JPH10278419A - Recording sheet for aqueous ink - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve water resistance, aqueous ink absorbing property, printability, and image reproducibility by making aqueous ink receiving layer that has the specified range of water absorbing capacities, which is obtained by mixing a cationic component and a crosslinking agent or a curing resin of the specified range of ratios to an absorptive resin, and crosslinking and curing them as at least one external layer. SOLUTION: A multilayer structure made up of a composition whose essential components are a cationic component of 1 to 250 pts.wt. and a crosslinking agent or a thermosetting resin of 1 to 10 pts.wt. in relation to a water absorptive resin of 10 pts.wt., and a composition that is crosslinked and cured by heat treatment or electron beam application and whose water absorption is 0.05 to 2.0 mg/cm<2> /μm. Since the aqueous ink receiving layer is crosslinked and cured, and an anionic dye component contained in the ink is adsorbed by the cationic component contained in the aqueous ink receiving layer and solidified very strongly. Therefore, oozing of aqueous ink can be controlled and water resistance is improved.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aqueous ink recording sheet. More specifically, the water-based ink recording sheet according to the present invention, for example, a sheet (including a film) that can be printed with an aqueous ink using an ink-jet printer, a pen plotter, or the like (including a film), has excellent water resistance, Since there is no transfer of ink even after storage for a long time, and ink bleeding hardly occurs, for example, an overhead projector (OHP), a gloss film, a substrate for poster advertisement, a sheet or film for electrolytic corrosion, a substrate for color filter,
It can be suitably used as a substrate for gravure or offset printing, a substrate for adhesive labels, and the like.

[0002]

2. Description of the Related Art Heretofore, printing, images and the like have been recorded and fixed with water-based ink using, for example, an ink jet printer or the like, and for example, an overhead projector (OH)
P), posters, advertisements, illuminations, color filters, gravure printing substrates, offset printing substrates, pressure-sensitive adhesive label substrates, etc., are aqueous plastic recording sheets, such as sheets made of various plastics. , A film, paper, nonwoven fabric, etc. are used as base paper, and a water-based ink recording sheet or recording base paper in which a water-soluble or water-absorbing polymer is coated on the surface of such base paper is generally used.

Further, for example, a water-absorbing resin or a hygroscopic resin (for example, a saponified ethylene-vinyl acetate copolymer) may be provided on at least one surface of a sheet made of, for example, a polyester-based polymer, with an adhesive layer if necessary. ), Etc., are sometimes seen.

However, a water-based ink recording base obtained by coating a water-soluble or water-absorbing polymer on the surface of a sheet of the above-mentioned polyester-based polymer or the like has poor water resistance and, when immersed in water, receives the coated ink. Since the strength of the layer cannot be maintained for a long time, there is a problem in handleability and storability, poor water absorption, poor printability after printing and drying, and poor dye reproducibility. Since components, pigments, and the like cannot be retained in the water-absorbent resin for aqueous ink recording, the ink easily migrates under high temperature and high humidity, and ink bleeding tends to occur.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above situation. An object of the present invention is to provide a water-based ink having excellent water resistance, water-based ink absorbency, printability, and image reproducibility, and having a reduced strength of an ink-receiving layer and little swelling whitening even when immersed in water or the like for a long time. Water-based ink recording sheet and recording base paper that have excellent reproducibility of prints, images, etc. recorded in, and do not cause ink bleeding even if the sheet on which the prints, images are recorded is stored under high temperature and high humidity for a long time To provide an adhesive label substrate and the like.

[0006]

Means for Solving the Problems The inventors of the present invention have focused on the fact that dye components (pigments) and the like contained in aqueous inks used in ink jet printers and the like are generally anionic, The study continued. As a result, the water-based ink-receiving layer (A) comprising a composition containing a water-absorbing resin, a cationic component and a cross-linking agent or a thermosetting resin as essential components is subjected to a heat treatment or an electron beam irradiation treatment and is cross-linked and cured. Therefore, the anionic dye component and the like contained in the aqueous ink are adsorbed by the cationic component contained in the aqueous ink receiving layer (A), and are fixed very strongly.
Migration in the aqueous ink receiving layer (A) is suppressed,
The present inventors have found that the bleeding of the aqueous ink can be prevented and that the water resistance is remarkably improved.

A feature of the present invention is that the composition comprises, as essential components, 1 to 250 parts by weight of a cationic component and 1 to 10 parts by weight of a crosslinking agent or a curable resin per 100 parts by weight of a water-absorbent resin; Crosslinked and cured by heat treatment or electron beam irradiation treatment, having a water absorption of 0.05 to 2.0 mg /
A water-based ink recording sheet having a multilayer structure in which a water-based ink-receiving layer (A) of cm ² / μm has at least one outer layer.

Further, it has a multilayer structure including an aqueous ink receiving layer (A), an adhesive layer (B) made of an adhesive resin, and a supporting base material layer (C). (A) / (B), (A) / (C)
, (A) / (B) / (A), (A) / (B) /
(C), (A) / (C) / (A), (A) / (C) /
(B) three layers, (A) / (B) / (C) / (B),
(A) / (B) / (C) / (A) four layers, (A) /
It is characterized by having a multilayer structure having five layers of (B) / (C) / (B) / (A).

The water-absorbing resin is a polyalkylene oxide compound and its derivative, a crosslinked polyalkylene oxide compound and its derivative, a reaction product of a polyalkylene oxide compound or its derivative and an isocyanate compound,
It is characterized by being at least one or two or more selected from polyacrylic resins, polyvinyl alcohol resins, polyether resins, polyvinyl acetal resins, polyvinylpyrrolidone resins, and cellulose derivatives.

The cationic component may be a secondary ammonium salt, a tertiary ammonium salt, a quaternary ammonium salt, a secondary ammonium salt type cationic surfactant, a tertiary ammonium salt type cationic surfactant, And at least one selected from the group consisting of a quaternary ammonium salt type cationic surfactant, an amine type or amine salt type cationic surfactant, fine particles having a positive charge, and a polymer having a cationic property.

The crosslinking agent is at least one selected from organic peroxides, and the thermosetting resin is a melamine-formalin resin, a urea-formalin resin, a glyoxal resin, a urethane-acrylic acid copolymer, It is characterized by being at least one selected from the group consisting of a vinyl ether-based resin, an acrylate-based resin, each of the above monomers (monomers) and low polymers (oligomers), and an epoxy-based resin.

[0012] The support base material layer is made of one of plastics, paper, and nonwoven fabric.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The water-absorbing resin according to the present invention includes polyalkylene oxide compounds and derivatives thereof, crosslinked polyalkylene oxide compounds and derivatives thereof, and reaction products of polyalkylene oxide compounds or derivatives thereof with isocyanate compounds. Products, polyacrylic resins, polyvinyl alcohol resins, polyether resins, polyvinyl acetal acid resins, polyvinylpyrrolidone resins, cellulose derivatives and the like. Also,
In the present invention, these may be used alone or in combination of two or more, but there is no particular limitation.

