets of different colors are in contact with each other, so that intercolor bleeding does not occur. Moreover, when it is 500 mgKOH / g or less, the water resistance is excellent.
  • the acid value here is a value measured by the following operation.
  • the glass transition temperature (Tg) of the resin particles of the already crosslinked vinyl emulsion can be adjusted by the composition of the ethylenically unsaturated monomer used for polymerization, but is preferably 0 to 100 ° C.
  • Tg glass transition temperature
  • blocking refers to a state in which the printed surface and the back surface of the base material are fused and cannot be easily peeled off
  • it is 100 ° C. or lower, the texture of the printed matter is excellent.
  • the glass transition temperature here is a value that can be calculated by the Fox method.
  • the Fox method (T.G. Fox, Phys. Rev., 86, 652 (1952)) is a method for estimating the Tg of a copolymer from the Tg of each homopolymer represented by the following formula. is there.
  • Tg is the glass transition temperature of the copolymer (absolute temperature display)
  • Tg 1 Tg 2 ⁇ Tg n is the glass transition temperature of the homopolymer of each monomer component (absolute display)
  • W 1 , W 2 ... W n represents the weight fraction of each monomer component.
  • the volume average particle size of the pre-crosslinked vinyl emulsion can be adjusted by the composition of the ethylenically unsaturated monomer used for polymerization, the type and amount of the surfactant used during the polymerization, the polymerization operation, etc. From the viewpoint of stability, it is preferably 10 nm or more, more preferably 30 nm or more, and further preferably 40 nm or more. Moreover, 500 nm or less is preferable, 400 nm or less is more preferable, and 250 nm or less is further more preferable. For example, the ranges of 10 to 500 nm, 30 to 250 nm, 40 to 400 nm, and 40 to 250 nm are preferable. Considering the stability of the particles, the coarse particles exceeding 1 ⁇ m are preferably 5% by weight or less.
  • the volume average particle diameter is measured by a dynamic light scattering method, and more specifically is a value measured by the following operation.
  • the cross-linked vinyl emulsion is diluted with water 200 to 1000 times depending on the solid content concentration.
  • About 5 ml of the diluted solution is injected into a cell of a measuring apparatus [Microtrack manufactured by Nikkiso Co., Ltd.], and the measurement is performed after inputting the solvent (water in the present invention) and the refractive index condition of the resin according to the sample.
  • the peak of the volume particle size distribution data (histogram) obtained at this time is defined as the volume average particle size.
  • the viscosity of a crosslinked vinyl-based emulsion at a solid content concentration of 10% by weight can be adjusted by the composition of the ethylenically unsaturated monomer used for polymerization, the type and amount of the surfactant used during polymerization, the polymerization operation, and the like. However, it is preferably 0.1 to 300 mPa ⁇ s. If the viscosity at a solid content concentration of 10% by weight is 300 mPa ⁇ s or less, there is no need to dilute and apply when forming the inkjet ink receiving layer.
  • the viscosity here is a value that can be measured by the following operation.
  • SP value of resin particles of pre-crosslinked vinyl emulsion by the Fedor method [R. F. Fedor, Polym. Eng. Sci. , 14 (2) 147 (1974)] can be adjusted by the composition of the ethylenically unsaturated monomer to be used for the polymerization, but it is 3.9 to 6.8 (J ⁇ cm ⁇ 3 ) 1/2 . It is preferably 4.9 to 5.9 (J ⁇ cm ⁇ 3 ) 1/2 . If it is 3.9 (J ⁇ cm ⁇ 3 ) 1/2 or more, the ink wettability and the ink absorption / drying properties are excellent, and the ink dots are sufficiently spread on the ink receiving layer. Does not occur. Further, ink droplets of different colors do not come into contact with each other, and bleeding between colors does not occur. If it is 6.8 (J ⁇ cm ⁇ 3 ) 1/2 or less, the water resistance is sufficient.
  • the surface tension value of the ink-receiving layer surface is close to the value of the dynamic surface tension of the water-based ink. Is preferred.
  • the surface tension value on the surface of the ink receiving layer is close to the value of the dynamic surface tension of the water-based ink used, the ink dots on the ink receiving layer are appropriately spread and a high-definition image can be obtained.
  • the SP value and the surface tension value of the resin particles of the already cross-linked vinyl emulsion serve as a reference for determining the compatibility (interaction) with the water-based ink, and the quality of the image changes depending on these values. Therefore, these numerical values can be adjusted to obtain a highly detailed image.
  • the coating agent for forming an ink receiving layer in this embodiment is composed of one of the above-mentioned already crosslinked vinyl emulsions, or a combination of two or more.
  • a copolymer (X) using an aromatic monomer as the monomer (C) It is preferable to use together with the copolymer (Y) which uses only monomers other than an aromatic type as a monomer (C).
  • an aromatic monomer and a non-aromatic monomer may be used in combination as the monomer (C).
  • the aromatic monomer (C) is preferably 1 to 79.9% by weight, more preferably 1%, out of a total of 100% by weight of the monomers to be subjected to emulsion polymerization. -50% by weight is included.
