JP2002264464A - Method for manufacturing ink jet recording sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing an ink jet recording sheet having high gloss, good surface quality, and excellent preservability of water resistance, ozone resistance, light resistance and the like of a recorded image or character. SOLUTION: The method for manufacturing the ink jet recording sheet comprises the steps of fixing a pigment to an ink acceptive layer provided on a support, forming the image, then adhering clear polymer particles charged in the presence of an electric field on the ink acceptive layer, melting the particles so as to form a continuous polymer layer on the ink acceptive layer with the clear polymer particles. Thus, the ink jet recording sheet having the excellent preservability can be formed.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an ink jet recording sheet, and more particularly, to a method for producing an image or character having high gloss and good surface quality, and having high water resistance and ozone resistance. And a method for producing an ink jet recording sheet having good storage stability such as light resistance.

[0002]

2. Description of the Related Art Ink jet recording systems are based on various operating principles typified by a deflection system, a cavity system, a thermojet system, a bubble jet system, a thermal ink jet system, a slit jet system and a spark jet system. It is used to record images and characters by flying fine ink droplets and attaching them to an ink jet recording sheet such as paper. However, high speed, low noise, easy multicoloring, and flexibility in recording patterns are achieved. It is advantageous in that it is large and does not require development-fixing, and is rapidly spreading in various applications as a recording device for various graphics including Chinese characters and color images. Furthermore, images formed by an inkjet method using multicolor inks containing dyes such as yellow, magenta, cyan, and black, respectively, are inferior to multicolor printing by a plate-making method and printing by a color photographic method. It is possible to obtain no recorded images. Further, in applications requiring a small number of copies, it is being widely applied to the field of full-color image recording because it is less expensive than development by silver halide photography.

An ink jet recording sheet used in such an ink jet recording method includes a general paper type such as high-quality paper and coated paper used for ordinary printing and writing, and an overhead projector (used for presentations at conferences and conferences). Transparent or translucent film types such as OHP) and backlight applications are known.

[0004] The ink used in such an ink jet recording system is prepared by dissolving various water-soluble dyes in an aqueous ink, that is, water or a mixed solvent of water and a hydrophilic solvent, and adding various additives as necessary. Most of the additives are added. Aqueous inks have a vivid and bright color tone after printing, high contrast of ink dots, easy adjustment of ink viscosity, relatively high density dissolution, and low clogging of head nozzles It has such advantages.

However, there is a drawback that the storage stability of the image area such as water resistance, ozone resistance and light resistance is poor.

[0006] As the ink receiving layer used in the ink jet recording sheet, for example, synthetic amorphous silica or a salt thereof, or a mixture thereof (JP-A-57-15778).
No. 6) has been proposed, but such an ink-receiving layer is excellent in ink absorbency, but has high opacity and is mat-like, so that it has a transparent or opaque film type. It cannot be applied to so-called transmission materials or high-gloss reflection materials, and the support itself is inferior in ink absorbency as compared with paper. Therefore, a more careful application of an ink receiving layer is required.

[0007] In view of such circumstances, as an ink receiving layer for a transmission material, for example, JP-A-1-97678, JP-A-2-276670, and JP-A-3-215082 mainly use inorganic ultrafine particles. By doing so, an ink receiving layer that is excellent in transparency and excellent in glossiness and ink absorption has been proposed.

Examples of the inorganic ultrafine particles include spherical, beaded, and cationically modified colloidal silica, silica synthesized by a gas phase method, amorphous, boehmite, pseudoboehmite and other alumina hydrates, and silica / alumina hybrids. Various things such as sols and smectite clays are known.

However, disadvantages of such inorganic ultrafine particles include water resistance, fading of the dye due to ozone, light and the like, and poor storage stability such as ozone resistance and light resistance. The problem had not yet been resolved.

[0010] On the other hand, ink jet recording sheets have been diversified in use, and are used for posters and POP arts, and are provided with an adhesive layer on the back surface and are tack-processed, and are used for price display labels and product display (bar code) display. Increasingly, it is used as a label such as a label for quality, a label for quality display, a label for weighing display, and a label for advertising (such as a sticker). In particular, a bar code label can make use of the high resolution of ink jet recording, and an advertisement label can be suitably used as a good advertisement medium because it has excellent sharpness and color. Application to these is at the level of a personal computer, and it is possible to easily obtain images with excellent image reproducibility and color reproducibility such as sharpness and color. I have. In particular, by tack processing, it adheres well to a wide range of adherends and it is easy to attach, so it can be used with a sheet that has been provided with heat-sensitive properties, magnetic properties, offset printing suitability via an adhesive layer on the other surface It is also possible to combine them into a composite function. In these applications, gloss, water resistance, ozone resistance,
Needless to say, preservability such as light resistance is more important.

