JP2002293012A - Ink jet system image recording material and image recording method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ink jet system image recording material, which can be effectively applied to an ink jet printing system and has a high quality and an excellent durability, and an image recording method, by which an image can be produced in a simple process with the image recording material. SOLUTION: This ink jet system image recording material consists of an at least four layer structure of an undercoating layer 12, an ink image accepting layer 14, an image protective layer 16 and an overcoat layer 18 on a support 10 in the order named. The overcoat layer 18 includes an ink transmissible hydrophilic polymer having the film thickness 0.01 times or more and 1.0 time or less as much as that of the image protective layer. The image protective layer preferably has a porous structure made of a thermoplastic resin latex. As the image recording method, ink is adsorbingly fixed to the ink image accepting layer 14 by thermally non-porizing the image protective layer 16 after the ink is printed on the image recording material 70.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image recording material of an ink jet recording system and an image recording method using the image recording material, and more particularly, to a discharge head of a recording head based on image information, for example, image information from a photographic film. The present invention relates to an ink jet type color image recording material for recording an image by attaching recording droplets discharged from an outlet to a material and an image recording method thereof.

[0002]

2. Description of the Related Art High quality, general speed, and low cost of color images in color image formation using silver halide color light-sensitive materials have spread and digitization of image creation has led to electrostatic transfer methods, sublimation thermal transfer methods, and inkjet methods. For example, full-color image creation methods are rapidly spreading. The method using silver halide color photographic material is excellent in image quality such as color reproducibility, image sharpness, image density, glossiness, and image durability, and is one of the goals in the development of the ink jet system in particular. I have.

In the ink jet system, full color conversion is relatively easy by inputting digital information of a color original image, selection of ink type, and the like, and printing noise is relatively low as compared with other systems. However, the ink used contains a relatively large amount of water or a solvent, and the absorption and removal of the droplets, the beading of continuous ejection of fine droplets, the prevention of sharpness deterioration due to bleeding, and the silver salt color Unlike image formation in a film of a material, image formation is performed by ejecting ink containing a dissolved or dispersed dye, and protection of the image and improvement in durability are particularly required.

Conventionally, as a substrate for a recording support, general paper and a sheet further provided with a water-resistant resin layer are used. Examples of such a substrate include, for example, JP-A-59-226.
No. 83, for example. In addition, a resin film, for example, a transparent film such as polyester or cellulose acetate described in JP-A-59-222381, a film filled with a white pigment, or synthetic paper is used. A transparent or opaque substrate described in JP-A-11-5362, which is integrated with a layer provided on the surface thereof, such as ink-absorbing paper or a porous resin film, to improve the ink absorptivity, Through processing, it is used as an oxygen-barrier support.

JP-A-59-222381, JP-A-59-222381
-22683, JP-A-8-2090, JP-A-9-1
04163, JP-A-11-5362, JP-A-2000
-43368, JP-A-2000-43369, etc.
It is described that an ink image receiving layer is provided on a substrate and an image protective layer and the like are provided on the surface thereof. Also, JP-A-7-23
No. 7348, JP-A-9-104163, JP-A-9-9-1
JP-A-56206, JP-A-11-5362 and the like describe that a porous adsorbent is provided as an ink image-receiving layer, which easily permeates ink and which easily permeates and fixes a hydrophilic binder and ink.

Further, JP-A-59-215885 and JP-A-59-103782 disclose a protective layer formed by laminating the surface of an ink image-receiving layer.
JP-A-59076, JP-A-62-56184, and especially JP-A-1-291990 describe that a protective layer is provided on the surface of an ink image-receiving layer by lamination coating, polymer dissolution coating or extrusion. JP-A-7-237348, JP-A-8-2090, and JP-A-2000-43368 also describe a method of forming an image using a porous polymer layer and then performing a heat treatment to provide a protective layer. I have. However, in these methods, the durability of the surface of the recording material before the heat treatment is not sufficient, and improvement in this durability is desired. JP-A-2000-225695
In Japanese Patent Application Laid-Open No. H10-163, a method is described in which a formed image is ejected by droplets to be protected by ink jet and attached to an image forming surface. However, in this method, the method of providing the image protection layer after image formation is not preferable in terms of the number of steps and the manufacturing cost.

[0007]

SUMMARY OF THE INVENTION The object of the present invention can be effectively applied to an ink jet printing system, and
An object of the present invention is to provide an ink jet type image recording material having high quality and excellent durability, and an image recording method capable of forming an image with a simple man-hour using this image recording material.

