WO2004043703A1 - インクジェット記録媒体およびその製造方法 - Google Patents
インクジェット記録媒体およびその製造方法 Download PDFInfo
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- WO2004043703A1 WO2004043703A1 PCT/JP2003/014354 JP0314354W WO2004043703A1 WO 2004043703 A1 WO2004043703 A1 WO 2004043703A1 JP 0314354 W JP0314354 W JP 0314354W WO 2004043703 A1 WO2004043703 A1 WO 2004043703A1
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- layer
- ink
- jet recording
- receiving layer
- gloss
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Classifications
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- 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
- B41M5/502—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording characterised by structural details, e.g. multilayer materials
- B41M5/506—Intermediate layers
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
- B41M2205/12—Preparation of material for subsequent imaging, e.g. corona treatment, simultaneous coating, pre-treatments
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- 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
- B41M5/502—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording characterised by structural details, e.g. multilayer materials
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- 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
- B41M5/5245—Macromolecular coatings characterised by the use of polymers containing cationic or anionic groups, e.g. mordants
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M7/00—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
- B41M7/0027—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock using protective coatings or layers by lamination or by fusion of the coatings or layers
Definitions
- the present invention relates to an ink jet recording medium, and more particularly to an ink jet recording medium having high glossiness and ink absorbability, and excellent color development and color reproducibility as well as obtaining good image quality.
- the ink jet recording method has been rapidly spread in recent years because it is easy to realize full color and printing noise is small.
- minute droplets of ink are made to fly and adhere at high speed from a nozzle to a recording medium to record an image, characters, etc., and the ink contains a large amount of solvent. Therefore, it is necessary for the recording medium to quickly absorb the ink.
- ink jet recording paper is required to have high color development, resolution and color reproducibility, and so-called coated paper provided with an ink receiving layer on the surface has been developed to cope with this.
- the present inventors have also proposed an inkjet recording comprising a support, and an ink absorbing layer and a colloidal silica layer sequentially provided on the support.
- a recording sheet has already been proposed (Japanese Patent Application Laid-Open No. 2000-1962).
- a method using a colloidal particle such as silica, which is a pigment having a small particle size, and a binder is often performed, but using spherical colloidal particles is preferable.
- the ink absorption rate is reduced because the post-film air gap is reduced.
- colloidal silica does not have internal voids unlike synthetic amorphous silica
- the ink receiving layer is required to obtain the required ink absorption capacity. Needs to be thickened. However, if the ink receiving layer is thickened, the powder dropping phenomenon is likely to occur. Therefore, when the amount of the binder is increased to prevent the powder from falling off, the ink absorption speed on the surface is particularly slow and a bleeding phenomenon occurs, resulting in a drawback that a high resolution print image can not be obtained.
- a layer containing cationic organic particles having a weight average particle diameter of 1 to 100 nm on a sheet-like support Ink jet recording sheets having at least one layer are known.
- the layer containing the cationic organic fine particles is a layer involved in ink reception, and a coating amount of about 20 g Zm 2 is required.
- it is necessary to carry out a force render process at about the same temperature as the glass transition temperature of the cationic organic fine particles Japanese Patent Application Laid-Open No. 2000-205965. . For this reason, the ink jet recording sheet obtained still had insufficient ink absorption.
- an ink jet recording sheet obtained by applying an acrylic-styrene-based polymer dispersion containing (meth) acrylic amide so as to give ink permeability for the purpose of imparting gloss.
- the polymer dispersion copolymerizes particularly water-soluble (meth) acrylamide, the ink permeability is particularly good.
- the copolymer is mainly composed of styrene and an acrylic monomer, the particles have a glass transition temperature sufficiently higher than that at room temperature, and in addition, the copolymer obtained by using a reactive emulsifier during polymerization.
- a first object of the present invention is to provide an ink jet recording medium capable of obtaining good image quality excellent in color development and color reproducibility as well as having high glossiness and good ink absorption. It is in.
- a second object of the present invention is to provide a method for producing an ink jet recording medium which has high glossiness and good ink absorbability, and is also excellent in color development and color reproducibility. Disclosure of the invention
- the present inventors provided an ink receiving layer mainly composed of inorganic fine particles having an average particle diameter of 10 nm to 500 nm on a support.
- an ink receiving layer mainly composed of inorganic fine particles having an average particle diameter of 10 nm to 500 nm on a support.
- an ink receiving layer mainly composed of inorganic fine particles having an average particle diameter of 10 nm to 500 nm and a polymer dispersion coated on the ink receiving layer on a support is provided.
- An ink jet recording medium having a layer, wherein the polymer dispersion copolymerizes at least a cationic monomer, (meth) acrylamide, styrene and methyl methacrylate as monomer components.
- a dispersion of uncrosslinked styrene / acrylic polymer fine particles, and a polymer fine particle in the polymer dispersion is present on the ink receiving layer while maintaining the particle shape to form the gloss layer It is characterized by
- the average particle diameter of the styrene-acrylic polymer particles in the polymer dispersion is preferably 100 to 200 nm.
- the inorganic fine particles when dispersed in the coating liquid for forming the ink receiving layer, may contain colloidal silica force in which a plurality of spherical colloidal silica forces having a primary particle diameter of 10 to 100 nm are aggregated. preferable. It is preferable that the 75 ° specular gloss of the surface on the side of the gloss layer is 50% or more, and a single layer of synthetic silica and a hydrophilic pinder be provided between the support and the ink receiving layer. It is preferable that Moreover, it is preferable that Moreover, it is preferable that Moreover, it is preferable that Moreover, it is preferable that the said polymer dispersion, as a monomer component, contain 2 to 30 weight% of said cationic monomers.