Examples of the above polyalkylene oxide compound include polyalkylene oxide compounds obtained by addition polymerization of ethylene oxide and / or propylene oxide. Examples of the polyalkylene oxide derivative include a polyalkylene oxide derivative obtained by addition-polymerizing ethylene oxide and / or propylene oxide to a polyhydric alcohol such as ethylene glycol, diethylene glycol, 1,4-butanediol, and 1,3-butanediol. No. The molecular weight of these polyalkylene oxide compounds or derivatives thereof is not particularly limited, but is usually preferably 20,000 or more.

As the cross-linked polyalkylene oxide compound and its derivative, those obtained by irradiating the above-mentioned polyalkylene oxide compound and its derivative with an electron beam at 3 to 40 Mrad or the above-mentioned polyalkylene oxide compound and its derivative can be prepared by using a conventionally known cross-linking agent ( Examples thereof include those crosslinked using diphenylmethane isocyanate, hexamethylene diisocyanate).

As the isocyanate-based compound which reacts with the polyalkylene oxide compound or a derivative thereof, conventionally known compounds can be widely used as long as they have at least one isonitrile group (-N = C = O) in the molecule. . For example, n-propyl isocyanate, n-hexyl isocyanate, cyclohexyl isocyanate, phenyl isocyanate, hexane diisocyanate, hexamethylene diisocyanate and the like can be mentioned.

Specific examples of the acrylic resin include a copolymer of ethylene and acrylonitrile, a saponified acrylate, and the like. Further, as the polyvinyl alcohol-based resin, for example, a vinyl acetate polymer or a copolymer of vinyl acetate and another copolymerizable monomer (eg, ethylene, propylene, vinyl chloride, methacrylic acid, esters thereof, and the like) is subjected to an acid saponification method or Examples include those obtained by an alkali saponification method. Examples of the polyether polyol-based resin include a resin obtained by adding an alkylene oxide to a compound containing two or more active hydrogens, such as a polyhydric alcohol, a polyhydric phenol, and an amine. Examples of the polyvinyl acetal resin include compounds having reactivity with hydroxyl groups in polyvinyl alcohol (aldehyde compounds, carboxyl compounds, epoxy compounds, isocyanate compounds, acid anhydrides, N-methylol compounds, activated vinyl compounds,
And polycondensation reaction products of polyvinyl alcohol and the like. Examples of the polyvinylpyrrolidone resin include polymers having a molecular weight of 2,000 to 200,000 obtained by radical polymerization of N-vinyl-2-hirolidone. As cellulose derivatives,
Examples thereof include carboxymethyl cellulose, methyl cellulose, and cationized carboxymethyl cellulose, but are not particularly limited.

Generally, most of the dye components and the like contained in the aqueous ink show an anionic property. Therefore, as the ink receiving layer (A) according to the present invention, a cationic component that adsorbs an anionic dye component is blended with the water-absorbing resin described above, and when printed, adsorbs an aqueous ink;
Those that fix an anionic dye are preferred. Such a cationic component includes a secondary ammonium salt, a tertiary ammonium salt, a quaternary ammonium salt, a secondary ammonium salt type cationic surfactant, a tertiary ammonium salt type cationic surfactant, a quaternary ammonium salt, Examples thereof include at least one selected from the group consisting of a quaternary ammonium salt type cationic surfactant, an amine type or amine salt type cationic surfactant, fine particles having a positive charge, and a polymer having a cationic property.

Specifically, benzyltrimethylammonium chloride, monoalkylammonium chloride, dialkylammonium chloride, tetramethylammonium chloride, octylcyclohexyldimethylammonium chloride, dihydroxyethylstearylamine, stearylamine hydrochloride, positively charged alumina hydrate Material or alumina sol, positively charged silica sol, cerium oxide, cationically modified acrylic resin,
Cationally modified polyacrylamide, polyallylamine, polyamine sulfone, polyvinylamine, polyethyleneimine, polyethyleneimine acrylonitrile adduct, polyethyleneimine acrylamide adduct, polyamide-epichlorohydrin reactant, polyamide-epichlorohydrin resin, polyvinylpyridinium halide, polyvinylalkylammonium halide And at least one selected from the group consisting of polyvinylbenzylalkylammonium and a polymer having a quaternary ammonium salt in the molecular structure, for example, a polymer obtained by introducing a quaternary ammonia group into a poly (ethylene acrylamide) copolymer.

The amount of the cationic component is 1 to 250 parts by weight, preferably 5 to 150 parts by weight, more preferably 10 to 100 parts by weight, based on 100 parts by weight of the water-absorbing resin. If the amount of the cationic component is less than 1% by weight, the aqueous ink tends to be adsorbed and the ink dye is fixed in the receiving layer (A), preventing the ink from bleeding.
If the amount exceeds 0 parts by weight, the water-absorbing properties of the water-based ink and the suitability for printing and image recording tend to be poor, which is not preferable.

Further, the aqueous ink recording sheet according to the present invention crosslinks the aqueous ink receiving layer (A) in order to more firmly fix the dye of the aqueous ink adsorbed on the aqueous ink receiving layer (A). It is hardened. On this occasion,
As a method for crosslinking and curing the aqueous ink receiving layer (A),
An aqueous ink-receiving layer (A) comprising a composition containing a water-absorbing resin, a cationic component and a crosslinking agent or a thermosetting resin as essential components is provided on a supporting substrate layer (for example, a polyester-based sheet).
After coating or laminating on at least one surface of the above, it is preferable to carry out a heat treatment or an electron beam irradiation treatment to carry out crosslinking and curing. At this time, an ultraviolet cross-linking agent (for example, methacrylic acid ester) may be added and cross-linked and cured by irradiation with ultraviolet light.

The crosslinking agent to be added to the water-absorbing resin is not particularly limited as long as it can cross-link and cure the water-absorbing resin by heat treatment or electron beam irradiation treatment, and is preferably an organic peroxide. Specific organic peroxides include, for example, dicumyl peroxide, t-butyl peroxybenzoate,
-Butyl cumyl peroxide, 2,5-dimethyl 2,
5-di (t-butylperoxy) hexane, 2,5-dimethyl2,5-di (t-butylperoxy) hexyne-
Selected from the group consisting of 3, a, a'-bis (t-butylperoxy) -di-isopropylbenzene, 1,1'-bis (t-butylperoxy) 3,3 ', 5-trimethylcyclohexane and the like At least one type can be exemplified.

At this time, it is preferable to add 1 to 10 parts by weight of the above-mentioned organic peroxide crosslinking agent based on 100 parts by weight of the water-absorbing resin. If the amount is less than 1 part by weight, sufficient crosslinking and curing cannot be obtained, and the water absorption is 2.0 mg / cm ² / μm
When immersed in water for a long time, the ink tends to swell and whiten, and since the coating strength of the aqueous ink receiving layer (A) decreases, the bleeding phenomenon of the water absorbing ink cannot be prevented. If the amount is more than 10 parts by weight, crosslinking hardening proceeds too much, and the water absorption tends to be less than 0.05 mg / cm ² / μm, and the absorptivity of the water-based ink is reduced. It is not preferable because it tends to be impossible.

