JP2003103905A - Method for forming ink jet recorded matter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for forming a recorded matter in which the gas resistance of a printed image formed on an ink jet recording material having a high photo-like gloss and a high ink absorbability is remarkably improved. SOLUTION: The method for forming the recorded matter comprises the steps of printing an ink jet recording material having a porous ink accepting layer containing an inorganic fine particles and a hydrophilic binder on a water resistant support, and then laminating a laminating film on the recorded surface.

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 recorded matter, and more specifically, it has an ink-absorbing property and a high photo-like gloss, and has an improved preservability after printing. It relates to a method of creating a product.

[0002]

2. Description of the Related Art As a recording material used in an ink jet recording system, pigments such as amorphous silica and alumina are composed of a water-soluble binder such as polyvinyl alcohol on a support called ordinary paper or ink jet recording paper. A recording material having a porous ink absorbing layer is known.

For example, JP-A-55-51583 and JP-A-5-51583.
No. 6-157, No. 57-107879, No. 57-10.
No. 7880, No. 59-230787, No. 62-160.
No. 277, No. 62-184879, No. 62-1833.
No. 82 and No. 64-11877, there are proposed recording materials obtained by coating a paper support with a silicon-containing pigment such as silica together with an aqueous binder.

On the other hand, Japanese Examined Patent Publication No. 3-56552 and Japanese Unexamined Patent Publication No.
-188287, 10-81064, 10
-119423, Dohei 10-175365, Dohei 1
0-193776, 10-203006, 10
-217601, Dohei 11-20300, Dohei 11
No. 20306, No. 11-34481, etc.
It has been disclosed to use synthetic silica fine particles produced by a vapor phase method (hereinafter referred to as vapor phase silica). Ultrafine particles with an average primary particle size of 30 nm or less, especially vapor phase silica,
It is characterized in that a recording material having good ink absorption and high gloss can be obtained. In recent years, with the demand for photo-like recording sheets, it is becoming more and more important for glossiness to be used, and water resistance of polyolefin resin coated paper (paper whose both surfaces are laminated with a polyolefin resin such as polyethylene) or polyester film A recording material has been proposed in which an ink receiving layer mainly composed of vapor grown silica is coated on a support.

Although the paper support that has been generally used conventionally has a role as an ink absorbing layer, the water-resistant support such as the polyolefin resin-coated paper described above is a paper support. Unlike the above, since it cannot absorb ink, the ink absorbability of the ink receiving layer provided on the support is important, and it is necessary to increase the porosity of the ink receiving layer. Therefore, it is necessary to increase the coating amount of the inorganic fine particles such as vapor-phase method silica and further reduce the ratio of the binder to the inorganic fine particles.

However, an ink jet recording material having a recording layer having a high porosity using inorganic ultrafine particles is very excellent in ink absorbency, but is inferior in water resistance or a printed image during storage after printing. Has a problem that it is easily discolored. That is, the recording medium having a void layer of inorganic ultrafine particles is not only poor in light resistance, but also the problem that fading easily occurs due to a trace gas in the atmosphere has not been sufficiently solved.

Compounds known as an anti-fading agent due to a trace amount of gas and a light resistance improver have the effect of preventing the fading due to a trace amount of gas when contained in a porous ink receiving layer composed of inorganic ultrafine particles (hereinafter It is not perfect even if it has gas resistance), and even if the light resistance is improved, the gas resistance is deteriorated. Therefore, it is extremely difficult to secure the storage stability equivalent to that of a silver salt photograph.

On the other hand, many techniques have been proposed in which a coating layer is provided on the surface of an image after printing to improve the image storability by its protective action. For example, Japanese Patent Laid-Open No. 11-277
No. 724, JP-A Nos. 2000-25370 and 2001-2001.
No. 18379, 2001-18380 and the like show a method of forming a coating layer by coating various resin solutions, but there are drawbacks such as an increase in size of the apparatus and a need for post-treatment of the coating layer. Have In addition, JP-A-8-174989
And Japanese Patent Application Laid-Open No. 2001-213044 disclose a method of thermally transferring an overcoat resin layer through a heat resistant film,
Furthermore, JP-A-8-252883 and 9-226107.
No. 11-301099, JP 2000-2806.
No. 01 and the like disclose a technique of laminating a laminated film on a recorded surface, but the effect of gas resistance was not sufficient for a recording material having a porous ink jet recording layer having a high porosity.

[0009]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to record a printed image formed on an ink jet recording material having photo-like high gloss and high ink absorbability, which is remarkably improved in gas resistance. To provide a method of creating.

