WO2024185795A1 - 被記録材用処理液、それで処理した被記録材及びそれらの製造法 - Google Patents

被記録材用処理液、それで処理した被記録材及びそれらの製造法 Download PDF

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WO2024185795A1
WO2024185795A1 PCT/JP2024/008397 JP2024008397W WO2024185795A1 WO 2024185795 A1 WO2024185795 A1 WO 2024185795A1 JP 2024008397 W JP2024008397 W JP 2024008397W WO 2024185795 A1 WO2024185795 A1 WO 2024185795A1
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polymer
water
particles
recording material
polyvalent metal
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English (en)
French (fr)
Japanese (ja)
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公彦 大屋
里津子 大平
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Mikuni Color Ltd
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Mikuni Color Ltd
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Priority to CN202480017153.9A priority patent/CN121127505A/zh
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
    • B41J2/01—Ink jet
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F6/00—Post-polymerisation treatments
    • C08F6/06—Treatment of polymer solutions
    • C08F6/12—Separation of polymers from solutions

Definitions

  • the present invention relates to a treatment liquid for recording materials that is suitable for inkjet printing using an inexpensive formulation and a simple coating method, recording materials treated with the treatment liquid, and a method for manufacturing the recording materials.
  • Printer inks are generally divided into organic solvent-based inks and water-based inks.
  • Organic solvent-based inks have excellent water resistance, but problems with bleeding on plain paper, odor, and safety have led to water-based inks becoming mainstream in recent years.
  • the inkjet recording method allows for the simple and inexpensive production of a wide variety of images in small quantities, and has been applied to a variety of printing fields for both liquid-absorbing and non-liquid-absorbing substrates, including printing of characters, documents, and photographs, label printing, fabric printing, marking, color filters, and special printing such as circuit printing.
  • Dyes and pigments that can be dispersed or dissolved in water are used as colorants in water-based inks.
  • the colorants are used in the inkjet method, which uses nozzles for spraying ink with a pore size of 200 ⁇ m or less
  • pigment inks such as anionic polymer-dispersed inks in which pigment is uniformly dispersed in water, inks in which pigment particles are encapsulated in anionic polymers, and inks in which pigment particles are self-dispersed, as well as water-soluble dye inks that are dissolved before use, particularly anionic direct dye inks and acid dye inks, are used.
  • These coloring components are designed to allow printing without clogging the nozzle.
  • the inkjet ink When the inkjet ink is used to record on media such as paper, film, or fabric, it is required that the images and characters have high density and vivid colors, that the ink is quickly absorbed by the medium and does not flow even when ink dots overlap, that the ink dots do not diffuse laterally more than necessary, and that the periphery is smooth and not blurred.
  • Water-based inks used in inkjet printing contain a lot of solvents, which can cause problems with degradation of image quality, such as print density on the recording material, bleeding and feathering (a phenomenon in which ink droplets applied to the recording material penetrate through the mesh of the fibers that make up the recording material, such as cellulose, into the periphery of the printed image, causing the printed image to look fuzzy), and bleeding that occurs when the solvent is not completely absorbed (a phenomenon in which the ink in the printed image bleeds into the unprinted area like whiskers at the boundary between the printed image and unprinted area). For this reason, various measures are taken with recording materials.
  • a known method to prevent bleeding is to coat the surface of the recording material with a water-absorbing polymer and inorganic porous pigment, which quickly absorbs the solvent in the ink.
  • a known method for improving image quality by preventing ink bleeding, feathering, and increasing print density is to incorporate a cationic substance into the surface of the recording material.
  • Patent Document 1 discloses a technology that can improve the water resistance of a recording material by using a recording material treatment liquid that contains water-insoluble organic composite particles that combine a cationic polymer and an anionic polymer, without incorporating an inorganic porous pigment.
  • the recording material that achieves both ink bleeding, feathering, print density, bleeding, etc. is highly effective on liquid-absorbing substrates such as paper and canvas, but when applied to liquid-non-absorbing substrates such as films, although the bleeding effect is manifested, there is a problem of stickiness due to the blocking phenomenon manifested by the characteristics of the cationic polymer, and the use of this ink on liquid-non-absorbing substrates such as films is limited.
  • Japanese Patent Application Laid-Open No. 2003-233633 discloses a technique for obtaining a recording material treatment liquid having a non-sticky coating film and high film strength by using a cationic polymer having crosslinking properties as a part of the cationic polymer.
  • a cationic polymer having crosslinking properties as a part of the cationic polymer.
  • the problem of stickiness caused by the blocking phenomenon due to the characteristics of cationic polymers was solved by crosslinking, but the high viscosity caused problems in application, and the crosslinking caused problems in storage stability of the product.
  • crosslinking caused ink bleeding, feathering, and reduced print density.
  • Patent Document 3 discloses a method in which, without using an inorganic pigment, a porous coating film is formed by curing a crosslinkable resin, and then the film is impregnated with a cationic composition or the like to impart functionality.
  • a porous coating film is formed by curing a crosslinkable resin, and then the film is impregnated with a cationic composition or the like to impart functionality.
  • the impregnated cationic composition may migrate due to the ink liquid or moisture after printing, causing problems such as ring bleeding.
  • Patent Document 4 discloses a method of applying a pretreatment agent, which is made of insoluble resin particles made of polyolefin resin and polyurethane resin, a flocculant, and water, by inkjet printing.