In response to such a demand, Japanese Patent Application Laid-Open No. 7-2373
No. 48, JP-A-8-142497, and the like disclose a technique in which a dye is fixed and recorded on an ink receiving layer, and then a polymer latex is applied, dried, and covered with a transparent polymer film. In this method, the ink jet recording sheet is not unnecessarily thick or costly unlike the case where a protective layer is provided by laminating after fixing recording. When a coating is formed by applying a high molecular compound of an aqueous solvent after recording, there is a problem that the dye is diffused together with the aqueous solvent and image bleeding occurs with the lapse of time. When the high molecular compound was used, it was not preferable from the viewpoint of safety and environment.

Further, regardless of the aqueous solvent or the organic solvent, application of the protective layer using such a solvent has a problem that handling is troublesome and burden of drying the solvent is required.

[0013]

SUMMARY OF THE INVENTION The present invention is directed to a continuous polymer layer on an imaged ink-receiving layer by a simple technique that is easily applied and provides a relatively thin protective layer (continuous polymer layer). Is provided. In particular, regardless of the aqueous solvent or the organic solvent, the continuous polymer layer is formed by a simple method without the burden of solvent drying in that the solvent is not used to form the continuous polymer layer, and the recorded image and There is an advantage that it is possible to provide a method for producing an ink jet recording sheet having good water resistance, ozone resistance, light resistance and the like of characters.

[0014]

Means for Solving the Problems After an image is formed by fixing a dye to an ink receiving layer provided on a support, charged clear polymer particles are adhered to the ink receiving layer in the presence of an electric field. By melting the clear polymer particles so that the clear polymer particles form a continuous polymer layer on the ink receiving layer, water resistance of recorded images and characters, ozone resistance, good light resistance and the like A method for manufacturing an ink jet recording sheet can be provided.

In particular, since the ink receiving layer is composed of inorganic ultrafine particles, a hydrophilic binder and a cationic dye fixing agent, an ink jet recording sheet having high gloss, good water resistance, ozone resistance, light resistance and the like can be obtained. The manufacturing method could be provided.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The present invention provides an ink receiving layer provided on a support, after fixing a dye to form an image, adhering charged clear polymer particles in the presence of an electric field on the ink receiving layer,
A method for producing an ink jet recording sheet comprising a step of melting the clear polymer particles so that the clear polymer particles form a continuous polymer layer on the ink receiving layer,
In particular, the ink receiving layer is composed of inorganic ultrafine particles, a hydrophilic binder, and a cationic dye fixing agent, so that it has high gloss and good surface quality, and has water resistance, ozone resistance, and light resistance of recorded images and characters. The present invention provides a method for producing an ink jet recording sheet having good storage stability.

The present invention comprises two steps: 1) application of the clear polymer particles to the surface of the ink receiving layer, and 2) melting of the clear polymer particles to the surface.

Applying electrostatically charged particles to the surface of the imaged ink receiving layer can be accomplished in a number of different ways. For example, a relatively insulating ink receiving layer can be placed in an electric field formed between a high voltage corona wire and a ground plane to accumulate surface charges on the ink receiving layer. When the oppositely charged clear polymer particles are brought into contact with the charged surface, the particles adhere.

An alternative to attracting the clear polymer particles to the surface of the ink receiving layer is to apply a bias between the charging roller and the particle counter electrode on the opposite side of the ink receiving layer to which the particles are applied (if present). A magnetic brush toning device formed therebetween is used. The electric field is adjusted so that the particles are driven off the magnetic brush and attracted to the surface of the ink receiving layer.

Another method of depositing the clear polymer particles on the surface of the ink receiving layer is to electrostatically attract the particles from a magnetic brush toning device to a relatively conductive intermediate transfer roller and bias the roller. And establishing an electrostatic transfer field that drives the adhered particles from the intermediate roller to the surface of the ink receiving layer. The particles can be charged, for example, by mixing with a magnetic carrier (eg, iron particles) in a mixing chamber. The charge level and polarity of the particles can be adjusted by adding a charge control agent to the particles or by polymer coating of a magnetic carrier.

The clear polymer particles are applied at a rate that provides a continuous coating of the desired thickness on the ink receiving layer. The preferred thickness is in the range from 0.2 to 50 μm.
A particularly preferred thickness is in the range of 1 to 10 μm. The lower limit of the thickness of the continuous polymer layer formed by the clear polymer particles depends on the roughness of the surface to which the particles are applied. A rougher surface requires a thicker coating. The upper limit of the overcoat thickness depends on the electric field required to form the coating.

After applying the clear polymer particles to the surface of the ink receiving layer, the particles are heated and / or melted under pressure to form a continuous polymer layer on the surface of the ink receiving layer. The melting is preferably performed by bringing a heated melting member (for example, a melting belt or a melting roller) into contact with the surface of the ink receiving layer. Therefore, for example, 100 to 20
A set of heating rollers heated to 0 ° C. has a moving speed of 0.0
The ink is melted by passing through the ink receiving layer at a pressure of 0.5 to 0.50 m / sec and a pressure of 5 to 15 MPa.