  • the non-aromatic monomer (C) is preferably contained in an amount of 0 to 78.9% by weight, more preferably 0 to 75% by weight.
  • the coating agent for forming the ink receiving layer may be blended with a film forming aid, a viscosity adjusting agent, an antifoaming agent, a leveling agent, an antiseptic, a pH adjusting agent, or other compounds, if necessary. Good. About these additives, it can select arbitrarily from a conventionally well-known compound according to the objective.
  • the film-forming aid is responsible for the temporary plasticizing function that helps the formation of the coating film and evaporates relatively quickly after the coating film is formed to improve the strength of the coating film.
  • a water-soluble solvent (G) as a film-forming aid, the surface tension of the coating agent for forming the ink-jet ink receiving layer is lowered, improving the wettability to the base material, and improving the adhesion of the coating film to the base material. The water resistance and abrasion resistance of the film can be improved.
  • water-soluble solvent (G) an organic solvent having a boiling point of 110 to 200 ° C. is preferably used.
  • the solubility parameter value is Fedors' method [R. F. Fedor, Polym. Eng. Sci. , 14 (2) 147 (1974)], and the SP value is preferably 8.0 to 16.0 (cal / cm 3 ) 1/2 .
  • the SP value is 8.0 or more, the hydrophobicity is not too high and the already crosslinked vinyl emulsion is stable, and when it is 16.0 or less, the hydrophilicity is not too high and the effect as a film forming aid is high.
  • water-soluble solvent examples include alcohol solvents, general formula (1) R 1 (OR 2 ) Z OR 3 (wherein R 1 and R 3 are each independently a hydrogen atom or an alkyl group having 1 or more carbon atoms, Z is an integer of 1 or more, R 2 is an ethylene group or a propylene group) And a nitrogen-containing or sulfur-containing or lactone-based solvent.
  • water-soluble solvent (G) corresponding to the alcohol solvent examples include linear or branched aliphatic alcohols such as methanol, ethanol, propanol, isopropanol, butanol, and n-amyl alcohol.
  • Examples of the water-soluble solvent (G) corresponding to the general formula (1) include glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol and dipropylene glycol, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, Propylene glycol n-propyl ether, propylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol monobutyl ether, diethylene glycol dibutyl ether, diethylene glycol monohexyl ether, diethylene glycol methyl ethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl Ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, triprop
  • water-soluble solvent (G) corresponding to the nitrogen-containing, sulfur-containing, or lactone solvent examples include 3-methyloxazolidinone, 3-ethyloxazolidinone, 2-pyrrolidone, 1-methyl-2-pyrrolidone, 1- Examples thereof include ethyl-2-pyrrolidone, ⁇ -butyrolactone, ⁇ -butyrolactam, ⁇ -caprolactone, ⁇ -caprolactam, ⁇ -valerolactone, ⁇ -valerolactam, dimethyl sulfoxide and ⁇ -alkoxypropionamides.
  • the water-soluble solvent (G) is preferably contained in an amount of 0.5 parts by weight or more, more preferably 5 parts by weight or more in 100 parts by weight of the coating agent for forming an ink-jet ink receiving layer. Further, it is preferably 50 parts by weight or less, more preferably 20 parts by weight or less, still more preferably 15 parts by weight or less, and particularly preferably 10 parts by weight or less. Within this range, for example, 0.5 to 15 parts by weight may be contained.
  • viscosity modifier examples include polysaccharides such as carboxymethyl cellulose, methyl cellulose, hydroxymethyl cellulose, and ethyl cellulose, polyvinyl alcohol, polyacrylic acid (and salts thereof), oxidized starch, phosphorylated starch, and casein. These viscosity modifiers may be used in an amount of 1 to 100 parts by weight based on 100 parts by weight of the already crosslinked vinyl emulsion.
  • the coating agent for forming an ink-jet ink receiving layer may be composed of the aforementioned crosslinked vinyl emulsion alone, or colloidal silica, colloidal alumina, or silica, alumina, calcium carbonate, magnesium carbonate, titanium oxide, barium sulfate, oxidation Zinc, silicon dioxide, calcium silicate, talc, kaolin, calcined kaolin, magnesium hydroxide, aluminum hydroxide, calcium sulfate, gypsum, diatomaceous earth, zeolite, bentonite clay and other inorganic fillers may be used in combination.
  • the inorganic filler may be added later to the cross-linked vinyl emulsion, or an aqueous dispersion of the inorganic filler may be added to the aqueous medium during the synthesis of the cross-linked vinyl emulsion.
  • the ink-jet ink receiving layer forming coating agent may be blended with an aqueous glossy resin in order to impart gloss to the ink receiving layer.
  • Specific examples include Jonkrill 52J, Jonkrill 62J, Jonkrill 70J, and Jonkrill 7667 manufactured by BASF, Luciden 400SF manufactured by Nippon Polymer Co., Ltd., Emmapoly SG-5157 manufactured by Gifcellac, and the like.
