JP3747635B2 - Inkjet recording paper - Google Patents

Inkjet recording paper Download PDF

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JP3747635B2
JP3747635B2 JP17812798A JP17812798A JP3747635B2 JP 3747635 B2 JP3747635 B2 JP 3747635B2 JP 17812798 A JP17812798 A JP 17812798A JP 17812798 A JP17812798 A JP 17812798A JP 3747635 B2 JP3747635 B2 JP 3747635B2
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Japan
Prior art keywords
jp
represents
layer
recording paper
ink
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JPH11348409A (en
Inventor
洋一 斎藤
美宏 望月
健三 笠原
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コニカミノルタホールディングス株式会社
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Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an ink jet recording paper, and more particularly to an ink jet recording paper having improved image bleeding after printing without deteriorating light resistance.
[0002]
[Prior art]
Ink-jet recording is a method in which micro droplets of ink are ejected according to various operating principles and deposited on a recording sheet such as paper to record images and characters. Has advantages such as being easy. With regard to nozzle clogging and maintenance, which has been a problem with this method, improvements have been made from both sides of ink and equipment, and now it is rapidly spreading in various fields such as various printers, facsimiles, and computer terminals. .
[0003]
The recording paper used in this ink jet recording system has a high density of printed dots, a bright and vivid color tone, and ink does not run out or bleed even when printed dots overlap quickly. In addition, it is required that the horizontal spread of the printed dots is not larger than necessary, and the periphery is smooth and unblurred.
[0004]
In particular, when the ink absorption speed is slow, when ink droplets of two or more colors are overlapped and recorded, the droplets cause repelling on the recording paper and become uneven, or the boundary areas of different colors Therefore, it is necessary for the recording paper to have high ink absorptivity because the colors tend to blur and the image quality is likely to be greatly reduced.
[0005]
In order to solve these problems, a great number of techniques have been conventionally proposed.
For example, a recording paper in which a low-size base paper described in JP-A-52-53012 is wetted with a coating for surface processing, and a support surface described in JP-A-55-5830 has ink absorptivity. A recording paper provided with a coating layer, a recording paper containing non-gelatin silica powder as a pigment in the coating layer described in JP-A-56-157, described in JP-A-57-107878 Recording paper using both inorganic pigments and organic pigments, recording paper having two pore distribution peaks described in JP-A No. 58-110287, upper and lower 2 described in JP-A No. 62-111782 Recording paper comprising a porous layer, recording paper having irregular cracks described in JP-A-59-68292, JP-A-59-123696, JP-A-60-18383, etc. No. 35786, 61-148092, and 62-149475, etc., recording paper having a fine powder layer, Japanese Patent Laid-Open Nos. 63-25279, 1-108083, 2-136279, JP-A-57-14091, JP-A-60-219083, JP-A-60-19083, recording paper containing pigments having specific physical properties and fine-particle silica described in JP-A-3-65376 and 3-27976, etc. 209984, 61-20797, 61-188183, JP-A-5-278324, 6-92011, 6-183134, 7-137431, 7-276789, etc. Recording paper containing fine particle silica such as colloidal silica, and JP-A-2-276671 and JP-A-3-67684 There are many recording papers containing fine particles of alumina hydrate described in JP-A-3-215082, JP-A-3-251488, JP-A-4-67986, JP-A-4-263993, and JP-A-5-16517. Are known.
[0006]
Among these, void type recording paper using minute inorganic fine particles and a hydrophilic binder and having minute voids formed in the ink receiving layer is preferable as a high-quality glossy paper because relatively high gloss can be obtained.
[0007]
The use of fine particle silica having an anionic surface as such inorganic fine particles is preferable because excellent gloss can be obtained, and the average particle size of primary particles synthesized by the vapor phase method is preferably 30 nm or less. Composite particles having an average particle size of 100 nm or less obtained by a combination of fine-particle silica and a cationic polymer are particularly preferable in that both glossiness and high porosity can be achieved.
[0008]
By the way, after ink jet recording, there is a problem that the image tends to bleed when the recorded image is stored under high humidity or when water droplets adhere.
In order to solve this problem, many techniques have been proposed.
JP-A-57-36692 uses a basic mordant latex, JP-A-53-49113, JP-A-59-198186 and JP-A-59-198188 describe a method of impregnating with polyethyleneimine. Japanese Patent Application Laid-Open No. 61-61887 discloses that an electrolyte polymer having a cationic group is contained in Japanese Patent Laid-Open No. 58-24492, and that a polymer having a cationic polymer mordant and a hydrophilic group is contained in Japanese Patent Laid-Open No. 63-307879. JP-A-61-72581, JP-A-61-252189 and JP-A-62-174184 use polyallylamine as a mordant, and JP-A-63-162275 uses a cationic mordant and a cationic surfactant in combination. In JP-A-6-143798, cation-modified polyvinyl call is disclosed in JP-A-8-14296. It is described to improve the water resistance in combination with certain two cationic polymers.