[0010]

The above object of the present invention is to print on an ink jet recording material having a porous ink receiving layer containing inorganic fine particles, a hydrophilic binder and a crosslinking agent on a water resistant support, This is achieved by a method for producing an inkjet recorded article, which comprises laminating a laminated film on the recorded surface.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
Fine particles of silica, alumina or alumina hydrate are preferably used in the ink jet recording material used in the present invention, and the ink is absorbed in the voids formed in the film by the vapor phase method silica ultra fine particles. .
In order to develop high ink absorbency, it is necessary to increase the void volume, and therefore it is necessary to coat a relatively large amount of inorganic fine particles on the support, and the amount of hydrophilic binder increases the porosity. It is preferable to reduce the amount.

[0012] preferably used inorganic ultrafine particles present invention preferably contain 8 g / m ² or more in the ink-receiving layer, and more preferably employed in the range of 10 to 30 g / m ^2. If it is less than this range, the ink absorbency is poor. The amount of hydrophilic binder is 5 to 40% by mass based on the inorganic fine particles.
(That is, the mass ratio (PB ratio) of the inorganic fine particles to the hydrophilic binder is 20 to 2.5), preferably 10 to 35.
It is preferable that it is mass% (that is, the PB ratio is 10 to about 2.9). By reducing the ratio of the hydrophilic binder as described above, the ink absorbability is improved, but the gas resistance after printing is particularly likely to decrease, and the present invention can remarkably improve the gas resistance.

In the present invention, the inorganic fine particles are contained mainly in the ink receiving layer, that is, 50% by mass or more, preferably 60% by mass or more, and more preferably 65% by mass or more based on the total solid content of the ink receiving layer. It is preferable.

The vapor phase silica is also called a dry method as opposed to a wet method, and is generally produced by a flame hydrolysis method. Specifically, a method of burning silicon tetrachloride with hydrogen and oxygen is generally known, but instead of silicon tetrachloride, silanes such as methyltrichlorosilane and trichlorosilane may be used alone or in the form of silicon tetrachloride. It can be used as a mixture with. Vapor phase silica is Aerosil from Japan Aerosil Co., Ltd., Q from Tokuyama Corporation
It is commercially available as S type and can be obtained.

The inorganic ultrafine particles used in the present invention, especially the primary particles of vapor phase silica, alumina or alumina hydrate, preferably have an average particle size of 30 nm or less. Particularly preferably, the primary particles have an average particle size of 3 to 20 nm and a BET specific surface area of 200 m ² / g or more (preferably 250).
˜500 m ² / g). The BET method referred to in the present invention is one of the methods for measuring the surface area of powder by the vapor phase adsorption method, and is a method for obtaining the total surface area of 1 g of a sample, that is, the specific surface area, from the adsorption isotherm. Nitrogen gas is often used as the adsorbed gas, and the most commonly used method is to measure the adsorbed amount from the change in pressure or volume of the adsorbed gas. The most prominent one for expressing the isotherm of multimolecular adsorption is the Brunauer, Emmett, Teller equation,
It is called the ET formula and is widely used to determine the surface area. BE
The adsorption amount is calculated based on the T formula, and the surface area is obtained by multiplying the area occupied by one adsorbed molecule on the surface.

In the present invention, as the hydrophilic binder used together with the inorganic ultrafine particles, various known binders can be used, but a hydrophilic binder having high transparency and high ink permeability can be preferably used. . In using the hydrophilic binder, it is important that the hydrophilic binder does not swell and block the voids at the initial penetration of the ink. From this viewpoint, a hydrophilic binder having a low swelling property at around room temperature is preferable. Used. Particularly preferred hydrophilic binders are fully or partially saponified polyvinyl alcohol or cation-modified polyvinyl alcohol.

Among the polyvinyl alcohols, those partially saponified or having a saponification degree of 80 or more are particularly preferable. Those having an average degree of polymerization of 200 to 5000 are preferable.

As the cation-modified polyvinyl alcohol, for example, as described in JP-A-61-10483, primary to tertiary amino groups and quaternary ammonium groups are added to the main chain or side chain of polyvinyl alcohol. It is polyvinyl alcohol contained therein.