[0008]

The above-mentioned objects are achieved by the following inventions. <1> An ink jet type image recording material comprising at least a four-layer structure including a support, an undercoat layer, an ink image receiving layer, an image protective layer, and an overcoat layer in this order. <2> The inkjet according to <1>, wherein the overcoat layer contains an ink-permeable hydrophilic polymer, and has a thickness of 0.01 to 1.0 times the thickness of the image protection layer. Image recording material. <3> The image protective layer has a porous resin structure using a thermoplastic resin latex, and the difference between the glass transition temperature of the polymer constituting the thermoplastic resin latex and the minimum film forming temperature (MFT) of the thermoplastic resin latex. Is smaller than 10 ° C., the image recording material of the ink jet system according to <1> or <2>. <4> The image forming layer has a minimum film forming temperature (M
FT), with a monodisperse distribution, ± 2 /
3. The ink-jet image recording material according to any one of <1> to <3>, wherein the material has a porous resin structure using a thermoplastic resin latex containing 90% or more particles in a region of No. 3. . <5> An image recording method using the image recording material according to any one of <1> to <4>. <6> The image recording method according to <5>, wherein the image recording material is subjected to a heat treatment after printing with ink. <7> The image recording method according to <6>, wherein the temperature of the heat treatment is equal to or higher than the minimum film forming temperature (MFT) of the thermoplastic resin latex of the image protective layer.

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The feature of the present invention is to separate the functions by a multilayer structure in order to avoid defects by taking advantage of various elements for obtaining a color image having high quality and excellent durability and weather resistance. Is to do. That is, the present invention comprises at least a four-layer structure including an undercoat layer, an ink image receiving layer, an image protective layer and an overcoat layer on a support in this order. FIG. 1 shows a preferred embodiment of the image recording material of the present invention, wherein 10 is a support, 12 is an undercoat layer, 14
Denotes an ink image recording layer, 16 denotes an image protective layer, 18 denotes an overcoat layer, and 19 denotes a back coat layer.

-Image Recording Material- [Support] As the support in the image recording material of the present invention, any of a transparent support made of a transparent material such as plastic and an opaque support made of an opaque material such as paper is used. it can. In order to take advantage of the transparency of the colorant receiving layer, it is preferable to use a transparent support or a high gloss opaque support.

As a material usable for the transparent support, a material having transparency and a property capable of withstanding radiant heat when used in an OHP or a backlight display is preferable. Examples of the material include polyesters such as polyethylene terephthalate (PET); polysulfone;
Examples thereof include polyphenylene oxide, polyimide, polycarbonate, and polyamide. Among them, polyesters are preferred, and polyethylene terephthalate is particularly preferred. The thickness of the transparent support is not particularly limited, but is preferably 50 to 200 μm from the viewpoint of handleability.

The high gloss opaque support preferably has a glossiness of 40% or more on the surface on which the ink image receiving layer is provided. The glossiness is JIS P-
8142 (Test method for 75-degree specular glossiness of paper and paperboard). In particular,
The following supports are mentioned.

For example, high gloss paper support such as baryta paper used for art paper, coated paper, cast coated paper, silver halide photographic support, etc .; polyesters such as polyethylene terephthalate (PET); nitrocellulose Plastic films such as cellulose esters such as cellulose acetate, cellulose acetate butyrate, etc .; and plastic films such as polysulfone, polyphenylene oxide, polyimide, polycarbonate, polyamide, etc., are made opaque by containing a white pigment or the like (the surface may be calendered). .) A high-gloss film; or a polyolefin coating layer containing or not containing a white pigment is provided on the surface of the various paper supports, the transparent support, or a high-gloss film containing a white pigment or the like. Support. Further, a white pigment-containing foamed polyester film (for example, foamed PET containing polyolefin fine particles and having voids formed by stretching) can also be suitably mentioned.

Further, the support is provided with a corona discharge treatment,
Those subjected to glow discharge treatment, flame treatment, ultraviolet irradiation treatment, or the like may be used.

The polyethylene covering the front and back surfaces of the base paper is mainly made of low-density polyethylene (LDPE) and / or
Alternatively, it is a high-density polyethylene (HDPE), but other LLDPE, polypropylene, or the like can be partially used.

In particular, the polyethylene layer on the side on which the ink image receiving layer is to be formed is formed by adding rutile or anatase type titanium oxide to polyethylene, as widely used in photographic printing paper, to obtain opacity and whiteness. It is preferable to improve the above. Here, the content of titanium oxide is preferably about 3 to 20% by weight with respect to polyethylene, and
3% by weight is more preferred.

The polyethylene-coated paper can be used as a glossy paper, or when a polyethylene is melt-extruded onto the surface of a base paper and coated by a so-called embossing process, a matte surface or the like which can be obtained with ordinary photographic printing paper. Those having a silk surface can also be used.