  • a pretreatment agent which is made of insoluble resin particles made of polyolefin resin and polyurethane resin, a flocculant, and water.
  • the improvement of bleeding which is a problem of liquid absorption, is achieved by constructing a coating film depending on the application method, etc., and this performance cannot be obtained by a simple application method.
  • Patent Document 6 the cationic polymer of Patent Document 1 is used, and a specific coating amount is applied to specific paper through specific processing.
  • a specific coating amount is applied to specific paper through specific processing.
  • the effect on the paper such as ink bleeding, feathering, print density, and bleeding, is exhibited, there are problems with the film, particularly with regard to the effects of bleeding and blocking.
  • Attempts to form a receiving layer without adding inorganic pigments are also disclosed in Patent Documents 5 to 7, and claim to increase the strength of the recording material, avoid coloring with inorganic pigments, and improve the color development of black ink.
  • the receiving layer For liquid-non-absorbent substrates, the receiving layer must have higher solvent absorbency than liquid-absorbent substrates. In addition, there is a need to prevent blocking caused by stickiness on the receiving layer surface, and to provide a coating with higher transparency and strength.
  • the present invention aims to provide a means for improving ink bleeding, feathering, and print density, even when applied to non-liquid-absorbent substrates such as resin films and glass, and for obtaining recorded images without bleeding or blocking.
  • the inventors of the present invention have conducted extensive research into the above-mentioned problems. They found that when the water-insoluble organic particles of Patent Document 1 were used, ink bleeding, feathering, print density, and bleeding were improved, but blocking occurred and the particles could not be used. They then discovered that blocking was caused by a specific cationic polymer. They then discovered that by changing the water-soluble cationic polymer to a polyvalent metal cation, water-insoluble particles could be precipitated, and that by forming a receiving layer using these particles, stickiness of the coating film could be avoided. They also found that because there is no need to include a crosslinkable polymer as in Patent Document 2 in these particles, there is no concern about the stability of the treatment liquid containing these particles even when stored for a long period of time.
  • the present invention provides (1) A method for producing polymer-metal composite particles, comprising mixing a water-soluble anionic polymer with a polyvalent metal cation to precipitate particles; (2) Polymer-metal composite particles obtained by mixing and precipitating a water-soluble anionic polymer and a polyvalent metal cation; (3) Polymer-metal composite particles, characterized by containing at least a polymer having an anionic functional group and a polyvalent metal; (4) The polymer-metal composite particles according to any one of (1) to (3) above, characterized in that the average dispersed particle size is 0.1 to 5 ⁇ m.
  • the polymer-metal composite particle according to any one of (1) to (3) above characterized in that the polymer having an anionic functional group is at least one of a styrene-acrylic acid copolymer, an ⁇ -methylstyrene-acrylic acid copolymer, and a styrene- ⁇ -methylstyrene-acrylic acid copolymer.
  • the polyvalent metal cation is at least one of calcium, magnesium, and aluminum cations.
  • a method for producing a dispersion containing polymer and metal composite particles comprising mixing a water-soluble anionic polymer and a polyvalent metal cation in a liquid medium to precipitate particles.
  • a method for producing a treatment liquid for recording material comprising a step of mixing a water-soluble anionic polymer and a polyvalent metal cation in a liquid medium to precipitate particles.
  • a method for producing a recording material comprising mixing a water-soluble anionic polymer and a polyvalent metal cation in a liquid medium to precipitate particles, and applying a liquid containing the particles to a substrate.
  • a method for recording on a recording material comprising treating a substrate with the recording material treatment liquid according to claim 9 and recording on the substrate with an ink containing a colorant.
  • An inkjet recording method comprising mixing a water-soluble anionic polymer and a polyvalent metal cation in a liquid medium to precipitate particles, and coating a substrate with the liquid containing the precipitated particles to form a recording material, and then performing inkjet printing on the recording material.
  • a method for producing a recording material by mixing a water-soluble anionic polymer and a polyvalent metal cation in a liquid medium to precipitate particles, and applying a liquid containing the particles to a substrate, the method being characterized in that the application to the substrate is performed by an inkjet method.
  • the present invention relates to a recordable material obtained by coating the recordable material treatment liquid described above on a substrate, regardless of the substrate.
  • the polymer metal composite particles of the present invention can be used as a treatment liquid for impregnating or coating (the coating method is not limited) various substrates (the substrates are not limited) with a dispersion containing the polymer metal composite particles, that is, as a treatment liquid for recording materials.
  • a layer containing the polymer metal composite particles can be formed on the substrate.
  • the formed layer functions as a so-called receiving layer that receives ink when ink such as colored ink is printed (regardless of whether it is characters, figures, or solid paint).
  • an inkjet ink receiving layer formed on the surface of printing paper for inkjet printing is a typical example, but is not limited thereto, and may be any layer formed on a substrate to be printed for the purpose of facilitating ink fixation, facilitating color development, etc.
  • the material on which such a receiving layer is formed is the recording material.
  • the receiving layer formed by the present invention improves inkjet printing performance such as ink bleeding, feathering, print density, and bleeding, and further, even when applied to a substrate such as a resin film or glass, the ink receiving layer is free from coating film blocking.
  • the present invention makes it possible to obtain a treatment liquid for a recording material capable of forming a recording material having a receiving layer with such excellent performance.