The clear polymer particles selected in the present invention are preferably compatible with the hydrophilicity of the ink receiving layer, and are preferably those that easily adhere. It is within the scope of one of ordinary skill in the art to select the appropriate particles in routine screening. Due to the vulnerability of the ink receiving layer to which the particles are applied, the particles should have a glass transition temperature Tg in the range of 45-80C, preferably 55-65C.

Examples of the clear polymer particles used in the present invention include polyvinyl chloride, polyvinylidene chloride, poly (vinyl chloride-co-vinylidene chloride), chlorinated polypropylene, poly (vinyl chloride-co-vinyl acetate), and poly (vinyl chloride-co-vinyl acetate). (Vinyl chloride-co-vinyl acetate-co-maleic anhydride), ethyl cellulose, nitrocellulose, polyacrylates, linseed oil-modified alkyd resin, rosin-modified alkyd resin, phenol-modified alkyd resin, phenolic resin, polyester , Polyvinyl butyral, polyisocyanate resin, polyurethane, polyvinyl acetate, polyamide, chroman resin, dammar resin, ketone resin, maleic acid resin, vinyl polymer (for example,
Polystyrene and polyvinyl toluene or copolymer of methacrylate or acrylate and vinyl polymer), poly (tetrafluoroethylene-hexafluoropropylene), low molecular weight polyethylene, phenol-modified pentaerythritol esters, poly (styrene-co-indene-co-acrylonitrile) ), Poly (styrene-co-indene), poly (styrene-co-acrylonitrile), poly (styrene-co-butadiene), polystearyl methacrylate containing polymethyl methacrylate,
It can be selected from among copolymers of siloxane and polyalkene. These polymers may be used alone or in combination. In a preferred embodiment of the invention, the particles comprise a polyester or poly (styrene-co-butyl acrylate). Preferred polyesters are based on ethoxylated and / or propoxylated bisphenol A and one or more of terephthalic acid, dodecenylsuccinic acid and fumaric acid.

To increase the abrasion resistance of the continuous polymer layer, a crosslinked or branched polymer may be used. For example, poly (styrene-co-indene-co-divinylbenzene), poly (styrene-co-acrylonitrile-co-divinylbenzene) or poly (styrene-
(Co-butadiene-co-divinylbenzene) can be used.

The clear polymer particles should be clear, ie, transparent, and are preferably colorless. However, as long as the image is visible through the continuous polymer layer, it is particularly conceivable that the particles have a certain color for the purpose of color correction or for a particular effect. Therefore, a pigment that exhibits a color can be incorporated into the particles. In addition, additives that impart the desired properties to the continuous polymer layer can be incorporated into the particles. For example, a UV absorber can be incorporated into the particles to make the continuous polymer layer UV absorbing and protect the image from UV discoloration.

[0027] In addition to the clear polymer particles that form the continuous polymer layer, other particles that change the surface properties of the ink receiving layer that are transferred to the ink receiving layer surface and incorporated into the continuous polymer layer can be combined. Such particles are solid and non-melting under the conditions in which the clear polymer particles melt, and include inorganic particles such as silica and organic particles such as methyl methacrylate beads and do not melt during the melting process. To give the continuous polymer layer a surface roughness. When mixed with the clear polymer particles, such particles may be mixed up to 80% by weight of the clear polymer particles.
% By weight.

The surface properties of this continuous polymer layer depend in large part on the physical properties of the polymer forming the clear polymer particles and the presence or absence of solid non-melting particles. However, the surface properties of the continuous polymer layer can be varied depending on the conditions under which this surface is melted. For example, the surface properties of the fused member used to fuse the particles to form a continuous polymer layer can be selected to provide the desired smoothness, texture, or pattern to the element surface. Thus, a high smoothness fusing member provides a glossy surface to the imaged ink receiving layer, a textured fusing member provides a matte or textured surface to the ink receiving layer, and a patterned fusing member provides the ink receiving layer surface. Pattern.

A contemplated method for use in the process of the present invention is to coat the entire surface of the imaged ink-receiving layer with a continuous polymer layer, but to provide the described areas on the ink-receiving layer surface. It is also particularly conceivable to apply the clear polymer particles only to discrete areas on the surface to give a specific effect.

The inorganic ultrafine particles in the ink jet recording sheet of the present invention include, for example, JP-A-1-97678, JP-A-2-275510, and 3-281383.
JP-A-3-285814, JP-A-3-28581
No. 5, No. 4-92183, No. 4-26718
Pseudo-boehmite sol proposed in JP-A Nos. 0, 4-275917, and the like, JP-A-60-219083, JP-A-61-19389, and JP-A-61-188183.
JP-A-63-178074, JP-A-5-51
No. 470, for example, colloidal silica described in JP-B-4-19037, JP-A-62-28.
No. 6787, a silica / alumina hybrid sol, and other smectite clays such as hectite and montmorillonite (JP-A-7-81210).
Publication), zirconia sol, chromia sol, yttria sol, ceria sol, iron oxide sol, zircon sol, antimony oxide sol, and the like, and commercially available inorganic ultrafine particles can be suitably used.