[0009]
Furthermore, JP-A-59-20696, 59-33176, 59-33177, 59-96987, 59-1555088, 60-11389, 60-49990, 60-83882. 60-109894, 61-277484, 61-293886, 62-19483, 62-198493, 63-49478, 63-115780, 63-203896, 63-274583, 63-280681, 63-260477, JP-A-1-9776, 1-224784, 1-40371, 3-133686, 6-234268, No. 7-125411 discloses many techniques for improving the fixability of an ink dye by adding a cationic mordant.
[0010]
However, most of the materials disclosed in the prior art tend to form aggregates when mixed with inorganic fine particles whose surface is anionic, such as silica. There was a problem such as a significant decrease in performance.
[0011]
In order to improve this point, the present applicant has applied for a patent in the previous application (Japanese Patent Application No. 9-23808) to use a water-soluble cationic polymer having an average molecular weight of 50,000 or less. As a result, sufficiently excellent water resistance and glossiness can be obtained.
[0012]
However, as a result of subsequent studies, it has been found that if images are overlaid for a relatively short time after being printed by an ink jet printer or stored in a clear file or the like, the image gradually bleeds over time, and further improvements have been desired.
It has been found that the bleeding over time depends on the kind of ink dye used and the content of the water-soluble high-boiling organic solvent, but also on the fixing degree of the dye on the recording paper.
[0013]
As a result of intensive studies on this point, the present inventor has found that the blur of the image after printing depends on the structure of the cationic polymer.
In particular, it has been found that the bleeding resistance is improved when the cationic component is a cationic monomer bonded to a mother nucleus such as styrene, but on the other hand, when this type of cationic polymer is used, light resistance tends to be lowered. It also turned out to be flawed.
[0014]
[Problems to be solved by the present invention]
The present invention has been made in view of the above circumstances, and the problem to be solved by the present invention is that, in an inkjet recording paper having a void layer composed of inorganic fine particles and a hydrophilic binder, high gloss and high porosity. It is an object of the present invention to provide an ink jet recording paper that has improved image bleeding after printing without adversely affecting light resistance.
[0015]
[Means for Solving the Problems]
  Above issuesThe present invention for solving the problems has the following configuration.
1. A hydrophilic binder on the support and inorganic fine particles having an average primary particle size of 30 nm or less and the following general formula (1)numberAverage molecular weight(This is a value converted to a polystyrene value obtained from gel permeation chromatography.)But2000 or moreAn ink jet recording paper comprising an ink absorbing layer containing cationic composite particles composed of 100,000 or less water-soluble cationic polymer.
[0016]
[Chemical formula 2]
  In the formula, R and R ′ represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms;1, R2, R3, R1', R2′ And R3'Represents an alkyl group and ARepresents —COO— or —CONH—, and J represents a single bond or —CONH—.Represents. X1 And X2 Represents an anionic group. Q represents a repeating unit derived from a monomer having an ethylenically unsaturated group. Q includes the case where two or more monomers are copolymerized. x is 10 to 95 mol%, y is 5 to 90 mol%, and z is 0 to 60 mol%. m represents a positive number from 1 to 6.
[0017]
DETAILED DESCRIPTION OF THE INVENTION
The present invention will be described in detail below.
Examples of inorganic fine particles having an average primary particle size of 30 nm or less used in the present invention include light calcium carbonate, heavy calcium carbonate, magnesium carbonate, kaolin, clay, talc, calcium sulfate, barium sulfate, and titanium dioxide. , Zinc oxide, zinc hydroxide, zinc sulfide, zinc carbonate, hydrotalcite, aluminum silicate, diatomaceous earth, calcium silicate, magnesium silicate, synthetic amorphous silica, colloidal silica, alumina, colloidal alumina, pseudoboehmite, aluminum hydroxide And white inorganic pigments such as lithopone, zeolite and magnesium hydroxide.
[0018]
In the present invention, silica or pseudoboehmite is preferable, particularly from the viewpoint of forming a fine void with high transparency of the film, and silica synthesized by a vapor phase method is most preferable.
As the fine particle silica synthesized by the vapor phase method, for example, Aerosil series manufactured by Nippon Aerosil Co., Ltd. is commercially available.
[0019]
Here, the average particle diameter of the inorganic fine particles is obtained as a simple average value (number average) by determining the particle diameter of 100 arbitrary particles by observing with an electron microscope. Here, each particle size is represented by a diameter assuming a circle equal to the projected area.
[0020]
In the present invention, the inorganic fine particles are used by forming cationic composite particles together with the cationic polymer represented by the general formula (1) having an average molecular weight of 50,000 or less.