  • the treatment liquid itself has excellent storage stability.
  • FIG. 1 is an image showing a process in which a water-soluble anionic polymer reacts with a polyvalent metal cation to produce a composite particle in the present invention.
  • FIG. 1 is a 30,000-fold electron microscope image of the dried polymer metal composite particle dispersion A obtained with formulation A.
  • FIG. 1 shows an electron microscope photograph of a dried polymer metal composite particle dispersion B obtained with formulation B at a magnification of 30,000.
  • FIG. 1 shows an electron microscope photograph of a dried polymer metal composite particle dispersion F obtained with formulation F at a magnification of 50,000.
  • the recording material treatment liquid of the present invention can be an aqueous dispersion in which water-insoluble polymer-metal composite particles are dispersed in an aqueous solvent, and can further contain a binder.
  • the polymer-metal composite particles are water-insoluble particles that contain a polymer component and a metal component. It is presumed that by mixing the water-soluble polymer with the polyvalent metal cation, the precipitated plate-like or spherical particles are layered on top of each other to form a porous layer, which absorbs and swells the liquid components in the ink, thereby preventing bleeding.
  • the anionic functional groups such as carboxyl groups of the water-soluble polymer fix the polyvalent metal cations, and the action of the polyvalent metal fixes the anionic pigment or dye to the water-soluble polymer via the polyvalent metal, thereby improving the inkjet printing performance, such as ink bleeding, feathering, and print density.
  • the migration of the polyvalent metal after application due to the ink liquid after printing or moisture after printing is suppressed, thereby improving poor water resistance such as ring bleeding.
  • the polymer metal composite particle of the present invention is characterized by containing a polymer having an anionic functional group and a polyvalent metal.
  • the polymer having an anionic functional group in the present invention is not particularly limited as long as it is a polymer that is generally called an anionic polymer, and the anionic functional group here may be either ionized or ionizable.
  • a carboxyl group is ionized by the addition of an alkali and exhibits anionic properties, so that the anionic functional group in the present invention is either ionized or not.
  • anionic polymers are solubilized by adding an alkaline substance to a polymer having an anionic functional group to ionize the anionic functional group, and are used as so-called water-soluble anionic polymers.
  • a water-soluble anionic polymer is mixed with a polyvalent metal cation described below, so that the anionic functional group of the polymer approaches the polyvalent metal cation and precipitates.
  • the polymer-metal composite particles containing the polymer having an anionic functional group of the present invention and a polyvalent metal can be obtained.
  • IR infrared spectroscopy
  • EDS energy dispersive X-ray analysis
  • the polymer metal composite particles of the present invention can be obtained by mixing at least one type of water-soluble anionic polymer with polyvalent metal cations, as described above.
  • the polyvalent metal cation used in the present invention is not limited in valence or element as long as it is a divalent or higher metal cation.
  • divalent or trivalent polyvalent metals such as calcium and magnesium are preferably used. Specifically, calcium (divalent), magnesium (divalent), and aluminum (trivalent) are preferred.
  • the method of mixing with the polyvalent metal cation is not particularly limited as long as it is a material that can release these metals as cations, but it can be easily performed by mixing with the salts of these metals, such as magnesium chloride, calcium chloride, and aluminum sulfate.
  • the amount and type of polyvalent metal that is blended affects the color development of the ink when used as a recording material and the pH of the recording material treatment liquid itself, so the amount and type of metal that is blended should be selected according to these systems, but basically any of the metal cations listed above can be used without any problems.
  • the water-soluble anionic polymer is not particularly limited as long as it is an anionic water-soluble polymer, but generally, an anionic polymer, that is, a polymer having an anionic functional group such as a carboxy group, a sulfonic acid group ( SO3H ), a sulfate ester group, or a phosphate ester group, which has been made water-soluble by anionizing it with an alkaline substance such as ammonia, an organic amine, or an alkali metal, can be used.
  • an anionic polymer that is, a polymer having an anionic functional group such as a carboxy group, a sulfonic acid group ( SO3H ), a sulfate ester group, or a phosphate ester group, which has been made water-soluble by anionizing it with an alkaline substance such as ammonia, an organic amine, or an alkali metal, can be used.
  • polymer having an anionic functional group examples include one or more of styrene-acrylic acid copolymer, ⁇ -methylstyrene-acrylic acid copolymer, styrene- ⁇ -methylstyrene-acrylic acid copolymer, styrene-acrylic acid copolymer, polyacrylic acid, styrene-maleic anhydride copolymer, acrylic acid ester-acrylic acid copolymer, polyester, salts thereof, etc.
  • anionic polymers can be used alone or in combination of two or more.
  • Alkaline substances for imparting water solubility include those generally known as neutralizing agents, such as organic amines such as trimethylamine, triethylamine, tri-n-propylamine, tributylamine, triethanolamine, aminomethylpropanol, aminomethylpropanediol, aminoethylpropanediol, trihydroxymethylaminomethane, monoethanolamine, and triisopropanolamine, as well as inorganic alkali salts such as ammonia water, potassium hydroxide, and sodium hydroxide, which are preferred because they can provide stable water solubility.
  • Ammonia water is particularly preferred because it is easily volatile and easy to remove.
  • the blocking of the coating film can be further improved. Furthermore, by selecting one with a high softening point, blocking can also be improved.