- an average particle diameter of 10 nm is provided on the under layer.
- an ink receiving layer mainly composed of inorganic fine particles of ⁇ 500 nm, and then at least cationic monomer, (meth) acrylamide, styrene and methyl metatalylate as monomer components.
- a polymer dispersion which is a dispersion of styrene-acrylic polymer particles not copolymerized and crosslinked, is coated on the ink receiving layer and dried to form a gloss layer, the surface of the gloss layer is 40 ° It is characterized in that soft calendar processing or machine force rendering processing is performed at room temperature or higher at C or lower.
- an undercoat layer comprising fine particle synthetic silica and a hydrophilic binder is provided on a support, if necessary, and then an average particle size of 100 is obtained on the binder layer.
- An ink receiving layer containing inorganic fine particles of about 500 nm as a main component is provided, and then at least a cationic monomer, (meth) acrylic amide, styrene, and methyl methacrylate are used as monomer components.
- the polymer dispersion which is a dispersion of styrene-acrylic polymer particles not polymerized and crosslinked, is coated on the ink receiving layer to form a gloss layer by drying and then calendering is not performed. It features. Brief description of the drawings
- FIG. 1 is a photograph showing an example of a gloss layer according to an embodiment of the present invention. -Best mode for carrying out the invention
- the support of the ink jet recording medium according to the present invention is not particularly limited, and it is not particularly limited, and is in the form of a sheet mainly made of wood fiber, plastics such as polyethylene, or non-woven fabric mainly made of wood fiber or synthetic fiber. Substances can be mentioned.
- a sheet mainly made of wood fiber, plastics such as polyethylene, or non-woven fabric mainly made of wood fiber or synthetic fiber Substances can be mentioned.
- an internal sizing agent and a filler can be appropriately added, and the presence or absence of a size press is not limited at all.
- wood pulp used as a raw material of paper used as a support of the present invention examples include chemical pulp such as LBKP and NBKP, mechanical pulp such as GP, PGW, RMP, TMP, CTMP, CMP and CGP, and waste paper pulp such as DIP Is included.
- various additives such as known fillers, binders, sizing agents, fixing agents, retention improvers, paper reinforcing agents, etc. are mixed with these wood pulps, if necessary.
- the ink receiving layer of the present invention contains, as a main component, inorganic fine particles having an average particle diameter of 10 nm to 500 nm.
- the average particle diameter is in this range, when the coating film is formed, the particles can be present in a dense state, and the gloss of the ink jet recording medium becomes high.
- a more preferred range of average particle size is 40 to 300 nm.
- the average particle size is smaller than the wavelength of visible light (300 nm or less), scattering hardly occurs and the transparency of the ink receiving layer is improved, and the coloring property when printing is improved.
- silica sol obtained by mechanically pulverizing colloidal silica or synthetic silica silica fine particles such as gas phase method silica, alumina fine particles such as alumina sol, gas phase method alumina or the like can be used.
- silica fine particles it is preferable to use silica fine particles, and in particular, colloidal silica is preferably used.
- the co-oidal silica is a synthetic silica having a primary particle diameter of several nm to about 100 nm, which is synthesized by a wet method, and includes cases where it agglomerates to become non-spherical secondary particles.
- an aqueous dispersion in which particles of a core / shell structure in which an acrylic polymer is bonded to the surface of spherical colloidal silica particles is dispersed in an aqueous solvent is also included in colloidal silica. Ru.
- the above secondary particle diameter and the inner diameter of the corenoshell structure are the average particle diameter of the inorganic fine particles.
- Colloidal silica is densely packed to increase the strength of the coated layer.
- the ink receiving layer can be composed of two or more layers. In addition, it is possible to mix and use two or more types of colloidal silica, if necessary.
- the ink receiving layer contains inorganic fine particles as a main component and other auxiliary agents as auxiliary components.
- the primary particles of the colloidal silica particles are spherical in shape, they have a certain degree of film-forming ability, and the tendency is more remarkable as the particle diameter is smaller.
- a binder is required to secure film forming property, and the sinking speed of the colloidal silica layer is rather reduced.
- spherical colloidal silica with a small particle size has good film-forming properties, but since the gaps between particles after film-forming become small, the ink absorption rate is small.
- colloidal silica present as secondary particles in a coating liquid for forming the ink receiving layer.
- colloidal silica present as secondary particles in a coating liquid for forming the ink receiving layer.
- colloidal silica present as secondary particles in a coating liquid for forming the ink receiving layer.
- the reason for this is not clear, but is considered to be due to the formation of an appropriate gap in the gloss layer.
- the presence of colloidal silica as secondary particles means that, in the state of being dispersed in the coating liquid for the ink receiving layer, a mixture of a plurality of spherical primary particles having a primary particle diameter of 10 to 100 nm and agglomerated.
- colloidal silica chain-like colloidal silica in which several to dozens of primary particles are linked in a chain (Snowtex UP series manufactured by Nissan Chemical Industries, Ltd. UP series, OUP series) or several primary particles are used.
- Pearl necklace-like colloidal silica (Snowtex PS series manufactured by Nissan Chemical Industries, Ltd.), ring-shaped aggregates like a dozen or more neckless, tufted codoidal silica connected in a tufted shape of Budo (Nissan Chemical Industry Co., Ltd. Company company Snowtex HS series).