In the present invention, in order to obtain an image recording material having a quality comparable to that of a silver halide color light-sensitive material, the whiteness and smoothness of a current baryta paper or a WP (a support in which both sides of a base paper are coated with a thermoplastic resin) are used. A high substrate is preferably used. Further, a substrate is preferred in which the support itself becomes oxygen-barrier after image formation.

[Undercoat layer] The undercoat layer is made of a hydrophilic resin such as polyvinyl alcohol or a modified product thereof, gelatin or a modified product thereof having good adhesion between the surface of the support and the ink image receiving layer, and a crosslinking curing agent is used. It is preferable to use a mixture of thermoplastic resin latex and the like. By providing such an undercoat layer, the adhesion between the support and the ink image receiving layer and the water absorption can be enhanced. In the undercoat layer, a white pigment such as barium sulfate, a fluorescent whitening agent, an antioxidant, a light stabilizer and the like can be mixed.

[Ink image receiving layer] A layer having a function of absorbing ink applied by ink jet with little bleeding, adsorbing dye and retaining an image. Inorganic pigments that mainly adsorb dyes, binders that have good ink permeability and do not inhibit pigment adsorption, and thermoplastic resin latex that protects images are used.

As inorganic pigments for adsorbing dyes, silica,
Known materials such as calcium carbonate, calcium sulfate, diatomaceous earth, calcium silicate, colloidal silica, alumina, pseudoboehmite, colloidal alumina and alumina hydrate are used. Particularly, alumina hydrate, silica, colloidal silica and the like are preferable. These inorganic pigments are formed in a void state in the ink image receiving layer, adsorb the dye, and can prevent ink bleeding.

The alumina hydrate can be produced by a known method such as hydrolysis of aluminum alkoxide and hydrolysis of sodium aluminate. The shape is not particularly limited, such as a cilia shape, a needle shape, a plate shape, a spindle shape, and the presence or absence of orientation is not limited. As the alumina hydrate used in the present invention, those commercially available or those processed from their raw materials can be used, and the characteristics of these alumina hydrates are transparency and gloss. It is more preferable that the material has a high dye-fixing property, does not have a crack or the like at the time of film formation, and has a good coating property. Commercially available products include, for example, A
S-2, AS-3, 520 manufactured by Nissan Chemical Industries, and the like. These alumina hydrates are usually fine, having a particle size of 1 μm or less, and have excellent dispersibility, so that a recording medium can have very good smoothness and gloss.

The binder for binding the inorganic pigment can be freely selected from water-soluble polymers. For example, polyvinyl alcohol or a modified product thereof,
Starch or a modified product thereof, gelatin or a modified product thereof, casein or a modified product thereof, gum arabic, cellulose derivatives such as carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, SBR latex, NBR latex, methyl methacrylate-butadiene copolymer, etc. Preferred are a conjugated diene copolymer latex, a functional group-modified polymer latex, a vinyl copolymer latex such as an ethylene vinyl acetate copolymer, polyvinylpyrrolidone, and an acrylate copolymer. These binders can be used alone or in combination of two or more.

The mixing ratio of the inorganic pigment, particularly the alumina hydrate and the binder, is preferably 1: 1 to 35:
1, more preferably from 5: 1 to 30: 1. If the amount of the binder is less than the above range, the mechanical strength of the ink image receiving layer may be insufficient, and cracks and powder fall may occur. By providing an overcoat layer described later in the present invention on the ink image receiving layer, the tendency of cracking and powder drop is reduced. Further, when the mixing ratio of the inorganic pigment, particularly the alumina hydrate and the binder, is larger than the above range, the pore volume is reduced, and the ink absorbency may be reduced.

The coating liquid for forming the ink image receiving layer contains, in addition to alumina hydrate and a binder, if necessary, a dispersant, a thickener, a pH adjuster, a lubricant, a fluidity modifier, It is also possible to add a surfactant, an antifoaming agent, a waterproofing agent, a release agent, a fluorescent whitening agent, an ultraviolet absorber, an antioxidant and the like.

The amount of the inorganic pigment, particularly alumina hydrate, applied to the substrate is 10 g in order to provide dye fixability.
/ M ² or more is preferred, and when the substrate has no ink absorbency, the coating amount is more preferably in the range of 30 to 50 g / m ^{2. When} the substrate has the ink absorbency, the coating amount is A range of 20 to 40 g / m ² is more preferable. The method of coating and drying is not particularly limited, but it is also possible to subject the alumina hydrate and the binder to a baking treatment, if necessary. By performing such a baking treatment, the crosslinking strength of the binder is increased, the mechanical strength of the ink receiving layer is improved, and the surface gloss of the alumina hydrate layer is improved.