  • the glass transition point refers to the temperature above which a resin becomes soft and rubbery, allowing molecular motion to occur more easily when heated, and is the temperature at which the properties of the resin change drastically.
  • the glass transition point is 50°C or higher, preferably 50°C to 140°C.
  • the glass transition point is higher as the monomer composition ratio of styrene and ⁇ -methylstyrene in styrene-acrylic acid copolymer, ⁇ -methylstyrene-acrylic acid copolymer, and styrene- ⁇ -methylstyrene-acrylic acid copolymer increases.
  • the composition ratio of styrene and ⁇ -methylstyrene in the polymer is 20% to 80%, preferably 50% to 80%, and more preferably 60% to 75%. Furthermore, the higher the ratio of ⁇ -methylstyrene in the composition ratio of styrene and ⁇ -methylstyrene, the higher the glass transition point.
  • the glass transition point is low, blocking problems may occur, and the particles formed may fuse together and the particle size may become large. If the glass transition point is too high, the composition ratio with acrylic acid containing a carboxylic acid group may be disrupted, and water solubility may not be achieved.
  • the higher the constituent ratio of ⁇ -methylstyrene the higher the hydrophobicity becomes, resulting in a polymer that is more rigid and less flexible, which leads to a further improvement in blocking properties.
  • the softening point indicates the temperature at which a resin softens and begins to deform when heated.
  • the softening point is 100° C. or higher, preferably 140° C. or higher, and more preferably 150° C. or higher. If the softening point is less than 100° C., blocking problems will occur. In applications where printed matter is transferred by heat, a low softening point can cause the printing matter to be transferred onto surfaces other than the printed surface.
  • the weight average molecular weight (Mw) of the polymer is preferably 20,000 to 5,000. More preferably, it is 10,000 to 18,000, and even more preferably, it is 10,000 to 17,000.
  • the glass transition point decreases and blocking is not improved, whereas if the molecular weight is too high, the composition ratio with acrylic acid or the like containing a carboxylic acid group is lost and water solubility is not possible.
  • the amount of carboxylic acid functionality is defined by the acid number.
  • ⁇ -methylstyrene-acrylic acid copolymer and styrene- ⁇ -methylstyrene-acrylic acid copolymer can be preferably used in terms of the coatability of the treatment liquid to the recording material, the printing characteristics during recording, and the improvement of blocking.
  • Specific examples include commercially available products such as Joncryl 678, 690, and JDX-C3080 (all manufactured by BASF Japan Ltd.), which can be solubilized with any alkaline agent as described above.
  • Joncryl 60J, 70J, and JDX-6180 which are products obtained by solubilizing these polymers having an anionic functional group, can also be used.
  • the pH of the water-soluble anionic polymer is usually set to 8 or more to obtain stable water solubility.
  • the acid value of the water-soluble anionic polymer is from 50 to 300 mgKOH/g, preferably from 60 to 250 mgKOH/g, and more preferably from 70 to 250 mgKOH/g, from the viewpoint of ink-jet printing performance such as ink bleeding, feathering, and print density. If the amount is less than 50 mgKOH/g, stable water solubility cannot be obtained, and if the amount is more than 300 mgKOH/g, the ink may bleed, feather, or the print density may decrease.
  • the polymer metal composite particles of the present invention are produced by mixing the water-soluble anionic polymer with a polyvalent metal cation.
  • a polyvalent metal cation for example, the water-soluble anionic polymer, the polyvalent metal cation, and optionally an additive are mixed in a dispersion medium such as water in a predetermined amount, and then mixed and stirred to produce particles.
  • the water-soluble anionic polymer and the stabilizer are homogenized in water, and then the polyvalent metal cation is added and precipitated while stirring, thereby forming stable particles.
  • the stabilizer is not particularly limited, but specifically, a polymer stabilizer, i.e., a so-called polymer dispersant, is a typical example, such as a styrene-maleic anhydride ethylene oxide adduct. It is presumed that by mixing the water-soluble anionic polymer with the polyvalent metal cation, the anion of the water-soluble anionic polymer and the polyvalent metal cation are attracted to each other and approach each other to form particles, as shown in Figure 1. That is, in the present invention, the water-soluble anionic polymer reacts with the polyvalent metal cation to form composite particles.
  • a polymer stabilizer i.e., a so-called polymer dispersant
  • the blending ratio of the water-soluble anionic polymer and the polyvalent metal cation is calculated from the amount of the water-soluble anionic polymer to be used and its acid value, and the polyvalent metal cation is added so that the molar ratio is 30% or more relative to the acid value of the water-soluble anionic polymer.
  • the addition may be in the form of a metal salt as described above.
  • excess residual polyvalent metal salt may lead to deterioration in water resistance and contamination, and may also lead to a decrease in color density and deterioration in image quality. Therefore, the maximum amount is preferably 200% by molar ratio relative to the acid value of the water-soluble anionic polymer. On the other hand, if the amount is too small, particles may not be formed.
  • the molar ratio is preferably 30 to 200% by molar ratio relative to the acid value of the water-soluble anionic polymer, more preferably 30 to 150%, and most preferably 30 to 100%.
  • the water-soluble anionic polymer and the polyvalent metal cation are mixed to produce particles, they may be blended, mixed, and stirred as described above.