[0021]
This composite particle is formed by mixing an aqueous solution containing a water-soluble cationic polymer with a dispersion containing inorganic fine particles whose surface is anionic and eliminating the aggregates generated at that time. Is obtained by dispersing.
[0022]
By carrying out this dispersion treatment, a dispersion of inorganic fine particles having been cation-converted can be obtained.
As this dispersion treatment method, various conventionally known dispersers such as a high-speed rotary disperser, a medium stirring disperser (ball mill, sand mill, etc.), an ultrasonic disperser, a colloid mill disperser, a roll mill disperser, and a high pressure disperser are used. Although it can be used, in the present invention, an ultrasonic disperser or a high-pressure disperser is preferably used from the viewpoint of efficiently dispersing the formed fine particles.
[0023]
The ultrasonic disperser is usually dispersed by concentrating energy on the solid-liquid interface by irradiating ultrasonic waves of 20 to 25 KHz, and is dispersed very efficiently, but a large amount of dispersion is adjusted. It is not very suitable when necessary.
[0024]
On the other hand, the high-pressure disperser is equipped with one or two homogeneous valves at the outlet of a high-pressure pump having three or five pistons, the gap of which can be adjusted by screws or hydraulic pressure. The liquid medium fed by the high-pressure pump is squeezed by the homogenous valve and pressure is applied, and minute dust material is pulverized at the moment of passing through the homogenous valve.
[0025]
This method is a particularly preferable method when a large amount of liquid is produced because a large amount of liquid can be dispersed continuously. The pressure applied to the homogeneous valve is approximately 50 to 1000 kg / cm.2The dispersion can be done in one pass or can be repeated many times.
[0026]
When adjusting the cationic dispersion, various additives can be added for adjustment.
For example, various nonionic or cationic surfactants (anionic surfactants are not preferred for forming aggregates), antifoaming agents, nonionic hydrophilic polymers (polyvinyl alcohol, polyvinylpyrrolidone, polyethylene oxide) , Polyacrylamide, various sugars, gelatin, pullulan, etc.), nonionic or cationic latex dispersion, water-miscible organic solvent (ethyl acetate, methanol, ethanol, isopropanol, n-propanol, acetone, etc.), inorganic salts, pH A regulator or the like can be appropriately used as necessary.
[0027]
In particular, a water-miscible organic solvent is preferable because formation of fine lumps when inorganic fine particles and a cationic polymer are mixed is suppressed. Such water-miscible organic solvents are used in the dispersion in an amount of 0.1 to 20% by weight, particularly preferably 0.5 to 10% by weight.
[0028]
The pH at which the cationic dispersion is prepared can vary widely depending on the type of inorganic fine particles, the type of cationic polymer, various additives, etc., but generally the pH is 1 to 8, especially 2 to 2. 7 is preferred.
Two or more kinds of the above dispersions can be used in combination.
[0029]
  The cationic polymer used in the present invention is represented by the general formula (1).
  In the general formula (1), R and R ′ are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom or a methyl group.
  R1, R2, R3, R1', R2′ And R3Each represents an alkyl group, preferably a methyl group or an ethyl group. Each of these alkyl groups may have a substituent.
  AIs-CONH- or -COO-TheJ is just a bond or-CONH-InThe
  X1 And X2 Represents an anion group (halogen ion, methyl sulfate ion, p-toluenesulfonate ion, etc.).
  Q represents a repeating unit derived from a monomer having an ethylenically unsaturated group.
  Specific examples of the monomer of Q include, for example, styrene, butadiene, methyl methacrylate, ethyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, hydroxyethyl methacrylate, vinyl acetate, vinyl ether, acrylamide, and N-methyl acrylamide. N-vinylimidazole, 4-vinylpyridine, N-vinylpyrrolidone, vinyl chloride and the like.
  Q includes a case where two or more monomers are copolymerized.
  x is 10 to 95 mol%, preferably 20 to 80 mol%, y is 5 to 90 mol%, preferably 10 to 60 mol%, and z is 0 to 60 mol%, preferably 0 to 40 mol%. %.
[0030]
Next, specific examples of the cationic polymer composition represented by the general formula (1) are shown.
In general formula (1),
[0031]
[Chemical Formula 3]
A repeating unit represented by:
[0032]
[Formula 4]
The repeating unit represented by may be a mixture of two or more repeating units.
[0033]
[Chemical formula 5]
[0034]
[Chemical 6]
[0035]
[Chemical 7]
[0036]
[Chemical 8]
[0037]
[Chemical 9]
[0038]
  The cationic polymer represented by the general formula (1) has a number average molecular weight.2000 or moreIt is necessary to be 100,000 or less.
  Here, the number average molecular weight is a value converted to a polystyrene value obtained from gel permeation chromatography.