In the present invention, a crosslinking agent (hardening agent) for the binder is used together with the hydrophilic binder. Specific examples of the cross-linking agent include formaldehyde,
Aldehyde compounds such as glutaraldehyde, ketone compounds such as diacetyl and chloropentanedione, bis (2-chloroethylurea), 2-hydroxy-4,6-
Dichloro-1,3,5 triazine, US Pat. No. 3,28
Reactive halogen-containing compounds as described in US Pat. No. 8,775, divinyl sulfone, US Pat. No. 3,635,718.
Compounds having a reactive olefin as described in US Pat. No. 2,732,316, N-methylol compounds as described in US Pat. No. 3,732,316, isocyanates as described in US Pat. No. 3,103,437, US Pat. Aziridine compounds such as those described in 017,280 and 2,983,611,
Carbodiimide compounds such as those described in U.S. Pat. No. 3,100,704, epoxy compounds such as those described in U.S. Pat. No. 3,091,537, halogen carboxaldehydes such as mucochloric acid, dioxane derivatives such as dihydroxydioxane, and chromium oxide. Ban, zirconium sulfate,
There are inorganic cross-linking agents such as boric acid and borate, and these can be used alone or in combination of two or more. Among these, boric acid or borate is particularly preferable.

The amount of the cross-linking agent used varies depending on the kind of the hydrophilic binder, the kind of the cross-linking agent, the kind of the inorganic fine particles, the PB ratio, etc.
The range is from ~ 600 mg, preferably from 10 to 500 mg.

The ink jet recording material used in the present invention preferably contains a cationic compound in combination with the inorganic fine particles. As the cationic compound,
Examples thereof include cationic polymers and water-soluble metal compounds. Examples of the cationic polymer include polyethyleneimine, polydiallylamine, polyallylamine, alkylamine polymers, and JP-A-59-20696 and 59-3.
No. 3176, No. 59-33177, No. 59-1550
No. 88, No. 60-11389, No. 60-49990.
No. 60-83882, No. 60-109894,
62-198493, 63-49478, 6
3-115780, 63-280681, JP-A-1-40371, 6-234268, 7-12.
Polymers having a primary to tertiary amino group and a quaternary ammonium base described in JP 5411, 10-193776, etc. are preferably used. The molecular weight of these cationic polymers is preferably 5,000 or more, more preferably 5,000 or more.
About 100 to 100,000 is preferable. The amount of these cationic polymers used is 0.1 to 20% by mass, preferably 1 to 10% by mass based on the inorganic ultrafine particles.

As the water-soluble metal compound, a water-soluble aluminum compound is particularly preferable. As the water-soluble aluminum compound, for example, as an inorganic salt, aluminum chloride or its hydrate, aluminum sulfate or its hydrate, ammonium alum and the like are known. Further, there is a basic polyaluminum hydroxide compound which is an inorganic aluminum-containing cationic polymer. Particularly, a basic polyaluminum hydroxide compound is preferable.

The basic polyaluminum hydroxide compound is represented by the following general formula 1, 2 or 3 and has, for example, [Al ₆ (OH) ₁₅ ] ³⁺ , [Al ₈ (OH) ₂₀ ] ⁴⁺ ,
It is a water-soluble polyaluminum hydroxide which stably contains basic and polymeric polynuclear condensed ions such as [Al ₁₃ (OH) ₃₄ ] ⁵⁺ and [Al ₂₁ (OH) ₆₀ ] ³⁺ . .

[Al ₂ (OH) _n Cl _6-n ] _m Formula 1 [Al (OH) ₃ ] _n AlCl ₃ Formula 2 Al _n (OH) _m Cl _(3n-m) 0 <m <3n Formula 3

These are water treatment agents under the name of polyaluminum chloride (PAC) from Taki Chemical Co., Ltd., under the name of polyaluminum hydroxide (Paho) from Asada Chemical Co., Ltd. It is marketed by Riken Green under the name Purachem WT and from other manufacturers for the same purpose, and various grades are easily available. In the present invention, these commercially available products can be used as they are,
Some have an inappropriately low pH, and in that case, the pH can be adjusted appropriately before use.

In the present invention, the content of the water-soluble metal compound in the ink receiving layer is preferably 0.1 to 10% by mass, and more preferably 1% by mass with respect to the vapor-phase process silica fine particles.
Is about 5% by mass.

The film surface pH of the ink receiving layer is preferably 3 to 6, and the film surface pH is determined according to J. According to the method described in TAPPI paper pulp test method N0.49, using distilled water, 30
Surface pH measured after seconds.

The ink receiving layer may contain various oil droplets in order to further improve the brittleness of the film. Such oil droplets have a solubility in water at room temperature of 0.
01 wt% or less of hydrophobic high-boiling organic solvent (for example, liquid paraffin, dioctyl phthalate, tricresyl phosphate, silicone oil, etc.) and polymer particles (for example,
Particles obtained by polymerizing one or more polymerizable monomers such as styrene, butyl acrylate, divinylbenzene, butyl methacrylate, hydroxyethyl methacrylate) may be included. Such oil droplets can be preferably used in the range of 10 to 50% by weight based on the hydrophilic binder.