  • the water-soluble anionic polymer is usually in the form of a 15 wt % to 60 wt % aqueous solution, it is often not necessary to newly add the above-mentioned dispersion medium such as water, and the polyvalent metal cation may also be in the form of an aqueous solution before being mixed.
  • the concentrations of these components during the reaction are not limited, but the amount of water contained in these aqueous solutions is sufficient to allow the reaction to proceed sufficiently uniformly, so considering the effort required to adjust the concentration to an appropriate level when made into a coating solution, there is no need to make the concentration excessively low or high, and there is no need to add a new dispersion medium.
  • the formation of the composite particles of the present invention may be hindered.
  • the presence of a water-soluble cationic polymer may cause the formation of a polymer complex with the water-soluble anionic polymer (Patent Documents 1 and 2), or the presence of an alkali metal may cause the formation of a metal salt (WO/2011/115280).
  • the presence of a water-soluble cationic polymer may cause stickiness, and when a crosslinkable water-soluble cationic polymer is used to suppress stickiness, the stability of the generated particles is low. For this reason, the presence of a water-soluble cationic polymer is avoided as much as possible, and it is preferable to set the amount of the water-soluble cationic polymer to 80 parts by weight or less, further 50 parts by weight or less, particularly 10 parts by weight or less, and most preferably 5 parts by weight or less, relative to 100 parts by weight of the water-soluble anionic polymer.
  • a resin emulsion not only does not contribute to the formation of a composite particle of a water-soluble anionic polymer and a polyvalent metal cation, but the surfactant required for emulsification may also hinder the stability of the composite particle. For this reason, the presence of a resin emulsion is avoided as much as possible, and it is preferable that the amount is 150 parts by weight or less, particularly 120 parts by weight or less, and further preferably 100 parts by weight or less, per 100 parts by weight of the water-soluble anionic polymer.
  • stirrers can be used, specifically, a dissolver mixer, a homogenizer, a shear mixer (homomixer, ultra mixer), a disperser mixer for high viscosity, etc. can be used.
  • the dispersion of the present invention is characterized by containing the above-mentioned polymer-metal composite particles.
  • the dispersion of the present invention can be obtained by mixing an aqueous solution of a water-soluble anionic polymer with a polyvalent metal cation, but it is preferable to disperse the particles after particle precipitation to break up the secondary agglomeration of the formed particles, since this will make the particles uniform, and if a stabilizer is added, will promote adsorption.
  • dispersion generally refers to a desired dispersion state that is more stabilized by applying a stronger shear than simple stirring to break up the secondary agglomeration of the formed particles.
  • dispersion stabilization For dispersion stabilization, the addition of a polyvalent metal cation to impart ionic repulsion and the steric hindrance of a stabilizer are effective, so these may be added during particle precipitation or during dispersion after particle precipitation, as necessary.
  • dispersion stabilization refers to obtaining a stable dispersion state. It is not necessary to carry out dispersion to the primary particle diameter of the generated particles, and it is sufficient to set the degree of dispersion (particle diameter, etc.) according to the coating method.
  • Media mills include ball mills, sand mills, per mills, spike mills, agitator mills, Cobo mills, and Ultravisco mills.
  • Media-less mills include high-shear mixers and high-pressure homogenizers, as well as jet mills, wet-type micronizers such as Starburst (manufactured by Sugino Machine Co., Ltd.), and ultrasonic dispersers.
  • the median diameter (d50) of the dispersed particles in the dispersion liquid is 0.1 to 5 ⁇ m. More preferably, it is 0.3 to 4 ⁇ m, and most preferably, it is 0.5 to 3 ⁇ m. In this range, the stability of the liquid and the performance of the receiving layer are particularly excellent.
  • the dispersed particle diameter is the particle diameter in the dispersion liquid, and is typically the median diameter (d50) calculated in mono-disperse mode using dynamic light scattering and frequency analysis with a product name: Nanotrac Wave II manufactured by Microtrac, Inc., and ion-exchanged water as the solvent during measurement.
  • the above-mentioned dispersion of the present invention can be used as it is, and a binder such as PVA (polyvinyl alcohol) can be further added.
  • a binder such as PVA (polyvinyl alcohol)
  • PVA polyvinyl alcohol
  • the binder is not particularly limited as long as it can form a film and is compatible with other components in the treatment liquid, and various cationic and nonionic binders can be selected in addition to PVA.
  • the amount of the binder is not particularly limited, and is 1 to 20% by weight, more preferably 1 to 10% by weight, and even more preferably 2 to 5% by weight, based on the entire treatment liquid.
  • the blending ratio with the polymer composite particle is 10 to 300 parts by weight, more preferably 20 to 200 parts by weight, and even more preferably 30 to 100 parts by weight, based on 100 parts by weight of the polymer composite particle.
  • the recording material processing liquid of the present invention may contain additives, such as viscosity modifiers such as polyvinylpyrrolidone and polyvinyl alcohol, and stabilizers such as styrene-maleic anhydride ethylene oxide adducts, for example, to improve fluidity, within the scope that does not impair the object of the present invention.