  When the number average molecular weight exceeds 100,000, when an aqueous solution of a cationic polymer is added to a dispersion containing inorganic fine particles whose surface is anionic, agglomerates are severely generated. It is difficult to form a uniform dispersion, and a large number of coarse particles are present, making it difficult to form a uniform dispersion. When such a composite fine particle dispersion liquid composed of a cationic polymer and inorganic fine particles is used and applied to glossy paper for inkjet, high glossiness cannot be obtained. Preferably it is 50,000 or less. Is the lower limit of the number average molecular weight the water resistance of the dye?Et al 2000 or more, and particularly preferably 5000 or more.
[0039]
  The ratio of the inorganic fine particles and the cationic polymer is generally 1: 0.01 to 1: 1, although it can vary depending on the kind and particle size of the inorganic fine particles, or the kind and average molecular weight of the cationic polymer.
  The cationic polymer used in the present invention is close to the above-described prior art (Japanese Patent Laid-Open No. Hei 8-142396), but the prior art uses a combination of different water-soluble polymers having two different types of repeating units.The present inventionIs different. Further, in the prior art, since the ink absorption layer is a so-called swelling type ink absorption layer, it is difficult to obtain a good ink absorption rate.The present inventionIs distinctly different.
[0040]
As the hydrophilic binder used in the recording paper of the present invention, various conventionally known hydrophilic binders are used, but hydrophilic properties that do not exhibit aggregation or significant thickening action when mixed with the cationic composite fine particles of the present invention. A binder is preferred. Examples of such a hydrophilic binder include gelatin (preferably acid-treated gelatin), polyvinylpyrrolidone (average molecular weight is preferably about 200,000 or more), pullulan, polyvinyl alcohol or a derivative thereof, polyethylene glycol (average molecular weight is 100,000 or more). Are preferable), hydroxyethyl cellulose, dextran, dextrin, and water-soluble polyvinyl butyral. These hydrophilic binders may be used alone or in combination of two or more.
A particularly preferred hydrophilic binder is polyvinyl alcohol or cation-modified polyvinyl alcohol.
[0041]
As the polyvinyl alcohol preferably used in the present invention, those having an average degree of polymerization of 300 to 4000 are preferably used, and in particular, a film having an average molecular weight of 1000 or more is preferable since the brittleness of the film is good. The saponification degree of polyvinyl alcohol is preferably 70 to 100%, particularly preferably 80 to 100%.
[0042]
The cation-modified polyvinyl alcohol can be obtained by saponifying a copolymer of an ethylenically unsaturated monomer having a cationic group and vinyl acetate.
Examples of the ethylenically unsaturated monomer having a cationic group include trimethyl- (2-acrylamide-2,2-dimethylethyl) ammonium chloride, trimethyl- (3-acrylamide-3,3-dimethylpropyl) ammonium chloride, N-vinylimidazole, N-vinyl-2-methylimidazole, N- (3-dimethylaminopropyl) methacrylamide, hydroxylethyltrimethylammonium chloride, trimethyl-(-methacrylamideamidopropyl) ammonium chloride, N- (1,1- And dimethyl-3-dimethylaminopropyl) acrylamide.
[0043]
The ratio of the cation-modified group-containing monomer of the cation-modified polyvinyl alcohol is 0.1 to 10 mol%, preferably 0.2 to 5 mol%, relative to vinyl acetate.
The polymerization degree of the cation-modified polyvinyl alcohol is usually 500 to 4000, preferably 1000 to 4000.
The degree of saponification of the cation-modified polyvinyl alcohol is usually 60 to 100 mol%, preferably 70 to 99 mol%.
[0044]
  Use amount of the above hydrophilic binderIsIn order to make the ink absorbing layer a void layer, it is preferably used in a relatively small amount with respect to the inorganic fine particles, and it is preferably used as little as possible within a range where the film is stably formed and the adhesiveness with the support can be sufficiently maintained. In general, the weight ratio with respect to the inorganic fine particles is approximately 1/3 to 1/10, particularly 1/4 to 1/8.
[0045]
In the ink jet recording paper of the present invention, the hydrophilic binder is preferably hardened with a hardener in order to obtain high gloss and high porosity without deteriorating the brittleness of the film.
[0046]
The hardener is generally a compound having a group capable of reacting with the hydrophilic binder or a compound that promotes the reaction between different groups of the hydrophilic binder, depending on the type of the hydrophilic binder. It is appropriately selected and used.
[0047]
Specific examples of the hardener include, for example, epoxy hardeners (diglycidyl ethyl ether, ethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-diglycidyl cyclohexane, N, N- Diglycidyl-4-glycidyloxyaniline, sorbitol polyglycidyl ether, glycerol polyglycidyl ether, etc.), aldehyde hardeners (formaldehyde, glioxal, etc.), active halogen hardeners (2,4-dichloro-4-hydroxy-1) , 3,5-s-triazine, etc.), active vinyl compounds (1,3,5-trisacryloyl-hexahydro-s-triazine, bisvinylsulfonylmethyl ether, etc.), boric acid and its salts, borax, aluminum alum, etc. Is mentioned.