- tuft-like means that substantially at least two spherical colloidal silicas are bonded when viewed from the lateral direction (direction perpendicular to the longest direction of the aggregate) of colloidal silica aggregated as secondary particles. I say that there is a part that is doing. Also, with “chain-like” A plurality of colloidal silicas are connected in the longitudinal direction, but there is only one coroidal silica in the lateral direction. “Pearl necklace-like” is a state in which chain-like colloidal silica forms a ring. In addition, when the colloidal silica in the dispersed state is observed, a single colloidal silica that does not aggregate may exist o
- colloidal silica which is agglomerated to form secondary particles
- the colloidal silicas are properly entangled at the time of film formation, and the dropping of the silica particles is suppressed even without using a binder.
- the average primary particle size and the average secondary particle size of colloidal silica can be measured using a dynamic light scattering photometer.
- a gloss layer is provided on the surface of the ink receiving layer.
- the gloss layer of the present invention (the layer provided by coating a coating solution containing a tensile polymer dispersion) mainly serves to impart gloss to recording paper, and it is also possible to use the ink absorbing layer. Since it is required not to inhibit the ink absorbability, it is preferable that the ink be thin and uniform. For this reason, when the particle diameter of the inorganic pigment used in the ink receiving layer under the gloss layer is large, the concave and convex shape of the pigment is reflected in the gloss layer, and the gloss is not improved. Therefore, in the ink receiving layer according to the present invention, the (10 nm to 500 nm) inorganic fine particles having a small particle diameter described above are used as a pigment.
- colloidal silica when colloidal silica is used in the ink receiving layer, since the colloidal silica originally has a film forming property by itself, it does not necessarily require a binder in the ink receiving layer, but binding is carried out as necessary.
- a binder for example, a water-soluble polymer such as polybul alcohol, casein, gelatin, or a water-dispersible polymer such as SB latex, NB latex, acrylic latex, or acetate acetate latex can be used.
- the compounding part number of the binder is preferably 0 to 10 parts by weight, particularly preferably 0 to 5 parts by weight with respect to 100 parts by weight of colloidal silica.
- the ink receiving layer of the present invention further contains a cationic compound.
- the cationic compound used in the present invention is a secondary amine which forms an insoluble salt with a water-soluble direct dye contained in an aqueous dye ink, a sulfonic acid group in a water-soluble acid dye, a carboxyl group, etc. It is a so-called dye fixer that contains a class of amin or quaternary ammonium salt.
- the cationic compounds may be used alone or in combination of two or more.
- a sizing agent for a sizing agent, a surfactant, a pigment dispersant, a thickener, a flowability improver, an antifoaming agent, an antifoaming agent, a release agent, a foaming agent.
- Permeabilizers, color dyes, fluorescent whitening agents, UV absorbers, antioxidants, preservatives, anti-piating agents, water-proofing agents, water-retaining agents, etc. can be appropriately blended.
- the coating amount of the ink receiving layer can be determined on the basis of the ink absorption capacity of the ink receiving layer and the adhesive strength between the ink receiving layer and the support to an extent that can be practically used.
- the dry coating amount per ink receiving layer is preferably 1 to 12 g / m 2 , more preferably 2 to 10 g / m 2 .
- the uniformity of the coated surface becomes insufficient.
- the dry coating amount per layer exceeds 12 g / m 2 , powder drops will occur and the coated layer after drying will have many cracks, and the ink will form cracks in the grooves during printing. It is not preferable because the phenomenon of flowing along the surface occurs and the image is disturbed.
- the layer configuration of the ink receiving layer provided on the support and the component configuration of each layer are not particularly limited. That is, the ink receiving layer may be coated on one side or both sides of the support a plurality of times, and the ink receiving layer may be provided in two or more layers. In this case, the respective ink receiving layers are provided to have the above-mentioned dry coating amount. When the coating liquid of the same component is applied a plurality of times, the apparent ink receiving layer may be a single layer. Further, in the present invention, when the ink receiving layer is provided on one side of the support, a coating layer can be provided on the opposite side for the purpose of curl correction, transportability improvement, and the like.
- an under layer between the ink receiving layer and the support.
- pigments used for the under layer synthetic silica, alumina and alumina hydrate (al Minasol, colloidal alumina, pseudoboehmite etc.)
- inorganic pigments such as aluminum hydroxide, styrenic plastic pigments, acrylic plastic pigments, and organic white pigments such as urea resin can also be used.
- fine particle synthetic silica having an average particle size of 5 m or less is most preferable.
- the binder for the under layer the same one as in the case of the ink receiving layer described above is preferably used
- the coating amount of the under layer can be appropriately determined depending on the purpose, but in the present invention, the dry coating amount is preferably in the range of 5 to 30 g / m 2 . If the dry coating amount is less than 5 g Zm 2 , it is difficult for the undercoat layer to completely cover the surface of the support, causing uneven absorption of the ink by the coating layer, resulting in poor printing performance. There will be an impact. In addition, when the dry coating amount exceeds 30 g / m 2 , the adhesive strength between the ink receiving layer and the support becomes a level that can not withstand practical use, and it is called powdering, and the coated layer from the support is Peeling etc. occur and serious problems occur.
- a dispersion of a cationic polymer is coated on the ink receiving layer so as to have ink permeability to form a gloss layer.
- the dispersion of the above-mentioned cationic polymer means a non-cross-linked styrene / acrylic copolymer obtained by copolymerizing at least a cationic monomer, (meth) acrylamide, styrene and methyl methacrylate as monomer components. It is a dispersion of fine polymer particles.