  • viscosity modifiers such as polyvinylpyrrolidone and polyvinyl alcohol
  • stabilizers such as styrene-maleic anhydride ethylene oxide adducts
  • additives such as surface sizing agents, gelatin, casein, starch, modified starch, starch derivatives, glue, cellulose derivatives such as carboxymethyl cellulose, surface sizing agents such as algin, synthetic rubber emulsions such as styrene butadiene rubber and acrylonitrile-butadiene rubber, styrene-maleic acid copolymers, polyvinyl acetate, ethylene vinyl acetate copolymers, ketene dimers, colloidal silicic acid unsaturated polyester resins, polyvinyl butyrate, alkyd resins, epoxy resins, pigment dispersants, thickeners, flow modifiers, defoamers, foam inhibitors, release agents, foaming agents, penetrating agents, water resistant agents, moisturizing agents, preservatives, antioxidants, fluorescent whitening agents, ultraviolet absorbing agents, coloring dyes, titanium oxide, calcium carbonate, satin white, barium sulfate, talc, silica
  • a separate organic cation component may be added according to the ink composition installed in the inkjet printer to be used. These materials are preferred because adding them to the dispersion of the present invention after the dispersion of the present invention is produced by mixing the specific polymer and metal cations described above to precipitate the composite particles of the present invention leads to improved quality of the processing liquid and receiving layer.
  • the treatment liquid for recording materials obtained in the above manner improves bleeding and feathering when printed by inkjet, increases print density, and improves water resistance.
  • the recording material of the present invention can be obtained by treating a coating film (substrate) with the recording material treatment liquid.
  • the coated material may be absorbent or non-absorbent.
  • paper made mainly from non-wood fiber or plant fiber that is wood fiber paper made from kenaf, a non-wood pulp material, and synthetic paper.
  • Woven fabric made from materials such as cotton, hemp, and polyester fibers.
  • Transparent or opaque resin sheets or films such as polyester, polystyrene, polyvinyl chloride, polyethylene, polycarbonate, polypropylene, polyolefin, polyethylene terephthalate, polycarbonate, polymethyl methacrylate, and cellulose acetate are examples, but the present invention is not limited to these examples.
  • the present invention has an excellent effect of preventing blocking, especially in non-absorbent materials such as polyvinyl chloride film, polyvinylidene chloride film, polyester film, polycarbonate film, polystyrene film, polyacrylonitrile film, ethylene-vinyl acetate copolymer film, ethylene-vinyl alcohol copolymer film, nylon film, and cellophane, especially polyethylene film and polypropylene film.
  • non-absorbent materials such as polyvinyl chloride film, polyvinylidene chloride film, polyester film, polycarbonate film, polystyrene film, polyacrylonitrile film, ethylene-vinyl acetate copolymer film, ethylene-vinyl alcohol copolymer film, nylon film, and cellophane, especially polyethylene film and polypropylene film.
  • Methods for treating the substrate (base material) with the treatment liquid for recording materials include, for example, coating methods, impregnation methods, and coating methods such as inkjet printing methods that apply the treatment liquid for recording materials to the substrate, and can be selected according to the type and material of the substrate used.
  • Examples of the coating method include size press methods such as horizontal size press method, roll bead coater method, and calendar size press method; knife coater methods such as air knife coater method; roll coater methods such as transfer roll coater methods such as gate roll coater method, direct roll coater method, reverse roll coater method, and squeeze roll coater method; blade coater methods such as bill blade coater method, short duel coater method, and two-stream coater method; bar coater methods such as rod bar coater method; cast coater method; gravure coater method; curtain coater method; die coater method; spray coater method; and brush coater method.
  • size press methods such as horizontal size press method, roll bead coater method, and calendar size press method
  • knife coater methods such as air knife coater method
  • roll coater methods such as transfer roll coater methods such as gate roll coater method, direct roll coater method, reverse roll coater method, and squeeze roll coater method
  • blade coater methods such as bill blade coater method, short duel coater method, and two-stream coat
  • the impregnation method includes, for example, the pre-wet method, the float method, the doctor bar method, etc.
  • the recording material treatment liquid is used as ink, and is applied to the required areas before printing color inks. Because the recording material treatment liquid does not contain inorganic pigment particles, it is less likely to cause nozzle clogging. Coating using this inkjet method can also be done continuously.
  • the amount of the recording material treatment liquid to be applied varies depending on the type of substrate (substrate) to be coated and cannot be determined in general.
  • the dry film thickness is 0.5 to 5 ⁇ m, preferably 0.7 to 5 ⁇ m. If the dry film thickness is thin, the ink liquid portion has low retention and bleeding occurs. If the dry film thickness is thick, the uniformity and smoothness of the coating film tend to be lost.
  • the substrate may be dried by any method, including hot air drying, infrared drying, drum drying, and the like.
  • the recording material thus obtained has been treated with the recording material treatment liquid, and therefore has the excellent property of improving the clarity and density of the recorded image. Furthermore, when the substrate is a transparent resin film, the recording material has an excellent transparency of the ink receiving layer, and is therefore suitable for use as packaging films, labels, stickers, etc. with high design appeal.
  • the receptive layer when used in transfer films for the DTF (direct to film) method, does not contain inorganic pigments during thermal transfer, and the polymer with a glass transition point becomes thermoplastic during thermal transfer, providing the function of a protective film for the image, making it ideal for use in improving the performance of transfer prints.
  • the recording material having a treatment liquid and a receiving layer containing the polymer metal composite particles of the present invention exhibits excellent performance, particularly in inkjet printers equipped with pigment inks, and is also suitable for use as printing inks for laser printers and gravure inks. These printing processes can also be carried out in a continuous manner.