The thermosetting resin blended in the aqueous ink receiving layer (A) for crosslinking and curing the water absorbing resin constituting the aqueous ink receiving layer (A) includes melamine-formalin resin, urea resin and the like. Formalin-based resins, glyoxal-based resins, urethane-acrylic acid copolymers, vinyl ether-based polymers, acrylate-based polymers, their respective monomers (monomers) and low polymers (oligomers), epoxy-based resins, polyamide-based resins Resin, polycarbodiimide resin,
At least one or two or more selected from a silanol group-containing polyurethane resin and the like can be exemplified.

The above-mentioned thermosetting resin is preferably used in an amount of 1 to 10 parts by weight based on 100 parts by weight of the water-absorbing resin constituting the aqueous ink receiving layer (A). If the amount is less than 1 part by weight, sufficient cross-linking and curing cannot be obtained, so that the water absorption tends to exceed 2.0 mg / cm ² / μm. Since the coating strength of (A) decreases, the bleeding phenomenon of the water-absorbing ink tends not to be prevented. If the amount exceeds 10 parts by weight, crosslinking and curing progresses, the resin becomes too hard, the water absorption tends to be less than 0.05 mg / cm ² / μm, and the absorptivity of the aqueous ink decreases. Recording tends to be unfavorable.

Further, the thermosetting resin may be used in combination with the crosslinking agent (organic peroxide) described above. By using a crosslinking agent and a thermosetting resin together, the aqueous ink receiving layer (A)
Of the aqueous ink recording sheet on which prints, images, etc. are recorded, even when stored for a long time under high temperature and high humidity, does not tend to cause bleeding of the aqueous ink. The amount used in combination is not particularly limited.
The total amount of the thermosetting resin and the crosslinking agent is 1 to 1 part by weight.
10 parts by weight are preferred. The mixing ratio of the thermosetting resin and the crosslinking agent may be appropriately selected without any particular limitation. If the total amount of the thermosetting resin and the crosslinking agent is less than 1 part by weight, the water resistance tends to be poor, and 10 parts by weight If it exceeds, the ink receiving layer (A) becomes too hard, the absorption amount of the water-based ink is reduced, and the recording property is reduced.
Printability tends to decrease.

If necessary, a crosslinking aid may be added to the crosslinking agent or the thermosetting resin, and there is no particular limitation. As a crosslinking aid, for example, ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate,
Examples thereof include organic amine catalysts such as triallyl cyanurate, triallyl isocyanurate, and ethylenediamine methacrylate, and metal salt catalysts. The compounding amount of the crosslinking assistant can be exemplified by 50% by weight or less based on the crosslinking agent or the thermosetting resin, but is not particularly limited and may be omitted. In this case, if the content exceeds 50% by weight, crosslinking hardening is strong, the water absorption is reduced, and the absorption of the aqueous ink is reduced, so that printing such as printing and images tends to be deteriorated.

The aqueous ink receiving layer (A) comprising a composition comprising a water absorbing resin, a cationic component and a crosslinking agent or a thermosetting resin as essential components constituting the aqueous ink recording sheet according to the present invention is crosslinked and cured. The aqueous ink layer (A)
Must be subjected to heat treatment or electron beam irradiation treatment.

As a method for heat-treating the aqueous ink-receiving layer (A) comprising a composition comprising a water-absorbent resin, a cationic component and a crosslinking agent or a thermosetting resin as essential components, the aqueous ink-receiving layer (A) may be heat-treated. Examples of treating the sheet laminated or coated on the supporting base material layer by wet heating, infrared heating, hot air heating, hot plate heating, roll (drum) heating, etc. Depending on the type of the curable resin and the like, the resin may be cured by heating under an appropriate method and heating conditions, and is not particularly limited. Generally, 14
A method in which the treatment is performed for several seconds to 5 minutes by a heating roll method or a hot air heating method set at 0 to 180 ° C. can be exemplified, but there is no particular limitation, and the treatment may be performed by other heating methods and conditions.

Further, in order to cross-link and harden the aqueous ink receiving layer (A) comprising a composition containing a water-absorbing resin, a cationic component and a cross-linking agent or a thermosetting resin as essential components, an electron beam irradiation treatment other than a heat treatment is required. May be applied. As a method of the electron beam irradiation treatment, an aqueous ink receiving layer (A) comprising a composition containing a water absorbing resin, a cationic component and a crosslinking agent or a thermosetting resin as essential components is laminated or coated on a supporting base material layer. Irradiating the aqueous ink receiving layer (A) surface (the opposite surface or both surfaces) of the resulting sheet with an electron beam generated from an appropriate electron beam irradiation device can be exemplified.

As such an electron beam irradiation apparatus, for example,
Electrons generated under a high vacuum are accelerated under a high voltage, radiated into the atmosphere (inert gas may be used), and irradiated on the surface of the aqueous ink receiving layer (A). Examples thereof include those which excite the crosslinking agent and the thermosetting resin contained in the layer (A) to crosslink and cure the water-absorbing resin and the thermosetting resin.

The conditions for electron beam irradiation are not particularly limited, and the irradiation dose is 40 Mrad or less, more preferably 3 Mrad.
rad or more and 25 Mrad or less are preferable. 40Mra
If d exceeds d, the aqueous ink-receiving layer (A) tends to deteriorate (color, decrease in film strength), the absorption amount of the aqueous ink decreases, and the printability of printing and images tends to decrease.
The depth of arrival of the electron beam may be appropriately selected depending on the thickness of the aqueous ink receiving layer (A). For example, the treatment may be performed at an electron beam acceleration voltage of about 50 to 300 kv. If the accelerating voltage is less than 50 kv, sufficient energy cannot be supplied, so that a sufficient cross-linking and curing reaction is not performed, and there is a tendency that the bleeding phenomenon of the aqueous ink cannot be suppressed. If it exceeds 300 kv, the energy efficiency tends to deteriorate, but the above numerical value is not particularly limited.

The water absorption of the crosslinked and cured aqueous ink receiving layer (A) constituting the aqueous ink recording sheet according to the present invention is preferably 0.05 to 2.0 mg / cm ² / μm. A water-based ink recording sheet having a water-based ink receiving layer (A) having a water absorption of less than 0.05 mg / mm 2 / μm tends to have a reduced water-absorbed amount of water-based ink and to have poor water-based ink recordability. The water absorption is 2.0mg
Aqueous ink recording sheet having an aqueous ink receiving layer (A) exceeding / cm ² / μm tends to swell when immersed in water, tends to have poor print and image reproducibility, and is added to the aqueous ink. Dye components and the like do not tend to be firmly fixed to the water-absorbent resin, and when stored under high temperature and high humidity for a long time, aqueous ink bleeds easily, which is not preferable.

The plastics resin forming the support base layer (C) of the aqueous ink recording sheet according to the present invention is not particularly limited as long as it is thermoplastic. For example, polyester-based resins, polyolefin-based resins, polyamide-based resins, polystyrene-based resins, cyclic olefin-based resins, polycarbonate-based resins, and the like can be given. Above all,
Polyester resins are particularly preferred because of their excellent transparency and rigidity. At this time, for example, the surface of the support substrate (C) is subjected to, for example, corona discharge treatment, and the wetting tension is set to 40 dyn.
When using a supporting substrate (C) made of a polypropylene resin having a thickness of / cm or more, lamination or coating is performed so that the treated surface is in contact with the layer (A) without using the adhesive layer (B), for example, (A) / (C) two-layer structure, (A) / (C)
/ (A), (A) / (C) / (B).