[Image Protective Layer] The image protective layer preferably forms a porous resin layer using a thermoplastic resin latex, and the latex preferably has a specific particle distribution. The average particle diameter of the resin latex is 0.1 to 10 μm, preferably 0.3 to 5 μm, and more preferably 0.3 to 5 μm.
To 3 μm. The distribution is preferably a monodisperse distribution, and is preferably a latex of uniform particles such that 90% or more of the particles fall within the range of ± 2/3, preferably ± 1/3 of the average particle size. In particular, it is preferable that fine particles of latex do not enter. The thermoplastic resin latex preferably has a particle solid content of about 10 to 60% by weight, does not impair ink permeability, and becomes a transparent resin film by heating.

The thermoplastic resin latex in the image protective layer is suitable for the processing temperature at the time of providing the image protective layer irrespective of the Tg of the resin because the overcoat layer described later is provided on the image protective layer. Minimum film formation temperature (MFT) 10 ° C or more higher than the processing temperature when forming the image protection layer
Is preferable, for example, 50 ° C. or higher, preferably 60 ° C. or higher. At these processing temperatures, the image protective layer is formed while maintaining the state of the porous layer containing the thermoplastic particles, and the ink penetrating from the overcoat layer can be adsorbed and fixed to the ink image receiving layer.

The thermoplastic resin used for the image protective layer is made nonporous by heat treatment at the time of image recording, and is formed into a film.
A resin having a property of protecting an image, particularly a resin containing a component having high ultraviolet absorption is preferable. For example, vinyl chloride-based, vinylidene chloride-based, styrene-based, acrylic-based, urethane-based, polyester-based, ethylene-based material or vinyl chloride-vinyl acetate-based, vinyl chloride-acrylic, vinyl chloride-vinylidene chloride-based, Latex such as vinylidene chloride-acrylic, SBR, NBR, etc.
Latexes of these two or more copolymers, for example, SB
Latexes such as R-based / NBR-based mixtures and vinyl chloride-acrylic / vinyl acetate-based mixtures are exemplified. The content of the component containing the conjugated double bond component is preferably 50% or less.

It is desirable that the image protective layer is mixed with 10 to 30% by weight of the silica gel image protective layer.
By including silica gel etc. in the image protective layer,
This has the effect of enhancing the adhesion between the image protective layer and the ink image receiving layer, preventing beading, and improving the sharpness of the image.
A hydrophilic binder used for the ink image-receiving layer, for example, a small amount of a binder such as polyvinyl alcohol, for the purpose of optimizing the adhesion between the image-protecting layer and the ink-image-receiving layer, or improving the sharpness of the image. It is desirable to add.

[Overcoat layer] In the present invention, an overcoat layer is provided on the thermoplastic porous resin layer. The overcoat layer has good adhesive absorption and permeability with the ink, protects the porous resin layer as a thin layer, and can surprisingly improve the sharpness of the image. The binder can be selected from hydrophilic polymers having good adhesion and absorption to the ink. For example, polyvinyl alcohol or a modified product thereof, polyvinylpyrrolidone, gelatin or a modified product thereof, casein or a modified product thereof, polyethylene oxide, polyacrylic acid, polyacrylamide, carboxymethylcellulose, hydroxyethylcellulose, and derivatives thereof such as hydroxyfluoromethylcellulose alone or A plurality of types can be mixed and used.
The overcoat layer desirably contains adsorbable inorganic fine particles or adsorbed fine resin latex, whereby the image quality can be remarkably improved. Among these, colloidal silica is preferable, and colloidal silica of 10 to 30% by weight with respect to the binder can be mixed with the binder to enhance the ink adhesion and improve the image quality. The overcoat layer is thinner than the image protective layer and preferably has a thickness of 0.01 times or more and 1.0 times or less. If the thickness of the overcoat layer is less than 0.01 times the thickness of the protective layer, the function of protecting the image protective layer is low, and if it is more than 1.0 times, the function of penetrating the ink into the image protective layer is likely to decrease. The thickness of the overcoat layer is preferably 1/20 to 2/5 of the image protective layer, more preferably 0.1 to 1 μm, and preferably 0.2 to 0.
5 μm.

[Backcoat layer] The backcoat layer includes:
It is desirable to apply a water-resistant resin latex, a matting agent for inorganic fine particles, a fluororesin, a lubricant, a surfactant, or the like. By providing the back coat layer, the transportability of the image recording material can be improved.

