WO2004106080A1 - Cast ink-jet recording paper - Google Patents

Cast ink-jet recording paper Download PDF

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Publication number
WO2004106080A1
WO2004106080A1 PCT/JP2003/006685 JP0306685W WO2004106080A1 WO 2004106080 A1 WO2004106080 A1 WO 2004106080A1 JP 0306685 W JP0306685 W JP 0306685W WO 2004106080 A1 WO2004106080 A1 WO 2004106080A1
Authority
WO
WIPO (PCT)
Prior art keywords
cast
recording paper
jet recording
ink jet
layer
Prior art date
Application number
PCT/JP2003/006685
Other languages
French (fr)
Japanese (ja)
Inventor
Mitsuru Kobayashi
Shinichi Asano
Motoko Hiraki
Original Assignee
Oji Paper Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Oji Paper Co., Ltd. filed Critical Oji Paper Co., Ltd.
Priority to AU2003241838A priority Critical patent/AU2003241838A1/en
Priority to PCT/JP2003/006685 priority patent/WO2004106080A1/en
Priority to CN03826535.4A priority patent/CN1771134A/en
Publication of WO2004106080A1 publication Critical patent/WO2004106080A1/en

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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52Macromolecular coatings
    • B41M5/5218Macromolecular coatings characterised by inorganic additives, e.g. pigments, clays
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/502Recording 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
    • B41M5/506Intermediate layers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52Macromolecular coatings