  • the coating agent for forming an ink-jet ink receiving layer may further contain a crosslinking agent, such as methylolated melamine, methylolated urea, methylolated hydroxypropylene urea, polyfunctional isocyanate compound, or polyfunctional epoxy compound. Can be mentioned.
  • a crosslinking agent such as methylolated melamine, methylolated urea, methylolated hydroxypropylene urea, polyfunctional isocyanate compound, or polyfunctional epoxy compound.
  • a coating agent for forming an ink jet ink receiving layer can be prepared by mixing the obtained cross-linked vinyl emulsion, the water-soluble solvent (G), and, if necessary, other components.
  • the substrate on which the coating agent for forming the ink-jet ink receiving layer is applied is not particularly limited.
  • Fine paper, medium paper, coated paper, art paper, glossy paper, newsprint, various information paper, and various special papers Paper such as synthetic paper or paperboard, or polyethylene terephthalate, diacetate, triacetate, polyacetate, acetylcellulose, cellophane, celluloid, polycarbonate, polyimide, polyvinyl chloride, polyvinylidene chloride, polyacrylate, polyethylene, polyester, polystyrene, A film made of a commonly used plastic such as polyvinyl alcohol, nylon, or polypropylene can be used.
  • processed paper such as coated paper, art paper, and glossy paper is preferable from the viewpoint of obtaining excellent image formation.
  • paper that has been appropriately sized, a sheet-like substance made of a film that has been made opaque by filling with inorganic substances or fine foaming, and the like.
  • a sheet made of glass or metal may be used.
  • the surface of the substrate can be subjected to corona discharge treatment or various undercoat treatments.
  • the surface of the substrate may be a smooth surface, an uneven surface, or transparent, translucent, or opaque. Further, two or more of these substrates may be bonded to each other. Furthermore, a peeling adhesive layer or the like may be provided on the opposite side of the printing surface, or an adhesive layer or the like may be provided on the printing surface after printing.
  • the image forming recording medium of this embodiment includes an ink jet ink receiving layer formed from a coating agent for forming an ink jet ink receiving layer on at least one surface of a substrate.
  • the ink-jet ink receiving layer (hereinafter also referred to as ink receiving layer) is preferably formed by coating and printing a coating agent for forming an ink receiving layer on the substrate by a known method.
  • a coating agent for forming an ink receiving layer on the substrate by a known method.
  • roll coating method blade coating method, air knife coating method, gate roll coating method, bar coating method, size press method, spray coating method, die coating method, lip coating method, comma coating method, spin coating method, or gravure coating method , Curtain coating method, flexographic printing, screen printing, dispenser printing, inkjet printing, and the like.
  • the ink receiving layer forming coating agent is filled in the ink cartridge of the ink jet printer, and printing can be performed simultaneously with or before the printing ink.
  • the drying method of the coating agent for forming the ink receiving layer is not particularly limited, and examples include those using hot air drying, infrared rays or a reduced pressure method.
  • the drying conditions depend on the film-forming property of the coating agent for forming the ink-receiving layer, the coating amount, or the selected additive, but heating with hot air at about 60 to 180 ° C. or infrared at about 20 to 160 ° C. is usually used. Heating may be used. Hot air drying and infrared drying may be used in combination.
  • the coating amount of the coating agent for forming the ink receiving layer is not particularly limited, but the dry weight is preferably 0.2 to 50 g / m 2 , more preferably 0.5 to 30 g / m 2 .
  • the coating amount is 0.2 g / m 2 or more, the color developability of the ink is excellent as compared with the case where the ink receiving layer is not provided.
  • it is 50 g / m 2 or less, the occurrence of curling can be suppressed.
  • the ink receiving layer may be provided only on one side of the substrate, or may be provided on both sides.
  • calendering or casting may be performed to smooth the ink receiving layer, improve glossiness, or improve surface strength.
  • an image is formed by inkjet ink on an ink receiving layer of an image forming recording medium.
  • inkjet inks examples include water-based inks, solvent-based inks, useless-based inks, and radiation-curable inks such as UV curable inks and EB curable inks.
  • Any of the pigments can be used and may be used alone or in combination. From the viewpoint of the durability of the printed material, it is preferable to use a pigment as the color material, and it is preferable to use water-based ink from the viewpoint of the environment.
  • the water-based ink preferably contains a pigment, a water-soluble solvent (H), water, and a pigment dispersion resin.
  • a pigment preferably contains a pigment, a water-soluble solvent (H), water, and a pigment dispersion resin.
  • pigment contained in the water-based ink conventionally known pigments can be used.
  • Examples of the black pigment contained in the water-based ink include carbon black produced by the furnace method and the channel method.
  • these carbon blacks have a primary particle size of 11 to 40 nm, a specific surface area by BET method of 50 to 400 m 2 / g, a volatile content of 0.5 to 10% by mass, a pH value of 2 to 10, and the like.
  • Those having the following are preferred.
  • the following are mentioned as a commercial item which has such a characteristic. For example, no.