[0048]
When polyvinyl alcohol and / or cation-modified polyvinyl alcohol are used as a particularly preferred hydrophilic binder, it is preferable to use a hardener selected from boric acid and salts thereof and an epoxy hardener.
[0049]
Most preferred is a hardener selected from boric acid and its salts.
In the present invention, boric acid or a salt thereof represents an oxygen acid having a boron atom as a central atom and a salt thereof, specifically, orthoboric acid, diboric acid, metaboric acid, tetraboric acid, pentaboric acid, and octaboric acid. And their salts.
[0050]
The amount of the hardener used varies depending on the kind of the hydrophilic binder, the kind of the hardener, the kind of the inorganic fine particles, the ratio to the hydrophilic binder, etc., but is generally 5 to 500 mg per gram of the hydrophilic binder, preferably 10 ~ 400 mg.
[0051]
  The above hardener may be added in the coating liquid for forming the void layer and / or in the coating liquid for forming another layer adjacent to the void layer when the coating liquid constituting the void layer is applied, or in advance. On the support on which a coating solution containing a hardener is applied, a coating solution for forming the void layer is applied, or a coating solution containing no hardener for forming the void layer is applied and dried. The hardener can be supplied to the void layer by overcoating with a hardener solution, etc., but preferably from the viewpoint of production efficiency, the coating liquid for forming the void layer or thisInIt is preferable to supply a hardener simultaneously with forming a void layer by adding a hardener to the coating solution of an adjacent layer.
[0052]
In addition to the above, various additives can be added to the ink absorbing layer of the ink jet recording paper of the present invention and other layers provided as necessary.
For example, organic latex fine particles such as polystyrene, polyacrylic acid esters, polymethacrylic acid esters, polyacrylamides, polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, or a copolymer thereof, urea resin, or melamine resin Oil droplets such as liquid paraffin, dioctyl phthalate, tricresyl phosphate, silicone oil, various surfactants such as cation or nonion, JP-A-57-74193, JP-A-57-87988, and JP-A-62-261476 JP-A-57-74192, JP-A-57-87989, JP-A-60-72785, JP-A-61465991, JP-A-1-95091 and JP-A-3-13376 Discoloration prevention described in gazettes, etc. Fluorescent whitening agents and sulfuric acid described in JP-A-59-42993, JP-A-59-52689, JP-A-62-280069, JP-A-61-228771 and JP-A-4-219266 Including various known additives such as pH adjusters such as phosphoric acid, citric acid, sodium hydroxide, potassium hydroxide, potassium carbonate, antifoaming agents, preservatives, thickeners, antistatic agents, matting agents, etc. You can also.
[0053]
The void volume of the ink absorbing layer of the ink jet recording paper of the present invention is generally 20 to 40 ml / m.2In addition, the porosity of this layer is approximately 0.5 to 0.8.
The ink absorbing layer may be composed of two or more layers. In this case, the structures of the ink absorbing layers may be the same or different from each other.
The film surface pH of the ink absorbing layer of the recording paper of the present invention is generally in the range of 3-6.
[0054]
As a support for inkjet recording paper in the present invention, a paper support, a plastic support, a composite support and the like known as conventional inkjet recording paper can be appropriately used. However, in order to obtain a clear image at a higher density, the support is used. It is preferable to use a hydrophobic support that does not allow ink liquid to penetrate into the body.
[0055]
As the hydrophobic support, a transparent or opaque plastic resin film support and a paper support in which the paper surface is laminated with polyethylene are preferably used.
[0056]
Examples of the transparent support include films made of materials such as polyester resins, diacetate resins, triatesate resins, acrylic resins, polycarbonate resins, polyvinyl chloride resins, polyimide resins, cellophane, and celluloid. Among them, those having a property to withstand radiant heat when used as OHP are preferable, and polyethylene terephthalate is particularly preferable. The thickness of such a transparent support is preferably about 10 to 200 μm. It is preferable to provide a known undercoat layer on the ink receiving layer side and the back layer side of the transparent support from the viewpoint of adhesion between the ink receiving layer and the back layer and the support.
[0057]
The support used when it is not necessary to be transparent includes, for example, resin-coated paper (so-called RC paper) having a polyolefin resin coating layer in which a white pigment or the like is added to at least one of the base paper, polyethylene terephthalate and white pigment. A so-called white pet obtained by adding the is preferred.
[0058]
For the purpose of increasing the adhesive strength between the support and the ink image-receiving layer, the support is preferably subjected to corona discharge treatment, subbing treatment or the like prior to application of the ink receiving layer. Further, the recording sheet of the present invention is not necessarily colorless, and may be a colored recording sheet.