Particularly, from the viewpoint of glossiness, alumina sol such as pseudo-boehmite which is fine inorganic ultrafine particles or fumed silica can be preferably used.

In the above description, the average particle diameter of the fine particles is determined by observing the cross section or surface of the particles themselves or the ink absorbing layer with an electron microscope, determining the particle diameter of 100 arbitrary particles, and calculating the simple average value (number average). Desired. Here, each particle size is represented by a diameter assuming a circle equal to the projected area.

The binder used in combination with the inorganic ultrafine particles in the ink receiving layer of the ink jet recording sheet of the present invention is preferably a binder made of a water-soluble polymer. In the case of a cationic emulsion, especially when recording with an aqueous ink, compatibility with the ink is poor, which causes a decrease in print density. As the binder used in the present invention,
Gelatin or a gelatin derivative, polyvinylpyrrolidone,
Pullulan, polyvinyl alcohol or derivatives thereof, polyethylene glycol, carboxymethylcellulose, hydroxyethylcellulose, dextran, dextrin, polyacrylic acid and its salts, agar, κ-carrageenan, λ-carrageenan, ι-carrageenan, xanthen gum, locust bean gum, alginic acid , Gum arabic, polyalkylene oxide-based copolymerizable polymers described in JP-A-7-195826 and JP-A-7-9957,
Water-soluble polyvinyl butyral or JP-A-62-2
No. 45260, a vinyl monomer having a carboxyl group or a sulfonic acid group alone, or a polymer such as a copolymer having these vinyl monomers repeatedly. These binders may be used alone or in combination of two or more.

Above all, it is preferable to contain polyvinyl alcohol from the viewpoints of hygroscopicity of the film, stickiness under high humidity, and less bleeding of the dye during ink jet recording.

The polyvinyl alcohol includes cation-modified, nonionic-modified and anion-modified polyvinyl alcohols. The average degree of polymerization of polyvinyl alcohol is preferably from 500 to 5000 from the viewpoint of film forming properties, and particularly preferably the average degree of polymerization is 1,000 or more.

The degree of saponification of polyvinyl alcohol is 70 to
100% is preferred, and 80-100% is particularly preferred. As the cation-modified polyvinyl alcohol, for example, as described in JP-A-61-10483, a tertiary amino group or a quaternary ammonium group is contained in the main chain or side chain of the polyvinyl alcohol. Polyvinyl alcohol, which is 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-acrylamido-2,2-dimethylethyl) ammonium chloride and trimethyl- (3-acrylamido-3,3-dimethylpropyl). Ammonium chloride, N-vinylimidazole, N-vinyl-2-methylimidazole, N
-(3-dimethylaminopropyl) methacrylamide,
Examples thereof include hydroxylethyltrimethylammonium chloride, trimethyl- (methacrylamidopropyl) ammonium chloride, and N- (1,1-dimethyl-3-dimethylaminopropyl) acrylamide.

The ratio of the cation-modified group-containing monomer in the cation-modified polyvinyl alcohol is preferably 0.1 to 10 mol%, particularly preferably 0.2 to 10 mol%, based on vinyl acetate.
~ 5 mol%.

The anion-modified polyvinyl alcohol is, for example, polyvinyl alcohol having an anionic group as described in JP-A-1-2060888, JP-A-61-237681, and JP-A-63-30797.
No. 9, a copolymer of vinyl alcohol and a vinyl compound having a water-soluble group, and a modified polyvinyl alcohol having a water-soluble group, as described in JP-A-7-285265 Is mentioned.

Examples of the nonion-modified polyvinyl alcohol include polyvinyl alcohol derivatives having a polyalkylene oxide group added to a part of vinyl alcohol as described in JP-A-7-9758, and JP-A-8-25795. And a block copolymer of a vinyl compound having a hydrophobic group and vinyl alcohol described in Japanese Patent Application Laid-Open Publication No. H11-157,086.

In the ink jet recording sheet of the present invention, the weight ratio of the inorganic ultrafine particles contained in the ink receiving layer to the binder is 4 to 20 times. When the ratio is less than 4 times, the ink absorbency decreases. When the ratio exceeds 20 times, the brittleness of the film is greatly deteriorated, and high-quality ink jet recording cannot be performed.