  • Examples 1 to 14, Comparative Examples 1 to 14 (1) Preparation of polymer-metal composite particle-containing dispersions According to the formulations A to W shown in Table 1, water-soluble anionic polymers, polyvalent metal cations, ion-exchanged water, and additives were mixed in a tank by stirring with a dissolver to precipitate particles, and then further mixed and stirred with a media mill.
  • polymer-metal composite particle-containing dispersions A to W The obtained dispersions (hereinafter referred to as "polymer-metal composite particle-containing dispersions A to W"; however, in formulation O, no particles were formed, and in formulations S and V, the particles formed immediately settled or separated, and stable dispersions were not obtained) were measured for viscosity, pH, dispersed particle size, and stability over time, and the results are shown in Table 1.
  • the amount of each polymer is the amount of the solution, and the polyvalent metal cations were mixed by dissolving the following polyvalent metal cation sources (powder) in ion-exchanged water in advance, but the amount in Table 1 is the amount of powder, and "water” in Table 1 is the total amount of ion-exchanged water and the ion-exchanged water used to dissolve the polyvalent metal cation source.
  • Water-soluble anionic polymer SA I Ammonium salt of styrene-acrylic acid copolymer (27% aqueous solution) (manufactured by BASF Japan Ltd., Joncryl JDX-6180, solid acid value 230, molecular weight 14,000, glass transition temperature 134°C, softening point >165°C)
  • SA II Ammonium salt of styrene-acrylic acid copolymer (30% aqueous solution) (manufactured by BASF Japan Ltd., Joncryl 70J, solid acid value 240, molecular weight 16500, glass transition temperature 102°C, softening point 155°C)
  • SA III Ammonium salt of styrene-acrylic acid copolymer (34% aqueous solution) (manufactured by BASF Japan Ltd., Joncryl 60J, solid acid value 215, molecular weight 8500, glass transition temperature 85° C., softening point
  • Cationic polymer C-P1 60% concentration of dimethylamine-ammonia-epichlorohydrin polymer (non-crosslinkable cationic polymer, manufactured by Senka Co., Ltd., Papiogen P-105)
  • C-P2 Aqueous solution of high-concentration amine condensate, polyamine condensate, with a concentration of 70% (non-crosslinkable cationic polymer, manufactured by Meisei Chemical Industry Co., Ltd., Palset JK173)
  • C-P3 Aqueous solution of highly cationic allyl polymer, polyamine condensate, and polyallylamine hydrochloride with a concentration of 40% (non-crosslinkable cationic polymer, manufactured by Meisei Chemical Industry Co., Ltd., Palset JK505)
  • C-P4 Polyamide polyamine-epichlorohydrin resin with a concentration of 25% (crosslinkable cationic polymer, manufactured by Seiko PMC Corporation, WS4020)
  • additive, stabilizer D-1 Styrene-maleic anhydride ethylene oxide adduct (NOF Corporation, Marialim AKM-0531)
  • D-2 15% benzyl group-containing water-soluble cationic polymer (Senka Co., Ltd., Senka Flock BM-60M)
  • D-3 20% benzyl group-containing water-soluble cationic polymer (Aromafix PT, manufactured by Meisei Chemical Industry Co., Ltd.)
  • the particle size of the polymer metal composite particles in the dispersion was measured by the following method.
  • the particle size was measured by dynamic light scattering and frequency analysis using a Microtrac product called Nanotrac Wave II, ion-exchanged water was used as the solvent, and the particle size (median size: d50) calculated in mono-disperse mode was used as the measured value.
  • the mixture formulation O did not form particles, and the mixture formulation S did not produce a stable dispersion because the particles that were formed immediately settled, so no measurement was performed and no subsequent evaluation was performed.
  • the viscosity of the polymer-metal composite particle-containing dispersion was measured by the following method.
  • the viscosity of the polymer-metal composite particle-containing dispersion was measured using a spindle viscometer at a liquid temperature of 25° C. and 60 rpm.
  • the rotor was changed according to the viscosity of the object to be measured.
  • the temporal stability of the polymer-metal composite particle-containing dispersion liquid was evaluated by the following method: The polymer-metal composite particle-containing dispersion liquid was placed in a sealed container, and left to stand at 40° C. for one week, after which the state of the liquid was observed. ⁇ : When mixed with a spoon, there is fluidity and no settling, etc. ⁇ : There is no fluidity and mixing with a spoon, etc. is not possible
  • formulation V which used a styrene-acrylic resin emulsion (SA IV)
  • SA IV styrene-acrylic resin emulsion
  • formulation W which used an acrylic resin with a low acid value (A I)
  • a I acrylic resin with a low acid value
  • the particles formed had an extremely large particle size. It is thought that the stability of the particles was not high due to the low Tg of the resin, and the particles formed were fused and coarsened. For this reason, an evaluation of stability over time was not performed.
  • Tables 2 and 3 The abbreviations in Tables 2 and 3 have the following meanings.
  • PVA Polyvinyl alcohol (Kuraray Co., Ltd., Kuraray Poval 28-98)
  • a 50 ⁇ m thick PET film product name: Lumirror, manufactured by Toray Industries, Inc.
  • white paper product name: Xerox-P, manufactured by Xerox Corporation
  • Coating was performed using a bar coater so that the film thickness when the coating liquid for the recording material dried to become a receiving layer would be 1.1 ⁇ m. Note that the thickness was set to 2.3 ⁇ m in Example 2 and 0.7 ⁇ m in Comparative Example 7.