  • Examples of yellow pigments contained in water-based inks include C.I. I. Pigment Yellow 1, 2, 3, 12, 13, 14, 16, 17, 20, 24, 74, 83, 86, 93, 94, 95, 109, 110, 117, 120, 125, 128, 137, 138, 139, 147, 148, 150, 151, 154, 155, 166, 168, 180, 185, 213 and the like.
  • magenta pigments contained in water-based ink include C.I. I. PigmentRed 5, 7, 9, 12, 31, 48, 49, 52, 53, 57, 97, 112, 122, 147, 149, 150, 168, 177, 178, 179, 202, 206, 207, 209, 238, 242, 254, 255, 269, C.I. I. PigmentViolet 19, 23, 29, 30, 37, 40, 50 and the like.
  • cyan pigments contained in water-based ink include C.I. I. PigmentBlue 1, 2, 3, 15: 3, 15: 4, 16, 22, C.I. I. Vat Blue 4, 6 and the like.
  • pigments contained in the water-based ink As the pigment contained in the water-based ink, newly produced pigments such as pigments other than those described above and self-dispersing pigments can also be used. These pigments may be used alone or in combination of two or more in each color ink.
  • the content of the pigment contained in the water-based ink is preferably 0.1% by weight or more, more preferably 1% by weight or more in terms of the weight ratio in the total mass of the ink. More preferably, it is 2% by weight or more. Moreover, 20 weight% or less is preferable, More preferably, it is 12 weight% or less. Examples thereof include 0.1 to 20% by weight, 0.1 to 12% by weight, 1 to 20% by weight, and 2 to 12% by weight.
  • a suitable medium contained in the water-based ink is a mixed solvent of water and a water-soluble solvent (H).
  • water ion-exchanged water (deionized water) is used instead of general water containing various ions. It is preferred to use.
  • water-soluble solvent conventionally known solvents can be used, but glycol ethers and diols are preferably used.
  • glycol ethers include ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monopentyl ether, diethylene glycol monohexyl ether, triethylene Glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monobutyl ether, propylene glycol monopropyl ether, pro Glycol monobutyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, and the like.
  • diethylene glycol monobutyl ether diethylene glycol monohexyl ether, and triethylene glycol monomethyl ether are preferably used from the viewpoints of wettability to the ink receiving layer, permeability, and ink moisture retention.
  • diols include ethylene glycol, propylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, , 3-butanediol, 1,2-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,3-hexanediol, 1,4-hexanediol, 1,5-hexanediol, 2, Examples include 3-hexanediol, 2,4-hexanediol, 1,6-hexanediol, and 2-methyl-2,4-pentanediol.
  • 1,2-propanediol, 1,2-butanediol, 1,3-butanediol, 1,2-hexanediol, 2 from the viewpoint of wettability to the ink receiving layer, penetrability, and moisture retention of the ink.
  • -Methyl-2,4-pentanediol is preferred.
  • water-soluble solvents (H) may be used alone in each color ink or may be used in combination.
  • water-soluble nitrogen-containing complex such as 2-pyrrolidone, N-methylpyrrolidone, N-ethylpyrrolidone, N-methyloxazolidinone, N-ethyloxazolidinone, etc. is used for the purpose of improving the solubility. Ring compounds can also be added.
  • the content of the water-soluble solvent (H) as described above in the ink is generally in the range of 3% by mass to 60% by mass, more preferably 3% by mass to 50% by mass of the total mass of the ink. % Or less.
  • the water content is in the range of 10% by mass to 90% by mass, more preferably 30% by mass to 80% by mass, based on the total mass of the ink.
  • pigment dispersion resin conventionally known ones can be used, but (meth) acrylic acid copolymers are generally used. This is because charge repulsion occurs between pigments in an aqueous solvent due to charge repulsion when the (meth) acrylic acid copolymer adsorbed on the pigment surface is ionized, and a stable pigment dispersion state can be maintained. Conceivable.
  • the pigment dispersion resin includes a monomer (D) having an alkyl group (meth) acrylate ester having 10 to 24 carbon atoms, a monomer having styrene, ⁇ -methylstyrene or benzyl (meth) acrylate (E ) And (meth) acrylic acid-containing monomer (F) is preferably a copolymer (copolymer) containing the copolymer composition.
  • the affinity between the water-based ink and the surface of the ink receiving layer is appropriately controlled, and the ink dots spread appropriately, so that images with no white spots, white stripes, or intercolor bleeding are suppressed.
  • Examples of the monomer (D) having an alkyl group (meth) acrylate ester having 10 to 24 carbon atoms include decyl (meth) acrylate, undecyl (meth) acrylate, lauryl (meth) acrylate, and tridecyl (meth). Examples include acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, and behenyl (meth) acrylate.
  • lauryl (meth) acrylate in order to further improve the storage stability, it is preferable to use lauryl (meth) acrylate, stearyl (meth) acrylate, or behenyl (meth) acrylate.
  • the reason why the number of carbon atoms is 10 or more and 24 or less is from the viewpoint of storage stability.