Definitions

  • the present invention relates to a photographic ink-jet recording paper having excellent gloss on a blank portion and a printing portion on which a recorded image is formed by using a water-based ink, and in particular, for a full-color image printed on an ink-jet recording paper.
  • the present invention relates to a cast-in jet recording paper which has a high print density, maintains ink absorbency, has excellent heat resistance and ozone resistance, and has excellent continuous operability.
  • the ink jet recording method in which water-based ink is ejected from a fine nozzle onto the ink jet recording paper to form an image, has low noise, enables high-speed recording, is easy to colorize, and has other features. Because they are cheaper than printing devices, they are used in a variety of applications, including terminal printers, facsimile machines, plotters, and form printing.
  • As ink jet recording paper high-quality paper devised to be rich in ink absorbency, and coated paper having a surface coated with a porous pigment are used.
  • all of these inkjet recording papers are mainly ink-jet recording papers with a low surface gloss, so-called matte tone, there is a demand for photographic ink-jet recording papers with high surface gloss and excellent appearance. .
  • inkjet recording paper is also preferred as inkjet recording paper.
  • advanced properties are required for inkjet recording paper, such as white paper and print gloss, ink absorption, image recording density, water resistance, light resistance, ozone resistance, heat resistance, etc.
  • inkjet recording paper that is excellent in quality and comparable to the silver halide method.
  • recording paper having a high surface gloss is coated with a plate-like pigment on the surface and, if necessary, subjected to a calender treatment, and is coated with high gloss or wet coating.
  • a so-called cast coated paper obtained by pressing and drying the layer on a heated drum surface having a mirror surface and copying the mirror surface is known, and is widely used as various printing papers.
  • the cast coated paper has higher surface gloss and better surface smoothness than a normal calender-finished coated paper, so that an excellent printing effect can be obtained. It is used exclusively for high-quality printed materials, etc., and has the same glossiness when used for inkjet recording paper, and is attracting attention as a relatively inexpensive recording medium among photographic ink jet recording papers. . A number of methods have been proposed to produce high-quality glossy ink jet recording paper satisfying the above characteristics by the cast coating method.
  • JP-A-62-95285 ink absorption is fast, drying is excellent, dimensional changes due to moisture absorption and dehumidification during recording and storage are unlikely to occur, and the area around the dot is A cast ink jet recording paper which is sharp, has a high resolution, and has a high smoothness and gloss on the coated surface is disclosed.
  • Japanese Patent Application Laid-Open No. 63-264391 discloses a good ink absorption.
  • a cast ink jet recording paper having both glossiness, water resistance of a recorded image, and dimensional stability has been disclosed.
  • Japanese Patent Application Laid-Open No. Hei 2-274758 discloses a multicolor ink jet using a water-based ink.
  • 5-9694 discloses a cast ink jet recording paper suitable for printing on ink, which is excellent in ink absorbency, smoothness and glossiness of the recording paper surface, and water resistance of the recording paper. Excellent density, sharpness and roundness, Japanese Patent Application Laid-Open No. 8-332771 discloses a cast ink jet recording paper capable of recording a full-color image with high image quality and high gradation, which is excellent in both ink absorption and productivity. Japanese Patent Application Laid-Open No. 2000-212128 discloses a cast ink jet recording paper having a high glossiness on the recording surface, a glossy smoothness close to that of a photograph, a high print density, excellent print water resistance, and excellent print water resistance. Also disclosed are methods for producing cast ink jet recording paper that maintain the fixability, absorbency, etc. of the ink jet ink.
  • the cast ink jet recording paper is not sufficiently peelable from the metal surface of the drum having a mirror-finished surface, resulting in poor continuous operability.
  • a cast inkjet recording paper generally has a bulky coating layer structure, so that the surface strength of the coating layer is lower than that of the cast coating paper used as printing paper. Low. Therefore, when the coating layer is pressed against the heated mirror drum and is dried, a part of the coating layer remains on the mirror drum, and there is a problem that the mirror drum surface becomes cloudy in proportion to the operation time.
  • a release agent used in the production of ordinary coated paper for printing or cast coated paper for printing can be used.
  • ozone properties it is necessary to select an excellent release agent that can withstand these quality requirements.
  • JP-A No. 1-77572 discloses an example in which the water resistance and the light resistance are particularly improved. This discloses that storage stability is improved by containing a cationic compound having a specific structure. Disclosure of the invention
  • the present invention relates to a photographic ink-jet recording paper having excellent glossiness of a blank portion and a printing portion on which a recorded image is formed using a water-based ink, and in particular, an image printed in full color on an ink-jet recording paper.
  • An object of the present invention is to provide a cast ink jet recording paper having a high print density, excellent heat resistance and excellent ozone resistance, and excellent continuous operation.
  • the present invention employs the following configuration in order to solve the above problems.
  • An undercoat layer containing a pigment, a cationic compound and an adhesive is provided on a base material.
  • the undercoat layer contains an adhesive, a fine pigment having an average secondary particle diameter of less than 1 m, and a release agent.
  • the cationic compound may be a copolymer of diarylamine and (meth) acrylamide, diarylamine and (meth) acrylamide, and another polymer copolymerizable with these.
  • a cast ink jet recording paper containing at least one selected from the group consisting of a fatty acid and a water-soluble salt thereof.
  • the present invention includes the following aspects.
  • BEST MODE FOR CARRYING OUT THE INVENTION The present inventors provided an undercoat layer containing a pigment, a cationic compound and an adhesive on a base material, and provided an adhesive and an average secondary particle on the undercoat layer.
  • the cationic compound is a copolymer of diarylamine and (meth) acrylamide, diarylamine. And a copolymer of (meth) acrylamide and another vinyl monomer copolymerizable therewith and substantially not containing a carboxyl group, or a salt thereof.
  • the continuous operability here means that there is no pick-shaped coating defect on the surface of the cast ink jet recording paper, and the mirror drum is not so dirty that the operation must be interrupted. is there.
  • the substrate used in the present invention is not particularly limited, and is a paper substrate such as acidic paper or neutral paper used for general coated paper, or a resin film having air permeability. Can be used.
  • the paper base is composed mainly of wood pulp and, if necessary, pigment.
  • wood pulp various chemical pulp, mechanical pulp, recycled pulp and the like can be used, and the degree of beating of these pulp can be adjusted by a beating machine in order to adjust paper strength, papermaking suitability, and the like.
  • the degree of freeness (freeness) of the pulp is not particularly limited, but is generally 250 to 5 It is about 50 ml (CSF: JIS -P- 8 1 2 1). Also, chlorine-free pulp such as so-called ECF and TCF pulp can be preferably used.
  • the pigment is blended for the purpose of imparting opacity or the like, or adjusting the ink absorbency, and calcium carbonate, calcined kaolin, silica, titanium oxide, or the like can be used.
  • the amount is preferably about 1 to 20% by mass, and if it exceeds 20% by mass, the paper strength may be reduced.
  • auxiliaries a sizing agent, a fixing agent, a paper strength enhancer, a cationizing agent, a retention improver, a dye, a fluorescent whitening agent and the like can be added.
  • starch, polybutyl alcohol, a cationic compound, and the like can be applied and impregnated to adjust the surface strength, degree of steak size, and the like.
  • the degree of steak size is preferably about 1 to 200 seconds. If the stick size is less than 1 second, there may be operational problems such as wrinkles during coating.If it is more than 200 seconds, the ink absorbency will decrease or ink strike-through will occur. Curling and cockling after printing may be significant.
  • the basis weight of the base material is not particularly limited, but is about 20 to 400 gZm 2 .
  • an undercoat layer containing a pigment, a cationic compound and an adhesive is provided on a substrate.
  • Examples of the cationic compound contained in the undercoat layer include a copolymer of diarylamine and (meth) acrylamide, diarylamine and (meth) acrylamide, and other vinyl monomers copolymerizable with these.
  • a copolymer of diarylamine and (meth) acrylamide, diarylamine and (meth) acrylamide, and other vinyl monomers copolymerizable with these By containing at least one kind of cationic compound selected from the group consisting of a copolymer containing no carboxyl group or a salt of any of these, storage stability such as gas resistance is improved. More — layers can be improved.
  • the molar fraction of diarylamine is in the range of 0.1 to 0.99, preferably in the range of 0.15 to 0.95, and (meth) acrylamide
  • the molar fraction is in the range of 0.01 to 0.9, preferably in the range of 0.05 to 0.85, and other vinyl monomers which are copolymerizable therewith, Molar fraction of those containing substantially no carboxyl groups Ranges from 0 to 0.3.
  • a salt of a copolymer containing diarylamine as a part of the monomer is also included, and either an inorganic acid salt or an organic acid salt may be used. If diarylamine is used in the form of a salt, a polymer in the form of a salt can be obtained.
  • the cationic compound may be used in the undercoat layer in an amount of preferably from 1 to 100 parts by mass, more preferably from 5 to 50 parts by mass, based on 100 parts by mass of the pigment. If the amount is less than 1 part by mass, not only the desired print density, heat resistance and ozone resistance effect cannot be obtained, but also the water resistance of the print may be impaired. On the contrary, not only the print density is reduced, but also the image may be blurred.
  • the undercoat layer may contain polyalkylene polyamines such as polyethylene polyamine / polypropylene pyrene polyamine used in conventional ink jet recording paper, or derivatives thereof, and tertiary amino groups.
  • polyalkylene polyamines such as polyethylene polyamine / polypropylene pyrene polyamine used in conventional ink jet recording paper, or derivatives thereof, and tertiary amino groups.
  • the weight-average molecular weight of the cationic compound is about tens of thousands or less, it is generally easy to be eluted in water, and the printing water resistance of a printing portion with a large amount of ink such as mixed color black is inferior.
  • cationic compounds having a weight-average molecular weight of 100,000 or more are generally hardly eluted in water and, for example, inhibit ink permeation like polybutyl alcohol and the like, and may reduce ink absorption. There is.
  • the weight average molecular weight of the cationic compound is 100,000 or more, the printing density of colors such as cyan, magenta, and yellow tends to be high, and when the weight average molecular weight is 50,000 or less, the printing density of the black tends to be high. .
  • Pigments in the undercoat layer include kaolin, clay, calcined clay, amorphous silica (also called amorphous silica), zinc oxide, aluminum oxide, aluminum hydroxide, carbonated calcium, sachin white, aluminum silicate, alumina, and colloidal silica.
  • Pigments known in the general coated paper manufacturing field such as plastic pigment, hydrotalcite, urea resin-based plastic pigment, and benzoguanamine-based plastic pigment, can be used alone or in combination.
  • amorphous silica, alumina, and zeolite having high ink absorbability it is preferable to use amorphous silica, alumina, and zeolite having high ink absorbability as main components.
  • the adhesive for the undercoat layer examples include proteins such as casein, soybean protein, and synthetic protein, various starches such as starch and oxidized starch, polybutyl alcohol, cationic polyvinyl alcohol, and silyl-modified polyvinyl alcohol.
  • Polybutyl alcohols, cenorellose derivatives such as carboxymethylcellulose / methinolecellulose, styrene-butadiene copolymer, conjugated gen-based polymer latex of methyl methacrylate-butadiene copolymer, latex of acryl-based polymer
  • Conventionally known adhesives generally used for coated paper, such as a butyl polymer latex such as a butyl acetate copolymer are used alone or in combination.
  • polyvinyl alcohols such as polyvinyl alcohol, cationic polyvinyl alcohol, and silyl-modified polyvinyl alcohol are preferably used to improve the surface strength of the undercoat layer. .
  • the mixing ratio of the pigment and the adhesive in the undercoat layer depends on the type thereof, but is generally 1 to 100 parts by mass, preferably 2 to 50 parts by mass with respect to 100 parts by mass of the pigment. It is adjusted within the range.
  • the undercoat layer paint composed of the above materials is generally adjusted to have a solid content concentration of about 5 to 50% by mass, and has a dry mass of 2 to 100 g Zm 2 , preferably 5 ⁇ 5 0 g Z m 2 approximately, more preferably you applied so that about 5 ⁇ 2 0 g / m 2.
  • the coating amount When the coating amount is small, the ink absorption is poor, and the bleeding of the recorded image or the gloss after coating the cast layer may be reduced. Further, in the case of a paper base material, the amount of ink absorbed by the paper base material increases, so that the paper after recording has a wavy or G), the press marks (spur marks) due to the printer spurs (paper rolls and gears after recording) may be noticeable.
  • the coating amount When the coating amount is large, the ink easily penetrates and is distributed not only on the cast layer side but also on the substrate side, so that the print density may be reduced. In addition, the strength of the undercoat layer may be reduced, and the powder may fall off or the surface may be easily damaged.
  • the coating for the undercoat layer is applied by various well-known coating apparatuses such as a blade coater, an air knife coater, a roll coater, a brush coater, a champlex coater, a no coater, a lip coater 1, a gravure coater, and a curtain coater. It is dried. Further, if necessary, the recording layer may be subjected to a smoothing process such as super calendering or brushing after drying.
  • the cast layer of the present invention comprises an adhesive, a fine pigment having an average secondary particle diameter of 1 ⁇ m or less, and a release agent.
  • the adhesive in the cast layer includes, for example, polyvinyl alcohol, cation-modified polyvinyl alcohol, silyl-modified polyvinyl alcohol, and other polyvinyl alcohol, casein, soy protein, synthetic protein, starch, and the like.
  • Senorelose derivatives such as carboxylmethyl cellulose methinoresenolylose, vinylinole acetate polymer emulsion, styrene-butadiene copolymer emulsion, ethylene acetate butyl copolymer emulsion, acrylyl copolymer emulsion, styrene Acrylic copolymer emulsions, aqueous acryl resins, aqueous polyurethane resins, aqueous polyester resins, and other generally known adhesives in the coated paper field can be used alone or in combination.
  • a styrene-acrylic copolymer emulsion is particularly preferred from the viewpoints of clearness and glossiness of a recorded image.
  • the weight average molecular weight of the emulsion used as an adhesive in the cast layer is preferably from 100,000 to 100,000, and more preferably from 500,000 to 500,000. If the molecular weight is lower than 100,000, the strength of the coating film tends to be insufficient, and if the molecular weight is higher than 100,000, the stability of the emulsion tends to be insufficient.
  • the average particle diameter of the emulsion is preferably in the range of 0.02 to 0.15 ⁇ m. If the average particle size of the emulsion is less than 0.02 ⁇ m, the ink absorbency will decrease.On the other hand, if the average particle size exceeds 0.15 ⁇ , the surface gloss and the sharpness of the color development of the recorded image will decrease. .
  • a copolymer emulsion having a glass transition temperature of the copolymer in the range of 50 to 150 ° C. is preferred.
  • the glass transition point of the copolymer is lower than 50 ° C, the film of the cast layer will advance too much during drying, and the porosity of the surface will decrease, resulting in a decrease in the ink absorption rate. There is. Conversely, if the glass transition point of the copolymer is higher than 150 ° C., film formation may be insufficient during drying, and the gloss may be insufficient. On the other hand, if the drying temperature is too high, the film formation proceeds too much, and the porosity of the surface decreases, so that the ink absorption rate decreases. Conversely, if the drying temperature is too low, gloss tends to decrease.
  • Examples of the fine pigment having an average secondary particle diameter of 1 ⁇ or less in the cast layer include kaolin, clay, calcined clay, amorphous silica (also referred to as amorphous silica), zinc oxide, and oxide.
  • amorphous silica also referred to as amorphous silica
  • Various pigments known and used in the general coated paper manufacturing field such as styrene-based plastic pigments, hydrotalcite, urea resin-based plastic pigments, and benzoguanamine-based plastic pigments, can be used alone or in combination.
  • amorphous silica, alumina, colloidal silica, or zeolite having high ink absorbability is preferable to use as a main component. More preferred is colloidal silica, and even more preferred is anionic colloidal silica.
  • the anionic colloidal silica has an average particle size of 0.01 to 0.15 / im, preferably 0.01 to 0.12 ⁇ m, and more preferably 0.01 to 0.12 ⁇ m. 2 to 0.10 ⁇ m. If the average particle size is less than 0.01 ⁇ m, the ink absorption may decrease.If it exceeds 0.15 ⁇ , gloss and The sharpness of coloring of a recorded image may be reduced.
  • composition ratio (solid content mass ratio) of the adhesive and the fine pigment in the cast layer is preferably
  • It is in the range of 60/40 to 3/97, more preferably in the range of 50/50 to 5/95, and still more preferably in the range of 40/60 to 7/93.
  • the release agent used in the cast layer at least one selected from the group consisting of fatty acids having 12 to 18 carbon atoms and water-soluble salts thereof is preferably used to obtain the effects of the present invention.
  • the number of carbon atoms is 19 or more, the dispersibility may be poor, and when the number of carbon atoms is less than 12, the releasability may not be sufficient.
  • fatty acids having 12 to 18 carbon atoms include lauric acid (12 carbon atoms), myristic acid (13 carbon atoms), palmitic acid (15 carbon atoms), stearic acid (18 carbon atoms) ), Oleic acid (18 carbon atoms), linoleic acid (18 carbon atoms), linolenic acid (18 carbon atoms), arachidonic acid (18 carbon atoms), and the like.
  • Examples thereof include a sodium salt, a potassium salt, and an ammonium salt of the fatty acid.
  • stearic acid or a water-soluble salt thereof stearic acid or a water-soluble salt thereof
  • oleic acid or a water-soluble salt thereof are preferable in terms of heat resistance and releasability of recording paper, and among these, stearic acid and oleic acid are further preferable.
  • Ammonium stearate, and ammonium oleate are particularly excellent.
  • the reason why the heat resistance and the release property are good is that the release agent is not easily oxidized in terms of the chemical structure, and the release property from the mirror drum is good. Further, in addition to the release agent, it is possible to use a release agent used in the production of ordinary coated paper for printing or cast paper for printing as long as the effects of the present invention are not impaired. .
  • the release agent is used in an amount of 0.1 to 10 parts by mass with respect to 100 parts by mass of the fine pigment. Preferably, 0.2 to 8 parts by mass is added. If the addition amount is less than 0.1 part by mass, continuous operability may be poor. If the addition amount exceeds 10 parts by mass, the print density may be reduced and the image quality may be reduced.
  • the image storability is improved.
  • the organic compound containing thioether include thioether compounds, thiourea compounds, disulfide compounds, mercapto compounds, sulfin oxide compounds, thiosulfonic acid compounds, and thiosulfinic acid compounds.
  • thioether compounds are preferable, and in particular, the inclusion of 1,2-bis (2-hydroxyxethylthio) ethane or 1,4-bis (2-hydroxyxethylthio) butane makes the image resistant to ozone. Cast ink jet recording paper with improved performance can be obtained.
  • the content of cast Inkjet recording during paper compound 0. 1 ⁇ 4 g / m 2 approximately, preferably 0. 2 ⁇ 2 g Z m 2 approximately.
  • the compound exhibits an effect when contained in either the undercoat layer or the cast layer.
  • the coating liquid for the cast layer contains an antifoaming agent, a coloring agent, and a defoaming agent used for general printing coated paper and ink jet recording paper in order to adjust whiteness, viscosity, fluidity, and the like.
  • Various auxiliaries such as a fluorescent whitening agent, an antistatic agent, a preservative and a dispersant, and a thickener are appropriately added. It is also possible to add a cationic compound to impart ink dye fixability.
  • the method of providing a cast layer in the present invention includes the steps of forming a coating liquid layer for a cast layer by using a mirror-finished drum (a drum of mirror-finished metal, plastic, glass, or the like), a mirror-finished metal plate, a plastic sheet, or the like. Dry on film, glass plate, etc. And transferring the smooth surface onto the coating layer, and obtaining a smooth and glossy cast coating layer surface by this method.
  • a mirror-finished drum a drum of mirror-finished metal, plastic, glass, or the like
  • a mirror-finished metal plate a plastic sheet, or the like. Dry on film, glass plate, etc.
  • transferring the smooth surface onto the coating layer and obtaining a smooth and glossy cast coating layer surface by this method.
  • the above-mentioned coating solution for a cast layer is applied on an undercoat layer, and the coated layer is pressed against a heated mirror-surface drum while the coating layer is in a wet state, and dried.
  • the method include a finishing method (wet casting method) and a method of once drying, re-wetting, pressing against a heated mirror drum, drying and finishing (rewet casting method), and the like.
  • a method in which the coating liquid for the cast layer is applied directly to the heated mirror-surface drum, followed by pressing and drying the undercoat layer surface of the base material provided with the undercoat layer should also be adopted. Can be.
  • the preferred range of the temperature of the heated mirror drum is 50 to 150 ° C, more preferably 70 to 120 ° C.
  • various known coating apparatuses such as a blade coater, an air knife coater, a rhono recorder, a brush coater, a chaplex coater, a bar coater, and a Daravia coater can be used.
  • the coating amount of the cast layer is preferably 1 ⁇ 3 0 g Z m 2 by dry weight, more preferably rather is 2 ⁇ 2 0 g / m 2, more preferably, 3 ⁇ 1 5 g Zm 2 .
  • it is less than 1 g Z m 2, may print density and gloss is not sufficient, 3 0 when g / m 2 a exceeds effect is saturated and workability load is imposed on the drying may be reduced .
  • a smoothing process can be further performed by using a super calender or the like. At this time, the calender can be heated.
  • ⁇ 5 ° surface gloss (JIS-Z8741) of the recording surface of the cast inkjet recording paper is preferably 50 to obtain excellent image quality and high-quality photographic recording. % Or more, more preferably 60% or more.
  • Amorphous silica as pigment (trade name: Fine Seal X-45, average primary particle diameter: 10 nm, average secondary particle diameter: 4.5 ⁇ m), 50 parts, Zeolite (manufactured by Tosoh Corporation) , Trade name: Toyobuilder, average particle size 1.5 ⁇ m) 50 parts, Silicone-modified polybutyl alcohol (Kuraray Co., trade name: PVA R-11 30) as adhesive 30 parts, as cationic compound 25 parts of diarylamine hydrochloride / acrylamide copolymer resin (Sumitomo Chemical Co., Ltd., trade name: Sumireze Resin 100 ⁇ ), 0.5 part of sodium polyphosphate as a dispersant, and a solid content concentration of 18 parts % Of a coating solution for an undercoat layer was prepared.
  • a coating liquid for a cast layer having a solid content concentration of 30% was prepared, comprising 5 parts of an alkyl bier ether / maleic acid derivative resin and 3 parts of a stearic acid aqueous dispersion (solid content ratio) as a release agent.
  • This coating solution for a cast layer is applied onto the above-mentioned undercoat layer using a roll coater, immediately pressed against a mirror drum having a surface temperature of 80 ° C, dried, released, and then cast. Inkjet recording paper was obtained.
  • the coating amount of the cast layer at this time was 12 g / m 2 in terms of solid content mass.
  • a cast ink jet recording paper was obtained in the same manner as in Example 1, except that 3 parts of aqueous stearic acid dispersion was added as a release agent in place of 3 parts of aqueous stearic acid.
  • 3 parts of aqueous stearic acid dispersion was added as a release agent in place of 3 parts of aqueous stearic acid.
  • a cast ink jet recording paper was obtained in the same manner as in Example 1, except that 3 parts of ammonium oleate was added as the release agent instead of 3 parts of the aqueous dispersion of stearic acid as a release agent. .
  • Example 4 A cast ink jet recording paper was obtained in the same manner as in Example 1 except that 50 parts of the cationic compound 25 was changed to 50 parts.
  • a cast ink jet recording paper was obtained in the same manner as in Example 1, except that 5 parts of the cationic compound 25 was changed to 5 parts.
  • a cast ink jet recording paper was obtained in the same manner as in Example 1, except that 80 parts of the following fine silica was used in place of the anionic colloidal silica as the fine pigment of the cast layer.
  • An aqueous silica dispersion having an average secondary particle diameter of 4.5 ⁇ (available from Tokuyama Corporation, trade name: Fine Seal X-45, average primary particle diameter 10 nm) was mixed with a pressure homogenizer (SMT). The pulverization treatment was repeated with a pressurized condition of 200 kg / m 2 using an ultra-high pressure homogenizer (GM-1 type, manufactured by the company) to obtain fine silica having an average secondary particle diameter of 0.8 ⁇ .
  • SMT pressure homogenizer
  • a cast ink jet recording paper was obtained in the same manner as in Example 1, except that 10 parts of 1,2-bis (2-hydroxyxethylthio) ethane was added to the coating liquid for the undercoat layer.
  • 10 parts of 1,2-bis (2-hydroxyxethylthio) ethane was added to the coating liquid for the undercoat layer.
  • Example 1 dicyandiamide-based resin (manufactured by Nikka Chemical Co., trade name: Neofix E-117) was used in place of 5 parts of diarylamine hydrochloride / acrylamide copolymer resin as the cationic compound.
  • a cast ink jet recording paper was obtained in the same manner as in Example 1 except that five copies were used.
  • a cast ink jet recording paper was obtained in the same manner as in Example 1 except that 3 parts of an aqueous dispersion of lecithin was used instead of 3 parts of an aqueous dispersion of stearic acid as a release agent.
  • a cast was prepared in the same manner as in Example 1 except that 3 parts of an aqueous dispersion of arachidic acid (C 2 ) was used as a release agent instead of 3 parts of an aqueous dispersion of stearic acid. Inkjet recording paper was obtained.
  • Example 1 a cast ink was prepared in the same manner as in Example 1, except that 3 parts of an aqueous dispersion of undecylic acid (Cu) was used as a release agent instead of 3 parts of an aqueous dispersion of stearic acid. A recording paper was obtained.
  • Cu undecylic acid
  • the cast ink jet recording paper obtained in the examples and comparative examples was printed using an Epson inkjet printer PM-800C, and the evaluation results are shown in Table 1.
  • the printing density of the black solid printing portion 24 hours after printing was measured using a Macbeth densitometer (trade name: RD_914) manufactured by Macbeth.
  • the ink absorbency was evaluated visually from the boundary of the mixed color black (80%) printed portion. :: The boundary is clear and there is no bleeding.
  • the cast ink jet recording paper prepared in each example and each comparative example was stored in a thermostat at 80 ° C. for 7 days without printing, and the degree of yellowing of the recording paper was visually evaluated. Evaluation criteria :
  • Ozone resistance which has a high correlation with long-term storage, was evaluated.
  • Solid printing of mixed black and cyan ink with one color mixture of cyan, magenta and yellow, and ISO-4 The printed image of 0 was left in a container having an ozone concentration of 10 ppm for 12 hours.
  • the print density after the test was measured.
  • the degree of discoloration was visually observed and evaluated.
  • The mirror surface drum is stained, and the glossiness of the recording paper is reduced, which causes a practical problem.
  • the glossiness of the obtained cast ink jet recording paper was measured using a gloss meter (trade name: GM-26D, manufactured by Murakami Color Research Laboratory Co., Ltd.) described in JIS-Z8741.
  • the outline of JIS-Z8741 is as follows. A non-polarizing light source was used. A light beam with a specified opening angle was incident on the sample surface at a specified incident angle, and a light beam with a specified opening angle reflected in a mirror-reflecting direction was measured by a light receiver. The optical axes of the incident side and the light receiving side intersect at the sample surface.
  • the unit of gloss is based on the specular gloss at the specified incident angle ⁇ on the glass surface whose refractive index is a constant value of 1.567 over the entire visible wavelength range. Expressed as%. table 1
  • the cast ink jet recording paper of the present invention has a high image print density and high ink absorbency. It is not only good, but also excellent in heat resistance and ozone resistance, excellent in continuous operation, and high in glossy cast ink jet recording paper. It is extremely practical.