-Image recording method- The image recording method of the present invention is to use the above-mentioned ink jet type image recording material. In particular, after printing the ink using the ink jet type image recording material of the present invention, heating is performed. It is desirable to process. This heat treatment is preferably carried out at a temperature condition and a treatment time necessary for rendering the ink image receiving layer formed of a porous layer containing thermoplastic resin particles nonporous. The layer has good weather resistance such as water resistance and light resistance, can impart gloss to the image, and can be printed with the ink permeated into the ink image receiving layer of the porous layer. By adsorbing and fixing in a layer, printed matter can be stored for a long time.

The heat treatment temperature at this time is desirably equal to or higher than the flow temperature of the thermoplastic resin particles, more preferably equal to or higher than the minimum film forming temperature (MFT), and varies depending on the type of the thermoplastic resin. The film temperature (MFT) is
The temperature at which the mainly used image protective layer becomes transparent by heating to form a film, and also depends on the processing time.

The heat treatment temperature is preferably such that the image protective layer is made nonporous and transparent at the same time. In this case, the T of the resin of the thermoplastic resin particles constituting the image protective layer is preferable.
g and minimum film formation temperature (MFT) of thermoplastic resin latex
It is desirable to use a resin latex having a difference of 10 ° C. or less.

As means for applying such an image recording method, it is desirable to have a means capable of heating at least a predetermined temperature of the printed image recording material after printing the ink on the image recording material of the present invention. .

The ink jet image recording material according to the present invention is preferably used for recording a high quality color image. In this case, the image recording apparatus is an apparatus having the above-described heating processing means, and is based on an image obtained by a development processing system of a silver halide photographic material, image information obtained from a high-quality color digital camera or the like. It is preferably used for an image recording system that performs continuous recording by an ink jet method, in particular. For example, Japanese Patent Application No. 2000-36151
It is preferably used as a recording material for the image recording apparatus described in No. 8.

This image recording apparatus, as shown in FIG.
The housing 20A of the inkjet printer 20 has a substantially box shape, and a magazine 72 for storing a long image recording material 70 wound around a reel 72A is set at one end of the housing 20A. You. Magazine 72 is housing 20
In the state set in A, the reel 72A is connected to a draw-out transport motor via a speed reduction mechanism (both are not shown), and is rotated by driving the draw-out transport motor. Thus, the image recording material 70 is pulled out of the magazine 72.

The image recording material 70 pulled out of the magazine 72 is directed to the other end of the housing 20A by a pair of conveying rollers 74, 76, 78, 80, 82 arranged on the downstream side in the drawing direction of the image recording material 70. Transported. The transport roller pair 74 is rotationally driven by the driving force of a pull-out transport motor, and the transport roller pairs 76, 78, 80, 82 are rotationally driven by the synchronous transport motor (not shown).

A loop forming mechanism (not shown) is provided between the pair of conveying rollers 74 and 76, and a loop of the image recording material 70 is formed between the pair of conveying rollers 74 and 76 by the loop forming mechanism. . In the vicinity of the loop forming position, there are provided loop sensors 84 each composed of a pair of a light emitting element and a light receiving element opposed to each other with the loop forming position interposed therebetween, at two different height positions.

Pull-out transport motor, synchronous transport motor, loop forming mechanism, and transport roller pairs 74, 76, 78, 8
Reference numerals 0 and 82 constitute a recording material transport unit 62. After the loop of the image recording material 70 is formed once by the loop forming mechanism, the printer control unit 56 controls the loop sensor 84 located on the upper side to perform recording. When the loop of the material 70 is not detected (the light emitted from the light emitting element is received by the light receiving element without being shielded by the recording material), the draw-out and conveyance motor is driven to drive the reel 72A and the conveyance roller pair. When the image recording material 70 is pulled out of the magazine 72 by rotating the image recording material 70 and the loop sensor 84 located below detects the loop of the image recording material 70 (the light emitted from the light emitting element is When the recording material 70 is shielded by the lowermost portion of the loop and cannot be received by the light receiving element), the drive of the pull-out and conveyance motor is stopped and the magazine is stopped. It repeated stopping the withdrawal of the image recording material 70 from 2.

By forming the above-mentioned loop, it becomes possible to convey the image recording material 70 on the downstream side of the loop asynchronously with the drawing of the image recording material 70 from the magazine 72. For this reason, the printer control unit (not shown) controls the image recording material 7 by the recording head 60 on the downstream side of the loop.
The synchronous transport motor is driven so that the image recording material 70 is transported in synchronization with the image recording to the transport roller pair 7.
6, 78, 80 and 82 are driven to rotate.

A recording head 60 is disposed above the pair of conveying rollers 76 and 78. The recording head 60 is arranged near the conveyance path of the image recording material 70. A cutter 100 for cutting the long image recording material 70 in units of individual information is provided downstream of the conveying rollers 82. The image recording material 70 cut for each image by the cutter 100 is placed on the tray 10 provided in the housing 20A.
It is discharged to 2.