The sheet or film of, for example, a polyester resin forming the support base layer (C) is prepared by mixing a white inorganic pigment (for example, titanium oxide, barium sulfate, calcium carbonate, etc.) with the polyester resin. It may be molded from a composition consisting of: Further, as the support base material layer (C), in addition to a sheet made of a thermoplastic resin, paper (Japanese paper, coated paper, neutral paper, etc.), sheets obtained by laminating a film made of paper and an appropriate plastic,
A sheet obtained by impregnating a paper with a resin component or a base material made of a fibrous material such as a nonwoven fabric made of synthetic fiber or natural fiber is also preferable.

As the polyester resin, a polyester resin synthesized by polycondensation of a dicarboxylic acid component and a diol component can be used. Examples of the dicarboxylic acid component include aliphatic dicarboxylic acids, aromatic dicarboxylic acids, alicyclic dicarboxylic acids, and the like, and mixtures thereof. Specifically, aliphatic dicarboxylic acids such as adipic acid, sebacic acid and dodecane carboxylic acid having 2 to 20 carbon atoms, and aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid include alicyclic dicarboxylic acids. Examples of the acid include cyclohexanedicarboxylic acid and the like. Examples of the diol component include aliphatic glycols, alicyclic glycols, and the like, and mixtures thereof. Specifically, as the aliphatic glycol, ethylene glycol, diethylene glycol, 1,3-propanediol, 1,6
-Hexanediol, 1,10-decanediol and the like,
Examples of the alicyclic glycol include 1,4-cyclohexanediol and the like.

The non-woven fabric is prepared by melt-spinning a polyolefin resin such as polypropylene, polyethylene or the like, a polyester resin, a polyamide thermoplastic resin, or a thermoplastic resin obtained by compounding them, by a known method. (Binder adhesion method, mechanical entanglement method, heat bond method, spun bond method, melt blow method, water flow entanglement method) and processed into a fibrous form with a basis weight of several g / m ² to several hundred g / m ² or natural fibers Fabrics composed of synthetic and natural fibers (silk,
Cotton, wool, etc.), but is not particularly limited.

The thickness of the aqueous ink recording sheet constituting the aqueous ink recording sheet according to the present invention is not particularly limited, but the aqueous ink receiving layer (A) has a thickness of 2 to 100 μm and has a two-layer structure, for example, (A) ) / (B) 5 to 200 μm, 3
Layer configuration, for example (A) / (B) / (A) or (A)
/ (B) / (C): 10 to 500 μm, 5 layers configuration,
For example, in the case of (A) / (B) / (C) / (B) / (A), 15 to 700 μm can be exemplified as a preferable one, but is not particularly limited. Further, for example, in the case of a two-layer structure of (A) / (C), which is composed of a (C) layer (wetting tension of 40 dayn / cm or more) subjected to corona discharge treatment and a (A) layer, for example, 7 to 350 μm, In the case of a three-layer structure of A) / (C) / (A), the thickness may be 9 to 500 μm, but is not particularly limited.

When the aqueous ink recording sheet according to the present invention is a laminated sheet, the adhesive resin constituting the layer (B) may be a polyolefin resin such as maleic acid,
A modified polymer obtained by copolymerizing unsaturated carboxylic acids such as acrylic acid, methacrylic acid, fumaric acid, and itaconic acid and / or their esters, acid anhydrides, metal salts, and derivatives thereof, for example, by graft copolymerization. Can be exemplified as a typical example.

Examples of the adhesive resin other than those described above include a mixture of the above-mentioned modified polymer and other components such as another olefin resin, an ionomer resin, an ethylene-ethyl acrylate resin, an ethylene-vinyl alcohol copolymer, -Saponified vinyl acetate copolymer and the like, but are not limited thereto, conventionally known hot melt adhesives, modified epoxy resins, aqueous urethane resins,
Examples thereof include an ultraviolet curable resin and a reactive polyolefin-based oligomer. In the present invention, these can be used alone or in combination of at least two kinds. At this time, in the case of a laminated structure in which the layer (B) appears on the surface, there is no particular limitation, but it is desirable to use an adhesive resin that does not easily generate blocking.

The method for preparing the composition constituting the receiving layer (A) comprising the water-absorbing resin, the cationic component and the crosslinking agent or the thermosetting resin as essential components according to the present invention is carried out by preparing a conventional polyolefin-based composition. The method may be performed by a known method used in the above. Specifically, a method of blending using a ribbon blender, a Hensel mixer, a tumbler, etc., a method of kneading using a kneader, a Banbury mixer, a roll, etc., melt-kneading with a single-screw or twin-screw extruder to form a strand. After extrusion, a method of producing pellets by cutting into an appropriate length with an appropriate cutter or the like can be exemplified, but there is no particular limitation.

The aqueous ink receiving layer (A), the adhesive layer (B), and the support base material layer (C) according to the present invention are provided with the properties of the aqueous ink recording sheet (for example, recording properties, transparency, water resistance, printing). ,
If necessary, various additive fillers, other thermoplastic resins, and the like may be blended within a range that does not inhibit ink bleeding of the image. For example, heat stabilizers as additives,
Light stabilizers, antioxidants, antistatic agents, lubricants, antibacterial agents, water-proofing agents, ultraviolet inhibitors, deodorants, film forming aids, pigments or dyes, etc., calcium carbonate, barium sulfate, hydroxide as filler Magnesium, talc, silica, titanium oxide, zirconia metal-based fine particles (antimony and the like), acrylic or silicon-based fine particles (particle diameter: 5 nm to 500 n)
m) and the like. As other thermoplastic resins,
For example, ionomers, thermoplastic elastomers and the like can be exemplified, but there is no particular limitation, and it is not necessary to mix them.

A preferred embodiment of the water-based ink recording sheet according to the present invention is a water-based ink receiving layer (A) comprising the above-mentioned water-absorbing resin, a cationic component and a composition comprising a crosslinking agent or a thermosetting resin as essential components. And at least two layers of an adhesive layer (B) made of an adhesive resin (A) /
(B) laminated sheet, coating sheet or (A)
A three-layer sheet (A) / (B) / (A) composed of a layer as a skin layer and a layer (B) as a core layer, or an aqueous ink-receiving layer (A), and a polyester-based resin or a polyolefin-based resin. And a supporting base material layer (C) made of a thermoplastic resin of any of a polyamide resin, a polystyrene resin, a cyclic polyolefin resin or a polycarbonate resin,
(A) / (B) / (C) three-layer laminated sheet composed of at least three layers via an adhesive layer (B), or (A)
/ (B) / (C) / (B) / (A).

Further, when paper is used for the support base material layer (C), the paper is impregnated with a composition liquid (coating liquid) for forming the aqueous ink receiving layer (A), and the ink is received by a resin extrusion method. Layer (A) is laminated on paper, or (A) / (C), (A) / (C) / (A), (A) /
(B) / (C), (A) / (B) / (C) / (B) /
(A) and the like can be exemplified.