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  • Inorganic Chemistry (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)

Abstract

A cast ink-jet recording paper such that the gloss of the white paper portion and printing portion where a record image is formed with an aqueous ink is excellent, the density of the image printed in full color is high, the heat resistance and ozone resistance are excellent, and the continuous operating rate is high. An undercoating layer is formed on a base. The undercoating layer contains a pigment, a copolymer of diallyl amine and (meth)acryl amide, a copolymer of diallyl amine, (meth)acryl amide, and a vinyl monomer copolymerizable with them and substantially not containing a carboxyl group, a cationic compound which is at least one kind selected from the group consisting of salts of them, and an adhesive. A cast layer is formed on the undercoating layer. The cast layer contains an adhesive, a fine pigment the mean secondary particle diameter of which is below 1 μm, and a releasing agent which is at least one kind selected from the group consisting of fatty acids having 12 to 18 carbon atoms and their water-soluble salts.

Description

明細書 キャス トインクジエツト記録用紙 技術分野  Description Cast inkjet recording paper Technical field
本発明は、 水性ィンクを用いて記録画像を形成する白紙部および印字部の光沢 に優れた写真調インクジェット記録用紙に関するものであり、 特に、 インクジェ ッ ト記録用紙上にフルカラーで印字された画像の印字濃度が高く、 インク吸収性 を維持し、 耐熱性ゃ耐オゾン性に優れ、 かつ連続操業性にも優れたキャス トイン クジエツト記録用紙に関するものである。 背景技術 The present invention relates to a photographic ink-jet recording paper having excellent gloss on a blank portion and a printing portion on which a recorded image is formed by using a water-based ink, and in particular, for a full-color image printed on an ink-jet recording paper. The present invention relates to a cast-in jet recording paper which has a high print density, maintains ink absorbency, has excellent heat resistance and ozone resistance, and has excellent continuous operability. Background art
水性ィンクを微細なノズルからィンクジ ット記録用紙に噴出して画像を形成 させるインクジェット記録方式は、 騒音が少なく、 高速記録が可能であり、 かつ、 カラー化が容易であり、 さら.に他の印刷装置より安価なために、 端末用プリンタ 一、 ファクシミリ、 プロッター、 あるいは帳票印刷など多方面で利用されている。 ィンクジェット記録用紙としては、 インク吸収性に富むように工夫された上質 紙や、 表面に多孔性顔料を塗工した塗工紙等が適用されている。 しかし、 これら のインクジェット記録用紙は、 すべて表面光沢の低い、 いわゆるマット調のイン クジェッ ト記録用紙が主体であるため、 表面光沢の高い、 優れた外観を持つ写真 調ィンクジェット記録用紙が要望されている。 近年のプリンター技術の高精細化、 高速化や、 デジタルカメラの高画質化に伴い、 インクジェット記録用紙としても 光沢の高いインクジェット記録用紙が好まれている。 同時に、 インクジェッ ト記 録用紙としての高度な特性が要求されており、 白紙及び印字光沢度、 インク吸収 性、 画像の記録濃度、 耐水性、 耐光性、 耐オゾン性及び耐熱性等の各種保存性に 優れた、 銀塩方式に匹敵するインクジェット記録用紙が強く要望されている。 ところで、 一般的に、 表面光沢の高い記録用紙としては、 表面に板状顔料を塗 ェし、 さらに必要に応じてキャレンダー処理を施した高光沢を有する塗工紙、 あ るいは湿潤塗工層を、 鏡面を有する加熱ドラム面に圧着 ·乾燥することにより、 その鏡面を写し取ることによって得られる、 いわゆるキャスト塗工紙が知られて おり、 各種の印刷用紙として幅広く使用されている。 The ink jet recording method, in which water-based ink is ejected from a fine nozzle onto the ink jet recording paper to form an image, has low noise, enables high-speed recording, is easy to colorize, and has other features. Because they are cheaper than printing devices, they are used in a variety of applications, including terminal printers, facsimile machines, plotters, and form printing. As ink jet recording paper, high-quality paper devised to be rich in ink absorbency, and coated paper having a surface coated with a porous pigment are used. However, since all of these inkjet recording papers are mainly ink-jet recording papers with a low surface gloss, so-called matte tone, there is a demand for photographic ink-jet recording papers with high surface gloss and excellent appearance. . In recent years, with the advancement of high-definition and high-speed printer technology and the high image quality of digital cameras, high-gloss inkjet recording paper is also preferred as inkjet recording paper. At the same time, advanced properties are required for inkjet recording paper, such as white paper and print gloss, ink absorption, image recording density, water resistance, light resistance, ozone resistance, heat resistance, etc. There is a strong demand for inkjet recording paper that is excellent in quality and comparable to the silver halide method. By the way, generally, recording paper having a high surface gloss is coated with a plate-like pigment on the surface and, if necessary, subjected to a calender treatment, and is coated with high gloss or wet coating. A so-called cast coated paper obtained by pressing and drying the layer on a heated drum surface having a mirror surface and copying the mirror surface is known, and is widely used as various printing papers.
前記キャス ト塗工紙は、 スーパーキャレンダー仕上げされた通常の塗工紙に比 較して、 高い表面光沢と、 より優れた表面平滑性を有し、 優れた印刷効果が得ら れることから、 高級印刷物等の用途に専ら利用され、 インクジェット記録用紙に 利用した場合にも同.様な光沢感を有し、 写真調ィンクジェット記録用紙の中では、 比較的安価な記録メディァとして注目されている。 上記特性を満たした高画質の 光沢ィンクジェッ ト記録用紙をキャストコ一ティング法により製造する方法は、 これまでにも数多く提案されている。 特開昭 6 2 _ 9 5 2 8 5号公報では、 イン ク吸収性が速く、 乾燥性に優れ、 記録時や保存時の吸湿及び脱湿による寸法変化 が起こりにく く、 ドッ ト周辺がシャープで解像度が高く、 しかも塗工面の平滑性 及び光沢が高いキャストインクジエツト記録用紙が開示されており、 特開昭 6 3 - 2 6 4 3 9 1号公報では、 ィンク吸収性が良好であると共に光沢性、 記録画像 の耐水性、 寸法安定性を併せ持つキャストインクジエツ ト記録用紙が開示されて おり、 特開平 2— 2 7 4 5 8 7号公報では、 水性インクを用いた多色インクジェ ッ ト記録に適したキャス トインクジエツト記録用紙が、 特開平 5 _ 5 9 6 9 4号 公報では、 インク吸収性、 記録紙表面の平滑性や光沢性及び記録紙の耐水性に優 れる上、 ドッ トの濃度、 シャープネス及び真円性に優れ、 高画質かつ高階調性の あるフルカラーの画像を記録することのできるキャストインクジヱッ ト記録用紙 が、 特開平 8— 3 3 2 7 7 1号公報では、 インク吸収性と生産性の両方に優れた キャストインクジェッ ト記録用紙が、 特開 2 0 0 0— 2 1 1 2 4 8号公報では、 記録面に高い光沢度、 —写真に近い光沢平滑感、 高い印字濃度、 優れた印字耐水性 及び優れたィンクジヱットインクの定着性、 吸収性等を保持したキャストインク ジヱット記録用紙の製造方法が、 それぞれ開示されている。  The cast coated paper has higher surface gloss and better surface smoothness than a normal calender-finished coated paper, so that an excellent printing effect can be obtained. It is used exclusively for high-quality printed materials, etc., and has the same glossiness when used for inkjet recording paper, and is attracting attention as a relatively inexpensive recording medium among photographic ink jet recording papers. . A number of methods have been proposed to produce high-quality glossy ink jet recording paper satisfying the above characteristics by the cast coating method. In JP-A-62-95285, ink absorption is fast, drying is excellent, dimensional changes due to moisture absorption and dehumidification during recording and storage are unlikely to occur, and the area around the dot is A cast ink jet recording paper which is sharp, has a high resolution, and has a high smoothness and gloss on the coated surface is disclosed. Japanese Patent Application Laid-Open No. 63-264391 discloses a good ink absorption. In addition, a cast ink jet recording paper having both glossiness, water resistance of a recorded image, and dimensional stability has been disclosed. Japanese Patent Application Laid-Open No. Hei 2-274758 discloses a multicolor ink jet using a water-based ink. Japanese Patent Application Laid-Open No. 5-9694 discloses a cast ink jet recording paper suitable for printing on ink, which is excellent in ink absorbency, smoothness and glossiness of the recording paper surface, and water resistance of the recording paper. Excellent density, sharpness and roundness, Japanese Patent Application Laid-Open No. 8-332771 discloses a cast ink jet recording paper capable of recording a full-color image with high image quality and high gradation, which is excellent in both ink absorption and productivity. Japanese Patent Application Laid-Open No. 2000-212128 discloses a cast ink jet recording paper having a high glossiness on the recording surface, a glossy smoothness close to that of a photograph, a high print density, excellent print water resistance, and excellent print water resistance. Also disclosed are methods for producing cast ink jet recording paper that maintain the fixability, absorbency, etc. of the ink jet ink.
これらの製造方法の特徴は、 いずれの場合も合成シリカを主成分とする顔料、 及び接着剤を主成分とした記録層塗工液を、 塗工して得られる層が湿潤状態にあ る間に、 加熱された鏡面ドラムに圧接、 乾燥して仕上げたことにより、 高光沢の キャストインクジエツ ト記録用紙を得るものであるが、 これらのキャス トインク ジ.エツ ト記録用紙における記録層の塗工量は、 いずれの場合も 1 5〜 3 0 g / m 2と高く、 湿潤塗工層中の多量の水分を通常のキャス ト塗工紙製造の場合と同 様に、 塗工層側から紙基材を通して非塗工面側で蒸発乾燥させることは容易でな いため、 生産性が極めて低いという欠点があった。 The features of these production methods are, in each case, a pigment mainly composed of synthetic silica, High-gloss coating is achieved by applying a recording layer coating liquid mainly composed of an adhesive and a coating to the heated mirror drum while the layer obtained by coating is wet, and then drying it. but it is intended to obtain a cast ink di Etsu preparative recording sheet, the coating amount of the recording layer in these Cass Twink di. Etsu DOO recording paper, in both cases as high as 1 5~ 3 0 g / m 2 , the wet coating As in the case of normal cast coated paper production, it is not easy to evaporate and dry a large amount of water in the coating layer from the coating layer side through the paper base material on the non-coated side, resulting in increased productivity. There was a drawback that it was extremely low.
更に、 上記方法により得られたキャス トインクジエツ ト記録用紙の製造方法で は、 キャス トインクジェッ ト記録用紙と、 鏡面仕上げ面を有する ドラムの金属面 との剥離性が十分でなく、 連続操業性に劣るという欠点があった。 例えば、 この ようなキャス トインクジェッ ト記録用紙は、 一般的に嵩高い塗工層構造を有して いるので、 印刷用紙として使用するキャス ト塗工紙に比べて、 塗工層の表面強度 が低い。 従って、 加熱された鏡面ドラムに塗工層が、 圧接され、 乾燥する過程で、 塗工層の一部が鏡面ドラムに残り、 操業時間に比例して鏡面ドラム表面が曇ると いう問題が発生すると同時に、 キャス トインクジエツ ト記録用紙と鏡面ドラム面 との剥離がしづらくなり、 結果的にはキャス トインクジェッ ト記録用紙の光沢度 が低下するという問題が発生する。 そのため、 一旦、 操業を停止して、 鏡面ドラ ムの金属面の汚れを除去しなければならず、 操業面での課題となっていた。  Furthermore, in the method for producing the cast ink jet recording paper obtained by the above method, the cast ink jet recording paper is not sufficiently peelable from the metal surface of the drum having a mirror-finished surface, resulting in poor continuous operability. There was a disadvantage. For example, such a cast inkjet recording paper generally has a bulky coating layer structure, so that the surface strength of the coating layer is lower than that of the cast coating paper used as printing paper. Low. Therefore, when the coating layer is pressed against the heated mirror drum and is dried, a part of the coating layer remains on the mirror drum, and there is a problem that the mirror drum surface becomes cloudy in proportion to the operation time. At the same time, it becomes difficult to separate the cast inkjet recording paper from the mirror surface of the drum, and as a result, the gloss of the cast inkjet recording paper is reduced. Therefore, it was necessary to temporarily stop the operation and remove the dirt on the metal surface of the mirror drum, which was a problem in the operation.
この問題を解決するため、 前記キャス ト層塗工液中に、 離型剤を配合させて操 業性を改善することが、 一般的に行われている。 操業性を改善するための離型剤 としては、 通常の印刷用塗工紙や印刷用キャスト塗工紙製造の際に用いられる離 型剤が使用できるが、 近年注目されている耐熱性ゃ耐オゾン性の改善のため、 こ れらの品質要望に耐え得るような優れた離型剤を選択する必要がある。  In order to solve this problem, it is common practice to improve the operability by incorporating a release agent into the casting layer coating liquid. As a release agent for improving operability, a release agent used in the production of ordinary coated paper for printing or cast coated paper for printing can be used. In order to improve ozone properties, it is necessary to select an excellent release agent that can withstand these quality requirements.
また、 近年インクジェッ ト記録用紙の保存性の向上が強く望まれており、 特に 耐水性や耐光性を向上させた例としては、 特開平 1— 7 7 5 7 2号公報がある。 これは特定の構造を有するカチオン性化合物を含有することにより、 保存性が向 上することを開示している。 発明の開示 Further, in recent years, there has been a strong demand for improvement in the preservability of the ink jet recording paper, and JP-A No. 1-77572 discloses an example in which the water resistance and the light resistance are particularly improved. This discloses that storage stability is improved by containing a cationic compound having a specific structure. Disclosure of the invention