[0059]
In the ink jet recording paper of the present invention, it is particularly preferable to use a paper support obtained by laminating both sides of a base paper support with polyethylene because the recorded image is close to photographic image quality and a high quality image can be obtained at low cost. Such a paper support laminated with polyethylene will be described below.
[0060]
The base paper used for the paper support is made from wood pulp as a main raw material, and if necessary, paper is made using synthetic pulp such as polypropylene or synthetic fiber such as nylon or polyester in addition to wood pulp. As wood pulp, any of LBKP, LBSP, NBKP, NBSP, LDP, NDP, LUKP, and NUKP can be used, but it is preferable to use more LBKP, NBSP, LBSP, NDP, and LDP with a large amount of short fibers. However, the ratio of LBSP and / or LDP is preferably 10% by weight or more and 70% by weight or less.
[0061]
The pulp is preferably a chemical pulp (sulfate pulp or sulfite pulp) with few impurities, and a pulp having a whiteness improved by bleaching is also useful.
[0062]
In the base paper, sizing agents such as higher fatty acids and alkyl ketene dimers, white pigments such as calcium carbonate, talc and titanium oxide, paper strength enhancing agents such as starch, polyacrylamide and polyvinyl alcohol, fluorescent whitening agents, polyethylene glycols A water retaining agent such as a dispersant, a softening agent such as a quaternary ammonium, and the like can be appropriately added.
[0063]
The freeness of the pulp used for papermaking is preferably 200 to 500 ml as defined by CSF, and the fiber length after beating is the weight of 24 mesh residue and 42 mesh residue as defined in JIS-P-8207. 30 to 70% is preferable. In addition, it is preferable that the weight% of 4 mesh remainder is 20 weight% or less.
The basis weight of the base paper is preferably 30 to 250 g, particularly preferably 50 to 200 g. The thickness of the base paper is preferably 40 to 250 μm.
[0064]
The base paper can be given high smoothness by calendering at the paper making stage or after paper making. Base paper density is 0.7-1.2g / m2(JIS-P-8118) is common. Furthermore, the base paper stiffness is preferably 20 to 200 g under the conditions specified in JIS-P-8143.
[0065]
A surface sizing agent may be applied to the surface of the base paper. As the surface sizing agent, a sizing agent similar to the size that can be added to the base paper can be used.
The pH of the base paper is preferably 5 to 9 when measured by a hot water extraction method defined in JIS-P-8113.
[0066]
The polyethylene covering the front and back surfaces of the base paper is mainly low-density polyethylene (LDPE) and / or high-density polyethylene (HDPE), but some other LLDPE, polypropylene, etc. can also be used.
[0067]
In particular, the polyethylene layer on the ink receiving layer side is preferably one in which rutile or anatase type titanium oxide is added to polyethylene to improve opacity and whiteness, as is widely done in photographic paper. The titanium oxide content is generally 3 to 20% by weight, preferably 4 to 13% by weight, based on polyethylene.
[0068]
Polyethylene-coated paper can be used as glossy paper. Also, when polyethylene is melt-extruded on the surface of the base paper and coated, a so-called molding process is performed to form a matte or silky surface that can be obtained with ordinary photographic paper. These can also be used in the present invention.
[0069]
The amount of polyethylene used on the front and back of the base paper is selected so as to optimize curling at low and high humidity after the ink receiving layer and the back layer are provided. The range is 40 μm and the back layer side is 10 to 30 μm.
[0070]
Further, the polyethylene-coated paper support preferably has the following characteristics.
(1) Tensile strength: The strength specified in JIS-P-8113 is preferably 2-30 kg in the vertical direction and 1-20 kg in the horizontal direction.
{Circle around (2)} The tear strength is preferably 10 to 200 g in the longitudinal direction and 20 to 200 g in the lateral direction according to a method defined by JIS-P-8116.
(3) Compression modulus ≧ 103 Kgf / cm2
(4) Surface Beck smoothness: 20 seconds or more is preferable as a glossy surface under the conditions specified in JIS-P-8119, but it may be less than this for so-called molded products.
(5) Opacity: Transmittance of light in the visible region is preferably 20% or less, particularly preferably 15% or less under the measurement conditions of linear light incidence / diffuse light transmission conditions.
[0071]
The method of applying various hydrophilic layers, which are appropriately provided as necessary, such as the void layer and the undercoat layer of the recording paper of the present invention, can be appropriately selected from known methods. A preferred method is obtained by coating a coating liquid constituting each layer on a support and drying. In this case, two or more layers can be applied at the same time. In particular, simultaneous application in which all the hydrophilic binder layers need only be applied once is preferable.
[0072]
As the coating method, a roll coating method, a rod bar coating method, an air knife coating method, a spray coating method, a curtain coating method, or an extrusion coating method using a hopper described in US Pat. No. 2,681,294 is preferably used.
[0073]
When recording an image using the ink jet recording paper of the present invention, a recording method using water-based ink is preferably used.