Inks (for example, C, M, Y, BK) of different colors are stored in a plurality of main tanks (not shown), and are supplied to the respective nozzle rows via ink chambers. Thereby, different colors of ink are ejected from each nozzle for each nozzle row.

A 3-line CCD sensor (an area sensor may be used) 98 for reading a color image (output image) recorded on the image recording material 70 is disposed between the transport rollers 80 and 82. I have. The CCD sensor 98 forms a part of an image reading unit, and an image signal output from the CCD sensor 98 is supplied to an amplifier included in the image reading unit,
The data is input to the printer control unit as output image data representing an output image via an A / D converter and a correction unit that performs correction such as darkness correction.

On the other hand, as an ejection method for ejecting ink from the nozzles, an arbitrary method can be adopted from various known ejection methods. For example, a typical method is a piezoelectric element provided in an ink chamber. Applying a pulse voltage to the piezoelectric element to deform the piezoelectric element changes the ink liquid pressure in the ink chamber, and uses the change in the ink liquid pressure to eject ink droplets from nozzles. A thermal method in which ink is heated by a heating element and ink droplets are ejected from nozzles by bubbles generated in the ink chamber by the heating can be adopted. The print head 60 is also provided with a pump 112 for generating a negative pressure to suck ink in all the ink chambers inside the print head 60 in order to eliminate clogging of the ejection openings of the nozzles.

When the image recording material of the present invention is applied to the image recording apparatus shown in FIG. 2, an image recording material having at least a four-layer structure is prepared in advance, and this long image recording material 70 is removed from the magazine 72. In taking out and transporting the inside of the image recording apparatus, as a result of having the overcoat layer on the surface of the image recording material 70, mechanical damage to the image protective layer and the ink image receiving layer can be prevented. In addition, after the ink is printed from the recording head 60 on the image recording material 70, the porous body can be made nonporous by performing the heat treatment in the heat treatment unit 64, and as a result, the surface planarity and the transparency And the printed ink is adsorbed and fixed in the ink image receiving layer, thereby improving the durability and weather resistance of the image recording material and sharpening the image.

[0048]

EXAMPLES Examples of the present invention will be described, but the present invention is not limited to these examples. (Example 1) 1. 1. Preparation of Recording Material of Ink-Jet System of the Present Invention 1.1 Preparation of Support and Undercoat Layer A paper support (thickness: 100 μm) laminated on both sides of polyethylene having a configuration usually used for manufacturing color printing paper was used. After performing a corona discharge treatment on the back surface, a 0.2 μm thick undercoat layer was formed using a solution obtained by adding 0.3% of an epoxy-based curing agent to a 5% by weight aqueous gelatin solution containing sodium dodecylbenzenesulfonate. Provided.

1.2 Preparation of Ink Image Receiving Layer In order to form an ink image receiving layer (porous inorganic pigment layer) on the undercoated support, a coating dispersion was prepared by the following method. Boehmite sol 10 having a crystal thickness in the (020) plane direction of 80 μm and a secondary aggregated particle diameter of 1.5 to 4 μm, which was synthesized by a hydrolytic glue method of aluminum isoproxide.
To 0 parts by weight, 11 parts by weight of polyvinyl alcohol (both in terms of solid content) and water are added, and the mixture is coated on an undercoating support using a coating solution to form a coating having a dry film thickness of 30 microns (ink image receiving layer). ). The coating film thus formed was a transparent porous film having a pore size of the alumina hydrate porous layer of 50 mm.

1.3 Preparation of Image Protecting Layer (1) Synthesis of acrylonitrile / vinylidene chloride / acrylic acid (mass ratio 15/79/6): (P-1) (1) 230 g of distillation in 400 ml eggplant type flask Water, (2) 0.8 g Triton-770, (3) 1
2.34 g of acrylonitrile, (4) 4.93 g of acrylic acid, (5) 64.96 g of vinylidene chloride,
(6) 0.204 g of potassium metabisulfite and (7) 0.102 g of potassium persulfate were sequentially added.
The flask was sealed and shaken at 30 ° C. for 18 hours. The polymerization mixture was freed of volatile residual monomers at room temperature under reduced pressure for 15 minutes. (Tg: 46 ° C) P-
2. For P-3, the particle diameter and the distribution of the latex obtained by changing the amount of the emulsifier Triton-770 and the shaking speed were measured by Microtrac UPA (manufactured by Nikkiso Co., Ltd.), and the results were suitable for the purpose. I chose the one. Sample (P-1) had an average particle diameter of 0.8 μm and had a monodisperse distribution in which 90% or more of the particles were in a diameter range of 0.5 to 1.1 μm.