- the outline of the manufacturing method is as follows.
- the ratio shown above represents the range of the amount of each compound charged.
- examples include trithiovinyl monomers having tertiary amines such as N, N-dimethylamino-2-hydroxypropyl (meth) acrylate, ⁇ , ⁇ ⁇ ⁇ ⁇ -dimethylaminopropyl (meth) acrylamide and the like.
- ethylenic monomers include lower esters such as (meth) acrylic acid ethyl, (meth) acrylic acid, carboxyl group-containing monomers such as itaconic acid, and sulfonic acid group-containing monomers such as styrene sulfonic acid and so on
- (meth) acrylamide, the above-mentioned cationic monomer, and a chain transfer agent such as thioglycolic acid in an aqueous cationic or nonionic emulsifier solution is dissolved, and a mixture of styrene, methyl methacrylate and other ethylenic monomers is added dropwise or mixed into this aqueous solution, and a cationic polymerization initiator is added while heating and stirring to polymerize the mixture. Neutralize after the reaction.
- a polymer dispersion in which polymer particles having an average particle diameter of about 100 to 200 nm are dispersed can be obtained.
- the polymer particles obtained by polymerization in the composition of the above-mentioned range are non-film forming polymer particles at ordinary temperature and are not crosslinked. Therefore, when it is dried or treated without applying temperature or excessive frictional heat used in the ordinary drying process, it has hydrophilic or cationic functional groups on the particle surface and maintains voids between polymer particles. A glossy layer having ink permeability can be formed.
- the average particle size of the polymer particles can be measured using a dynamic light scattering photometer as well as the colloidal silica force.
- the shape of each polymer particle is dispersed in the polymer dispersion. It means that the boundary between polymer particles does not disappear by fusion with other adjacent polymer particles without losing the fine particle shape. In this way, adjacent polymer particles come in contact with each other at their surfaces, or bond by point adhesion at a part of the surface, but they do not fuse together and the boundary disappears. It is believed that there is a minute air gap in the center and the ink absorption becomes good.
- the polymer particles may be fused with other adjacent polymer particles, and the boundary between the two may be almost integrated and the boundary may become unclear. It can be mentioned. In such a case, when observing the surface of the glossy layer after film formation, for example, each particle becomes a uniform surface where the boundaries melt away.
- FIG. 1 is a photograph showing an example of the gloss layer of the present invention as viewed from the surface.
- the originally spherical polymer particle in the upper left region of the figure, is deformed into a substantially hexagonal shape (a shape that can be tightly packed) and is in contact with adjacent particles via a slight gap. The boundaries between particles do not fuse and disappear.
- the polymer particles in the lower region of the figure, maintain a spherical shape at the time of dispersion and are in point contact with adjacent particles. In this case, the void at the boundary between particles is rather large. Also in this case, boundaries between particles can be clearly seen.
- a monomer having two or more carbon-carbon double bonds in one molecule that is, a monomer having a crosslinking property or an emulsifying agent is not used, but is crosslinked. Not get polymer particles.
- the polymer particles are crosslinked, the polymer particles, in particular, the surface layer portion becomes hard, and leveling during coating drying becomes difficult to occur. Therefore, the smoothness of the surface of the coating layer is lowered, and a high gloss expression effect is hardly obtained, and it becomes difficult to obtain an inkjet recording medium having a desired high gloss.
- the glass transition temperature (T g) of the polymer is the glass transition temperature of the homopolymer of each monomer contained in the polymer (T gn: unit in the formula of F o X) and the absolute value of each monomer It can be obtained by the following formula of F 0 X using a weight fraction (wn).
- colloidal silica as a coating, prepare a base paper dried, then disperse the above-mentioned cationic polymer dispersion and, if necessary, a hydrophilic binder for bonding the above-mentioned cationic polymer in an amount of 0 to 1 °% by weight
- the mixed solution is applied to the surface of the primed paper to provide a gloss layer.
- the glossy layer in the present invention is preferably thinly and uniformly coated, and is coated and dried so that the amount of application per one side is about 0.3 to 3.0 g / m 2 in terms of solid content.
- the glossiness is improved even if the coating amount is small, there is a risk that a uniform polymer fine particle layer can not be formed if the coating amount is less than 0.3 g Z m 2 ; conversely, the coating amount If the amount of V is too large, it is not possible to maintain the above-mentioned gaps between the polymer particles, and the ink absorbability is deteriorated.
- various conventional blade coater is the coating apparatus, the mouth 1 to Noreko 1 ⁇ ' ⁇ air-Naifuko 1 to people ⁇ ⁇ , / - co-1 ⁇ ' ⁇ , r' ⁇ Toro 1 to Noreko 1 to ⁇ -, a curtain coater, short Due Norre coater, gravure coater, flexo Dara via coater, a size such as a press
- Various devices can be used on-machine or off-machine.
- a calender device such as a machine calender, super calender, soft calender or the like, whereby the glossiness is further improved.
- a calender device such as a machine calender, super calender, soft calender or the like, whereby the glossiness is further improved.
- a calender device such as a machine calender, super calender, soft calender or the like
- select the pressure and temperature so that polymer particles are not melted to form a film (that is, the gaps between particles do not disappear), especially for the gloss layer. This is important.
- the ink absorptivity of the ink jet recording medium tends to be poor, and in the case of the ink jet recording medium of the present invention, the dispersion of the cationic polymer is coated on the ink receiving layer. Since it has high glossiness at the time of drying, calendering is not necessary. Rather, it is preferable to perform no force rendering because it is possible to obtain an ink jet recording medium with excellent ink absorption.