In the present invention, a surfactant can be added to the ink receiving layer. The surfactant used may be any of anionic type, cationic type, nonionic type, betaine type, and low molecular weight type or high molecular weight type. One or more kinds of surfactants are added to the ink receiving layer coating liquid, but two or more kinds of surfactants can be used in combination. The amount of the surfactant added is preferably 0.001 to 5 g, and more preferably 0.01 to 100 g of the binder constituting the ink receiving layer.
~ 3g.

In the present invention, the ink receiving layer further comprises
Various known additives such as coloring dyes, coloring pigments, fixing agents for ink dyes, ultraviolet absorbers, antioxidants, pigment dispersants, defoamers, leveling agents, preservatives, optical brighteners, viscosity stabilizers, etc. Can also be added.

The water resistant support used in the present invention is a plastic resin film such as polyester resin such as polyethylene terephthalate, diacetate resin, triacetate resin, acrylic resin, polycarbonate resin, polyvinyl chloride, polyimide resin, cellophane and celluloid. , And resin-coated paper obtained by laminating a polyolefin resin on both sides or one side of paper. The thickness of the water resistant support used in the present invention is about 50 to 300 μm.
About m is preferable.

The base paper which constitutes the resin-coated paper preferably used in the present invention is not particularly limited, and commonly used paper can be used, but more preferably, it is smooth as used for a photographic support. Raw base paper is preferred. As the pulp constituting the raw paper, one kind or a mixture of two or more kinds of natural pulp, recycled pulp, synthetic pulp and the like is used. This base paper has a sizing agent, a paper strengthening agent, a filler, an antistatic agent, an optical brightening agent, which is generally used in papermaking,
Additives such as dyes are blended. In addition, surface sizing agents,
A surface paper strength agent, a fluorescent whitening agent, an antistatic agent, a dye, an anchoring agent and the like may be applied on the surface.

There is no particular limitation on the thickness of the base paper, but it is preferable that the paper has good surface smoothness such as compression by applying pressure with a calender during or after paper making, and the basis weight is 30. ˜250 g / m ² is preferred.

As the resin for the resin-coated paper, a polyolefin resin or a resin curable with an electron beam can be used.
The polyolefin resin is a homopolymer of olefins such as low-density polyethylene, high-density polyethylene, polypropylene, polybutene, and polypentene, or a copolymer of two or more olefins such as ethylene-propylene copolymer and a mixture thereof. Various densities and melt viscosity indexes (melt indexes) can be used alone or in combination.

In the resin of the resin-coated paper, white pigments such as titanium oxide, zinc oxide, talc and calcium carbonate, fatty acid amides such as stearic acid amide and arachidic acid amide, zinc stearate, calcium stearate and stearic acid. Aluminum, fatty acid metal salts such as magnesium stearate, antioxidants such as Irganox 1010 and Irganox 1076, blue pigments and dyes such as cobalt blue, ultramarine blue, cesianian blue and phthalocyanine blue, cobalt violet, fast violet, manganese purple It is preferable to add various additives such as magenta pigments and dyes, fluorescent whitening agents, and ultraviolet absorbers in an appropriate combination.

The resin-coated paper, which is a support preferably used in the present invention, is produced by a so-called extrusion coating method in which a heat-melted resin is cast in the case of a polyolefin resin on a running base paper, and both surfaces of the resin are coated. Is covered by. In the case of a resin that is cured by an electron beam, the resin is applied by a commonly used coater such as a gravure coater or a blade coater, and then the resin is irradiated with an electron beam to cure and coat the resin. Further, it is preferable to perform activation treatment such as corona discharge treatment or flame treatment on the base paper before coating the base paper with the resin. The surface (surface) of the support to which the ink receiving layer is applied has a glossy surface, a matte surface or the like depending on the application, and the glossy surface is particularly predominantly used. It is not necessary to coat the back surface with a resin, but it is preferable to coat the resin from the viewpoint of preventing curling. The back surface is usually a matte surface, and the front surface or both front and back surfaces can be subjected to activation treatment such as corona discharge treatment and flame treatment, if necessary. The thickness of the resin coating layer is not particularly limited, but it is generally coated on the surface or both front and back sides with a thickness of 5 to 50 μm.