The aqueous ink referred to in the present invention is a recording liquid comprising the following colorant, liquid medium, and other additives. As the colorant, water-soluble dyes or water-dispersible pigments such as direct dyes, acid dyes, basic dyes, reactive dyes or food dyes known by inkjet can be used.
[0074]
Examples of the solvent for the water-based ink include water and various water-soluble organic solvents such as alcohols such as methyl alcohol, isopropyl alcohol, n-butyl alcohol, tert-butyl alcohol, and isobutyl alcohol; amides such as dimethylformamide and dimethylacetamide. Ketones or ketone alcohols such as acetone and diacetone alcohol; ethers such as tetrahydrofuran and dioxane; polyalkylene glycols such as polyethylene glycol and polypropylene glycol; ethylene glycol, propylene glycol, butylene glycol, triethylene glycol, 1, 2 Polyhydric alcohols such as 1,6-hexanetriol, thiodiglycol, hexylene glycol, diethylene glycol, glycerin, triethanolamine Le ethers, ethylene glycol methyl ether, diethylene glycol methyl (or ethyl) ether, lower alkyl ethers of polyhydric alcohols such as triethylene glycol monobutyl ether.
[0075]
Among these many water-soluble organic solvents, polyhydric alcohols such as diethylene glycol, triethanolamine and glycerin, lower alkyl ethers of polyhydric alcohols such as triethylene glycol monobutyl ether are preferable.
[0076]
  Examples of other water-based ink additives include pH adjusters, metal sequestering agents, antibacterial agents, viscosity modifiers, surface tension adjusters, wetting agents, surfactants, and rust inhibitors.
  Water-based ink is wettable with recording paperTheIn order to be good, it is preferable to have a surface tension in the range of 25-60 dyn / cm, preferably 30-50 dyn / cm at 20 ° C.
[0077]
【Example】
Examples of the present invention will be described below, but the present invention is not limited to these examples. In the examples, “%” means absolute dry weight% unless otherwise specified.
[0078]
  Example 1
  18% aqueous solution A1 (pH = 2.5, containing 3% by weight of ethanol) of vapor-phase process silica (Nippon Aerosil Kogyo Co., Ltd .: A200) having an average particle size of primary particles uniformly dispersed in advance of about 0.012 μm ) 4500 ml of an aqueous solution C1 (pH = 2.5, Sannobuco) containing 12% by weight of exemplary cationic polymer P-1 (average molecular weight = about 25,000), 3% by weight of n-propanol, and 1% by weight of ethanol It was added to 1000 ml (containing 0.2 g of antifoaming agent SN381) with stirring at room temperature. Next, a 1: 1 mixed aqueous solution of boric acid and borax (borate and borax are respectively50Contains by weightIs done.) 400 ml was slowly added with stirring. Next, 500Kg / cm with a high-pressure homogenizer manufactured by Sanwa Industry Co., Ltd.2A uniform and almost transparent dispersion liquid B1 was obtained by dispersing under the following conditions.
[0079]
Next, the following four types of coating solutions were prepared using the dispersion B1.
Preparation of coating solution for the first layer (amount per liter of coating solution)
620 ml of silica dispersion B1
Fluorescent brightener dispersion (below) 30ml
Titanium oxide dispersion (below) 20ml
Polyvinyl alcohol (Kuraray PVA203) 10% aqueous solution 5ml
270 ml of 5% aqueous solution of polyvinyl alcohol (PVA235 manufactured by Kuraray Co., Ltd.)
Latex dispersion (AE803, Showa Polymer Industries Co., Ltd.) 30ml
Pure water (total volume is 1000ml)
[0080]
Second layer coating solution (amount per liter of coating solution)
Silica dispersion B1 640ml
Fluorescent brightener dispersion (below) 25ml
Polyvinyl alcohol (Kuraray PVA203) 10% aqueous solution 5ml
270 ml of 5% aqueous solution of polyvinyl alcohol (PVA235 manufactured by Kuraray Co., Ltd.)
Latex dispersion (AE803, Showa Polymer Industries Co., Ltd.) 30ml
Pure water (total volume is 1000ml)
[0081]
Third layer coating solution (amount per liter of coating solution)
Silica dispersion B1 650ml
Optical brightener dispersion (below) 20ml
Polyvinyl alcohol (Kuraray PVA203) 10% aqueous solution 5ml
270 ml of 5% aqueous solution of polyvinyl alcohol (PVA235 manufactured by Kuraray Co., Ltd.)
Latex dispersion (AE803, Showa Polymer Industries Co., Ltd.) 15ml
Pure water (total volume is 1000ml)
[0082]
[0083]
Optical brightener dispersion: 100% oil-treated optical brightener (UVITEX-OB) manufactured by Ciba Geigy in 100 ml of 3% acid-treated gelatin aqueous solution (containing 4 g of saponin and 2 g of cationic polymer P-9) A solution obtained by heating and dissolving 6 g and 12 g of diisodecyl phthalate in 25 ml of ethyl acetate is added, emulsified and dispersed with an ultrasonic homogenizer, and the whole amount is made up to 140 ml with pure water.