In the present invention, a hardener can be used in the ink receiving layer for the purpose of improving water resistance and dot reproducibility. Specific examples of hardeners include formaldehyde, aldehyde compounds of glutaraldehyde,
Diacetyl, ketone compound of chloropentanedione, bis (2-chloroethylurea), 2-hydroxy-4,6
Dichloro-1,3,5-triazine, U.S. Pat.
No. 88,775, compounds having a reactive halogen, divinyl sulfone, compounds having a reactive olefin described in US Pat. No. 3,635,718, US Pat.
No. 732,316, N-methylol compounds, isocyanates described in U.S. Pat. No. 3,103,437, aziridine compounds described in U.S. Pat. Nos. 3,017,280 and 2,983,611, U.S. Pat. , 100,704
Carbodiimide compounds described in U.S. Pat.
No. 1,537, such as an epoxy compound, a halogen carboxaldehyde of mucochloric acid, a dioxane derivative of dihydroxydioxane, an inorganic hardener of chromium alum, potassium alum, zirconium sulfate, and the like. They can be used in combination. The amount of the hardener added is 100 g of the binder that constitutes the ink receiving amount.
The amount is preferably 0.01 g to 10 g, more preferably 0.1 to 5 g.

The cationic dye fixing agent used in the ink receiving layer of the ink jet recording sheet of the present invention includes secondary amines, tertiary amines, quaternary ammonium salts, and the like. To form an insoluble salt with the water-soluble direct dye, which is the dye component of the aqueous ink in the layer, and the sulfonic acid group, carboxyl group, etc. in the water-soluble acid dye, the dye is captured in the ink receiving layer, and the color By the improvement and the formation of insoluble salts, it is possible to suppress the flow and bleeding of the ink due to the dripping of water and the absorption of moisture, thereby improving the water resistance.

The ink receiving layer may be formed as a single layer,
It is also possible to apply a certain amount of coating in several times. As a method of applying the ink receiving layer by dividing it into several times, there may be mentioned a method of applying by drying each layer and a method of applying a plurality of layers simultaneously by wet-on-wet. When the ink receiving layer is applied in several divided portions, the cationic dye fixing agent is disclosed in JP-A-6-183131.
Addition to the ink receiving layer close to the support as disclosed in JP-A-6-183134, or addition to the outermost layer farther from the support as disclosed in JP-A-9-263441, of course, may be performed in each ink receiving layer. You can do it.

In the ink receiving layer of the present invention, other additives such as a pigment dispersant, a thickener, a flow improver, a defoamer, a foam inhibitor, a release agent, a foaming agent, a penetrant, A coloring dye, a coloring pigment, a fluorescent whitening agent, an ultraviolet absorber, an antiseptic, an antibacterial agent, a waterproofing agent, a wet paper strength enhancer, a dry paper strength enhancer and an antioxidant do not impair the object of the present invention. It can be appropriately added within the range.

As the support in the present invention, for example,
Biaxially stretched synthetic resin films such as polyethylene terephthalate, polypropylene, polyethylene, polyester, polycarbonate, norbornene, vinylon, polyvinyl alcohol, nylon, etc. and translucent and opaque materials that contain pigments, foaming agents, etc. to reduce transparency 2
Axial stretched synthetic resin film, chemical pulp such as LBKP, NBKP, GP, PGW, RMP, TMP, CTM
Based on mechanical pulp such as P, CMP and CGP, wood pulp such as waste paper pulp such as DIP, and conventionally known pigments as main components, binders and sizing agents, fixing agents, yield improvers, cationizing agents, paper strength agents, etc. 1 of various additives
The size press and anchor coat layer with starch, polyvinyl alcohol, etc. are provided on the base paper manufactured by various devices such as fourdrinier paper machine, circular net paper machine, twin wire paper machine, etc. Base paper, coated paper such as art paper, coated paper, cast-coated paper, etc. provided with a coating layer thereon, and a calendering machine such as a machine calender, TG calender, soft calender, etc. Such base paper, high-density, low-density polyethylene, polypropylene, resin-coated paper coated with polyester, etc. on both sides or one side of the coated paper by melt extrusion, or the surface of these supports, corona discharge treatment, flame treatment, It is possible to suitably use those having improved adhesion such as plasma treatment and anchor layer coating treatment. The basis weight of the support is usually 50 to 300
g / m ² .

As a method for providing the ink receiving layer on the support in the present invention, a hydrophilic organic solvent such as water or alcohol, or a mixed solvent thereof may be used, for example, using a conventionally known air knife coater, curtain coater, or the like. The coating can be performed on the support by various devices such as a die coater, a blade coater, a gate roll coater, a bar coater, a rod coater, a roll coater, a bill blade coater, a short dwell blade coater, and a size press. After the application of the ink receiving layer, a smoothing treatment can be performed using a calender such as a machine calender, a TG calender, a super calender, and a soft calender.

The coating amount of the ink receiving layer of the present invention is not particularly limited, but is preferably 1 to 50 g / m ² . 1g coating amount
/ M ² is not preferable because sufficient print density and ink absorbency cannot be obtained, and the coating amount is 50 g / m ^2.
Exceeding the range is not preferred because the curl properties of the recording sheet may deteriorate.

A back coat layer may be provided on the opposite surface of the ink receiving layer with the support interposed therebetween in order to impart curl aptitude.