When a nonwoven fabric is used for the support base material layer (C), the nonwoven fabric is impregnated with a composition liquid (coating solution) for forming the aqueous ink receiving layer (A), and the ink receiving layer is formed by resin extrusion. After laminating (A) onto a nonwoven fabric and then applying heat and pressure to impregnate the resin component into the nonwoven fabric, the ink receiving layer (A) is laminated on the nonwoven fabric by a resin extrusion method, or (A) / (C ), (A) / (C) /
(A), (A) / (B) / (C), (A) / (B) /
(C) / (B) / (A) can be exemplified.

At this time, the surface of the thermoplastic resin (C) is subjected to, for example, a corona discharge treatment and a wet tension of 40 dyn.
/ Cm or more, the (A) layer is laminated or coated on the treated surface of the (C) layer to form a two-layer structure of (A) / (C), and the (A) / (C) / (B) Three-layer structure, (A) /
A laminated sheet having a four-layer constitution of (B) / (C) / (A) and a three-layer constitution of (A) / (C) / (A) can be exemplified as long as both surfaces of the (C) layer are treated. .

The aqueous ink recording sheet according to the present invention comprises:
If necessary, recordability, water resistance, water absorption, curl prevention,
(B) and / or within a range that does not impair the ink bleeding prevention property and the like.
Alternatively, an appropriate layer made of one or more resins may be laminated on the surface of (C) or between (A) and (B) and / or between (A) and (C). The resin constituting the appropriate layer is not particularly limited, but may be a resin of the same type as (A), (B) or (C) or a resin of a different type. As the different types of resins, resins having a water absorbing property different from those of the present invention, for example, saponified ethylene-vinyl acetate copolymer, ethylene-
Preferred examples include a vinyl alcohol copolymer and a polyvinyl acetal-based resin. However, the material is not particularly limited as long as it does not inhibit the properties of the aqueous ink recording sheet.

The sheet for aqueous ink recording according to the present invention comprises:
In the case of a laminated structure composed of at least (A), (B) and (C), the laminating method is, for example, (A) / (B)
/ Co-extrusion method of co-extruding and laminating so as to be (C),
(B) is melt-extruded on the surface of (A) or (C),
(A) or (C) is melt-extruded on the surface of (B),
(A) / (B) / (C) by an extrusion lamination method in which the layers are laminated so as to be (A) / (B) / (C), or (A) / (B) / (C) via an adhesive. Dry laminating method of laminating so as to satisfy (A), (B), (C)
Are separately formed and laminated by thermocompression bonding so as to obtain (A) / (B) / (C). Further, (A) is applied to at least one surface of (B) or (C). Although a coating method and the like can be exemplified, it is not particularly limited.

Further, as a method of laminating the aqueous ink recording sheet comprising at least (A) and (B), a coextrusion method, an extrusion lamination method, a dry lamination method, a thermocompression bonding method, and a lamination method in the same manner as described above. A coating method and the like can be exemplified, and there is no particular limitation. On the other hand, as a method of laminating a laminated sheet in which the (B) layer is not interposed between layers such as (A) / (C) or (A) / (C) / (A), at least one of the (C) layers is laminated. The surface is subjected to, for example, corona discharge treatment (surface wetting tension of 40 dyn / cm or more) in the step of forming the layer (C) at the same time as the film formation or in another step after the film formation. Are (A) / (C), (A) / (C) /
A method of laminating by thermocompression bonding to obtain (A), a method of coating (A) on the treated surface of layer (C), and the like can be exemplified, but there is no particular limitation.

In the method for producing the aqueous ink recording sheet according to the present invention, when the supporting base material layer (C) is made of a thermoplastic resin,
It is preferable to manufacture by co-extrusion using a T-die method capable of melt lamination, but there is no particular limitation. Specifically, the water absorbent resin 1
A composition obtained by mixing 1 to 250 parts by weight of a cationic component and 1 to 10 parts by weight of a crosslinking agent or a thermosetting resin to 00 parts by weight was prepared.
The mixture is melt-kneaded with a twin-screw extruder set at 00 to 130 ° C., extruded into strands, air-cooled or water-cooled, and then cut to form pellets having a particle diameter of 3 mm and a length of 4 mm which form the aqueous ink receiving layer (A). Granulate.

The aqueous ink receiving layer (A) composed of the above-mentioned pellets and the supporting base material layer (C) are laminated via an adhesive layer (B) composed of an adhesive resin, for example, (A) / (B) /
The water-based ink recording sheet having the constitution (C) comprises a pellet for forming the ink receiving layer (A), a support base material layer, and a hopper of at least three independent extruders in which co-extrusion T dies are commonly connected. For example, a polyester resin and an adhesive resin which form (C) are charged, and then each resin (preferably a pellet) is not particularly limited, but is preferably 100 to 13
It is melt-extruded by an extruder heated to 0 ° C., cooled and solidified by a cooling roll, water or air cooling, and molded. Further, as another configuration, similarly, using five independent extruders,
For example, 5 such as (A) / (B) / (C) / (B) / (A)
What is necessary is just to form a water-based ink recording sheet having a layer structure. Further, for example, the structure of (A) / (B) or (A) /
A three-layer structure of (B) / (A) may be molded in the same manner as above.

As another manufacturing method, a water-absorbing resin, a cationic component and a water-absorbing resin for forming the aqueous ink-receiving layer (A) are provided on at least one surface of the adhesive layer (B) or the supporting substrate layer (C) made of paper or nonwoven fabric. And a method of coating a coating agent obtained by dissolving a composition containing a crosslinking agent or a thermosetting resin as an essential component in an appropriate solvent. The coating method is not particularly limited, and may be any suitable method such as gravure coating, reverse roll coating, dip coating, air knife coating, and bar coating.

As a specific coating agent, the composition for forming the aqueous ink-receiving layer (A) may be prepared by using an organic solvent such as methyl alcohol, ethyl alcohol, isopropyl alcohol, chloroform, ethyl acetate or the like, 5 to 30% by weight of a coating agent dissolved in a mixed solvent of water (30 parts by weight) and water (30 parts by weight). When the amount is less than 5% by weight, the coating film tends to be thin when coated, and the absorbability of the aqueous ink is reduced. 30
If the amount is more than 10% by weight, the viscosity of the coating solution increases, so that it is difficult to control the thickness of the coating film and the workability tends to decrease.

The total thickness of the aqueous ink recording sheet according to the present invention is, for example, 10 to 300 μm. 10μ
If it is less than m, the mechanical strength tends to decrease,
If it exceeds m, it tends to be too rigid, resulting in poor moldability and the like, and the practicality tends to be limited.

The sheet for aqueous ink recording according to the present invention comprises:
(A) / (B) comprising the aqueous ink receiving layer (A) and the adhesive layer (B) made of an adhesive resin, or the aqueous ink receiving layer (A) is subjected to, for example, a corona discharge treatment to have a surface wetting tension of 40 dyn. / A / C or a two-layer structure composed of a supporting base material layer (C) having a total thickness of 10 / cm or more.
３００300 μm, the thickness of the aqueous ink receiving layer (A) is 2-1.
For example, the thickness of the adhesive layer (B) or the supporting base material layer (C) may be 5 to 250 μm. If the thickness of the aqueous ink-receiving layer (A) is less than 2 μm, the water absorption tends to be smaller and the recording properties tend to be reduced. If it exceeds 300 μm, the water absorption becomes larger and the absorption of the water-based ink increases, so that it is difficult to firmly fix the water-based ink,
Under high temperature and high humidity, ink bleeding tends to occur.