Titanium oxide dispersion: A dispersion containing 40% by weight of titanium oxide (W10) manufactured by Ishihara Sangyo Co., Ltd.
The viscosity of each coating solution was 30 to 40 cp at 40 ° C. and 10,000 to 20,000 at 15 ° C.
[0084]
The coating solution obtained as described above was 170 g / m.2A paper support coated with polyethylene on both sides of the base paper (240 μm thick, containing 6 wt% anatase-type titanium dioxide in a polyethylene layer with a thickness of about 35 μm on the recording surface side, and a polyethylene layer with a thickness of about 30 μm on the back) Upper recording surface side (75 ° glossiness of support is 32%, gelatin about 0.1 g / m2Each layer was applied to the first layer (50 μm), the second layer (50 μm), the third layer (50 μm), and the fourth layer (50 μm) in this order. The inside of parenthesis showed each wet film thickness, and the 1st layer-the 4th layer were applied simultaneously.
[0085]
Each coating solution is applied with a four-layer slide hopper at 40 ° C, cooled for 20 seconds in a cooling zone maintained at 0 ° C immediately after coating, and then subjected to air at 20 to 30 ° C for 60 seconds and 45 ° C. For 60 seconds and 50 ° C. for 60 seconds to obtain recording paper-1 of the present invention.
The resulting recording paper was then stored at 35 ° C. for 2 days.
[0086]
Next, in the recording paper-1, the cationic polymer is changed as shown in Table 1, and the dispersions B2 to B10 are prepared in the same manner as the dispersion B1. It was made in the same manner as -1.
[0087]
The following items were evaluated for the obtained inkjet recording paper.
(1) Image bleeding: M, C, and K lines were printed with a width of about 0.3 mm using an ink jet printer PM750C manufactured by Seiko Epson Corporation, and after 10 minutes from printing, they were placed in a clear file and stored for 30 days. .
After storage, the line width of each line was measured with a microdensitometer to determine the line width spread ratio (ratio of the line width after storage to the original line width).
[0088]
(2) Light resistance: Using the ink jet printer used in (1), a magenta image was formed on each recording paper, and this was irradiated with light with a xenon fade meter for 200 hours to examine the residual ratio of density after light irradiation. It was. The obtained results are shown in Table 1.
[0089]
(3) Glossiness: 75 degree specular glossiness was measured with a variable angle photometer (VGS-1001DP) manufactured by Nippon Denshoku Industries Co., Ltd.
[0090]
[Table 1]
[0091]
Embedded image
[0092]
From the results shown in Table 1, it can be seen that the recording papers -1 to 6 of the present invention all have little bleeding even when stored in a clear file after printing, and exhibit good light resistance.
On the other hand, since the average molecular weight of the recording paper-7 exceeds 100,000, the glossiness decreases, and the recording paper-8 using the comparative cationic polymer RP1 has good light resistance but poor image bleeding. . Further, the recording papers 9 and 10 using the comparative cationic polymers RP2 and RP3 have good image bleeding but are inferior in light resistance to the present invention.
[0093]
【The invention's effect】
According to the present invention, it is possible to obtain an ink jet recording sheet with improved image bleeding even when stored in a high-humidity state after printing or when stored in an overlapping manner.

Claims (1)

  1. A hydrophilic binder on the support, inorganic fine particles having an average primary particle size of 30 nm or less, and a number average molecular weight represented by the following general formula (1) (converted to a polystyrene value determined from gel permeation chromatography) An ink-absorbing layer containing cationic composite particles composed of a water-soluble cationic polymer having a molecular weight of 2000 to 100,000.
    In the formula, R and R ′ represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R 1 , R 2 , R 3 , R 1 ′, R 2 ′ and R 3 ′ each represent an alkyl group. A represents -COO- or -CONH-, and J represents a single bond or -CONH- . X 1 - and X 2 - represents an anion group. Q represents a repeating unit derived from a monomer having an ethylenically unsaturated group. Q includes a case where two or more monomers are copolymerized. x is 10 to 95 mol%, y is 5 to 90 mol%, and z is 0 to 60 mol%. m represents a positive number from 1 to 6.
JP17812798A 1998-06-10 1998-06-10 Inkjet recording paper Expired - Fee Related JP3747635B2 (en)

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US6919109B2 (en) 2002-04-01 2005-07-19 Fuji Photo Film Co., Ltd. Fine particle dispersion, coating solution for accepting layer for coloring agent for ink-jet recording sheet, ink-jet recording sheet using the dispersion, and method for producing fine particle dispersion
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