- an ink jet recording medium having high glossiness and good ink absorbability and good image quality excellent in color development and color reproducibility can be obtained.
- the reason is not clear, but it is as follows: Presumed. That is, since the glass transition temperature of the polymer becomes sufficiently high as compared with room temperature by copolymerizing styrene and methyl methacrylate as main components, the copolymer polymer has a particle shape when the coating layer is dried. Since the particles are adhered to each other to form a layer structure having voids, the particles are presumed to be penetrated from the voids because the particles adhere to each other to form a layer structure having voids.
- the particle size of colloidal silica is very small, the surface of the ink receiving layer becomes very smooth. Furthermore, since the average particle diameter of one cationic polymer particle coated on the ink receiving layer is extremely small, about 100 to 200 nm, light in the low wavelength region of visible light is hardly scattered. Thereby, irregular reflection of light is suppressed, and an inkjet recording medium having high glossiness can be obtained.
- Dilution with water was performed to obtain a dispersion of cationic polymer fine particles having a solid concentration of 28%, a viscosity of 1 OmPa * s, an average particle diameter of 140 nm, and a glass transition temperature of 103 ° C.
- Dilution with water was performed to obtain a dispersion of cationic polymer fine particles having a solid concentration of 33%, a viscosity of 18 mPa ⁇ s, an average particle diameter of 120 nm, and a glass transition temperature of 75 ° C.
- Dilution with water was performed to obtain a dispersion of cationic polymer fine particles having a solid concentration of 26%, a viscosity of 22 mPa ⁇ s, an average particle size of 150 nm, and a glass transition temperature of 98 ° C.
- the temperature was raised to C, and a mixture of 140 parts of styrene, 86 parts of methyl methacrylate, 10 parts of ethyl acrylate and 1 part of acrylic acid was added dropwise over 2 hours. At the same time, 25 parts of a 2% aqueous ammonium persulfate solution was added dropwise over 2 hours and 15 minutes. Then, the polymerization is terminated by holding at 85 ° C. for 2 hours, ammonia water is added to neutralize to pH 8.0, solid concentration 38%, viscosity 11 OmPa ⁇ ⁇ , average particle diameter 82 nm, glass A dispersion of fine particles of an ionizable polymer having a transition temperature of 97 ° C. was obtained.
- Dilution with water was carried out to obtain a dispersion of cationic polymer fine particles having a solid concentration of 29%, viscosity of 15 mPa ⁇ s, average particle size of 13 O nm, and glass transition temperature of 98 ° C.
- Colloidal silica having an average primary particle size of 15 nm, an average secondary particle size of 70 nm, and secondary particles having a chain-like shape on a support coated with the under layer paint produced as described above.
- Tex UP 100 parts of Nissan Chemical Industries, Ltd. trade name, 6 parts of dye fixing agent (PF 700: trade name of Showa Highpolymer Co., Ltd.) Using a bar blade coater, the coating amount was 5 gZm 2 .
- the coating liquid of the above was coated on a support having the ink receiving layer formed thereon and dried so that the coating amount would be 1.0 gZm 2 , to obtain the ink jet recording medium of Example 1.
- a support was produced in exactly the same manner as in Example 1.
- Example 2 In exactly the same manner as in Example 1, a coated paper having an under layer as a coated layer was obtained. Ink receiving layer
- the secondary particles In place of the colloidal silica used in Example 1, the secondary particles have an average primary particle size of 40 nm and an average secondary particle size of 150 nm, and the secondary particles have a pearl necklace shape (a chain-like shape as well).
- colloidal silica Snowtex PS-L: a trade name of Nissan Chemical Industries, Ltd.
- the ink receiving layer was formed. did.
- Example 2 The ink jet recording medium of Example 2 was obtained in the same manner as in Example 1 except that the cationic polymer dispersion prepared in the above Synthesis Example 2 was used instead of the cationic polymer dispersion used in Example 1. .
- a support was produced in exactly the same manner as in Example 1.
- An ink receiving layer was formed in the same manner as in Example 1 except that the coating amount was 10 g / m 2 .
- the under layer was not provided.
- the gloss layer was coated in the same manner as in Example 1 to obtain an ink jet recording medium of Example 3.
- An ink jet recording medium is manufactured in exactly the same manner as in Example 1, and calendered in a room at a temperature of 30 ° C. by a soft epp calender machine at a line pressure of 9 80.7 NZ cm according to Example 4. An ink jet recording medium was obtained. At this time, the surface temperature of the calender roll in contact with the gloss layer was 35.degree.
- An ink jet recording medium was manufactured in exactly the same manner as in Example 1, and calendered at a linear pressure of 98.7 NZ cm by a soft nip calender machine to obtain an ink jet recording medium of Example 4. At this time, the calender bite itself in contact with the gloss layer was heated to a surface temperature of 45 ° C.
- Synthetic amorphous silica two-sided distilling AY- 601: 100 parts of Nippon Silica Co., Ltd. trade name), 100 parts of polyvinyl alcohol (PVA 17 17: trade name of Kuraray Co., Ltd.), 20 parts of ethylene vinyl acetate (BE 7000: trade name of Chuo Rika Kogyo Co., Ltd.) 1 part 5, sizing agent (SS 33 5: trade name of Japan PMC Co., Ltd.) 2 parts, dye fixing agent (Unisense CP-1 03: Dilution water was added to 5 parts of Senforce Co., Ltd. and mixed and stirred to obtain a paint having a solid content concentration of 20%. This paint was coated on the support using a bar blade coater at a coating amount of 12 g / m 2 to obtain a coated paper having an undercoat layer as a coated layer. .