(2) Image Protecting Layer A coating liquid containing a thermoplastic resin latex (P-1) is applied on the ink image receiving layer with a bar coater, dried at 52 ° C., and has a pore size of about 5 μm. A latex layer (image protective layer) was prepared.

1.4 Preparation of Overcoat Layer A coating solution obtained by adding a hardening agent alum equivalent to 0.3% by weight as a solid content as an overcoat layer to a 5% by weight aqueous solution of alkali-treated gelatin was coated on the image protective layer. And about 0.2μ
m of the overcoat layer. By the above steps, the recording material sample No. of the present invention was obtained. 1 was obtained.

2. Image formation The obtained ink jet image recording material No. 1 and an image was obtained using the ink jet printer shown in FIG. Data sent to the inkjet printer is converted into digital information, corrected and corrected by the A / D mechanism using a film scanner to convert a film having a color negative image using the color negative film supvia400 manufactured by Fuji Photo Film Co., Ltd. Is input to the image data storage unit. The image recording material according to the present invention is combined with a magazine (72) of an ink jet printer (20) with a leader band wound on a reel (72A), and the continued recording material is passed through rollers (74, 76). , And through the loop sensor (84) so as to match the recording head (60). The image information input to the image data storage unit is
Ink C, M, Y, and BK of different colors are ejected from each level of the recording head (60) through the printer control unit to form an image. The image recording material from which the ink image is obtained is heated by an edge roller (78) and sent to a drying unit (64).
Heat treatment at about 120-140 ° C., roller (80, 8
According to 2), the image quality is checked by the CCD sensor and sent, and cut into a predetermined size by the cutter (100) and sent to the tray (102).

3. Evaluation Image quality: Hue, sharpness, etc. of the obtained images were visually compared and observed. Image weather resistance: Image recorded material can be used outdoors (including under direct sunlight)
For 10 days, and changes in the image were visually observed. Ink absorption: Ink bleeding, uniformity, and beading were visually observed. Abrasion resistance: A weight of 1 kg is placed on the recording medium and the image, and the degree of scuffing is evaluated by comparative visual evaluation. Evaluation method: ◎ particularly excellent ○ more excellent △ equivalent (slightly inferior in practice but usable) × inferior

4. Preparation of Comparative Sample a In Comparative Example 1, an image recording material without an overcoat was prepared.

Image recording material No. Table 1 shows the evaluation results of Sample No. 1 and Comparative Sample a.

[Table 1]

(Example 2) In Example 1, the image recording material No. A polymer latex having an average particle size of 0.6 μm of the thermoplastic resin latex and a particle size distribution of only 10% or less in a region other than 0.36 to 0.84 μm. Image recording material N used for
o. 2 was obtained. Further, the comparative recording material No. b was obtained. Image recording material No. No. 1, the polyvinyl alcohol (PVA117 manufactured by Kuraray Co., Ltd.) was used in place of the gelatin in the overcoat layer. 3 was obtained. Evaluation was performed in the same manner as in Example 1, and the results in Table 2 were obtained.

[0058]

[Table 2]

(Example 3) In the synthesis of the resin latex (P-1) of (1) in the image protective layer of Example 1,
By changing the composition, the glass transition point can be changed. The heat treatment temperature of the produced image recording material in the ink jet printer is T
g or more, it is set to conform to the minimum film formation temperature (MFT). The composition of the resin latex sample and its Tg are shown below. Tg (° C) Sample P-2 acrylonitrile / vinylidene chloride / acrylic acid mass ratio (39/69/2) 79 ° C Sample P-3 acrylonitrile / vinylidene chloride / acrylic acid mass ratio (15/83/2) 25 ° C Sample P-4 Methyl methacrylate / butyl acrylate / styrene Mass ratio (65/5/30) 90 ° C. Both MFTs were Tg and MF depending on the use conditions.
When the difference in T is 10 ° C. or less, a transparent image protective layer can be formed. Thermoplastic resin latex sample no. P-1 was replaced with P-2, P-3, and P-4, and the drying temperature was changed to produce an image protective layer. 3 in the same manner as in image recording material sample No. 3. 4, 5 and 6 were obtained. The image recording material sample No. In the overcoat layer, about 20% by weight of a fine particle silica (particle diameter of about 0.05 μm, particles of 0.15 μm or more were hardly found) was mixed with the binder of the polyvinyl alcohol in the overcoat layer. 7 was obtained. Image recording material sample No. No. 8 is an image recording material sample No. This is a sample using a recording medium similar to that described above and having a drying temperature of 50 ° C. and no heat treatment. The image obtained in the same manner was evaluated. The results are shown in Table 3 below.