Further, for example, (A) / (B) comprising the aqueous ink receiving layer (A) and the adhesive layer (B) according to the present invention.
/ (A) or (A) / (B) / (C) comprising an aqueous ink receiving layer (A), an adhesive layer (B), and a support base material layer (C) made of, for example, a polyester resin. Layer structure or (A) / (B) / (C) / (B) / (A)
In the case of the five-layer constitution, the thickness of the aqueous ink receiving layer (A) is 2
To 100 μm. If it is less than 2 μm, the water absorption becomes smaller and the absorption of the water-based ink becomes small, so that the recording properties of printing and images tend to decrease. If it exceeds 100 μm, the water absorption increases and the ink absorption improves. When water is immersed in water, it swells and whitens, and the transparency and the strength of the aqueous ink receiving layer (A) tend to be reduced. Tends to occur. The thickness of the adhesive layer (B) is (A)
It is not particularly limited as long as it is capable of firmly adhering (A) and (A) or (C), and is not particularly limited, and may be, for example, 10 μm or less, preferably 5 μm or less, and more preferably 1 to 3 μm.

Further, the aqueous ink receiving layer (A) according to the present invention is treated with, for example, corona discharge treatment and has a surface wetting tension of 4%.
In the case of a three-layer constitution (A) / (C) / (A) comprising a support base layer (C) of 0 dyn / cm or more, the thickness of the aqueous ink receiving layer (A) can be exemplified by 2 to 100 μm. , 2μ
If it is less than m, the absorbability of the aqueous ink tends to be poor and the recording property tends to decrease. Water-based ink bleeding tends to occur. At this time, the thickness of the support base material layer (C) is not particularly limited, but may be, for example, 5 to 250 μm. If it is less than 5 μm, the mechanical strength tends to decrease. If it exceeds 250 μm, it tends to be rigid and the printability by a printing machine tends to be poor.
Uses are limited.

The coating material dissolved in the organic solvent constituting the aqueous ink receiving layer (A) according to the present invention is subjected to at least one surface or surface treatment (for example, corona discharge treatment) of the adhesive layer (B) to reduce the surface wetting tension. (A) / (B), (A) / (B) / (A) or (A) / (C), (A) / (B) formed by coating the treated surface of the support base material layer (C) having a thickness of 40 dyn / cm or more. In the case of A) / (C) / (A) configuration,
For example, the total thickness is 10 to 300 μm, the thickness of the aqueous ink receiving layer (A) is 2 to 100 μm, and the thickness of the adhesive layer (B) or the supporting base material layer (C) is 5 to 250 μm.
When the thickness of the aqueous ink receiving layer (A) is less than 2 μm, the absorbability of the aqueous ink is poor, and the recording properties tend to be reduced,
If it exceeds 100 μm, the water resistance tends to decrease.
The thickness of the adhesive layer (B) or the supporting base material layer (C) is 5 μm.
If it is less than m, the mechanical strength tends to decrease, and if it exceeds 250 μm, the rigidity tends to increase, and the printability by a printing machine decreases, and the use is limited.

The aqueous ink recording sheet according to the present invention comprises:
For example, with an aqueous inkjet printer, an overhead projector (OH
P) sheet, poster substrate printed with aqueous ink,
It can be suitably used as a substrate for print lamination, a substrate for advertising, a substrate for barcode printing, a sheet or film for illumination, a substrate for color filters, a glossy film, and a gravure or offset printing substrate. Further, the water-based ink recording sheet according to the present invention can also be used as a packaging film, an agricultural sheet, a dew-prevention sheet, a cooking sheet, and the like, and is not particularly limited.

[0060]

Hereinafter, the present invention will be described based on examples, but the present invention is not limited to the following examples.

In the following examples of the present invention, measurement and evaluation of each inspection item were performed by the following methods. [Water absorption]: The amount of increase in weight per original total area was determined according to JIS K-7209, and the result was divided by the thickness of the aqueous ink receiving layer.

[Water resistance-1]: After printing with water-based ink using a water-based ink BJ printer [BJC-600J manufactured by Canon Inc.], immersing in water for 5 days, ink bleeding, and the degree of ink drop-off were visually observed. The evaluation and the coating strength of the aqueous ink receiving layer (A) were evaluated by touch. The ranking is
5: No ink bleeding or ink detachment was observed at all, and the film strength was strong. 4: Almost no ink bleeding or falling off was observed,
Maintains film strength. 3: Bleeding and falling off of the ink were easily recognized, and the film strength was weak. 2: Ink bleeding and dropping were so severe that it was difficult to judge printing, and a part of the coating was peeled off. 1:
It was evaluated that all the ink dropped off and the coating was easily peeled off.

[Waterfastness-2]: Water-based ink Printing with water-based ink using a BJ printer [BJC-600J manufactured by Canon Inc.], immersion in water for 7 days, and ink reception after drying at room temperature The change of the layer (A) was visually evaluated, and the following ranking was performed. 5: No whitening and swelling, maintaining transparency before immersion (can be used for OHP). 4: Whitens somewhat, but maintains transparency (can be used for OHP). 3: considerably whitened, but somewhat transparent (not possible with OHP).
2: Whitened but not swollen (not possible with OHP). 1: Whitening and swelling, no transparency (not possible with OHP).

[Preservability]: Water-based ink Printed with water-based ink using a BJ printer [BJC-600J manufactured by Canon Inc.] and left in a thermo-hygrostat adjusted to 40 ° C. and 90% RH for 7 days. Were visually evaluated for ink bleed and ranked. 5: No ink bleeding was observed at all. 4: Almost no ink bleeding was observed. 3: Some ink bleeding was observed. 2: Ink bleeding is observed. 1: Ink bleeds frequently and cannot be used.

[Recording property]: Printing was carried out with a water-based ink using a water-based ink BJ printer [BJC-600J manufactured by Canon Inc.], and the recording property was visually evaluated as follows. 5: Excellent clear printing is obtained. 4: Clear printing is obtained.
3: Printing without practical problems is obtained. 2: The outline of the print is blurred. 1: Ink does not fix.

[Printability]: Using a water-based ink BJ printer [BJC-600J manufactured by Canon Inc.], solid coating of each color expressed by a mixture of inks of four colors of magenta, yellow, cyan, and black ( (1 cm square) A pattern was printed so that the printed portions were in contact with each other, and disturbance (beading) of the image at the contact portions was visually evaluated as follows. 5;
Excellent clear images without beading can be obtained.
4: A clear image is obtained although slight beading occurs. 3: An image in which beading occurs but has no practical problem is obtained. 2: Beading occurs and the outline is blurred. 1: Being occurs, ink is mixed, and image recognition is difficult.

[Transparency]: A haze value was measured and evaluated using a haze meter [Nippon Denshoku Industries Co., Ltd. digital haze meter NDH2D] according to ASTM D-882.