- Colloidal silica having an average primary particle size of 30 nm and an average secondary particle size of 280 nm, and secondary particles having a tufted shape instead of the colloidal silica used in Example 1 (Snowtex HS-M- 20: Nissan An ink receiving layer was formed in the same manner as in Example 1 except that Chemical Industries, Ltd. (trade name) was used.
- Synthetic amorphous silica (Silojet P-409: trade name of Grace Co.) 100 parts, polyvinyl alcohol (PVA-1 17: trade name of Kuraray Co., Ltd.) 30 parts, styrene butadiene latex (LX 4 3 8 C: trade name of Nippon Zeon Co., Ltd.) 5 parts, Ethylene vinyl acetate (BE 700: trade name of Chuo Rika Kogyo Co., Ltd.) 5 parts, sizing agent (Polymeron 360: trade name of Arakawa Chemical Industries, Ltd.) 2 parts, dye fixing agent ( Polyfix 700: trade name of Showa Highpolymer Co., Ltd.
- Dilution water was added to 8 parts, mixed and stirred to obtain a paint having a solid content concentration of 20%.
- This paint was coated on the support using a ball blade coater so that the coating amount would be 12 g Zm 2 , to obtain a coated paper having an under layer as a coated layer.
- spherical core silica having an average primary particle diameter of 50 nm was used instead of the colloidal silica used in Example 1.
- a dye fixing agent (Epomin P 1 0 0 0: Nippon Catalyst ( A paint having a solid content concentration of 16%, which is a mixture of 6 parts of a trade name, manufactured by Co., Ltd., was applied using a bar blade coater so that the coating amount was 3 g Zm 2 .
- a gloss layer was formed in the same manner as in Example 1 except that the cationic polymer dispersion prepared in Synthesis Example 4 was used instead of the cationic polymer dispersion used in Example 1.
- the ink jet recording medium of Example 7 was obtained.
- a comparative example was prepared in exactly the same manner as in Example 1, except that the anionic polymer dispersion prepared in Comparative Synthesis Example 1 was used instead of the cationic polymer dispersion used in Example 1 as the gloss layer. An ink jet recording medium of 1 was obtained.
- cationic acrylic resin emulsion (NM-1 1: trade name of Mitsui Chemical Co., Ltd.) (average particle diameter 1 2 5 ink of Comparative Example 2 in the same manner as in Example 1 except that the glass transition temperature: 20.degree. C., and styrene was not contained as a monomer).
- NM-1 1 trade name of Mitsui Chemical Co., Ltd.
- An under layer was formed on the same support as used in Example 1 in the same manner as in Example to obtain an under paper.
- the paint for the under layer used in Example 1 was used as the coating liquid for the ink receiving layer, and the ink receiving layer was formed using a per-band coater so that the dry coating amount would be 5 g / m 2 .
- the synthetic amorphous silica (Fine seal X-3 7 B: trade name of Tokuma Co., Ltd.) in the paint for the under layer has a particle diameter of 3 7 00 nm (3. 7 1 1 1). .
- a gloss layer was coated on the ink receiving layer in the same manner as in Example 1 to obtain an ink jet recording medium of Comparative Example 3.
- An ink jet recording medium was manufactured in exactly the same manner as in Example 1, and calendered at a linear pressure of 98.7 NZ cm by a soft nip calender machine to obtain an ink jet recording medium of Comparative Example 4.
- the calender bite in contact with the gloss layer was heated, and the surface temperature was adjusted to be 80 ° C.
- the gloss layer is a resin layer consisting of a uniform surface, there are no voids in the layer, and the particle shape is maintained. It was not possible to observe polymer particles.
- Comparative Example in the same manner as Example 1 except that the cationic polymer dispersion prepared in Comparative Synthesis Example 2 was used instead of the cationic polymer dispersion used in Example 1 as the gloss layer. 5 ink jet recording media were obtained.
- the recording media obtained in Examples 1 to 7 and Comparative Examples 1 to 5 were evaluated according to the following method. In each item, ⁇ ⁇ or more evaluation should be put to practical use it can.
- the 75 ° specular gloss of the coated surface was measured according to JIS-P-142 using a Murakami Color Research Laboratory specular gloss meter (GM- 26 fo r 75 °).
- the specular gloss is 60% or more.
- the specular gloss is 50% or more and less than 60%.
- a solid image of black, cyan, magenta, and yellow printed with spreadsheet software “Etacel” was printed.
- the sample after printing is left in a constant temperature and humidity chamber for 24 hours, and then the print density of each color is measured using a Macbeth densitometer (RD 915, manufactured by Macbeth), and the total of the measured values is obtained. evaluated.
- RD 915 manufactured by Macbeth
- ⁇ The total of four colors is 7.5 or more.
- the total of four colors is 7.0 or more and less than 7.5.
- X 4-color total is less than 7.0.
- the solid printed areas of cyan, magenta, yellow, red, green and black are measured using a spectral color difference meter (NF 999, manufactured by Nippon Denshoku Kogyo Co., Ltd.) with a D 65 light source at a 10 ° field of view.
- the L * a * b * values were determined. For each color (six colors), plot the area of a hexagon with the points of each six colors as vertices by plotting the a * value on the x-axis and the b * value on the y-axis G amu t area) was measured and evaluated by this value.