The support of the present invention may be coated with various back coat layers for antistatic property, transport property, curl preventive property and the like. The back coat layer may contain an inorganic antistatic agent, an organic antistatic agent, a hydrophilic binder, a latex, a curing agent, a pigment, a surfactant and the like in an appropriate combination.

In the present invention, the coating method of the ink receiving layer is not particularly limited, and a known coating method can be used. For example, there are a slide lip method, a curtain method, an extrusion method, an air knife method, a roll coating method, a rod bar coating method and the like.

In the present invention, the ink jet recording material may be provided with an ink absorbing layer, an ink fixing layer, an intermediate layer, a protective layer and the like, in addition to the layer containing at least one inorganic fine particle, especially vapor grown silica. . For example, a water-soluble polymer layer may be applied as a lower layer, and a swelling layer or a porous layer may be applied as an upper layer. In particular, by providing the porous upper layer of alumina or alumina hydrate with a coating amount smaller than that of the vapor-phase-process silica of the lower layer, it is possible to obtain an ink jet recording material having high printing density and excellent storage stability.

As the dye of the ink composition used in the present invention, there are many generally known direct dyes, acid dyes, food dyes, basic dyes, reactive dyes, disperse dyes, vat dyes, soluble vat dyes. , Reactive disperse dyes, oil-based dyes and the like can be used, and among them, water-soluble dyes are preferably used in view of the performance of the recording liquid.

Particularly preferred are C.I. I. Direct Red-2, -4, -9, -23, -26, -3
1, -39, -62, -63, -72, -75, -7
6, -79, -80, -81, -83, -84, -8
9, -92, -95, -111, -173, -184,
-207, -211, -212, -214, -218,
-221, -223, -224, -225, -226,
-227, -232, -233, -240, -241,
-242, -243, and -247, C.I. I. Direct Violet-7, -9, -47, -48, -51,
-66, -90, -93, -94, -95, -98,-
100, and -101, C.I. I. Direct Yellow-
8, -9, -11, -12, -27, -28, -29,
-33, -35, -39, -41, -44, -50,-
53, -58, -59, -68, -86, -87, -9
3, -95, -96, -98, -100, -106,-
108, -109, -110, -130, -132,-
142, -144, -161, and -163, C.I. I.
Direct Blue-1, -10, -15, -22, -2
5, -55, -67, -68, -71, -76, -7
7, -78, -80, -84, -86, --87, -9
0, -98, -106, -108, -109, 151,
-156, -158, -159, -160, -168,
-189, -192, -193, -194, -199,
-200, -201, -202, -203, -207,
-211, -213, -214, -218-225,-
229, -236, -237, -244, -248,-
249, -251, -252, -264, -270,-
280, -288, -289, and -291.

C. I. Direct Black-9, -1
7, -19, -22, -32, -51, -56, -6
2, -69, -77, -80, -91, -94, -9
7, -106, -154, -166, -168, -17
3, and -199, C.I. I. Acid Red -35,-
42, -52, -57, -62, -80, -82, -1
11, -114, -118, -119, -127, -1
28, -131, -143, -151, -154, -1
58, -249, -254, -261, -263, -2
66, -289, -299, -301, -305, -3
36, -337, -361, -396, and -397,
C. I. Acid Violet-5, -34, -43,
-47, -48, -90, -103, and -126,
C. I. Acid Yellow -17, -19, -23,-
25, -39, -40, -42, -44, -49, -5
0, -61, -64, -76, -79, -110, -1
27, -135, -143, -151, -159, -1
69, -174, -190, -195, -196, -1
97, -199, -218, -219, -222, and -227.

C. I. Acid Blue-9, -25,-
40, -41, -62, -72, -76, -78, -8
0, -82, -92, -106, -112, -113,
-120, 127: 1, -129, -138, -14
3, -175, -181, -205, -207, -22
0, -221, -230, 232, -247, -25
8, -260, -264, -271, -277, -27
8, -279, -280, -288, -290, and-
326, C.I. I. Acid Black-7, -24, -2
9, -48, -52: 1, and -172-1, C.I. I.
Reactive Red -3, -13, -17, -19,-
21, -22, -23, -24, -29, -35, -3
7, -40, -41, -43, -45, -49, and-
55, C.I. I. Reactive Violet-1, -3,
-4, -5, -6, -7, -8, -9, -16, -1
7, -22, -23, -24, -26, -27, -3
3, and -34, C.I. I. Reactive Yellow-2,
-3, -13, -14, -15, -17, -18, -2
3, -24, -25, -26, -27, -29, -3
5, -37, -41, and -42, C.I. I. Reactive Blue -2, -3, -5, -8, -10, -13,-
14, -15, -17, -18, -19, -21, -2
3, -26, -27, -28, -29, and -38.