[Quick drying]: Using a water-based ink BJ printer [BJC-600J manufactured by Canon Inc.], solid printing patterns of each color are printed in magenta, yellow, cyan, and black, and ink is attached by touching. The time (seconds) until it stopped being measured was measured.

[Stickiness]: After printing with an aqueous ink using a water-based ink BJ printer [BJC-600J manufactured by Canon Inc.], touch the stickiness when left at 40 ° C. and 90% RH. The evaluation was as follows. 3: There is no stickiness at all. 2: Slightly sticky, but practically no problem. 1: Very sticky.

[Surface electric resistance value]: JIS K-601
The measurement and evaluation were performed according to 1.

Example 1 Aqua Coke T [manufactured by Sumitomo Chemical Co., Ltd .: water absorbing resin] 100 parts by weight Alumina sol [manufactured by Nissan Chemical Industries, Ltd .: cationic component] 20 parts by weight (active ingredient 20% by weight aqueous solution) A composition consisting of a cylinder temperature of 120 ° C. and a die temperature of 1
The mixture was extruded into a strand from a 30 ° C. vent extruder, cooled, and cut to produce pellet-1. Next: 120 parts by weight of the above-mentioned pellet-1 Leorex [Cationic component: Daiichi Kogyo Seiyaku Co., Ltd.] 40 parts by weight Peroxide crosslinking agent [2,5-dimethyl 2,5- (t-butylperoxy) ) Hexin-3] 5 parts by weight of the above composition was extruded in a strand form from an extruder set at a cylinder temperature of 110 ° C and a die temperature of 100 ° C, cooled and cut to obtain 3 x 4 mm pellet-2. .

As the aqueous ink receiving layer (A), the above-mentioned pellet-2 was used. As the adhesive layer (B), an adhesive resin obtained by modifying a polyethylene resin with maleic acid was used as the support base material layer (C).
, A polyester resin was used. T for three-layer coextrusion
The pellet-2 obtained above was used in one of three independent extruders connected to a die, the adhesive resin obtained by modifying a polyethylene resin with maleic acid in another one, and the other one in another. Polyester resin is supplied, and the barrel temperature of layer (A) is 1
The mixture was melt-kneaded at a temperature of 30 ° C., a barrel temperature of the layer (B) of 180 ° C., a barrel temperature of the layer (C) of 270 ° C., and a die temperature of 270 ° C., extruded, cooled, and cooled (A) / (B) / ( C) = 10
A laminated sheet having a three-layer configuration of / 3/100 = 113 μm was formed. Subsequently, the laminated sheet was heat-treated in an oven at about 150 ° C. for about 3 minutes to obtain a water-based ink recording sheet having a cross-linked and hardened water-based ink receiving layer (A). Table 1 shows the results of the water absorption, water resistance, storability, recording properties, printability, transparency, quick drying, stickiness, and surface electrical resistance of the aqueous ink recording sheet.

[0073]

[Table 1]

Example 2 Adhesion obtained by modifying the pellet-2 composed of the composition obtained in Example 1 as the aqueous ink receiving layer (A) and modifying the polyethylene resin with maleic acid as the adhesive layer (B) A conductive resin was used. One of two independent extruders connected to a two-layer co-extrusion T-die, one of the extruders, the pellet-2 serving as the aqueous ink receiving layer (A), and the other one, polyethylene serving as the adhesive layer (B). An adhesive resin obtained by modifying a base resin with maleic acid is supplied, and the barrel temperature of the (A) layer is 130 ° C., and (B)
The layer was melt-kneaded at a barrel temperature of 180 ° C. and a die temperature of 270 ° C., extruded, cooled, and (A) / (B) = 20 /
A water-based ink recording sheet was obtained in the same manner as in Example 1 except that a laminated sheet having a two-layer structure of 2 = 22 μm was formed. Table 1 shows the results of the water absorption, water resistance, storability, recording properties, printability, transparency, quick drying, stickiness, and surface electrical resistance of the aqueous ink recording sheet.

Example 3 Aqueous ink-receiving layer (A) formed by a usual T-die method using pellet-2 composed of the composition obtained in Example 1.
And a polyester resin (C) in a separate process
And (A) / (B) / (C) a two-layer laminated sheet (B) / (C) formed by coextrusion of an adhesive resin (B) obtained by modifying a polyethylene resin with maleic acid. ) At a temperature of 80 ° C and a pressure of 30 kg / cm2.
Thermocompression bonding for 5 seconds, (A) / (B) / (C) = 25/3
A laminated sheet having a three-layer configuration of / 100 μm = 128 μm was formed. Subsequently, heat treatment was performed at 150 ° C. for 3 minutes to obtain a water-based ink recording sheet having a water-based ink-receiving layer (A) crosslinked and cured. Table 1 shows the results of the water absorption, water resistance, storability, recording properties, printability, transparency, quick drying, stickiness, and surface electrical resistance of the aqueous ink recording sheet.

Example 4 Aqua Coke [manufactured by Sumitomo Chemical Co., Ltd .: water-absorbing resin] 70 parts by weight Saponified ethylene-vinyl acetate copolymer (30% by weight of active ingredient in water / isopropanol solution) 100 parts by weight Chemistat 6300H [Manufactured by Sanyo Kasei Kogyo Co., Ltd .: Cationic component] (Active ingredient 33% by weight aqueous solution) 151 parts by weight Sumitex Resin AR-8 [Sumitomo Chemical Co., Ltd .: Polyamide thermosetting resin] (Active ingredient 25 wt. % Aqueous solution) 18 parts by weight Glass beads MB-20 (particle size: 10 μm) [manufactured by Toshiba Microbeads] 0.45 parts by weight Methyl alcohol 200 parts by weight A coating solution comprising the above composition was coated to a thickness of 100 μm.
One side of Melinex (manufactured by ICI: polyester-based film (anchor treated)) is coated with a wire bar coater, and dried at 100 ° C. for 2 minutes and then at 135 ° C. for 5 minutes. A heat curing reaction was performed to obtain a water-based ink recording sheet having a water-based ink receiving layer crosslinked and cured by a thickness of 20 μm. Water absorption, water resistance, storage properties, recording properties, printability,
Table 1 shows the results of the transparency, quick-drying property, stickiness resistance and surface electric resistance value.

Example 5 Merpol F320 [manufactured by Sanyo Chemical Industries, Ltd .: water-soluble polyether] (20% by weight aqueous solution of active ingredient) 250 parts by weight Leorex [manufactured by Daiichi Kogyo Seiyaku Co., Ltd .: cationic component] 5% by weight of active ingredient in methanol solution) 500 parts by weight Alumina sol 520 [Cationic fine particles manufactured by Nissan Chemical Industries, Ltd.] (20% by weight aqueous solution of active ingredient) 100 parts by weight Polyglycidyl ether [Epoxy thermosetting resin] 3% by weight Part Trialkyl isocyanate [crosslinking assistant] 0.3 part by weight A corona discharge treated surface wetting tension of 54 dyn / cm, 100 μm thick sheet of a coating solution comprising the above composition and a polyester resin containing a white inorganic pigment. After applying a coating on the corona discharge treated surface of the above by using a wire bar coater, 12 ℃, the heat treatment is performed for 5 minutes, then 150 kV, performs electron beam irradiation treatment under conditions of 200 Mrad, to obtain an aqueous ink recording sheet having an aqueous ink-receiving layer having a thickness of 25μm to (A). Table 1 shows the results of the water absorption, water resistance, storability, recording properties, printability, transparency, quick drying, stickiness, and surface electrical resistance of the aqueous ink recording sheet.