- the red is in the first quadrant on the X–y axis
- the yellow is on the y axis (y> 0)
- the green is in the second quadrant
- the cyan is in the third quadrant
- the blue is on the y axis ( y x 0)
- Magenta is located in the fourth quadrant.
- G amut area is greater than 9000 and less than 1 1 000.
- X: Gamut area is less than 9000.
- the evaluation results are as shown in Table 1. There is no problem in practical use if it is the evaluation of ⁇ or in the table, but there is a problem in practical use in the evaluation of X.
- the “average particle size of silica” in the table is the secondary particle size when secondary particles are agglomerated, and the primary particle (core / shell structure) is not agglomerated as primary particles. The diameter was taken as the value.
- Methyl methacrylate 28.1 37.4 28.1 28.1 28.1 25.5 21.7 43.1 38.1 28.1 28.1 39.3 mouth
- the inkjet recording medium of each example has high glossiness and good ink absorption, and at the same time, is excellent in color development and color reproduction, while dispersing anionic fine polymer particles.
- Comparative Example 1 in which the material is used for the gloss layer, it is understood that although the white paper glossiness and the ink absorbency are good, the color reproducibility is particularly poor.
- Comparative Example 2 in which a polymer-fine particle dispersion containing no styrene was used for the gloss layer, and in Comparative Example 4 in which the calender treatment was carried out at a high temperature, although the white paper glossiness was relatively good, At the time of calendering, the polymer layer of the glossy layer was melted and formed into a film by heat, so that there was almost no void between particles, resulting in particularly poor ink absorption.
- the ink jet recording medium obtained by the present invention can obtain good image quality not only having high glossiness and good ink absorbability but also excellent in color developability and color reproducibility. To demonstrate that.
- an ink jet recording medium having high glossiness and good ink absorptivity, as well as good image quality excellent also in color developability and color reproducibility.
Landscapes
- Ink Jet Recording Methods And Recording Media Thereof (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Ink Jet (AREA)
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2003280732A AU2003280732A1 (en) | 2002-11-12 | 2003-11-12 | Ink-jet recording medium and process for producing the same |
US10/532,531 US20060057310A1 (en) | 2002-11-12 | 2003-11-12 | Ink-jet recording medium and process for producing the same |
EP03772691A EP1561589B1 (en) | 2002-11-12 | 2003-11-12 | Ink-jet recording medium and process for producing the same |
DE2003620671 DE60320671T2 (de) | 2002-11-12 | 2003-11-12 | Tintenstrahlaufzeichnungsmedium und herstellungsverfahren dafür |
HK06101591A HK1078834A1 (en) | 2002-11-12 | 2006-02-07 | Inkjet recording medium and a method for manufacturing thereof |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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JP2002-328289 | 2002-11-12 | ||
JP2002328289 | 2002-11-12 |
Publications (1)
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WO2004043703A1 true WO2004043703A1 (ja) | 2004-05-27 |
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ID=32310541
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PCT/JP2003/014354 WO2004043703A1 (ja) | 2002-11-12 | 2003-11-12 | インクジェット記録媒体およびその製造方法 |
Country Status (8)
Country | Link |
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US (1) | US20060057310A1 (ja) |
EP (1) | EP1561589B1 (ja) |
JP (1) | JP3907619B2 (ja) |
CN (1) | CN100363189C (ja) |
AU (1) | AU2003280732A1 (ja) |
DE (1) | DE60320671T2 (ja) |
HK (1) | HK1078834A1 (ja) |
WO (1) | WO2004043703A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106480777A (zh) * | 2016-11-28 | 2017-03-08 | 南通华润新材料有限公司 | 一种高光泽耐水相纸的上光层涂液及其制备方法 |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
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US20070242124A1 (en) | 2004-05-18 | 2007-10-18 | Mitsui Chemicals, Inc. | Organic Particle for Inkjet Recording Sheet and Recording Sheet |
JP2006084911A (ja) * | 2004-09-17 | 2006-03-30 | Toppan Printing Co Ltd | カラーフィルタ基板及びその製造方法 |
JP2006103210A (ja) * | 2004-10-06 | 2006-04-20 | Oji Paper Co Ltd | インクジェット記録体の製造方法 |
KR100948121B1 (ko) * | 2004-11-08 | 2010-03-18 | 아크조 노벨 엔.브이. | 수성 분산물 형태의 안료 조성물 |
EP1967545A1 (en) * | 2007-03-09 | 2008-09-10 | Rohm and Haas France SAS | Cationic polymer latex |