  • the PET film was dried at 80° C. for 3 minutes, and the white paper was dried at 125° C. for 1 minute, to give a recording material with a receiving layer on each side.
  • the recording materials obtained in Examples 1 to 10, 13, and 14 were not sticky, and had good color development, image quality, and water resistance.
  • the coating film of Comparative Examples 1 to 6 was sticky, and was not suitable for use as a non-absorbent recording material.
  • Comparative Examples 7 to 9 the color development and image quality were deteriorated depending on the film thickness of the receiving layer and the ratio of polymer metal composite particles in the coating film.
  • Comparative Example 10 which used polymer metal composite particles D with a large amount of polyvalent metal cation added, both the color development and image quality were deteriorated.
  • Comparative Example 11 which used a polymer metal composite particle dispersion containing polymer metal composite particles R obtained by blending more than 10 parts by weight of a crosslinkable cationic polymer, which is a water-soluble cationic polymer, with 100 parts by weight of a water-soluble anionic polymer, the color development, i.e., the printing performance, was also poor.
  • Comparative Example 12 which did not contain polymer metal composite particles, the color development of the printed matter was poor.
  • Examples 11 and 12 and Comparative Examples 13 and 14 are evaluation results using western paper, which is an absorbent substrate. Compared to Comparative Example 13, which was not coated with the recording material treatment liquid, Examples 11 and 12, which were coated with the recording material treatment liquid, showed improved print density and higher color development. On the other hand, Comparative Example 14, which did not contain polymer metal composite particles, showed bleeding and feathering, and a clear image could not be obtained.
  • the observed primary particle size was uniform at about 100 nm for polymer metal composite particle dispersion A, and had a wide distribution range of about 100 to 300 nm for polymer metal composite particle dispersion B. When these were used as a receiving layer, it is presumed that dense pores were generated between the particles, which helped absorb the solvent. In addition, since the particle surfaces contain polyvalent metal cations, it is presumed that the color development of the ink was quickly improved on the particle surfaces after the solvent was absorbed.
  • Polymer metal composite particle dispersion F was diluted 2000 times with ion-exchanged water, and the particles were captured using a JEOL Nanopercolator (Nuclepore membrane filter, pore size 0.6 ⁇ m), and tungsten was vapor-deposited to prevent electron charging.
  • the formed receiving layer has improved ink jet printing performance, such as ink bleeding, feathering, print density, and bleeding, and further, even when applied to substrates such as resin films and glass, a treatment liquid for recorded materials can be obtained that is capable of forming an ink receiving layer without coating film blocking, and excellent polymer metal composite particles can be obtained to obtain such a treatment liquid.

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PCT/JP2024/008397 2023-03-06 2024-03-05 被記録材用処理液、それで処理した被記録材及びそれらの製造法 Ceased WO2024185795A1 (ja)

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JPS57179209A (en) * 1981-04-09 1982-11-04 Roehm Gmbh Manufacture of powder-form ion bridged acryl elastomer
JPH0616864A (ja) * 1992-06-30 1994-01-25 Toyota Motor Corp 複合材含有金属イオン架橋型ポリマー粉体及びその製造方法
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JPH0665312A (ja) * 1992-08-19 1994-03-08 Toyota Motor Corp 金属イオン架橋型ポリマー微粉末の製造方法
JPH0665313A (ja) * 1992-08-19 1994-03-08 Toyota Motor Corp 金属イオン架橋型ポリマー微粉末の製造方法
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JP2012519093A (ja) * 2009-02-27 2012-08-23 イーストマン コダック カンパニー 画像品質が改良されたインクジェット媒体システム
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS56154582A (en) * 1980-04-24 1981-11-30 Japan Exlan Co Ltd One side priting method
JPS57179209A (en) * 1981-04-09 1982-11-04 Roehm Gmbh Manufacture of powder-form ion bridged acryl elastomer
JPH0616864A (ja) * 1992-06-30 1994-01-25 Toyota Motor Corp 複合材含有金属イオン架橋型ポリマー粉体及びその製造方法
JPH0657034A (ja) * 1992-08-06 1994-03-01 Toyota Motor Corp 金属イオン架橋型ポリマー基複合材料
JPH0665312A (ja) * 1992-08-19 1994-03-08 Toyota Motor Corp 金属イオン架橋型ポリマー微粉末の製造方法
JPH0665313A (ja) * 1992-08-19 1994-03-08 Toyota Motor Corp 金属イオン架橋型ポリマー微粉末の製造方法
JPH06172428A (ja) * 1992-12-10 1994-06-21 Toyota Motor Corp 金属イオン架橋型ポリマー微粉末の製造方法
JPH06226765A (ja) * 1993-02-08 1994-08-16 Toyota Motor Corp ポリマー粉末成形体の製造方法
JPH07102016A (ja) * 1993-10-07 1995-04-18 Toyota Motor Corp 金属化合物イオン架橋型ポリマー及びその製造方法
JP2012519093A (ja) * 2009-02-27 2012-08-23 イーストマン コダック カンパニー 画像品質が改良されたインクジェット媒体システム
JP2016193576A (ja) * 2015-04-01 2016-11-17 北越紀州製紙株式会社 インクジェット記録用光沢紙

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