[0060]

[Table 3]

Image recording material No. 4 and No. 4. When the color image obtained in No. 6 was compared in L size, the quality of the print image obtained using silver halide color photographic paper was equivalent to that of a print image obtained in practical use. Image recording material No. Sample No. 8 was slightly different from Sample No. 8 in terms of image quality and weather resistance. Although it was inferior to 4, it was sufficiently practical.

[0062]

According to the image recording material of the present invention, since an overcoat layer is provided on the surface of the image recording material, mechanical damage to the ink image receiving layer and the image protective layer can be prevented. According to the image recording material of claim 2, when the overcoat layer contains an ink-permeable hydrophilic polymer and has a predetermined thickness, ink printed in addition to the above-described effect penetrates the overcoat layer. In addition, the ink can be absorbed and fixed to the ink image receiving layer through the image protective layer. According to the image recording material of claim 3, the image protective layer is a porous resin layer using a thermoplastic resin latex, and the relationship between the glass transition temperature of the resin and the minimum film forming temperature is maintained in a predetermined relationship. If the printed ink penetrates into the porous resin layer and is then subjected to heat treatment, the image protective layer can be made nonporous, and the ink can be adsorbed to the ink image receiving layer within the image protective layer. It can be fixed, and the durability and weather resistance of the image recording material can be improved. According to the image recording material of the fourth aspect, it is possible to permeate the ink and to make the image protective layer non-porous, and to hold the ink in the image protective layer at a higher level. According to the image recording method of the fifth aspect, image recording is performed while preventing mechanical damage to the image recording material conveyed during image recording and preventing mechanical damage to the ink image receiving layer and the image protective layer. be able to. According to the image recording method of claim 6, after producing an image recording material having at least four layers, the image recording material is set in a recording device, and ink is printed on the image recording material, and the ink is applied to the image protective layer. Can be absorbed and fixed to the ink image receiving layer by ink absorption, and the image protective layer can be made nonporous by heat treatment.
Therefore, while preventing beading of the ink with a simple man-hour, the penetrability of the ink is increased, and the durability of the sharp image is improved.
The weather resistance can be improved. According to the image recording method of the seventh aspect, the effect of the seventh aspect can be achieved at a higher level. In particular, it can be printed as an ink jet image by being combined with a developing system of a photographing silver halide photographic material. As a result, it is possible to obtain a print having an image quality practically equivalent to that of a photographic paper obtained with a silver halide photosensitive material.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view of an image recording material of the present invention.

FIG. 2 is a schematic configuration diagram of an ink jet printer used in an example.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 10 Support 12 Undercoat layer 14 Ink image receiving layer 16 Image protective layer 18 Overcoat layer 19 Back coat layer 20 Ink jet printer 60 Recording head 64 Heat processing part 70 Image recording material

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Yoshio Ishii 210 Nakanuma, Minamiashigara-shi, Kanagawa Prefecture Fuji Photo F-term (reference) 2C056 EA13 EC14 EC29 FC06 HA46 2H086 BA05 BA16 BA34 BA41 BA45 2H113 AA04 DA43 DA44 DA52 DA54 EA02 EA07 FA06 FA29 FA48

Claims (7)

[Claims] 1. A support comprising an undercoat layer, an ink image receiving layer, an image protective layer and an overcoat layer on a support in this order.
An ink jet type image recording material comprising at least four layers. 2. The image forming apparatus according to claim 1, wherein the overcoat layer contains an ink-permeable hydrophilic polymer and has a thickness of 0.01 to 1.0 times the thickness of the image protective layer. Ink jet image recording material. 3. The image protective layer has a porous resin structure using a thermoplastic resin latex, and has a glass transition temperature of a polymer constituting the thermoplastic resin latex and a minimum film forming temperature (MFT) of the thermoplastic resin latex. 3. The ink jet image recording material according to claim 1, wherein the difference is less than 10 ° C. 4. The thermoplastic resin according to claim 1, wherein the image protective layer has a minimum film-forming temperature (MFT) of 50 ° C. or more, has a monodispersed distribution, and contains 90% or more of particles in a range of ± 2/3 of the average particle diameter. 4. The ink jet type image recording material according to claim 1, which has a porous resin structure using a resin latex. 5. An image recording method of an ink jet system, comprising using the image recording material according to claim 1. Description: 6. The image recording method according to claim 5, wherein a heat treatment is performed on the image recording material after printing with ink. 7. The image recording method according to claim 6, wherein the temperature of the heat treatment is not lower than the minimum film forming temperature (MFT) of the thermoplastic resin latex of the image protective layer.