C. I. Reactive Black-4,-
5, -8, -14, -21, -23, -26, -31,
-32, and -34, C.I. I. Basic Red-1
2, -13, -14, -15, -18, -22, -2
3, -24, -25, -27, -29, -35, -3
6, -38, -39, -45, and -46, C.I. I. Basic Violet-1, -2, -3, -7, -1
0, -15, -16, -20, -21, -25, -2
7, -28, -35, -37, -39, -40, and-
48, C.I. I. Basic Yellow-1, -2, -4,
-11, -13, -14, -15, -19, -21,-
23, -24, -29, -32, -36, -39, and -40, C.I. I. Basic Blue-1, -3, -5,
-7, -9, -22, -26, -41, -45, -4
6, -47, -54, -57, -60, -62, -6
5, -66, -69, and -71, C.I. I. Basic Black 8 and the like can be mentioned. Examples of the copper phthalocyanine dye include C.I. I. Direct Blue -86, -87, -1
99 etc. are mentioned.

Among these dyes, the dyes having relatively poor gas resistance are direct dyes, particularly copper phthalocyanine dyes such as C.I. I. Direct Blue 199 etc. Therefore, in the practice of the present invention, recording is performed on an inkjet recording material having a porous ink receiving layer containing inorganic fine particles on a water resistant support, using at least one ink composition containing a direct dye as a dye. In that case, the effect of the present invention is remarkably exhibited.

In the ink composition used in the present invention, a polyhydric alcohol is preferably used as an organic solvent. The amount of polyhydric alcohol added is preferably about 1 to 30% by mass, and more preferably 3 to 20% by mass. Specific examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, 1,3-propanediol, 1,5-pentanediol, 1,2,6.
-Hexanetriol, glycerin, and mixtures thereof.

Further, glycol ethers are preferably used in the ink composition used in the present invention. Examples of the glycol ethers include ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether,
Examples include dipropylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, triethylene glycol monobutyl ether, and the like. The addition amount is 3 to 3
It is preferably about 0% by mass, more preferably 5 to 15% by mass.

In the present invention, after printing on the above-mentioned ink jet recording material by the ink jet method, a transparent laminating film is laminated on the surface of the image before or after the ink image has dried. The bonding may be performed with or without heating.

As the laminate film, a transparent base material coated with an adhesive or an adhesive is preferably used.
As the transparent substrate, polyethylene, polypropylene, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyphenylene sulfite,
Examples include various films such as polyether sulfone and polyvinyl chloride. The thickness of the transparent substrate is generally 20.
˜200 μm, preferably about 30 to 100 μm. These base materials include benzophenones such as 2-hydroxybenzophenone and 2,4-dihydroxybenzophenone, and ultraviolet absorbers such as (2-hydroxyphenyl) benzotriazole and (2-hydroxyphenyl-5-methylphenyl) benzotriazole. May be included.

A heat-sealing type or pressure-sensitive adhesive type resin is publicly used as the pressure-sensitive adhesive or adhesive. As the resin, any of styrene type, butadiene type, acrylic type, urethane type and the like can be used, but acrylic adhesives are preferable, for example, methyl methacrylate, ethyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, Acrylic monomers such as N-methylolacrylamine and copolymers such as ethylene-based monomers and styrene-based monomers copolymerizable therewith can be used.

[0051]

The present invention will be described in detail below with reference to examples, but the contents of the present invention are not limited to the examples. In addition, a part means a solid content mass part.

Example 1 A 1: 1 mixture of bleached hardwood kraft pulp (LBKP) and bleached softwood sulfite (NBSP) was beaten to a Canadian standard freeness of 300 ml to prepare a pulp slurry. Alkyl ketene dimer as a sizing agent to 0.5% by mass of pulp,
1.0% by mass of polyacrylamide to the pulp, 2.0% by mass of cationized starch to the pulp, and 0.5% by mass of polyamide epichlorohydrin resin to the pulp as a strengthening agent, and diluted with water to 1%. It was made into a slurry. This slurry was made into paper by a Fourdrinier paper machine so as to have a basis weight of 170 g / m ² , dried and conditioned to obtain a base paper for polyolefin resin-coated paper. A polyethylene resin composition, in which 10% by mass of anatase-type titanium was uniformly dispersed in 100% by mass of a low-density polyethylene resin having a density of 0.918 g / cm ³ , was melted at 320 ° C. in a paper-making base paper, and 200 m / 35 μm in thickness
Extrusion coating was carried out so as to be, and extrusion coating was carried out using a cooling roller having a finely roughened surface. On the other surface, 70 parts by mass of a high density polyethylene resin having a density of 0.962 g / cm ³ and 30 parts by mass of a low density polyethylene resin having a density of 0.918 were similarly melted at 320 ° C. to obtain a thickness of Extrusion coating to 30 μm,
It was extrusion coated using a roughened cooling roll.