  • Examples of the monomer (E) include monomers having styrene, ⁇ -methylstyrene or benzyl (meth) acrylate, and among them, styrene is used in order to further improve the storage stability. It is preferable.
  • the pigment-dispersed resin is preferably a copolymer containing the monomers (D), (E) and (F) as described above in the copolymer composition, and in addition to these monomers, other than the monomer (E)
  • a monomer having an aromatic group and a monomer having an acidic functional group other than the monomer (F) may be copolymerized.
  • Examples of the monomer having an acidic functional group other than the monomer (F) include the following vinyl compounds having an acidic functional group such as methacrylic acid, maleic acid, maleic acid half ester, itaconic acid, icotan. Acid half ester, fumaric acid, fumaric acid half ester, vinyl sulfonic acid, vinyl phosphonic acid and the like can be mentioned.
  • the ratio of the monomer (D) to the monomer (E) is 1/9 or more, the hydrophobic property of the pigment dispersion resin is high, the adhesion of the pigment dispersion resin to the pigment surface is high, and the storage stability of the water-based ink Is excellent.
  • the ratio (weight) of the monomer (F) is preferably 1 to 60 when the total of the monomers (D) to (F) is 100.
  • the ratio of the total amount of the monomers (D), (E), and (F) in the total amount of the pigment dispersion resin is preferably 70 to 100% by mass.
  • the pigment-dispersed resin preferably has a weight average molecular weight in the range of 2,000 to 30,000, and more preferably has a weight average molecular weight in the range of 5,000 to 20,000.
  • the acid value of the pigment-dispersed resin can be adjusted by the composition of the monomer having an anionic functional group used for polymerization, and is preferably in the range of 50 mgKOH / g to 400 mgKOH / g, Is more preferably in the range of 80 mgKOH / g to 300 mgKOH / g.
  • the acid value of the pigment dispersion resin is 50 mgKOH / g or more, the dispersion stability of the pigment ink is high and the ejection stability is good.
  • the acid value of the pigment dispersion resin is 400 mgKOH / g or less, the adhesion of the pigment dispersion resin to the pigment surface does not decrease, and the storage stability of the water-based ink is high.
  • an image is formed with an aqueous pigment ink on the ink receiving layer, there is no white spot / white streak or intercolor bleeding, image formation is good, and water resistance of the printed matter is excellent.
  • weight average molecular weight and acid value are values measured by a conventional method, and are values obtained by the measurement method described in the method for forming an ink-jet ink receiving layer.
  • the pigment dispersion resin is preferably neutralized with a basic compound. This is because the pigment dispersion resin is stably dispersed or dissolved in the aqueous liquid medium by neutralization. However, if the alkalinity is too strong, it may cause corrosion of various members used in the ink jet recording apparatus. Therefore, the pH is preferably in the range of 7 to 10.
  • the neutralizing agent used in this case include various organic amines such as ammonia, dimethylaminoethanol, diethanolamine, and triethanolamine, and alkali metal hydroxides such as sodium hydroxide, lithium hydroxide, and potassium hydroxide.
  • An inorganic alkali agent, an organic acid, a mineral acid, or the like can be used.
  • the pigment dispersion resin can be synthesized by a conventionally known solution polymerization method, emulsion polymerization method, suspension polymerization method, bulk polymerization method, or the like.
  • the pigment-dispersed resin described above is preferably contained in the range of 0.1% by mass to 8% by mass with respect to the total mass of the water-based ink.
  • natural resins such as rosin, shellac and starch, and synthetic resins which are not the above-described pigment dispersion resins can be preferably used as necessary.
  • the natural resin or the synthetic resin is preferably contained in an amount not exceeding the amount of the pigment-dispersed resin added.
  • the water-based ink preferably contains water-dispersible resin particles in order to improve the resistance of the printed coating film.
  • water-dispersible resin particles By containing the water-dispersible resin particles, it is possible to improve the resistance of the printed coating film without significantly increasing the ink viscosity. Thereby, the water resistance, solvent resistance, scratch resistance, etc. of the printed matter are improved. Even if a water-soluble resin is added, the durability can be expected to improve to some extent, but the viscosity of the ink tends to increase.
  • inkjet ink there is a suitable range for the viscosity at which ink can be ejected from the nozzle, and if the viscosity is too high, it may become impossible to eject the ink, so it is important to suppress the increase in viscosity.
  • the content of the water-dispersible resin particles in the aqueous ink is preferably in the range of 2 to 30% by weight, more preferably in the range of 3 to 20% by weight, based on the solid content concentration of the emulsion.
  • water-dispersible resin particles examples include water-dispersible waxes, and examples thereof include water dispersions of natural wax and synthetic wax.
  • Natural waxes include petroleum waxes such as paraffin wax, microcrystalline wax, and petrolatum, or plant waxes such as carnauba wax, candelilla wax, rice wax, and wood wax, and also animal plant waxes such as lanolin, Mention may be made of beeswax and the like.