本発明は、 水性ィンクを用いて記録画像を形成する白紙部および印字部の光沢 に優れた写真調インクジェット記録用紙に関するものであり、 特に、 インクジェ ッ ト記録用紙上に、 フルカラーで印字された画像の印字濃度が高く、 耐熱性ゃ耐 オゾン性に優れ、 連続操業性にも優れたキャストインクジエツ ト記録用紙を提供 することにある。 The present invention relates to a photographic ink-jet recording paper having excellent glossiness of a blank portion and a printing portion on which a recorded image is formed using a water-based ink, and in particular, an image printed in full color on an ink-jet recording paper. An object of the present invention is to provide a cast ink jet recording paper having a high print density, excellent heat resistance and excellent ozone resistance, and excellent continuous operation.
本発明は、 上記課題を解決するため、 下記の構成を採用する。  The present invention employs the following configuration in order to solve the above problems.
即ち、 本発明は、  That is, the present invention
①基材上に、 顔料、 カチオン性化合物及び接着剤を含有する下塗り層を設け、 前記下塗り層上に、 接着剤、 平均二次粒子径が 1 m未満の微細顔料及び離型剤 を含有するキャスト層を設けたキャス トインクジェット記録用紙において、 前記 カチオン性化合物が、 ジァリルァミンと (メタ) アクリルアミ ドとの共重合体、 ジァリルァミンと (メタ) アクリルアミ ドとこれらに共重合可能な他のビュル系 モノマーであって実質的にカルボキシル基を含有しないものとの共重合体、 又は これらのいずれかの塩から成る群より選ばれる少なくとも一種であり、 かつ前記 離型剤として、 炭素数が 1 2〜 1 8の脂肪酸及びその水溶性塩から成る群より選 ばれる少なく とも一種を含有するキャストインクジェット記録用紙である。  (1) An undercoat layer containing a pigment, a cationic compound and an adhesive is provided on a base material. The undercoat layer contains an adhesive, a fine pigment having an average secondary particle diameter of less than 1 m, and a release agent. In a cast ink jet recording paper provided with a cast layer, the cationic compound may be a copolymer of diarylamine and (meth) acrylamide, diarylamine and (meth) acrylamide, and another polymer copolymerizable with these. A copolymer with a monomer that does not substantially contain a carboxyl group, or at least one selected from the group consisting of salts thereof, and wherein the release agent has 12 carbon atoms. A cast ink jet recording paper containing at least one selected from the group consisting of a fatty acid and a water-soluble salt thereof.
本発明は以下の態様を含む。  The present invention includes the following aspects.
②前記離型剤が、 ステアリン酸、 ォレイン酸、 ステアリン酸の水溶性塩、 およ びォレイン酸の水溶性塩から成る群より選ばれる少なく とも一種である①記載の キャストインクジェット記録用紙。  (2) The cast inkjet recording paper according to (2), wherein the release agent is at least one selected from the group consisting of stearic acid, oleic acid, a water-soluble salt of stearic acid, and a water-soluble salt of oleic acid.
③前記カチオン性化合物を、 前記顔料 1 0 0質量部に対し、 1〜 1 0 0質量部 含有する①または②記載のキャストインクジェッ ト記録用紙。  (3) The cast ink jet recording paper according to (1) or (2), wherein the cationic compound is contained in an amount of 1 to 100 parts by mass with respect to 100 parts by mass of the pigment.
④前記離型剤を、 前記微細顔料 1 0 0質量部に対し、 0 . 1〜 1 0質量部含有 する①〜③のいずれかに記載のキャストインクジヱット記録用紙。  (4) The cast ink jet recording paper as described in any of (1) to (3), wherein the release agent is contained in an amount of 0.1 to 10 parts by mass based on 100 parts by mass of the fine pigment.
⑤前記下塗り層及び前記キャスト層の少なく とも 1層中に、 含ィォゥ有機化合 物を含有する①〜④のいずれかに記載のキャストインクジエツ ト記録用紙。 ⑥キャス ト層表面の 7 5 ° 表面光沢度 ( J I S— Z 8 7 4 1に基づく光沢度) が、 5 0 %以上である①〜⑤のいずれかに記載のキャス トインクジェッ ト記録用 紙。 発明を実施するための最良の形態 本発明者等は、 基材上に、 顔料、 カチオン性化合物及び接着剤を含有する下塗 り層を設け、 前記下塗り層上に、 接着剤、 平均二次粒子径が 1 μ m未満の微細顏 料及び離型剤を含有するキャス ト層を設けたインクジエツ ト記録用紙において、 前記カチオン性化合物が、 ジァリルァミンと (メタ) アクリルアミ ドとの共重合 体、 ジァリルァミンと (メタ) アクリルアミ ドとこれらに共重合可能な他のビニ ル系モノマーであって実質的にカルボキシル基を含有しないものとの共重合体、 又はこれらのいずれかの塩から成る群より選ばれる少なく とも一種を使用し、 か つキャス ト層の離型剤として、 炭素数 1 2〜1 8の脂肪酸及びその水溶性塩から 成る群より選ばれる少なく とも一種を使用することにより、 画像の印字濃度が高 く、 インク吸収性を維持しながら耐熱性ゃ耐オゾン性に優れ、 更に連続操業性に も優れたキャス トインクジェッ ト記録用紙が得られることを見出した。 なお、 こ こでいう連続操業性とは、 キャストインクジエツ ト記録用紙の表面にピック状の 塗工欠陥がなく、 かつ操業を中断せざるを得ないほど鏡面ドラムが汚れたり しな いことである。 {The cast ink jet recording paper according to any one of <1> to <4>, wherein at least one of the undercoat layer and the cast layer contains an organic compound. (4) The cast ink jet recording paper according to any one of (1) to (5), wherein the cast layer surface has a 75 ° surface glossiness (glossiness based on JIS-Z8741) of 50% or more. BEST MODE FOR CARRYING OUT THE INVENTION The present inventors provided an undercoat layer containing a pigment, a cationic compound and an adhesive on a base material, and provided an adhesive and an average secondary particle on the undercoat layer. In an ink jet recording paper provided with a fine pigment having a diameter of less than 1 μm and a casting layer containing a release agent, the cationic compound is a copolymer of diarylamine and (meth) acrylamide, diarylamine. And a copolymer of (meth) acrylamide and another vinyl monomer copolymerizable therewith and substantially not containing a carboxyl group, or a salt thereof. Use at least one selected from the group consisting of fatty acids having 12 to 18 carbon atoms and water-soluble salts thereof as a mold release agent for the cast layer. More, the printing density of the image rather high, while maintaining ink absorbency excellent heat resistance Ya ozone resistance, was found to further cast Inkjet recording sheet excellent in continuous operation can be obtained. The continuous operability here means that there is no pick-shaped coating defect on the surface of the cast ink jet recording paper, and the mirror drum is not so dirty that the operation must be interrupted. is there.
基材:  Base material:
本発明で用いる基材としては、 特に限定されるものではなく、 一般の塗工紙に 使用される酸性紙、 あるいは中性紙等の紙基材、 または透気性を有する樹脂フィ ルムシ一ト類を用いることができる。  The substrate used in the present invention is not particularly limited, and is a paper substrate such as acidic paper or neutral paper used for general coated paper, or a resin film having air permeability. Can be used.
紙基材は、 木材パルプと必要に応じ顔料を主成分として構成される。 木材パル プは、 各種化学パルプ、 機械パルプ、 再生パルプ等を使用することができ、 これ らのパルプは、 紙力、 抄紙適性等を調整するために、 叩解機により叩解度を調整 できる。 パルプの叩解度 (フリーネス) は特に限定しないが、 一般に 2 5 0〜 5 5 0m l (C S F : J I S -P- 8 1 2 1) 程度である。 またいわゆる E CF、 TC Fパルプ等の塩素フリーパルプも好ましく使用できる。 また、 必要に応じて、 顔料は、 不透明性等を付与したり、 インク吸収性を調整する目的で配合し、 炭酸 カルシウム、 焼成カオリン、 シリカ、 酸化チタン等が使用できる。 この場合、 配 合量は 1〜 2 0質量%程度が好ましく、 2 0質量%より多いと紙力が低下するお それがある。 助剤としてサイズ剤、 定着剤、 紙力増強剤、 カチオン化剤、 歩留り 向上剤、 染料、 蛍光増白剤等を添加することができる。 さらに、 抄紙機のサイズ プレス工程において、 デンプン、 ポリ ビュルアルコール、 カチオン性化合物等を 塗布 ·含浸させ、 表面強度、 ステキヒ トサイズ度等を調整できる。 特に、 髙ぃ光 沢度を得るためには、 カチオン性化合物をサイズプレスすることが好ましい。 ス テキヒ トサイズ度は、 1〜 20 0秒程度が好ましい。 ステキヒ トサイズ度が 1秒 より低いと、 塗工時に皺が発生する等の操業上問題となる場合があり、 2 0 0秒 より高いと、 インク吸収性が低下したり、 インクの裏抜けが発生したり、 印字後 のカールやコックリングが著しくなる場合がある。 基材の坪量は、 特に限定され ないが、 20〜4 0 0 gZm2程度である。 The paper base is composed mainly of wood pulp and, if necessary, pigment. As the wood pulp, various chemical pulp, mechanical pulp, recycled pulp and the like can be used, and the degree of beating of these pulp can be adjusted by a beating machine in order to adjust paper strength, papermaking suitability, and the like. The degree of freeness (freeness) of the pulp is not particularly limited, but is generally 250 to 5 It is about 50 ml (CSF: JIS -P- 8 1 2 1). Also, chlorine-free pulp such as so-called ECF and TCF pulp can be preferably used. If necessary, the pigment is blended for the purpose of imparting opacity or the like, or adjusting the ink absorbency, and calcium carbonate, calcined kaolin, silica, titanium oxide, or the like can be used. In this case, the amount is preferably about 1 to 20% by mass, and if it exceeds 20% by mass, the paper strength may be reduced. As auxiliaries, a sizing agent, a fixing agent, a paper strength enhancer, a cationizing agent, a retention improver, a dye, a fluorescent whitening agent and the like can be added. Furthermore, in the size press process of a paper machine, starch, polybutyl alcohol, a cationic compound, and the like can be applied and impregnated to adjust the surface strength, degree of steak size, and the like. In particular, in order to obtain a sufficient brightness, it is preferable to size-press the cationic compound. The degree of steak size is preferably about 1 to 200 seconds. If the stick size is less than 1 second, there may be operational problems such as wrinkles during coating.If it is more than 200 seconds, the ink absorbency will decrease or ink strike-through will occur. Curling and cockling after printing may be significant. The basis weight of the base material is not particularly limited, but is about 20 to 400 gZm 2 .
下塗り層 :  Undercoat layer:
本発明においては、 基材上に、 顔料、 カチオン性化合物および接着剤を含有す る下塗り層を設ける。  In the present invention, an undercoat layer containing a pigment, a cationic compound and an adhesive is provided on a substrate.
下塗り層に含まれるカチオン性化合物としては、 ジァリルァミンと (メタ) ァ ク リルァミ ドとの共重合体、 ジァリルァミンと (メタ) アタリルァミ ドとこれら に共重合可^な他のビュル系モノマーであって実質的にカルボキシル基を含有し ないものとの共重合体、 又はこれらのいずれかの塩から成る群より選ばれる少な く とも一種のカチオン性化合物を含有することで、 耐ガス性などの保存性をより —層向上させることが可能である。 共重合体を構成するモノマー単位中、 ジァリ ルァミンのモル分率は 0. 1〜0. 9 9の範囲、 好ましくは 0. 1 5〜0. 9 5 の範囲であり、 (メタ) アク リルアミ ドのモル分率は 0. 0 1〜0. 9の範囲、 好ましくは 0. 0 5〜0. 8 5の範囲であり、 またこれらと共重合可能な他のビ 二ノレ系モノマーであって、 実質的にカルボキシル基を含有しないもののモル分率 は 0〜0 . 3の範囲である。 ジァリルアミンをモノマーの一部とする共重合体の 塩も含まれ、 無機酸塩または有機酸塩のいずれでもよい。 ジァリルアミンを塩の 形で用いれば、 塩の形になった重合体が得られる。 Examples of the cationic compound contained in the undercoat layer include a copolymer of diarylamine and (meth) acrylamide, diarylamine and (meth) acrylamide, and other vinyl monomers copolymerizable with these. By containing at least one kind of cationic compound selected from the group consisting of a copolymer containing no carboxyl group or a salt of any of these, storage stability such as gas resistance is improved. More — layers can be improved. Among the monomer units constituting the copolymer, the molar fraction of diarylamine is in the range of 0.1 to 0.99, preferably in the range of 0.15 to 0.95, and (meth) acrylamide The molar fraction is in the range of 0.01 to 0.9, preferably in the range of 0.05 to 0.85, and other vinyl monomers which are copolymerizable therewith, Molar fraction of those containing substantially no carboxyl groups Ranges from 0 to 0.3. A salt of a copolymer containing diarylamine as a part of the monomer is also included, and either an inorganic acid salt or an organic acid salt may be used. If diarylamine is used in the form of a salt, a polymer in the form of a salt can be obtained.
前記カチオン性化合物の下塗り層における含有量としては、 顏料 1 0 0質量部 に対し、 好ましくは 1〜 1 0 0質量部、 より好ましくは 5〜 5 0質量部の範囲で 使用することができる。 1質量部より少ないと、 所望の印字濃度、 耐熱性ゃ耐ォ ゾン性の効果が得られないだけでなく、 印字の耐水性までもが損なわれる場合が あり、 1 0 0質量部を超えると、 逆に印字濃度が低下するだけでなく、 画像の二 ジミが発生するおそれがある。  The cationic compound may be used in the undercoat layer in an amount of preferably from 1 to 100 parts by mass, more preferably from 5 to 50 parts by mass, based on 100 parts by mass of the pigment. If the amount is less than 1 part by mass, not only the desired print density, heat resistance and ozone resistance effect cannot be obtained, but also the water resistance of the print may be impaired. On the contrary, not only the print density is reduced, but also the image may be blurred.
また、 下塗り層には、 前記のカチオン性化合物の他に、 従来インクジェッ ト記 録用紙に使用されているポリエチレンポリアミンゃポリプロ 'ピレンポリアミンな どのポリアルキレンポリアミン類、 またはその誘導体、 第 3級アミノ基ゃ第 4級 アンモェゥム基を有するァクリル樹脂、 ジァクリルァミン等のカチオン性化合物 を、 印字画像の耐水性を向上させる目的で、 耐熱性ゃ耐オゾン性等の品質を損な わない範囲で使用することができる。.  In addition, in addition to the above-mentioned cationic compound, the undercoat layer may contain polyalkylene polyamines such as polyethylene polyamine / polypropylene pyrene polyamine used in conventional ink jet recording paper, or derivatives thereof, and tertiary amino groups.カ チ オ ン A cationic compound such as acryl resin or diacrylamine having a quaternary ammonium group can be used for the purpose of improving the water resistance of the printed image within a range that does not impair the heat resistance and ozone resistance. it can. .