After the high-frequency corona discharge treatment was applied to the surface of the above polyolefin resin-coated paper, the undercoat layer was coated with gelatin.
A support was prepared by coating and drying so as to give 0 mg / m ² .

Vapor phase silica and Charol DC902P
An aqueous solution containing (cationic polymer) is dispersed with a high-pressure homogenizer, and polyvinyl alcohol or the like is added to prepare an ink receiving layer coating solution having the following composition. The coating amount of vapor-phase method silica is 18 g / m 2 in solid content. ^An ink jet recording sheet was prepared by coating and drying so as to be ² . Each recording sheet was adjusted so that the film surface pH of the ink receiving layer was 4.0.

<Recording Sheet 1A> 100 parts of gas phase method silica (average primary particle size: 7 nm, specific surface area by BET method: 300 m ² / g) 100 parts Dimethyldiallylammonium chloride polycondensate 3 parts (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., Brand name Charol DC902P) Polyvinyl alcohol 27 parts (Brand name: PVA235, Kuraray Co., Ltd., saponification degree 88%, average degree of polymerization 3500) Basic polyaluminum hydroxide (Riken Green Co., Ltd., Purachem WT) 3 parts Amphoteric Surfactant 0.3 parts (Product name: SWAM AM-2150, made by Nippon Surfactant)

<Recording sheet 2A> The same as the recording sheet 1 except that 4 parts of boric acid was added to the ink receiving layer of the recording sheet 1.

Each of the obtained ink jet recording sheets was evaluated as follows.

<Ink absorbency> Using an ink jet printer (PM-800C manufactured by Seiko Epson Corporation),
Print C, M, and Y at 100% each and print PP immediately after printing.
The C paper was overlaid on the printing portion and lightly pressure-bonded, and the degree of the amount of ink transferred to the PPC paper was visually observed and evaluated according to the following criteria. ◯: No transfer is performed. Δ: Transfer a little. X: Transfers considerably.

<Water resistance> A thin wire with a width of 100 μm is 100 μm
After printing at m intervals and left for 1 day, the plate was placed under the conditions of 35 ° C. and 90% relative humidity (RH) for 2 days, and then bleeding of fine lines was evaluated according to the following criteria. ◯: Almost no blurring, and the interval between fine lines is clear. Δ: There is bleeding, but the space between the thin lines is not completely crushed. X: Fine lines are blurred and there is no space between the fine lines.

<Light resistance> Using an inkjet printer (PM-770C manufactured by Seiko Epson Corporation), CYMK
After solid printing with each ink, and irradiating at 600 W / m ² with Suntest CPS photobleaching tester manufactured by Atlas Co., Ltd. for 30 hours, the density of the printed part was measured, and the image residual ratio (concentration after irradiation / before irradiation Of the CMYK images, and the one with the lowest residual rate was displayed.

<Gas resistance> After printing in the same manner as in the light fastness test, after exposure to air at room temperature for 2 months, the density of the printed part was measured, and the image residual ratio (density after exposure / density before exposure) ) Was obtained, and the CMYK image with the lowest residual rate was displayed.

<Glossiness> The glossiness was measured according to the method described in JIS P-8142 (Testing method for 75-degree specular glossiness of paper and board).

[0063]

[Table 1] ──────────────────────────────────   Recording sheet Ink absorbency Water resistance Gloss retention (%) Remarks                                       Light resistance Gas resistance ──────────────────────────────────    1A △ ○ 58 76 70 Comparison    2A ○ ○ 61 76 72 Comparison ──────────────────────────────────

On the other hand, after the ink images of the other recording sheets 1A and 2A have dried, a laminate film (a film having an adhesive layer and a thickness of 50 μm: LAMI CORPORA) is used.
A recording sheet is sandwiched between TAMI; LAMINATING FILM) and a laminator (NAKABAYAS).
HI Co. Product made by LTD; PACLAMI PRO; Mo
Del PLP-325) was applied at a heating temperature of 125 ° C. to prepare recording sheets 1B and 2B, respectively. Also, instead of laminating, urethane-based water-soluble UV
The cured resin solution was applied and dried using a wire bar so that the dry film thickness was 2 μm, to prepare recording sheets 1C and 2C, respectively. The glossiness, light resistance and gas resistance were evaluated as described above, and the results are shown in Table 2.