  • the synthetic wax include polyethylene wax that is a synthetic hydrocarbon wax, Fischer-Tropsch wax, and the like, or paraffin wax derivatives, montan wax derivatives, and microcrystalline wax derivatives that are modified waxes.
  • water-dispersible waxes can be used alone or in combination of two or more in each color ink.
  • Commercially available water-dispersible waxes include, for example, AF-41, AG-73 (HDPE), A-514 (LDPE), A-329, A-206 (microcrystalline), AD manufactured by Gifu Seratech Manufacturing Co., Ltd. -62 (paraffin), X-8512 (lanolin), XA-35 (amide resin), AF-20 (beeswax), XD-075 (carnauba), AQUACER 531 (HDPE) manufactured by Big Chemie Japan.
  • the content of the water-dispersible wax as described above in the water-based ink is in the range of 0.2 to 5% by weight, more preferably 0.3 to 2% by weight of the total weight of the ink in terms of solid content. It is a range.
  • additives such as surfactants, antifoaming agents, preservatives and the like should be added as appropriate to the water-based ink in order to obtain ink having desired physical properties as necessary. Can do.
  • 0.05 mass% or more and 10 mass% or less, preferably 0.2 mass% or more and 5 mass% or less is suitable with respect to the total mass of the water-based ink.
  • part represents “part by weight”
  • % represents “% by weight”.
  • the acid value, glass transition temperature, and SP value were obtained by the methods already described in this specification.
  • the remaining pre-emulsion and the remaining 5% strength aqueous solution of potassium persulfate are maintained for 2 hours while maintaining the internal temperature at 75-80 ° C
  • the mixture was added dropwise, and stirring was further continued for 2 hours.
  • the temperature was cooled to 30 ° C.
  • the solid content concentration was adjusted to 30% with ion-exchanged water to obtain a cross-linked vinyl emulsion 1.
  • the solid content concentration was determined from the residue after drying in a hot air oven under conditions of 150 ° C.-20 minutes.
  • Table 1 shows the results of acid value and glass transition temperature (Tg) for the crosslinked vinyl emulsions obtained in Synthesis Examples 1 to 26.
  • the mixture was further reacted at 110 ° C. for 3 hours, 0.6 parts of V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the reaction was further continued at 110 ° C. for 1 hour, whereby the pigment dispersion resin 1 solution was obtained. Obtained.
  • the weight average molecular weight of the pigment dispersion resin 1 was about 16000.
  • 37.1 parts of dimethylaminoethanol was added for neutralization. This is the amount that neutralizes 100% of acrylic acid.
  • 200 parts of water was added to make it aqueous. 1 g of this was sampled, heated and dried at 180 ° C.
  • Pigment-dispersed resin production examples 2 to 5 Synthesis was performed in the same manner as in Pigment-dispersed resin production example 1 except that the raw materials, preparation amounts, and reaction temperatures described in Table 2 were used, and solutions of pigment-dispersed resins 2 to 5 were obtained.
  • the weight average molecular weights of the pigment dispersion resins 2 to 5 were all about 16000. Further, dimethylaminoethanol was added so that the neutralization rate was 100%, and the mixture was made aqueous in the same manner as in Production Example 1 of the pigment dispersion resin, whereby aqueous solutions of the pigment dispersion resins 2 to 5 were obtained.
  • Table 2 shows the acid values of the pigment dispersion resins obtained in Production Examples 1 to 5 of the pigment dispersion resin.
  • pigment As pigment, C.I. I. Instead of Pigment Blue 15: 3, C.I. I. Pigment Red 122, C.I. I. Pigment Yellow 74, C.I. I. By using Pigment Black 7, magenta ink, yellow ink, and black ink were adjusted, respectively, and water-based ink 1 was obtained.
  • Example 1 To 100 parts of the vinyl emulsion obtained in Synthesis Example 1, 200 parts of ion-exchanged water was blended to prepare a coating agent for forming an inkjet ink receiving layer having a solid content concentration of 10%. This coating agent was applied to coated paper [Oji Paper Co., Ltd., OK Top Coat Plus] with a wire bar No. 2 and dried in a hot air oven at 60 ° C. for 2 minutes to produce a recording medium having an inkjet ink receiving layer laminated thereon.
  • the four-color water-based ink obtained in the water-based ink adjustment example 1 was filled into a cartridge of an ink jet printer (“PM-750C” manufactured by Epson), and pattern printing was performed to prepare a printed matter for evaluation.
  • PM-750C manufactured by Epson
  • Examples 2 to 22 (Comparative Examples 1 to 4) A printed matter for evaluation was produced in the same manner as in Example 1 except that the cross-linked vinyl emulsion of Synthesis Example 1 was changed to the cross-linked vinyl emulsion shown in Table 4.
  • Example 23 to 28 A printed matter for evaluation was produced in the same manner as in Example 1, except that the four-color water-based ink of Preparation Example 1 was changed to the four-color water-based ink shown in Table 4.
  • Table 4 shows the evaluation results of white spots / white stripes, dryness, and water resistance. A specific evaluation method will be described below.