前記カチオン性化合物の重量平均分子量が、 数万程度以下の場合は、 一般的に 水に溶出され易く、 混色黒等のインク量の多い印字部分の印字耐水性が劣る。 ま た、 重量平均分子量が 1 0万以上のカチオン性化合物は、 一般的に水に溶出され 難く、 例えばポリビュルアルコール等と同様にインクの浸透を阻害するため、 ィ ンク吸収性が低下するおそれがある。  When the weight-average molecular weight of the cationic compound is about tens of thousands or less, it is generally easy to be eluted in water, and the printing water resistance of a printing portion with a large amount of ink such as mixed color black is inferior. In addition, cationic compounds having a weight-average molecular weight of 100,000 or more are generally hardly eluted in water and, for example, inhibit ink permeation like polybutyl alcohol and the like, and may reduce ink absorption. There is.
カチオン性化合物の重量平均分子量が 1 0万以上では、 シアン、 マゼンタ、 ィ エローなどのカラーの印字濃度が高くなり、 重量平均分子量 5万以下では、 ブラ ックの印字濃度が高くなる傾向がある。  When the weight average molecular weight of the cationic compound is 100,000 or more, the printing density of colors such as cyan, magenta, and yellow tends to be high, and when the weight average molecular weight is 50,000 or less, the printing density of the black tends to be high. .
下塗り層中の顔料は、 カオリン、 クレー、 焼成クレー、 非晶質シリカ (無定形 シリカともいう) 、 酸化亜鉛、 酸化アルミニウム、 水酸化アルミニウム、 炭酸力 ルシゥム、 サチンホワイ ト、 珪酸アルミニウム、 アルミナ、 コロイダルシリカ、 ゼォライ ト、 合成ゼォライ ト、 セピオライ ト、 スメクタイ ト、 合成スメクタイ ト、 珪酸マグネシウム、 炭酸マグネシウム、 酸化マグネシウム、 珪藻土、 スチレン系 プラスチックピグメント、 ハイ ドロタルサイ ト、 尿素樹脂系プラスチックピグメ ント、 ベンゾグアナミン系プラスチックビグメント等、 一般塗工紙製造分野で公 知公用の各種顔料が単独、 あるいは併用することが出来る。 Pigments in the undercoat layer include kaolin, clay, calcined clay, amorphous silica (also called amorphous silica), zinc oxide, aluminum oxide, aluminum hydroxide, carbonated calcium, sachin white, aluminum silicate, alumina, and colloidal silica. , Zeolite, synthetic zeolite, sepiolite, smectite, synthetic smectite, magnesium silicate, magnesium carbonate, magnesium oxide, diatomaceous earth, styrene Pigments known in the general coated paper manufacturing field, such as plastic pigment, hydrotalcite, urea resin-based plastic pigment, and benzoguanamine-based plastic pigment, can be used alone or in combination.
これらの中でも、 インク吸収性の高い非晶質シリカ、 アルミナ、 ゼォライ トを 主成分として使用するのが好ましい。  Among these, it is preferable to use amorphous silica, alumina, and zeolite having high ink absorbability as main components.
下塗り層の接着剤としては、 カゼイン、 大豆蛋白、 合成蛋白等の蛋白質類、 澱 粉や酸化澱粉等の各種澱粉類、 ポリ ビュルアルコール、 カチオン性ポリ ビュルァ ルコール、 シリル変性ポリ ビュルァノレコール等のポリ ビュルアルコール類、 カル ボキシメチルセルロースゃメチノレセルロース等のセノレロース誘導体、 スチレン一 ブタジエン共重合体、 メチルメタクリ レート一ブタジエン共重合体の共役ジェン 系重合体ラテックス、 アク リル系重合体ラテックス、 エチレン一酢酸ビュル共重 合体等のビュル系重合体ラテックス等、 一般に塗工紙用として用いられている従 来公知の接着剤が単独、 あるいは併用して用いられる。 その中でも、 ポリ ビニル アルコール、 カチオン性ポリ ビュルアルコール、 シリル変性ポリ ビニルアルコー ル等のポリ ビニルアルコール類は下塗り層の表面強度を向上させるため、 好まし く用いられる。 .  Examples of the adhesive for the undercoat layer include proteins such as casein, soybean protein, and synthetic protein, various starches such as starch and oxidized starch, polybutyl alcohol, cationic polyvinyl alcohol, and silyl-modified polyvinyl alcohol. Polybutyl alcohols, cenorellose derivatives such as carboxymethylcellulose / methinolecellulose, styrene-butadiene copolymer, conjugated gen-based polymer latex of methyl methacrylate-butadiene copolymer, latex of acryl-based polymer, Conventionally known adhesives generally used for coated paper, such as a butyl polymer latex such as a butyl acetate copolymer, are used alone or in combination. Among them, polyvinyl alcohols such as polyvinyl alcohol, cationic polyvinyl alcohol, and silyl-modified polyvinyl alcohol are preferably used to improve the surface strength of the undercoat layer. .
前記下塗り層中の顔料と接着剤の配合割合は、 その種類にもよるが、 一般に顔 料 1 0 0質量部に対し、 接着剤 1〜 1 0 0質量部、 好ましくは 2〜 5 0質量部の 範囲で調節される。  The mixing ratio of the pigment and the adhesive in the undercoat layer depends on the type thereof, but is generally 1 to 100 parts by mass, preferably 2 to 50 parts by mass with respect to 100 parts by mass of the pigment. It is adjusted within the range.
その他、 下塗り層中には一般塗工紙の製造において使用される分散剤、 増粘剤、 消泡剤、 帯電防止剤、 防腐剤、 蛍光染料、 着色剤等の各種助剤が適宜添加される。 上記材料をもって構成される下塗り層用塗料は、 一般に、 固形分濃度を 5〜5 0質量%程度に調整し、 紙基材上に乾燥質量で 2〜 1 0 0 g Z m 2、 好ましくは 5〜 5 0 g Z m2程度、 更に好ましくは 5〜 2 0 g / m2程度になるように塗工す る。 In addition, various auxiliaries such as dispersants, thickeners, antifoaming agents, antistatic agents, preservatives, fluorescent dyes, and coloring agents used in the production of general coated paper are appropriately added to the undercoat layer. . The undercoat layer paint composed of the above materials is generally adjusted to have a solid content concentration of about 5 to 50% by mass, and has a dry mass of 2 to 100 g Zm 2 , preferably 5 ~ 5 0 g Z m 2 approximately, more preferably you applied so that about 5~ 2 0 g / m 2.
,塗工量が少ない場合は、 インク吸収性が劣り、 記録画像のニジミや、 キャス ト 層塗工後の光沢が低下したりする場合がある。 また、 紙基材の場合、 前記紙基材 に吸収されるインクが多くなるために、 記録後の用紙が波打ったり (コックリン グ) 、 プリ ンターの拍車 (記録後の用紙抑えロールや歯車) による押さえ跡 (拍 車跡) が目立つことがある。 When the coating amount is small, the ink absorption is poor, and the bleeding of the recorded image or the gloss after coating the cast layer may be reduced. Further, in the case of a paper base material, the amount of ink absorbed by the paper base material increases, so that the paper after recording has a wavy or G), the press marks (spur marks) due to the printer spurs (paper rolls and gears after recording) may be noticeable.
塗工量が多い場合は、 インクが浸透し易くなり、 キャス ト層側ばかりでなく基 材側にも分布するようになるために、 印字濃度が低下する場合がある。 また、 下 塗り層の強度が低下し、 粉落ちや表面に傷が付き易くなる場合がある。  When the coating amount is large, the ink easily penetrates and is distributed not only on the cast layer side but also on the substrate side, so that the print density may be reduced. In addition, the strength of the undercoat layer may be reduced, and the powder may fall off or the surface may be easily damaged.
下塗り層用塗料は、 ブレー ドコーター、 エアーナイフコーター、 ロールコータ 一 ブラシコ一ター、 チャンプレツクスコ一ター、 ノ ーコーター、 リ ップコータ 一、 グラビアコーター、 カーテンコーター等の各種公知公用の塗工装置により塗 ェ、 乾燥される。 さらに、 必要に応じて記録層の乾燥後にスーパーキャレンダー、 ブラシ掛け等の平滑化処理を施すこともできる。  The coating for the undercoat layer is applied by various well-known coating apparatuses such as a blade coater, an air knife coater, a roll coater, a brush coater, a champlex coater, a no coater, a lip coater 1, a gravure coater, and a curtain coater. It is dried. Further, if necessary, the recording layer may be subjected to a smoothing process such as super calendering or brushing after drying.
キャス ト層 :  Cast layer:
本発明のキャス ト層は、 接着剤、 平均二次粒子径が 1 μ m以下の微細顔料およ び離型剤からなる。  The cast layer of the present invention comprises an adhesive, a fine pigment having an average secondary particle diameter of 1 μm or less, and a release agent.
キャス ト層中の接着剤は、 例えば、 ポリ ビニルアルコール、 カチオン変性ポリ ビニルァノレコール、 シリル変性ポリ ビュルアルコール等のポリ ビニノレアノレコーノレ 類、 カゼイン、 大豆蛋白、 合成蛋白質類、 澱粉類、 カルボキシルメチルセルロー スゃメチノレセノレロース等のセノレロース誘導体、 酢酸ビニノレ系重合体ェマルジョン、 スチレン一ブタジエン共重合体エマノレジョン、 エチレン酢酸ビュル共重合体エマ ルジョ ン、 アク リル系共重合体ェマルジヨ ン、 スチレン一アク リル系共重合体ェ マルジヨ ン、 水性アタ リル樹脂、 水性ポリ ウレタン樹脂および水性ポリエステル 樹脂等、 その他一般に塗工紙分野で従来公知の各種接着剤が単独、 あるいは併用 して使用できる。  The adhesive in the cast layer includes, for example, polyvinyl alcohol, cation-modified polyvinyl alcohol, silyl-modified polyvinyl alcohol, and other polyvinyl alcohol, casein, soy protein, synthetic protein, starch, and the like. Senorelose derivatives such as carboxylmethyl cellulose methinoresenolylose, vinylinole acetate polymer emulsion, styrene-butadiene copolymer emulsion, ethylene acetate butyl copolymer emulsion, acrylyl copolymer emulsion, styrene Acrylic copolymer emulsions, aqueous acryl resins, aqueous polyurethane resins, aqueous polyester resins, and other generally known adhesives in the coated paper field can be used alone or in combination.
前記ェマルジヨンの中でも特に、 記録画像の鮮明性と光沢感の点から、 スチレ ンーァクリル系共重合体ェマルジョンが好ましい。  Among the above emulsions, a styrene-acrylic copolymer emulsion is particularly preferred from the viewpoints of clearness and glossiness of a recorded image.
前記キャス ト層に接着剤として用いるェマルジヨ ンの重量平均分子量は、 1 0 0 0〜 1 0 0 0万が好ましく、 より好ましくは、 5 0 0 0〜 5 0 0万である。 分 子量が 1 0 0 0より低いと、 塗工膜の強度が不十分となりやすく、 分子量が 1 0 0 0万より高いと、 ェマルジョンの安定性が不十分となりやすい。 前記ェマルジヨ ン平均粒子径は、 0. 0 2〜0. 1 5 μ mの範囲が好ましい。 ェマルジヨ ン平均粒子径が、 0. 0 2 μ m未満であると、 インクの吸収性が低下 し、 一方 0. 1 5 μπιを超えると、 表面光沢および記録画像の発色の鮮明性が低 下する。 The weight average molecular weight of the emulsion used as an adhesive in the cast layer is preferably from 100,000 to 100,000, and more preferably from 500,000 to 500,000. If the molecular weight is lower than 100,000, the strength of the coating film tends to be insufficient, and if the molecular weight is higher than 100,000, the stability of the emulsion tends to be insufficient. The average particle diameter of the emulsion is preferably in the range of 0.02 to 0.15 μm. If the average particle size of the emulsion is less than 0.02 μm, the ink absorbency will decrease.On the other hand, if the average particle size exceeds 0.15 μπι, the surface gloss and the sharpness of the color development of the recorded image will decrease. .
前記共重合体のガラス転移温度が、 5 0〜 1 5 0°Cの範囲にある共重合体エマ ルジョンが好ましレ、。  A copolymer emulsion having a glass transition temperature of the copolymer in the range of 50 to 150 ° C. is preferred.
前記共重合体のガラス転移点が 5 0°Cより低いと、 乾燥の際にキャス ト層の成 膜が進みすぎ、 表面の多孔性が低下するために、 インクの吸収速度が低下する場 合がある。 逆に前記共重合体のガラス転移点が 1 5 0°Cより高いと、 乾燥の際に 成膜が不十分となり、 光沢が不足する場合がある。 また、 乾燥温度が高すぎると、 成膜が進みすぎ、 表面の多孔性が低下するために、 インクの吸収速度が低下し、 逆に乾燥温度が低すぎると、 光沢が低下する傾向が有る。  If the glass transition point of the copolymer is lower than 50 ° C, the film of the cast layer will advance too much during drying, and the porosity of the surface will decrease, resulting in a decrease in the ink absorption rate. There is. Conversely, if the glass transition point of the copolymer is higher than 150 ° C., film formation may be insufficient during drying, and the gloss may be insufficient. On the other hand, if the drying temperature is too high, the film formation proceeds too much, and the porosity of the surface decreases, so that the ink absorption rate decreases. Conversely, if the drying temperature is too low, gloss tends to decrease.
前記キャス ト層中の平均二次粒子径が 1 μ πι以下の微細顔料としては、 例えば、 カオリ ン、 ク レー、 焼成ク レー、 非晶質シリカ (無定形シリカともいう) 、 酸化 亜鉛、 酸化アルミニウム、 水酸化アルミニウム、 炭酸カルシウム、 サチンホワィ ト、 珪酸アルミニウム、 アルミナ、 コロイダルシリカ、 ゼォライ ト、 合成ゼオラ ィ ト、 セピオライ ト、 スメクタイ ト、 合成スメクタイ ト、 珪酸マグネシウム、 炭 酸マグネシウム、 酸化マグネシウム、 珪藻土、 スチレン系プラスチックビグメン ト、 ハイ ドロタルサイ ト、 尿素樹脂系プラスチックピグメント、 ベンゾグァナミ ン系プラスチックビグメント等、 一般塗工紙製造分野で公知公用の各種顔料が単 独、 あるいは併用して使用できる。  Examples of the fine pigment having an average secondary particle diameter of 1 μπι or less in the cast layer include kaolin, clay, calcined clay, amorphous silica (also referred to as amorphous silica), zinc oxide, and oxide. Aluminum, aluminum hydroxide, calcium carbonate, satin white, aluminum silicate, alumina, colloidal silica, zeolite, synthetic zeolite, sepiolite, smectite, synthetic smectite, magnesium silicate, magnesium carbonate, magnesium oxide, diatomaceous earth, Various pigments known and used in the general coated paper manufacturing field, such as styrene-based plastic pigments, hydrotalcite, urea resin-based plastic pigments, and benzoguanamine-based plastic pigments, can be used alone or in combination.