The ink referred to in the present invention is a recording liquid comprising the following dye, solvent, and other additives. As the dye, for example, good coloring properties, clearness, stability, and the like can be used.
CIDirect Yellow 12, CIDirect Yellow 24, CIDi
rect Yellow 26, CIDirectYellow 44, CIDirect Ye
llow 86, CIDirect Yellow 98, CIDirect Yellow 1
00, CIDirect Yellow 142, CIDirect red 1, CID
irect red 4, CIDirect red 17, CIDirect red 2
8, CIDirect red 83, CIDirect Orenge 34, CIDi
rect Orenge 39, CIDirect Orenge 44, CIDirect O
renge 46, CIDirect Orenge 60, CIDirect Violet
47, CIDirect Violet 48, CIDirectBlue 6, CIDi
rect Blue 22, CIDirect Blue 25, CIDirect Blue
71, CIDirect Blue 86, CIDirect Blue 90, CIDi
rect Blue 106, CIDirect Blue 199, CIDirect Bla
ck 17, CIDirect Black 19, CIDirect Black 32,
CIDirect Black 51, CIDirect Black 62, CIDire
ct Black 71, CIDirectBlack 108, CIDirect Black
146, direct dyes such as CIDirect Black 154, CIAcid
Yellow 11, CIAcid Yellow 17, CIAcid Yellow 2
3, CIAcid Yellow25, CIAcid Yellow 29, CIAcid
Yellow 42, CIAcid Yellow 49, CIAcid Yellow 6
1, CIAcid Yellow 71, CIAcid red1, CIAcid red
6, CIAcidred 8, CIAcid red 32, CIAcid red 3
7, CIAcidred 51, CIAcid red 52, CIAcid red 8
0, CIAcid red 85, CIAcid red 87, CIAcid red
92, CIAcid red 94, CIAcid red 115, CIAcid re
d 180, CIAcid red 256, CIAcid red 317, CIAci
d red 315, CIAcid Orenge 7, CIAcidOrenge 19,
CIAcid Violet 49, CIAcid Blue 9, CIAcid Blue
22, CIAcid Blue 40, CIAcid Blue 59, CIAcid
Blue 93, CIAcid Blue 102, CIAcid Blue104, CI
Acid Blue 113, CIAcid Blue 117, CIAcid Blue 12
0, CIAcid Blue167, CIAcid Blue 229, CIAcid B
lue 234, CIAcid Blue 254, CIAcidBlack 2, CIA
cid Black 7, CIAcid Black 24, CIAcid Black 2
6, CIAcid Black31, CIAcid Black 52, CIAcid B
Acid dyes such as lack 63, CIAcid Black 112 and CIAcid Black 118, as well as water-soluble dyes such as basic dyes, reactive dyes and food colorings, and pigments such as carbon black can be used.

As a solvent for the ink, water and various water-soluble organic solvents such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl Alkyl alcohols having 1 to 4 carbon atoms such as alcohol; amides such as dimethylformamide and dimethylacetamide; ketones or ketone alcohols such as acetone and diacetone alcohol; ethers such as tetrahydrofuran and dioxane; polyethylene glycol and polypropylene glycol Polyalkylene glycols; ethylene glycol, propylene glycol, butylene glycol, triethylene glycol, 1, 2, 6
-Alkylene glycols having 2 to 6 alkylene groups such as hexanetriol, thiodiglycol, hexylene glycol, diethylene glycol; and many such as glycerin, ethylene glycol methyl ether, diethylene glycol methyl (or ethyl) ether, and triethylene glycol monomethyl ether. And lower alkyl ethers of polyhydric alcohols.

Among the above water-soluble organic solvents, polyhydric alcohols such as diethylene glycol and lower alkyl ethers of polyhydric alcohols such as triethylene glycol monomethyl ether and triethylene glycol monoethyl ether are particularly preferable.

In addition to the above-mentioned water-soluble organic solvents, non-water-soluble insulating solvents having excellent safety such as flammability and toxicity represented by high-boiling aliphatic hydrocarbons may be used. Organic pigments and the like are often used as pigments.

In the recording on the ink receiving layer of the ink jet recording sheet in the present invention, any recording sheet using a liquid ink at the time of recording may be used.

The common feature of these recording sheets is that the ink is in a liquid state at the time of recording. The liquid ink permeates or diffuses in the depth direction or the horizontal direction of the ink receiving layer of the recording sheet until it is cured, fixed or fixed. The above-described recording sheets require absorptivity according to each system, and the inkjet recording sheet of the present invention may be used as the above-described various recording tack sheets.

Other additives to be added to the ink include, for example, a pH regulator, a sequestering agent, an antioxidant,
Examples include a fungicide, a viscosity modifier, a surface tension modifier, a wetting agent, a surfactant, and a rust inhibitor.