  • ⁇ Water resistance> Drop a drop of water with a dropper on a solid printing part with a printing rate of 100%, wipe off the water with a tissue paper after 1 minute, and visually evaluate it. The ones that were taken were marked with ⁇ , and the ones without change were marked with ⁇ . In particular, among those that did not change visually, those that did not change visually even when rubbed 5 times with a cotton swab wetted with water were rated as ⁇ .
  • the water resistance is very excellent according to the coating agent for forming an ink image-receiving layer of Examples 9 and 19 to 21 using monomers having an aromatic group as the monomer (C).
  • Example 101 ⁇ Preparation example of coating agent for forming inkjet ink receiving layer> (Example 101) To 100 parts of the vinyl emulsion obtained in Synthesis Example 101, 50 parts of purified water was blended to prepare a vinyl emulsion liquid (X) having a solid content of 20%. 20 parts of diethylene glycol monobutyl ether was mixed with 80 parts of purified water to prepare an aqueous solution (Y) having a solvent concentration of 10%. A coating agent for forming an ink-jet ink receiving layer having a solid content of 10% and a diethylene glycol monobutyl ether concentration of 5% mixed so that Y was 100 parts by weight with respect to 100 parts by weight of X was prepared.
  • X vinyl emulsion liquid
  • Y aqueous solution
  • Example 102 A coating agent for forming an inkjet ink receiving layer was prepared in the same manner as in Example 101 except that Synthesis Example 101 was changed to Synthesis Example 102.
  • Example 103 A coating agent for forming an ink-jet ink receiving layer was prepared in the same manner as in Example 101 except that Synthesis Example 101 was changed to Synthesis Example 103.
  • Example 104 A coating agent for forming an inkjet ink receiving layer was prepared in the same manner as in Example 101 except that Synthesis Example 101 was changed to Synthesis Example 104.
  • Example 105 A coating agent for forming an inkjet ink receiving layer was prepared in the same manner as in Example 101 except that Synthesis Example 101 was changed to Synthesis Example 105.
  • Example 106 To 100 parts of the vinyl emulsion obtained in Synthesis Example 101, 50 parts of purified water was blended to prepare a vinyl emulsion liquid (X) having a solid content of 20%. To 40 parts of diethylene glycol monobutyl ether, 60 parts of purified water was blended to prepare an aqueous solution (Y) having a solvent concentration of 20%. A coating agent for forming an ink-jet ink receiving layer having a solid content of 10% and a diethylene glycol monobutyl ether concentration of 10% mixed so that Y was 100 parts by weight with respect to 100 parts by weight of X was prepared.
  • X vinyl emulsion liquid
  • Y aqueous solution
  • Example 10-7 To 100 parts of the vinyl emulsion obtained in Synthesis Example 101, 50 parts of purified water was blended to prepare a vinyl emulsion liquid (X) having a solid content of 20%. 20 parts of purified water was mixed with 80 parts of diethylene glycol monobutyl ether to prepare an aqueous solution (Y) having a solvent concentration of 40%. A coating agent for forming an inkjet ink receiving layer having a solid content of 10% and a diethylene glycol monobutyl ether concentration of 20% mixed so that Y was 100 parts by weight with respect to 100 parts by weight of X was prepared.
  • Example 108 A coating agent for forming an ink-jet ink receiving layer was prepared in the same manner as in Example 101 except that the water-soluble solvent (G) was changed from diethylene glycol monobutyl ether to isopropanol.
  • Example 109 A coating agent for forming an ink-jet ink receiving layer was prepared in the same manner as in Example 101 except that the water-soluble solvent (G) was changed from diethylene glycol monobutyl ether to ethylene glycol monobutyl ether.
  • Example 110 A coating agent for forming an ink-jet ink receiving layer was prepared in the same manner as in Example 101 except that the water-soluble solvent (G) was changed from diethylene glycol monobutyl ether to diethylene glycol monohexyl ether.
  • Example 111 A coating agent for forming an ink-jet ink receiving layer was prepared in the same manner as in Example 101 except that the water-soluble solvent (G) was changed from diethylene glycol monobutyl ether to propylene glycol monobutyl ether.
  • Example 112 A coating agent for forming an inkjet ink receiving layer was prepared in the same manner as in Example 101 except that the water-soluble solvent (G) was changed from diethylene glycol monobutyl ether to 2-pyrrolidone.
  • Example 113 A coating agent for forming an ink-jet ink receiving layer was prepared in the same manner as in Example 101 except that the water-soluble solvent (G) was changed from diethylene glycol monobutyl ether to ⁇ -butyrolactone.
  • Example 114 A coating agent for forming an ink-jet ink receiving layer was prepared in the same manner as in Example 101 except that the water-soluble solvent (G) was changed from diethylene glycol monobutyl ether to dimethyl sulfoxide.
  • Comparative Example 102 A coating agent for forming an ink-jet ink receiving layer was prepared in the same manner as in Comparative Example 101 except that Synthesis Example 101 was changed to Synthesis Example 103.