これらの中でも、 インク吸収性の高い非晶質シリカ、 アルミナ、 コロイダルシ リカ、 ゼォライ トを主成分として使用するのが好ましい。 より好ましくは、 コロ ィダルシリカであり、 さらに好ましくは、 ァニオン性コロイダルシリカである。 前記ァニオン性コロイダルシリカの平均粒子径は、 0. 0 1〜0. 1 5 /i mで あり、 好ましくは、 0. 0 1 5〜0. 1 2 μ mであり、 さらに好ましくは、 0. 0 2〜0. 1 0 μ mである。 平均粒子径が、 0. 0 1 μ m未満の場合は、 インク 吸収性が低下することがあり、 また、 0. 1 5 μ ιηを超える場合は、 光沢および 記録画像の発色の鮮明性が低下することがある。 Among these, it is preferable to use amorphous silica, alumina, colloidal silica, or zeolite having high ink absorbability as a main component. More preferred is colloidal silica, and even more preferred is anionic colloidal silica. The anionic colloidal silica has an average particle size of 0.01 to 0.15 / im, preferably 0.01 to 0.12 μm, and more preferably 0.01 to 0.12 μm. 2 to 0.10 μm. If the average particle size is less than 0.01 μm, the ink absorption may decrease.If it exceeds 0.15 μιη, gloss and The sharpness of coloring of a recorded image may be reduced.
キャスト層の接着剤と微細顔料との組成比 (固形分質量比) は、 好ましくは、 The composition ratio (solid content mass ratio) of the adhesive and the fine pigment in the cast layer is preferably
6 0 / 40〜 3 / 9 7の範囲であり、 より好ましくは、 5 0/ 50〜 5/9 5の 範囲であり、 さらに好ましくは、 40/6 0〜 7/9 3の範囲である。 It is in the range of 60/40 to 3/97, more preferably in the range of 50/50 to 5/95, and still more preferably in the range of 40/60 to 7/93.
接着剤の比率が 6 0質量%を超えると、 記録画像の発色の鮮明性が低下する傾 向にあり、 3質量%未満では光沢が低下する傾向にある。  When the ratio of the adhesive exceeds 60% by mass, the sharpness of the color development of the recorded image tends to decrease, and when the ratio is less than 3% by mass, the gloss tends to decrease.
前記キャス ト層に用いる離型剤としては、 炭素数 1 2〜 1 8の脂肪酸及びその 水溶性塩から成る群より選ばれる少なく とも一種が、 本発明の効果を得るために 好ましく用いられる。 炭素数が 1 9以上の場合は、 分散性が劣る場合があり、 炭 素数が 1 2未満の場合は、 充分な離型性を有さない場合がある。  As the release agent used in the cast layer, at least one selected from the group consisting of fatty acids having 12 to 18 carbon atoms and water-soluble salts thereof is preferably used to obtain the effects of the present invention. When the number of carbon atoms is 19 or more, the dispersibility may be poor, and when the number of carbon atoms is less than 12, the releasability may not be sufficient.
炭素数 1 2〜 1 8の脂肪酸の具体例としては、 ラウリン酸 (炭素数 1 2) 、 ミ リスチン酸 (炭素数 1 3) 、 パルミチン酸 (炭素数 1 5) 、 ステアリン酸 (炭素 数 1 8) 、 ォレイ ン酸 (炭素数 1 8) 、 リノール酸 (炭素数 1 8) 、 リノレン酸 (炭素数 1 8) 、 ァラキドン酸 (炭素数 1 8) 等が挙げられ、 またこれらの水溶 性塩としては、 前記脂肪酸のナトリ ウム塩、 カリ ウム塩、 及びアンモユウム塩等 が挙げられる。 これらの脂肪酸及びその水溶性塩の内、 ステアリン酸またはその 水溶性塩、 ォレイン酸またはその水溶性塩が、 記録用紙の耐熱性と離型性の点で 好ましく、 この中でもさらにステアリン酸、 ォレイン酸、 ステアリン酸アンモニ ゥム、 およびォレイン酸アンモニゥムが特に優れる。  Specific examples of fatty acids having 12 to 18 carbon atoms include lauric acid (12 carbon atoms), myristic acid (13 carbon atoms), palmitic acid (15 carbon atoms), stearic acid (18 carbon atoms) ), Oleic acid (18 carbon atoms), linoleic acid (18 carbon atoms), linolenic acid (18 carbon atoms), arachidonic acid (18 carbon atoms), and the like. Examples thereof include a sodium salt, a potassium salt, and an ammonium salt of the fatty acid. Of these fatty acids and water-soluble salts thereof, stearic acid or a water-soluble salt thereof, oleic acid or a water-soluble salt thereof are preferable in terms of heat resistance and releasability of recording paper, and among these, stearic acid and oleic acid are further preferable. , Ammonium stearate, and ammonium oleate are particularly excellent.
耐熱性及び離型性が良好な理由としては、 前記離型剤が化学構造の点で酸化さ れにく く、 かつ鏡面ドラムからの剥離性が良好であるからであると考えられる。 また、 前記離型剤の他に、 通常の印刷用塗工紙や印刷用キャスト紙製造の際に 用いられる離型剤を、 本発明の効果を損なわない範囲で使用することが可能であ る。  It is considered that the reason why the heat resistance and the release property are good is that the release agent is not easily oxidized in terms of the chemical structure, and the release property from the mirror drum is good. Further, in addition to the release agent, it is possible to use a release agent used in the production of ordinary coated paper for printing or cast paper for printing as long as the effects of the present invention are not impaired. .
具体的には、 ポリエチレンワックス、 ポリプロピレンワックス等のポリオレフ インワックス類、 レシチン、 シリコーンオイル、 シリコーンワックス等のシリコ —ン化合物、 ポリテトラフルォロエチレン等のフッ素化合物等が挙げられる。 前記離型剤は、 微細顔料 1 0 0質量部に対して 0. 1質量部〜 1 0質量部、 好 ましくは 0 . 2質量部〜 8質量部添加するのが良い。 添加量が 0 . 1質量部未満 では連続操業性が劣る場合があり、 1 0質量部を超えると印字濃度が低下し、 画 質が低下する場合がある。 Specific examples include polyolefin waxes such as polyethylene wax and polypropylene wax, silicone compounds such as lecithin, silicone oil and silicone wax, and fluorine compounds such as polytetrafluoroethylene. The release agent is used in an amount of 0.1 to 10 parts by mass with respect to 100 parts by mass of the fine pigment. Preferably, 0.2 to 8 parts by mass is added. If the addition amount is less than 0.1 part by mass, continuous operability may be poor. If the addition amount exceeds 10 parts by mass, the print density may be reduced and the image quality may be reduced.
また、 本発明のキャス トインクジェッ ト記録用紙において、 下塗り層、 または キャス ト層の少なく とも 1層中に、 含ィォゥ有機化合物を含有させると画像の保 存性が改良される。 含ィォゥ有機化合物としては、 チォエーテル系化合物、 チォ ウレァ系化合物、 ジスルフイ ド系化合物、 メルカプト系化合物、 スルフィン酸化 合物、 チォスルホン酸化合物、 及びチォスルフィン酸化合物が例示できる。 中で もチォエーテル系化合物が好ましく、 特に 1 , 2 _ビス ( 2—ヒ ドロキシェチル チォ) ェタンまたは 1 , 4—ビス ( 2—ヒ ドロキシェチルチオ) ブタンを含有さ せることにより、 画像の耐オゾン性が向上したキャス トインクジヱッ ト記録用紙 が得られる。 特に、 シアン染料としてフタロシアニン系染料を用いたインクに対 し、 極めて優れた保存性を有する。 また、 前記化合物が酸化されて生じる化合物 は無色のため、 キャス トインクジヱッ ト記録用紙が黄変する等の問題点を生じな いことも大きな特徴である。  Further, in the cast ink jet recording paper of the present invention, when at least one of the undercoat layer and the cast layer contains an organic compound containing an organic compound, the image storability is improved. Examples of the organic compound containing thioether include thioether compounds, thiourea compounds, disulfide compounds, mercapto compounds, sulfin oxide compounds, thiosulfonic acid compounds, and thiosulfinic acid compounds. Among them, thioether compounds are preferable, and in particular, the inclusion of 1,2-bis (2-hydroxyxethylthio) ethane or 1,4-bis (2-hydroxyxethylthio) butane makes the image resistant to ozone. Cast ink jet recording paper with improved performance can be obtained. In particular, it has extremely excellent storability with respect to ink using a phthalocyanine dye as a cyan dye. Another major feature is that since the compound generated by oxidizing the compound is colorless, there is no problem such as yellowing of the cast ink jet recording paper.
前記化合物のキャス トインクジェッ ト記録用紙中の含有量としては、 0 . 1〜 4 g / m 2程度、 好ましくは 0 . 2〜 2 g Z m 2程度である。 因みに、 0 . l g / m 2より少ないと、 耐オゾン性等の保存性改善効果が不十分となり、 また 4 g / m 2より多いと、 画質の低下を招くため好ましくない。 前記化合物は、 下塗り層、 キャス ト層のいずれに含有しても効果を発揮する。 The content of cast Inkjet recording during paper compound, 0. 1~ 4 g / m 2 approximately, preferably 0. 2~ 2 g Z m 2 approximately. By the way, if it is less than 0.1 lg / m 2, the effect of improving storage stability such as ozone resistance becomes insufficient, and if it is more than 4 g / m 2 , the image quality deteriorates, which is not preferable. The compound exhibits an effect when contained in either the undercoat layer or the cast layer.
前記キャス ト層用塗工液には、 白色度、 粘度、 流動性等を調節するために、 一 般の印刷用塗工紙やインクジエツ ト記録用紙に使用されている消泡剤、 着色剤、 蛍光増白剤、 帯電防止剤、 防腐剤及び分散剤、 増粘剤等の各種助剤が適宜添加さ れる。 また、 カチオン性化合物を配合し、 インク染料定着性を付与させることも 可能である。  The coating liquid for the cast layer contains an antifoaming agent, a coloring agent, and a defoaming agent used for general printing coated paper and ink jet recording paper in order to adjust whiteness, viscosity, fluidity, and the like. Various auxiliaries such as a fluorescent whitening agent, an antistatic agent, a preservative and a dispersant, and a thickener are appropriately added. It is also possible to add a cationic compound to impart ink dye fixability.
本発明におけるキャス ト層を設ける方法は、 キャス ト層用塗工液層を、 平滑性 を有する鏡面ドラム (鏡面仕上げした金属、 プラスチック、 ガラス等のドラム) 、 鏡面仕上げした金属板、 プラスチックシートやフィルム、 ガラス板等の上で乾燥 し、 平滑面を塗工層上に写し取ることであり、 この方法により平滑で光沢のある キャスト塗工層表面を得る。 The method of providing a cast layer in the present invention includes the steps of forming a coating liquid layer for a cast layer by using a mirror-finished drum (a drum of mirror-finished metal, plastic, glass, or the like), a mirror-finished metal plate, a plastic sheet, or the like. Dry on film, glass plate, etc. And transferring the smooth surface onto the coating layer, and obtaining a smooth and glossy cast coating layer surface by this method.
キャス ト層を設ける方法としては、 上記のキャス ト層用塗工液を下塗り層上に 塗工して、 前記塗工層が湿潤状態にある間に加熱された鏡面ドラムに圧接、 乾燥 して仕上げる方法 (ウエッ トキャス ト法) 、 あるいは一旦乾燥後、 再湿潤した後、 加熱された鏡面ドラムに圧接、 乾燥して仕上げる方法 (リ ウヱッ トキャス ト法) 等が例示できる。 また加熱された鏡面ドラムに直接キャス ト層用塗工液を塗工し た後、 下塗り層を設けた基材の下塗り層面に圧接、 乾燥して仕上げる方法 (プレ キャス ト法) も採用することができる。  As a method of providing a cast layer, the above-mentioned coating solution for a cast layer is applied on an undercoat layer, and the coated layer is pressed against a heated mirror-surface drum while the coating layer is in a wet state, and dried. Examples of the method include a finishing method (wet casting method) and a method of once drying, re-wetting, pressing against a heated mirror drum, drying and finishing (rewet casting method), and the like. In addition, a method in which the coating liquid for the cast layer is applied directly to the heated mirror-surface drum, followed by pressing and drying the undercoat layer surface of the base material provided with the undercoat layer (pre-cast method) should also be adopted. Can be.
加熱された鏡面ドラムの温度の好ましい範囲は, 5 0〜 1 5 0 °C、 より好まし くは 7 0〜 1 2 0 °Cである。  The preferred range of the temperature of the heated mirror drum is 50 to 150 ° C, more preferably 70 to 120 ° C.
キャス ト層用塗工液を塗工する場合、 ブレードコーター、 エアーナイフコータ 一、 ローノレコーター、 ブラシコーター、 チャンプレックスコーター、 バーコータ 一、 ダラビアコーター等の各種公知の塗工装置が使用できる。  In the case of applying the coating liquid for a cast layer, various known coating apparatuses such as a blade coater, an air knife coater, a rhono recorder, a brush coater, a chaplex coater, a bar coater, and a Daravia coater can be used.
キャス ト層の塗工量は、 好ましくは乾燥質量で 1〜 3 0 g Z m 2、 より好まし くは 2〜2 0 g /m2、 さらに好ましくは、 3〜 1 5 g Zm2である。 ここで、 1 g Z m2未満では、 印字濃度や光沢が十分でない場合があり、 3 0 g / m2を超え ると効果は飽和し、 乾燥に負担がかかり操業性が低下するおそれがある。 The coating amount of the cast layer is preferably 1~ 3 0 g Z m 2 by dry weight, more preferably rather is 2~2 0 g / m 2, more preferably, 3~ 1 5 g Zm 2 . Here, it is less than 1 g Z m 2, may print density and gloss is not sufficient, 3 0 when g / m 2 a exceeds effect is saturated and workability load is imposed on the drying may be reduced .
前記キャス ト層を設けた後、 必要に応じてさらにスーパーキヤレンダ一等によ り平滑化処理を行うこともできる。 また、 この時にキャレンダーを加熱すること も可能である。  After providing the cast layer, if necessary, a smoothing process can be further performed by using a super calender or the like. At this time, the calender can be heated.
キャス トインクジェッ ト記録用紙の記録する面の Ί 5 ° 表面光沢度 ( J I S— Z 8 7 4 1 )は、 優れた画質および写真調の高品位の記録を得るために、 好まし くは 5 0 %以上、 より好ましくは 6 0 %以上である。  Ί5 ° surface gloss (JIS-Z8741) of the recording surface of the cast inkjet recording paper is preferably 50 to obtain excellent image quality and high-quality photographic recording. % Or more, more preferably 60% or more.
実施例  Example
以下に実施例を挙げて、 本発明をより具体的に説明するが、 勿論これらに限定 されるものではない。 また、 例中の部おょぴ%は特に断らない限り、 それぞれ質 量部および質量%を示す。 · 実施例 1 Hereinafter, the present invention will be described in more detail with reference to Examples, but it is needless to say that the present invention is not limited thereto. In addition, parts and percentages in the examples indicate mass parts and mass%, respectively, unless otherwise specified. · Example 1