[0065]

[Table 2] ──────────────────────────────────   Recording sheet Gloss retention (%) Remarks                            Light resistance Gas resistance ──────────────────────────────────    1B 60 77 77 78 Comparison    2B 66 78 99 The present invention    1C 62 78 75 Comparison    2C 65 78 81 Comparison ──────────────────────────────────

As is clear from the above results, the recording sheet 2B in which the laminate film is attached to the recording sheet 2 used in the present invention has high light absorption and high gas resistance while maintaining high ink absorption and high water resistance. It turns out that it will be improved.

Example 2 The vapor phase silica used in Example 1 had an average primary particle size of 15 n.
The same test was carried out except that m was replaced. As a result, almost the same results were obtained for ink absorbency and storability.

Example 3 The laminate film of Example 1 was evaluated in the same manner using a transparent vinyl chloride film having a thickness of 80 μm and containing an ultraviolet absorber coated with an acrylic adhesive. The recording sheet of No. 1 was also slightly better than that of Example 1, and the gas resistance was similar to that of Example 1.

Example 4 The same result as in Example 1 was obtained by the same test as in Example 1 except that a polyester film was used as the support in Example 1.

Example 5 On the support of Example 1, coating liquids of ink receiving layers A and B having the following two types of compositions were simultaneously coated with a slide bead coating device and dried. The coating liquids for the ink receiving layer A for the lower layer and the ink receiving layer B for the upper layer shown below, which were close to the support, were prepared after dispersing the inorganic fine particles by a high pressure homogenizer so that the solid content concentration was 9% by mass. These coating solutions were applied to the ink-receiving layer A so that the vapor-phase method silica was 16 g / m ^{2 in} solid and the pseudo-boehmite in the ink-receiving layer B was 4 g / m ² and dried.

[0071] <Ink receiving layer A coating liquid> 100 parts of vapor phase silica   (Average primary particle size 7 nm) Dimethyldiallylammonium chloride polycondensate 4 parts  (Daiichi Kogyo Seiyaku Co., Ltd., trade name Charol DC902P) Boric acid 4 parts Polyvinyl alcohol 20 parts   (Saponification degree 88%, average degree of polymerization 3500) Surfactant 0.3 parts Zirconium acetate 2 parts

[0072] <Ink receiving layer B coating liquid> 100 copies of pseudo-boehmite   (A flat plate with an average primary particle size of 15 nm and an aspect ratio of 5) Boric acid 4 parts Polyvinyl alcohol 20 parts   (Saponification degree 88%, average degree of polymerization 3500) Surfactant 0.3 parts Zirconium acetate 2 parts

The drying conditions after coating are shown below. 3 at 5 ° C
After cooling for 0 seconds, the total solid content concentration is 90% by mass at 45 ° C.
It was dried at 10% RH and then at 35 ° C. 10% RH.

The ink jet recording sheet prepared as described above was tested in the same manner as in Example 1. As a result, the effect of the laminate film was similar to that in Example 1, and particularly the gas resistance was perfect.

[0075]

INDUSTRIAL APPLICABILITY According to the present invention, a photo-like ink jet recorded material having high ink absorbency, high water resistance, high gloss, and dramatically excellent storage stability, particularly gas resistance can be obtained.

Claims (6)

[Claims] 1. After printing on an ink jet recording material having a porous ink receiving layer containing inorganic fine particles, a hydrophilic binder and a cross-linking agent on a water resistant support, a laminate film is stuck on the recorded surface. A method for producing a characteristic inkjet recorded matter. 2. The method for producing an ink jet recorded matter according to claim 1, wherein the inorganic fine particles are inorganic fine particles having a primary average particle diameter of 30 nm or less. 3. The method for producing an ink jet recorded matter according to claim 1, wherein the mass ratio of the inorganic fine particles to the hydrophilic binder is 2.5 or more. 4. The method for producing an ink jet recorded matter according to claim 1, wherein the inorganic fine particles are vapor phase silica, alumina or alumina hydrate. 5. The method for producing an ink jet recorded matter according to claim 1, wherein the crosslinking agent is boric acid or a salt thereof. 6. The method for producing an ink jet recorded article according to claim 1, wherein the water resistant support is a polyolefin resin laminated paper, and an ink receiving layer is provided on the laminated paper.