  • Example 103 A coating agent for forming an inkjet ink receiving layer was prepared in the same manner as in Example 101 except that Synthesis Example 101 was changed to Synthesis Example 106.
  • aqueous solution (X) was prepared. 20 parts of diethylene glycol monobutyl ether was mixed with 80 parts of purified water to prepare an aqueous solution (Y) having a solvent concentration of 10%.
  • a coating agent for forming an ink-jet ink receiving layer having a solid content of 10% and a diethylene glycol monobutyl ether concentration of 5% mixed so that Y was 100 parts by weight with respect to 100 parts by weight of X was prepared.
  • the “Aquaric YS100” is an anionic water-soluble resin.
  • Each ink-jet ink receiving layer forming coating agent was coated on coated paper [Oji Paper Co., Ltd., OK Top Coat Plus] with a wire bar No. 2 and dried in a hot air oven at 60 ° C. for 2 minutes to produce a recording medium having an inkjet ink receiving layer laminated thereon.
  • the aqueous pigment ink was filled in a cartridge of an ink jet printer (“PM-750C” manufactured by Epson Corporation), and pattern printing was performed to prepare a printed matter for evaluation.
  • Table 6 shows the evaluation results of white spots / white stripes and water resistance. A specific evaluation method will be described below.
  • white spots and white streaks are clearly observed x, white spots and white streaks are slightly generated, but usable ones are ⁇ , white spots are white -The one without white streak was marked as ⁇ .
  • “A” indicates that there is no white spot or white streak and there is no density unevenness and a uniform solid print portion is obtained.
  • Comparative Examples 101 and 102 did not have a water-soluble solvent, high water resistance could not be obtained. Moreover, in Comparative Example 103, it can be seen that the water resistance cannot be obtained because the emulsion has no cross-linking. In Comparative Example 104, it can be seen that the ink-jet ink receiving layer-forming coating agent is a water-soluble resin, and water resistance cannot be obtained. Further, in Comparative Example 5, since the coating agent for forming the ink jet ink receiving layer is a cationic resin, it is found that sufficient ink wetting cannot be obtained, and many white spots and white streaks are generated. It was. On the other hand, it was found that the coating agent for forming an ink-jet ink receiving layer of the present invention has excellent white streaks, water resistance, and glossiness in practical areas and is excellent.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Ink Jet (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)

Abstract

Dans le but d'obtenir une matière imprimée qui présente une excellente résistance à l'eau et dont les points blancs, les traînées blanches et le flou entre couleurs dans des images sont diminués, la présente invention propose un agent de revêtement pour former une couche de réception d'encre pour jet d'encre, ledit agent de revêtement étant caractérisé en ce qu'il contient un solvant soluble dans l'eau et une émulsion vinylique réticulée qui est obtenue par polymérisation en émulsion d'un mélange de monomères qui contient (A) un monomère ayant au moins deux groupes à insaturation éthylénique, (B) un monomère ayant un groupe carboxyle et un groupe à insaturation éthylénique et (C) un monomère ayant un groupe hydrophobe ayant 1-12 atomes de carbone et un groupe à insaturation éthylénique.
PCT/JP2012/069049 2011-07-26 2012-07-26 Agent de revêtement pour former une couche de réception d'encre pour jet d'encre, support d'enregistrement l'utilisant et matière imprimée Ceased WO2013015387A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2011163584A JP2013027979A (ja) 2011-07-26 2011-07-26 インクジェット印刷物
JP2011-163585 2011-07-26
JP2011-163584 2011-07-26
JP2011163585A JP2013027980A (ja) 2011-07-26 2011-07-26 インクジェットインキ受容層形成用コート剤、それを用いた記録媒体及び印刷物

Publications (1)

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WO2013015387A1 true WO2013015387A1 (fr) 2013-01-31

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105189131A (zh) * 2013-04-11 2015-12-23 花王株式会社 热喷墨记录方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001232932A (ja) * 2000-02-21 2001-08-28 Seiko Kagaku Kogyo Co Ltd インクジェット記録用紙用表面サイズ剤およびインクジェット記録用紙
JP2009161885A (ja) * 2008-01-08 2009-07-23 Arakawa Chem Ind Co Ltd 製紙用表面サイズ剤
JP2009214318A (ja) * 2008-03-07 2009-09-24 Fuji Xerox Co Ltd 記録装置、及び記録用の材料

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001232932A (ja) * 2000-02-21 2001-08-28 Seiko Kagaku Kogyo Co Ltd インクジェット記録用紙用表面サイズ剤およびインクジェット記録用紙
JP2009161885A (ja) * 2008-01-08 2009-07-23 Arakawa Chem Ind Co Ltd 製紙用表面サイズ剤
JP2009214318A (ja) * 2008-03-07 2009-09-24 Fuji Xerox Co Ltd 記録装置、及び記録用の材料

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105189131A (zh) * 2013-04-11 2015-12-23 花王株式会社 热喷墨记录方法
CN105189131B (zh) * 2013-04-11 2017-12-26 花王株式会社 热喷墨记录方法

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