顔料として非晶質シリカ (トクャマ社製、 商品名 : ファインシール X— 45、 平均一次粒子径 1 0 nm、 平均二次粒子径 4. 5 μ m) 50部、 ゼォライ ト(東 ソ一社製、 商品名 : トョビルダー、 平均粒子径 1. 5 μ m) 5 0部、 接着剤とし て珪素変性ポリ ビュルアルコール(クラレ社製、 商品名 : PVA R— 1 1 30) 30部、 カチオン性化合物としてジァリルアミン塩酸塩 ·ァクリルアミ ド共重合 体樹脂(住友化学社製、 商品名 : スミ レーズレジン 1 00 ί ) 25部、 分散剤と して、 ポリ燐酸ソーダ 0. 5部を添加し、 固形分濃度 1 8%の下塗り層用塗工液 を調製した。 この下塗り層用塗工液を、 米坪 1 0 0 g/m2の紙基材の片面に、 乾燥質量で 1 0 g Zm2になるように、 エアーナイフコーターで塗工、 乾燥した。 次に、 平均粒子径が 0. 05 μπιのァニオン性コロイダルシリカ 80部とスチ レン ' アク リル共重合体ェマルジヨ ン 20部の混合物 (ライオン社製、 商品名 : エルサード 740) 、 增粘 ·分散剤としてアルキルビエルエーテル · マレイン酸 誘導体樹脂 5部、 離型剤としてステアリン酸の水分散物 3部 (固形分比) よりな る固形分濃度が 30%のキャスト層用塗工液を調製した。 Amorphous silica as pigment (trade name: Fine Seal X-45, average primary particle diameter: 10 nm, average secondary particle diameter: 4.5 μm), 50 parts, Zeolite (manufactured by Tosoh Corporation) , Trade name: Toyobuilder, average particle size 1.5 μm) 50 parts, Silicone-modified polybutyl alcohol (Kuraray Co., trade name: PVA R-11 30) as adhesive 30 parts, as cationic compound 25 parts of diarylamine hydrochloride / acrylamide copolymer resin (Sumitomo Chemical Co., Ltd., trade name: Sumireze Resin 100ί), 0.5 part of sodium polyphosphate as a dispersant, and a solid content concentration of 18 parts % Of a coating solution for an undercoat layer was prepared. The subbing layer coating solution on one surface of the basis weight 1 0 0 g / m 2 paper substrate, such that 1 0 g Zm 2 by dry weight, the coating with an air knife coater, and dried. Next, a mixture of 80 parts of anionic colloidal silica having an average particle diameter of 0.05 μπι and 20 parts of styrene'acrylic copolymer emaldione (Lion Corporation, trade name: Elsard 740), a viscous dispersant A coating liquid for a cast layer having a solid content concentration of 30% was prepared, comprising 5 parts of an alkyl bier ether / maleic acid derivative resin and 3 parts of a stearic acid aqueous dispersion (solid content ratio) as a release agent.
このキャス ト層用塗工液を、 上記の下塗り層上に、 ロールコーターを用いて塗 ェした後、 ただちに表面温度が 80°Cの鏡面ドラムに圧接し、 乾燥後、 離型させ、 キャス トインクジェット記録用紙を得た。 このときのキャスト層の塗工量は、 固 形分質量で、 1 2 g/m2であった。 This coating solution for a cast layer is applied onto the above-mentioned undercoat layer using a roll coater, immediately pressed against a mirror drum having a surface temperature of 80 ° C, dried, released, and then cast. Inkjet recording paper was obtained. The coating amount of the cast layer at this time was 12 g / m 2 in terms of solid content mass.
実施例 2 ' Example 2 '
実施例 1において、 離型剤としてステアリン酸の水分散物 3部の代わりに、 ス テアリン酸アンモ-ゥム 3部を添加した以外は、 実施例 1 と同様にしてキャスト インクジエツ ト記録用紙を得た。  A cast ink jet recording paper was obtained in the same manner as in Example 1, except that 3 parts of aqueous stearic acid dispersion was added as a release agent in place of 3 parts of aqueous stearic acid. Was.
実施例 3 Example 3
実施例 1において、 離型剤としてステアリ ン酸の水分散物 3部の代わりに、 ォ レイン酸アンモニゥム 3部を添加した以外は、 実施例 1と同様にしてキャストイ ンクジェット記録用紙を得た。  A cast ink jet recording paper was obtained in the same manner as in Example 1, except that 3 parts of ammonium oleate was added as the release agent instead of 3 parts of the aqueous dispersion of stearic acid as a release agent. .
実施例 4 実施例 1において、 カチオン性化合物 2 5部を、 5 0部とした以外は、 実施例 1 と同様にしてキャス トインクジエツ ト記録用紙を得た。 Example 4 A cast ink jet recording paper was obtained in the same manner as in Example 1 except that 50 parts of the cationic compound 25 was changed to 50 parts.
実施例 5 Example 5
実施例 1において、 カチオン性化合物 2 5部を、 5部とした以外は、 実施例 1 と同様にしてキャス トインクジエツ ト記録用紙を得た。  A cast ink jet recording paper was obtained in the same manner as in Example 1, except that 5 parts of the cationic compound 25 was changed to 5 parts.
実施例 6 Example 6
実施例 1において、 キャス ト層の微細顔料をァニオン性コロイダルシリカの代 わりに、 下記微細シリカ 8 0部を使用した以外は、 実施例 1 と同様にしてキャス トインクジエツ ト記録用紙を得た。  A cast ink jet recording paper was obtained in the same manner as in Example 1, except that 80 parts of the following fine silica was used in place of the anionic colloidal silica as the fine pigment of the cast layer.
微細シリ力 :  Fine force:
平均二次粒子径 4. 5 μ ιηの非晶質シリカ (トクャマ社製、 商品名 : ファイン シール X— 4 5、 平均一次粒子径 1 0 nm) の水分散液を、 圧力式ホモジナイザ 一 (SMT社製、 商品名 :超高圧ホモジナイザ一 GM— 1型) にて、 加圧条件 2 0 0 k g /m2で粉砕処理を繰り返し、 平均二次粒子径 0. 8 μπιの微細シリカ を得た。 An aqueous silica dispersion having an average secondary particle diameter of 4.5 μιη (available from Tokuyama Corporation, trade name: Fine Seal X-45, average primary particle diameter 10 nm) was mixed with a pressure homogenizer (SMT). The pulverization treatment was repeated with a pressurized condition of 200 kg / m 2 using an ultra-high pressure homogenizer (GM-1 type, manufactured by the company) to obtain fine silica having an average secondary particle diameter of 0.8 μπι.
実施例 7 Example 7
実施例 1において、 下塗り層用塗工液中に 1, 2—ビス (2—ヒ ドロキシェチ ルチオ) ェタン 1 0部を添加した以外は、 実施例 1 と同様にしてキャス トインク ジェッ ト記録用紙を得た。  A cast ink jet recording paper was obtained in the same manner as in Example 1, except that 10 parts of 1,2-bis (2-hydroxyxethylthio) ethane was added to the coating liquid for the undercoat layer. Was.
比較例 1 Comparative Example 1
実施例 1において、 カチオン性化合物としてジァリルァミン塩酸塩 · アクリル アミ ド共重合体樹脂 2 5部の代わりに、 ジシアンジアミ ド系樹脂 (日華化学社製、 商品名 : ネオフィックス E— 1 1 7) 2 5部を使用した以外は、 実施例 1 と同. 様にしてキャス トインクジエツ ト記録用紙を得た。  In Example 1, dicyandiamide-based resin (manufactured by Nikka Chemical Co., trade name: Neofix E-117) was used in place of 5 parts of diarylamine hydrochloride / acrylamide copolymer resin as the cationic compound. A cast ink jet recording paper was obtained in the same manner as in Example 1 except that five copies were used.
比較例 2 Comparative Example 2
実施例 1において、 離型剤としてステアリン酸の水分散物 3部の代わりに、 レ シチンの水分散物 3部を用いた以外は、 実施例 1 と同様にしてキャス トインクジ ッ ト記録用紙を得た。 比較例 3 A cast ink jet recording paper was obtained in the same manner as in Example 1 except that 3 parts of an aqueous dispersion of lecithin was used instead of 3 parts of an aqueous dispersion of stearic acid as a release agent. Was. Comparative Example 3
実施例 1において、 離型剤としてステアリン酸の水分散物 3部の代わりに、 ァ ラキン酸 (C 2。) の水分散物 3部を用いた以外は、 実施例 1 と同様にしてキャス トインクジェッ ト記録用紙を得た。 A cast was prepared in the same manner as in Example 1 except that 3 parts of an aqueous dispersion of arachidic acid (C 2 ) was used as a release agent instead of 3 parts of an aqueous dispersion of stearic acid. Inkjet recording paper was obtained.
比較例 4 Comparative Example 4
実施例 1において、 離型剤としてステアリン酸の水分散物 3部の代わりに、 ゥ ンデシル酸 (C u ) の水分散物 3部を用いた以外は、 実施例 1 と同様にしてキヤ ス トインクジエツ ト記録用紙を得た。  In Example 1, a cast ink was prepared in the same manner as in Example 1, except that 3 parts of an aqueous dispersion of undecylic acid (Cu) was used as a release agent instead of 3 parts of an aqueous dispersion of stearic acid. A recording paper was obtained.
実施例および比較例で得たキャス トインクジエツ ト記録用紙について、 ェプソ ン社製インクジェッ トプリンター P M— 8 0 0 Cを用いて、 印字を行い、 評価し た結果を表 1に示した。  The cast ink jet recording paper obtained in the examples and comparative examples was printed using an Epson inkjet printer PM-800C, and the evaluation results are shown in Table 1.
(印字濃度)  (Print density)
印字後 2 4時間経過したブラックのベタ印字部の印字濃度をマクベス濃度計 (マクベス社製、 商品名 : R D _ 9 1 4 ) を用いて測定した。  The printing density of the black solid printing portion 24 hours after printing was measured using a Macbeth densitometer (trade name: RD_914) manufactured by Macbeth.
(ィンク吸収性)  (Ink absorption)
混色黒 (8 0 % ) の印字部分の境界から、 インク吸収性を目視で評価した。 〇 :境界が明瞭で、 ニジミがない。  The ink absorbency was evaluated visually from the boundary of the mixed color black (80%) printed portion. :: The boundary is clear and there is no bleeding.
X :境界が明瞭でなく、 二ジミがある。  X: The boundary is not clear and there are two blemishes.
(耐熱性)  (Heat-resistant)
各実施例及び各比較例で作成したキャス トインクジヱッ ト記録用紙を、 印字せ ずに 8 0 °Cの恒温槽に 7 日間保存し、 記録用紙の黄変の度合を目視評価した。 評価基準 :  The cast ink jet recording paper prepared in each example and each comparative example was stored in a thermostat at 80 ° C. for 7 days without printing, and the degree of yellowing of the recording paper was visually evaluated. Evaluation criteria :
◎ : 耐熱性に優れる。  ◎: Excellent heat resistance.
〇 :記録用紙がわずかに黄変するが、 実用上問題ない。  〇: The recording paper slightly yellows, but there is no practical problem.
X :記録用紙が黄変し、 改善が必要。  X: The recording paper turned yellow and needs improvement.
(耐オゾン性)  (Ozone resistance)
長期保存性との相関の高い耐オゾン性を評価した。 シアン、 マゼンタ、 イエロ 一混色によるミ ックスブラックおよびシアンィンクのベタ印字および I S O— 4 0 0の印字した画像を、 オゾン濃度 1 0 p p mの容器に 1 2時間放置した。 ベタ 印字の場合には、 試験後の印字濃度を測定した。 一方、 画像の場合には目視によ り変色の度合いを観察し、 評価した。 Ozone resistance, which has a high correlation with long-term storage, was evaluated. Solid printing of mixed black and cyan ink with one color mixture of cyan, magenta and yellow, and ISO-4 The printed image of 0 was left in a container having an ozone concentration of 10 ppm for 12 hours. In the case of solid printing, the print density after the test was measured. On the other hand, in the case of an image, the degree of discoloration was visually observed and evaluated.
印字濃度の低下と目視の結果を総合して下記評価基準により評価した。  The reduction in print density and the result of visual observation were combined and evaluated according to the following evaluation criteria.
評価基準:  Evaluation criteria:
◎:変褪色がみられない。  A: No discoloration is observed.
〇:変褪色がややみられるが、 実用上問題なし。  〇: Discoloration is slightly observed, but there is no practical problem.
X :変褪色が著しく、 実用上問題あり。  X: Discoloration is remarkable, and there is a problem in practical use.
(連続操業性)  (Continuous operability)
各実施例及び各比較例のキャスト層の塗工に際し、 操業時に鏡面ドラム上の汚 れの程度を目視評価した。  During the coating of the cast layer of each of the examples and comparative examples, the degree of contamination on the mirror drum during operation was visually evaluated.
評価基準:  Evaluation criteria:
◎:鏡面ドラムの曇りが発生せず、 連続操業性が良好である。  :: Mirror surface drum does not fog, and continuous operation is good.
〇 :鏡面ドラムの曇りがわずかに発生するが、 実用上、 連続操業性に問題はな レ、。  〇: Slight fogging of the mirror drum occurs, but practically there is no problem with continuous operation.
△ :鏡面ドラムの汚れがあり、 記録用紙の光沢度が低下して実用上問題あり。  Δ: The mirror surface drum is stained, and the glossiness of the recording paper is reduced, which causes a practical problem.
:鏡面ドラムの塗料が残存し、 連続操業不可。 記録用紙に光沢度の高低によ るまだらが発生。  : The paint on the mirror drum remains, making continuous operation impossible. Mottle occurs on the recording paper due to the degree of glossiness.
( 7 5度表面光沢度)  (75 degree surface gloss)
得られたキャストインクジエツト記録用紙の J I S— Z 8 7 4 1記載の 7 5度 光沢度を光沢度計 (村上色彩研究所社製、 商品名 : G M— 2 6 D ) を用いて測定 した。 J I S— Z 8 7 4 1の概要は以下のとおりである。 光源には偏光性のない ものを用い、 試料面に規定された入射角で規定の開き角度の光束を入射し、 鏡面 反射方向に反射する規定の開き角の光束を受光器で測定した。 入射側及び受光側 の光軸は、 試料面で交わるものとした。 また、 光沢度の単位は屈折率が可視波長 範囲全域にわたって一定値 1 . 5 6 7であるガラス表面において、 規定された入 射角 Θでの鏡面光沢度を基準とし、 この値を 1 0 0 %として表した。 表 1 The glossiness of the obtained cast ink jet recording paper was measured using a gloss meter (trade name: GM-26D, manufactured by Murakami Color Research Laboratory Co., Ltd.) described in JIS-Z8741. The outline of JIS-Z8741 is as follows. A non-polarizing light source was used. A light beam with a specified opening angle was incident on the sample surface at a specified incident angle, and a light beam with a specified opening angle reflected in a mirror-reflecting direction was measured by a light receiver. The optical axes of the incident side and the light receiving side intersect at the sample surface. The unit of gloss is based on the specular gloss at the specified incident angle Θ on the glass surface whose refractive index is a constant value of 1.567 over the entire visible wavelength range. Expressed as%. table 1
Figure imgf000019_0001
Figure imgf000019_0001
*比較例 4については鏡面ドラムに貼りついてしまい作成不可 産業上の利用可能性 表 1から明らかなように、 本発明のキャス トインクジェッ ト記録用紙は、 画像 の印字濃度が高く、 インク吸収性が良好なだけでなく、 耐熱性ゃ耐オゾン性に優 れ、 しかも連続操業性に優れ、 かつ光沢度の高いキャス トインクジェッ ト記録用 紙であり、 きわめて実用性の高いものである。  * Comparative Example 4 was stuck on the mirror drum and could not be created.Industrial applicability As is evident from Table 1, the cast ink jet recording paper of the present invention has a high image print density and high ink absorbency. It is not only good, but also excellent in heat resistance and ozone resistance, excellent in continuous operation, and high in glossy cast ink jet recording paper. It is extremely practical.