[0057]

EXAMPLES The present invention will be described below with reference to examples of the present invention, but the present invention is not limited to these examples. Further, “parts” and “%” shown in the examples are parts by weight and% by weight unless otherwise specified.

[Evaluation Method] (1) Gloss The surface of each ink jet recording sheet was measured according to JIS-
The 60 degree specular gloss specified in Z-8741 was measured. A: 81 ゜ or more B: 71１〜80 ゜ C: 61 ゜ 70５ D: 51 ゜ 60 ゜ E: 50 ゜ or less

(2) Water resistance An ink jet printer (MJ-700V2 manufactured by EPSON) is provided on the ink receiving layer of each ink jet recording sheet.
After performing solid printing of black ink in C), using an ink jet recording sheet provided with a continuous polymer layer by melting the clear polymer particles, 1 ml of water was dropped using a syringe at the boundary between the white paper and the printing, and then 24 Left for hours.
The degree of bleeding after standing was visually evaluated. Practically, water resistance is a problem for C and D. A: No bleeding is observed. B: Very slight bleeding was observed. C: Bleeding occurred, and partial blotting was observed. D: The bleeding was severe, and the entire water drop was stained.

(3) Ozone resistance An ink jet printer (MJ-700V2 manufactured by EPSON) is provided on the ink receiving layer of each ink jet recording sheet.
After performing solid printing with black ink in C), the inkjet recording sheet provided with a continuous polymer layer by melting the clear polymer particles is placed in a glass container having an ozone inlet and an outlet, and an ozonizer OS manufactured by Mitsubishi Electric Corporation is used. -1
Was continuously introduced for 15 minutes. The ozone concentration at this time was about 80 ppm. The color difference of the magenta ink color of these inkjet recording sheets before and after the ozone treatment was measured. The color difference is L ^* a ^* b ^* (CI
Based on the result of measuring the color of the sample before and after light irradiation according to E1976), it can be defined by the following equation (1). The larger the color difference is, the more the color deterioration occurs, and if the color difference is less than 3.0, there is no visually significant difference in color.

[0061]

[Equation 1] ΔE = ｛(△ L^*)^Two+ (△ a^*)^Two+ (△ b^*)^Two｝^1/2  Here, ΔE is the color difference, ΔL^*And △ a^*And △ b^*Is each
L before and after light irradiation^*And a^*And b^*Is the difference.

(4) Lightfastness An ink jet printer (MJ-700V2 manufactured by EPSON) is provided on the ink receiving layer of each ink jet recording sheet.
After performing solid printing of black ink in C), the inkjet recording sheet provided with a continuous polymer layer by melting the clear polymer particles was applied to a black panel temperature of 63 ° C. and a relative temperature of 64 ° C. using a Xenon arc fade meter and Atlas Ci-35f. The color difference of the black ink color before and after the light irradiation for 30 hours in an environment of a humidity of 65% RH was measured. The color difference measurement method is based on the ozone resistance test.

Example 1 As a support, an opaque white polyethylene terephthalate film having a thickness of 100 μm (manufactured by Diafoil Hoechst)
Was applied and dried on a support with an air knife coater so as to have a dry coating amount of 15 g / m ² with a first ink receiving layer coating liquid having the following composition (solid content: 15%). [Coating liquid of first ink receiving layer] Synthetic amorphous silica 100 parts Cationic polyvinyl alcohol 25 parts Cationic dye fixing agent 15 parts

A second ink receiving layer having the following composition was applied on the surface of the first ink receiving layer. [Coating Liquid for Second Ink-Receiving Layer] Gas-Phase Silica 100 parts Cationic Polyvinyl Alcohol 30 parts This composition was prepared at a solid content concentration of 20%, and dried with an air knife coater to obtain a coating amount of 8 g / m2. Coated to ² and dried, so that the coated surface is in contact with the chilled roll,
A calendar treatment was performed under the conditions of a chilled roll surface temperature of 50 ° C. and a linear pressure of 100 kg / cm to obtain a recording sheet of Example 1.

After forming an image on this recording sheet using an ink jet printer (MJ-700V2C, manufactured by EPSON), clear polymer particles are adhered and fused by the following method to form a continuous polymer layer on the ink receiving layer. did.

The imaged ink jet recording sheet was placed in a holder of 800 g of developer containing 10% polyester particles and 90% iron / strontium (6: 1) ceramic magnetic carrier particles to form clear polymer particles. . These particles are KAO Inc. brand name KA
It comprised polyester sold under OM ™. The particles had an average particle size of 10 μm and the carrier had a nominal particle size of 30-50 μm. By rotating the shell magnet, the carrier moved the particles to an offset roller. The inkjet recording sheet was fed between the offset roller and the backing roller at a speed of 8 cm / sec with the emulsion side facing the offset roller. Apply a bias voltage of 2500 volts to the backing roller and apply 1 m
About 8 to 11 g of the particles per ² were transferred. No carrier was detected on the final recording sheet.