JP2012086490A (ja) * | 2010-10-21 | 2012-05-10 | Nitto Denko Corp | シート |
JP2014198426A (ja) * | 2013-03-29 | 2014-10-23 | 大日本印刷株式会社 | 熱転写受像シートおよびその製造方法 |
CN106142857A (zh) * | 2015-04-02 | 2016-11-23 | 深圳市通印投资有限公司 | 一种名片的快速打印制作方法 |
CA2985196A1 (en) | 2015-05-08 | 2016-11-17 | Evonik Degussa Gmbh | Color-bleed resistant silica and silicate pigments and methods of making same |
CN111384270B (zh) | 2018-12-29 | 2021-07-30 | Tcl科技集团股份有限公司 | 量子点发光二极管的制备方法 |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0717125A (ja) * | 1993-07-06 | 1995-01-20 | Mitsubishi Paper Mills Ltd | インクジェット記録シート |
JP2000043408A (ja) * | 1998-07-31 | 2000-02-15 | Mitsubishi Paper Mills Ltd | インクジェット記録シート |
JP2001010215A (ja) * | 1999-06-30 | 2001-01-16 | Mitsubishi Paper Mills Ltd | インクジェット記録媒体、その製造方法、及びそれを使用した記録物の作成方法 |
JP2001347750A (ja) * | 2000-06-12 | 2001-12-18 | Oji Paper Co Ltd | インクジェット記録用紙 |
JP2002046340A (ja) * | 2000-08-03 | 2002-02-12 | Oji Paper Co Ltd | インクジェット記録用紙 |
JP2002086905A (ja) * | 2000-07-11 | 2002-03-26 | Mitsui Chemicals Inc | インクジェット用記録シート及びその製造方法 |
JP2002264474A (ja) * | 2001-03-09 | 2002-09-18 | Mitsubishi Paper Mills Ltd | インクジェット記録シート及びその製造方法 |
JP2003335048A (ja) * | 2002-05-21 | 2003-11-25 | Konica Minolta Holdings Inc | インクジェット記録用紙及びその製造方法 |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR0184324B1 (ko) * | 1933-06-15 | 1999-05-15 | 미따라이 하지메 | 잉크 제트 기록용 캐스트 피복지 |
US5576088A (en) * | 1994-05-19 | 1996-11-19 | Mitsubishi Paper Mills Limited | Ink jet recording sheet and process for its production |
US5605750A (en) * | 1995-12-29 | 1997-02-25 | Eastman Kodak Company | Microporous ink-jet recording elements |
EP0889080A1 (en) * | 1996-12-10 | 1999-01-07 | Daicel Chemical Industries, Ltd. | Porous films, process for producing the same, and laminate films and recording sheets made with the use of the porous films |
WO2000015552A1 (fr) * | 1998-09-10 | 2000-03-23 | Nissan Chemical Industries, Ltd. | Solution colloidale de silice moniliforme, procede de production associe et support d'enregistrement de jets d'encre |
US6372329B1 (en) * | 1998-11-30 | 2002-04-16 | Arkwright, Incorporated | Ink-jet recording media having ink-receptive layers comprising modified poly(vinyl alcohols) |
JP2002172850A (ja) * | 2000-12-07 | 2002-06-18 | Konica Corp | インクジェット記録用紙 |
-
2003
- 2003-11-12 JP JP2003382426A patent/JP3907619B2/ja not_active Expired - Fee Related
- 2003-11-12 CN CNB2003801029399A patent/CN100363189C/zh not_active Expired - Fee Related
- 2003-11-12 WO PCT/JP2003/014354 patent/WO2004043703A1/ja active IP Right Grant
- 2003-11-12 US US10/532,531 patent/US20060057310A1/en not_active Abandoned
- 2003-11-12 AU AU2003280732A patent/AU2003280732A1/en not_active Abandoned
- 2003-11-12 EP EP03772691A patent/EP1561589B1/en not_active Expired - Lifetime
- 2003-11-12 DE DE2003620671 patent/DE60320671T2/de not_active Expired - Fee Related
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2006
- 2006-02-07 HK HK06101591A patent/HK1078834A1/xx not_active IP Right Cessation
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0717125A (ja) * | 1993-07-06 | 1995-01-20 | Mitsubishi Paper Mills Ltd | インクジェット記録シート |
JP2000043408A (ja) * | 1998-07-31 | 2000-02-15 | Mitsubishi Paper Mills Ltd | インクジェット記録シート |
JP2001010215A (ja) * | 1999-06-30 | 2001-01-16 | Mitsubishi Paper Mills Ltd | インクジェット記録媒体、その製造方法、及びそれを使用した記録物の作成方法 |
JP2001347750A (ja) * | 2000-06-12 | 2001-12-18 | Oji Paper Co Ltd | インクジェット記録用紙 |
JP2002086905A (ja) * | 2000-07-11 | 2002-03-26 | Mitsui Chemicals Inc | インクジェット用記録シート及びその製造方法 |
JP2002046340A (ja) * | 2000-08-03 | 2002-02-12 | Oji Paper Co Ltd | インクジェット記録用紙 |
JP2002264474A (ja) * | 2001-03-09 | 2002-09-18 | Mitsubishi Paper Mills Ltd | インクジェット記録シート及びその製造方法 |
JP2003335048A (ja) * | 2002-05-21 | 2003-11-25 | Konica Minolta Holdings Inc | インクジェット記録用紙及びその製造方法 |
Non-Patent Citations (1)
Title |
---|
See also references of EP1561589A4 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106480777A (zh) * | 2016-11-28 | 2017-03-08 | 南通华润新材料有限公司 | 一种高光泽耐水相纸的上光层涂液及其制备方法 |
Also Published As
Publication number | Publication date |
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JP3907619B2 (ja) | 2007-04-18 |
JP2004175113A (ja) | 2004-06-24 |
DE60320671D1 (de) | 2008-06-12 |
AU2003280732A1 (en) | 2004-06-03 |
CN1711174A (zh) | 2005-12-21 |
EP1561589A4 (en) | 2006-05-03 |
HK1078834A1 (en) | 2006-03-24 |
DE60320671T2 (de) | 2009-06-10 |
EP1561589B1 (en) | 2008-04-30 |
EP1561589A1 (en) | 2005-08-10 |
US20060057310A1 (en) | 2006-03-16 |
CN100363189C (zh) | 2008-01-23 |
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