Claims

請求の範囲 The scope of the claims
1 . 基材上に、 顔料、 カチオン性化合物及び接着剤を含有する下塗り層を設け、 前記下塗り層上に、 接着剤、 平均二次粒子径が 1 μ m未満の微細顔料及び離型剤 を含有するキャス ト層を設けたキャストインクジェッ ト記録用紙において、 前記カチオン性化合物が、 ジァリルァミンと (メタ) アクリルアミ ドとの共重 合体、 ジァリルァミンと (メタ) アクリルアミ ドとこれらに共重合可能な他のビ ニル系モノマーであって実質的にカルボキシル基を含有しないものとの共重合体、 又はこれらのいずれかの塩から成る群より選ばれる少なく とも一種であり、 かつ 前記離型剤として、 炭素数が 1 2〜1 8の脂肪酸及びその水溶性塩から成る群よ り選ばれる少なく とも一種を含有することを特徴とするキャス トインクジェッ ト 記録用紙。 1. An undercoat layer containing a pigment, a cationic compound and an adhesive is provided on a substrate, and an adhesive, a fine pigment having an average secondary particle diameter of less than 1 μm, and a release agent are provided on the undercoat layer. In a cast ink jet recording paper provided with a cast layer, the cationic compound can be copolymerized with diarylamine and (meth) acrylamide, or copolymerized with diarylamine and (meth) acrylamide. At least one selected from the group consisting of a copolymer with another vinyl monomer which does not substantially contain a carboxyl group, or a salt of any of these, and as the release agent, A cast ink jet recording paper containing at least one selected from the group consisting of fatty acids having 12 to 18 carbon atoms and water-soluble salts thereof.
2 . 請求項 1記載のキャストインクジヱッ ト記録用紙であって、 2. The cast ink jet recording paper according to claim 1, wherein
前記離型剤が、 ステアリン酸、 ォレイン酸、 ステアリン酸の水溶性塩、 および ォレイン酸の水溶性塩から成る群より選ばれる少なく とも一種であるキャス トイ ンクジェッ ト記録用紙。  A cast ink jet recording sheet, wherein the release agent is at least one selected from the group consisting of stearic acid, oleic acid, a water-soluble salt of stearic acid, and a water-soluble salt of oleic acid.
3 . 請求項 1または 2記載のキャス トインクジヱッ ト記録用紙であって、 前記カチオン性化合物を、 前記顔料 1 0 0質量部に対し、 1〜 1 0 0質量部含 有するキャス トインクジヱッ ト記録用紙。 3. The cast ink jet recording sheet according to claim 1, wherein the cationic compound is contained in an amount of 1 to 100 parts by mass with respect to 100 parts by mass of the pigment.
4 . 請求項 1または 2記載のキャス トインクジヱッ ト記録用紙であって、 前記離型剤を、 前記微細顔料 1 0 0質量部に対し、 0 . 1〜 1 0質量部含有す るキャス トインクジェッ ト記録用紙。 3. The cast ink jet recording sheet according to claim 1 or 2, wherein the release agent is contained in an amount of 0.1 to 10 parts by mass with respect to 100 parts by mass of the fine pigment. Recording sheet.
5 · 請求項 1または 2記載のキャス トインクジヱッ ト記録用紙であって、 前記下塗り層及び前記キャス ト層の少なく とも 1層中に、 含ィォゥ有機化合物 を含有するキャス トインクジェッ ト記録用紙。 5.The cast ink jet recording sheet according to claim 1, wherein at least one of the undercoat layer and the cast layer contains an organic compound containing an organic compound. Cast inkjet recording paper containing.
6. 請求項 1または 2記載のキャス トインクジェッ ト記録用紙であって、 キャス ト層表面の 7 5° 表面光沢度 ( J I S— Z 8 74 1に基づく光沢度) 5 0 %以上であるキャス トインクジェッ ト記録用紙。 6. The cast ink jet recording paper according to claim 1 or 2, wherein the cast layer surface has a surface gloss of 75 ° (gloss based on JIS-Z8741) of 50% or more. Inkjet recording paper.
PCT/JP2003/006685 2003-05-28 2003-05-28 Cast ink-jet recording paper WO2004106080A1 (en)

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Citations (9)

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US5576088A (en) * 1994-05-19 1996-11-19 Mitsubishi Paper Mills Limited Ink jet recording sheet and process for its production
JP2000263923A (en) * 1999-03-17 2000-09-26 Mitsubishi Paper Mills Ltd Ink jet recording sheet
EP1195259A2 (en) * 2000-10-05 2002-04-10 Oji Paper Co., Ltd. Sheet for ink jet-recording
WO2002072360A1 (en) * 2001-03-14 2002-09-19 Mitsubishi Paper Mills Limited Inkjet recording sheets
JP2002293006A (en) * 2001-03-29 2002-10-09 Mitsubishi Paper Mills Ltd Manufacturing method for ink jet recording sheet
JP2003080840A (en) * 2001-06-26 2003-03-19 Oji Paper Co Ltd Ink-jet recording sheet
JP2003103909A (en) * 2001-09-28 2003-04-09 Mitsubishi Paper Mills Ltd Ink jet recording sheet
JP2003165268A (en) * 2001-11-30 2003-06-10 Oji Paper Co Ltd Cast ink jet recording form

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Publication number Priority date Publication date Assignee Title
US5576088A (en) * 1994-05-19 1996-11-19 Mitsubishi Paper Mills Limited Ink jet recording sheet and process for its production
JPH08150773A (en) * 1994-11-28 1996-06-11 Mitsubishi Paper Mills Ltd Ink jet recording sheet
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