The sample with the particles attached was moved through a belt fuser to achieve melting. Image is 1.2MP from 2.6cm pressure roller
through the nip heated to 155 ° C. under the pressure of
Move at cm / sec. As it passed through the nip, the particle-adhered portion of each element was brought into contact with the stainless steel belt and kept in contact for an additional 50 cm when the particles were cooled. The element was cooled while in contact with the belt to reduce offset and provide a high gloss surface. The resulting continuous polymer layer had a thickness of 9 μm.

Example 2 Recording of Example 1 using polymer particles comprising a Picotoner 1221 ™ poly (styrene-cobutyl acrylate) copolymer from Hercules Inc., milled to an average particle size of 10 μm. After recording an image on the ink receiving layer formed in the same manner as the sheet, a continuous polymer layer was formed in the same manner as in Example 1.

Example 3 A polymer particle comprising propoxylated bisphenol A
After recording an image on the ink receiving layer prepared in the same manner as the recording sheet of Example 1, using particles comprising polyester based on one or more of terephthalic acid, dodecenyl succinic acid and fumaric acid, In the same manner as in Example 1, a continuous polymer layer was formed.

Example 4 As a support, an opaque white polyethylene terephthalate film having a thickness of 100 μm (manufactured by Diafoil Hoechst)
And using a wire bar to apply an ink receiving layer coating liquid of the following composition using an inorganic pigment so that the dry coating amount is 25 g / m ^2, and drying is performed at a drying temperature of 100 ° C. for 5 minutes. Was. (Ink receiving layer coating liquid formulation) Gas-phase silica 100 parts Polyvinyl pyrrolidone 30 parts Cationic dye fixing agent 15 parts

After an image was formed on the recorded material using an ink jet printer (MJ-700V2C, manufactured by EPSON), a continuous polymer layer was formed in the same manner as in Example 1.

Comparative Example 1 An opaque white polyethylene terephthalate film having a thickness of 100 μm (manufactured by Diafoil Hoechst) was used as a support.
And using a wire bar to apply an ink receiving layer coating liquid of the following composition using an inorganic pigment so that the dry coating amount is 20 g / m ^2, and drying is performed at a drying temperature of 100 ° C. for 5 minutes. Was. (Ink receiving layer coating liquid formulation) Gas-phase silica 100 parts Cationic polyvinyl alcohol 20 parts

After forming an image on this recording sheet using an ink jet printer (MJ-700V2C, manufactured by EPSON), a 10% aqueous solution of polyvinyl alcohol (PVA117, manufactured by Kuraray), which is a water-soluble polymer compound, is brushed. The resultant was applied, dried by heating in an atmosphere of 100 ° C., and a coating of a water-soluble polymer having a thickness of about 4 μm was formed.

Comparative Example 2 A recorded matter of Comparative Example 2 was obtained in the same manner as in Example 1 except that a continuous polymer layer was not provided after forming an image on the ink receiving layer.

The above Examples 1 to 4 and Comparative Example 1
Table 1 collectively shows the evaluation results of the respective ink jet recording sheets of Nos. 1 to 2.

[0076]

[Table 1]

In the present invention, the clear polymer particles are coated with inorganic ultrafine particles to prevent the coloring matter from contacting water, reacting with oxygen, ozone, NOx in the air, or volatilizing, and furthermore, the ultraviolet rays. It has the function of shielding Even when the base material is a material such as paper or cloth that transmits air or the like, the dye is also effective because the dye is more fixed on the clear polymer side of the ink receiving layer. In the ink jet recording sheets of Examples 1 to 4 according to the present invention, since the dye in the ink receiving layer is protected by the coating with the clear polymer, glossiness, surface quality, water resistance, ozone resistance, light resistance, etc. Excellent storage stability.

However, the ink jet recording sheet of Comparative Example 1 was poor in water resistance because the protective film was made of a water-soluble polymer instead of the clear polymer particles. In Comparative Example 2, since no continuous polymer layer was provided, the glossiness was low, and the storability such as water resistance, ozone resistance, and light resistance was extremely poor.

[0079]

According to the production method of the present invention, there is provided an ink jet recording sheet having excellent storage stability such as water resistance, ozone resistance and light resistance, and having storage stability for maintaining high image quality for a long period of time. In particular, it is suitable for recording using aqueous ink. Further, the production method of the present invention also has an effect that preferable glossiness can be imparted to a recorded matter.

Claims (2)

[Claims] 1. An ink receiving layer provided on a support,
After fixing the dye and forming an image, charged clear polymer particles are adhered on the ink receiving layer in the presence of an electric field, and the clear polymer particles are so formed as to form a continuous polymer layer on the ink receiving layer. A method for producing an ink jet recording sheet, comprising a step of melting clear polymer particles. 2. The method for producing an ink jet recording sheet according to claim 1, wherein the ink receiving layer comprises inorganic fine particles, a hydrophilic binder and a cationic dye fixing agent.