Example 6 Aqua Coke [manufactured by Sumitomo Seika Co., Ltd .: water-absorbent resin] 100 parts by weight Chemistat 7300H [manufactured by Sanyo Chemical Industries, Ltd .: cationic surfactant] (active ingredient 30% by weight aqueous solution) 200 Parts by weight Alumina sol 520 (manufactured by Nissan Chemical Industries, Ltd .: cationic fine particles) (20% by weight of active ingredient in water) 150 parts by weight Neidral [manufactured by Taki Kagaku: cerium oxide ultraviolet absorber] (15% by weight of active ingredient) 58 parts by weight Sumitec Resin M-3 [Melamine-formalin-based resin manufactured by Sumitomo Chemical Co., Ltd.] (80% by weight of active ingredient) 4 parts by weight Amine-based crosslinking assistant (aqueous solution of 20% by weight of active ingredient) 6 parts by weight Crosslinked polystyrene-based fine particles SBX [manufactured by Sekisui Chemical Co., Ltd .: lubricant] (particle diameter: 6 μm) 1 part by weight One side of a film (anchor-treated) as a base material layer (C) made of a stell-based resin having a thickness of 100 μm is coated using a wire bar coater, and is coated with an oven at 100 ° C.
After drying at 130 ° C for 5 minutes, heat treatment
An aqueous ink recording sheet having an aqueous ink receiving layer (A) crosslinked and cured by μm was obtained. Table 1 shows the results of the water absorption, water resistance, storability, recording properties, printability, transparency, quick drying, stickiness, and surface electrical resistance of the aqueous ink recording sheet.

Example 7 (coating on paper) Aqua coke 70 parts by weight EVOH solution 30 parts by weight (30% water / IPA solution) Chemistat 6300H 151 parts by weight (33% aqueous solution) Sumitex resin AR-8 18 parts by weight ( (25% aqueous solution) (Sumitomo Chemical's polyamide-based crosslinking agent) Glass beads 0.45 parts by weight (Toshiba Micro Beads MB-20 particle size 10 μm) A solution consisting of 250 parts by weight of methanol is applied to untreated paper having a basis weight of 85 g and a thickness of 188 μm. After impregnation and drying with hot air at 80 ° C. for 3 minutes, the treated paper was thermocompression-bonded while being heated and cross-linked with a pressure roll (linear pressure 5 kg / cm) heated to 130 ° C. to obtain an aqueous ink printing paper. The processed paper had a thickness of 180 μm and a basis weight of 100 g. Table 1 shows the characteristic values.

Example 8 (Lamination to Nonwoven Fabric) Aqua Coke 100 parts by weight Leorex 50 parts by weight Alumina sol 100 parts by weight (20% aqueous solution) Benzotriazole-based ultraviolet absorber 1 part by weight 3 × 4 mm pellets were obtained with a kneader (cylinder 140 ° C., die 120 ° C.). The above pellets were mixed with a single layer T-die extruder at a ratio of 100 parts by weight of an organic peroxide crosslinking agent 5 parts by weight (2.5 dimethyl 2,5- (t-butylperoxy) hexyne) (cylinder 12).
(0 ° C., die 110 ° C.) using a basis weight of 60 g and a thickness of 1
Extruded onto a 20 μm polyester nonwoven fabric, 5 ° C
After cooling and solidifying with a cooled chill roll, a nonwoven fabric sheet for aqueous ink printing was obtained after a pressure treatment while heating and cross-linking with a heat-pressing roll (140 ° C.) having a linear pressure of 10 kg / cm. The sheet thickness after the treatment was 115 μm and the weight per unit area was 73 g.

Comparative Example 1 Aqua Coke T [manufactured by Sumitomo Chemical Co., Ltd .: water absorbent resin] 100 parts by weight Leorex [manufactured by Daiichi Kogyo Seiyaku Co., Ltd .: cationic component] 40 parts by weight Alumina sol [Nissan Chemical Industries, Ltd. Co., Ltd .: Cationic component] 20 parts by weight (20% by weight aqueous solution of active ingredient) In the same manner as in Example 1 except that the above composition was used as the aqueous ink receiving layer (A) and that no heat treatment was performed ( An aqueous ink recording sheet having a three-layer constitution of A) / (B) / (C) was obtained. Table 2 shows the results of the water absorption, water resistance, storability, recording properties, printability, transparency, quick drying, stickiness and surface electrical resistance of the aqueous ink recording sheet.

[0082]

[Table 2]

Comparative Example 2 The procedure of Example 1 was repeated except that a pellet made of the composition obtained in Comparative Example 1 was used as the aqueous ink receiving layer (A), and that no heat treatment was performed. A water-based ink recording sheet having a two-layer structure (B) was obtained. Table 2 shows the results of the water absorption, water resistance, storability, recording properties, printability, transparency, quick drying, stickiness and surface electrical resistance of the aqueous ink recording sheet.

Comparative Example 3 Aqua Coke [manufactured by Sumitomo Chemical Co., Ltd .: water-absorbent resin] 80 parts by weight Saponified ethylene-vinyl acetate copolymer (30% by weight of active ingredient in water / isopropanol solution) 60 parts by weight Chemistat 6300H [Manufactured by Sanyo Chemical Industries, Ltd .: Cationic component] (Active ingredient 33% by weight aqueous solution) 150 parts by weight Glass beads MB-20 (particle size 10 μm) [manufactured by Toshiba Microbeads] 0.45 parts by weight Methyl alcohol 350 parts by weight A water-based ink recording sheet having a water-based ink-receiving layer was obtained in the same manner as in Example 4, except that the coating solution composed of the above composition was used and the heat curing reaction was not performed. Table 2 shows the results of the water absorption, water resistance, storability, recording properties, printability, transparency, quick drying and stickiness of the aqueous ink recording sheet.

Comparative Example 4 Aqua Coke [manufactured by Sumitomo Seika Co., Ltd .: water absorbent resin] 100 parts by weight Chemistat 7300H [manufactured by Sanyo Chemical Industries, Ltd .: cationic surfactant] (30% by weight aqueous solution of active ingredient) 200 Parts by weight Alumina sol 520 (manufactured by Nissan Chemical Industries, Ltd .: cationic fine particles) (20% by weight of active ingredient in water) 150 parts by weight Neidral [manufactured by Taki Kagaku: cerium oxide ultraviolet absorber] (15% by weight of active ingredient) 38 parts by weight Crosslinked polystyrene-based fine particles SBX [manufactured by Sekisui Chemical Co., Ltd .: lubricant] (particle size: 6 μm) 0.1 part by weight Except for using a coating solution comprising the above composition and not performing a heat curing reaction. A water-based ink recording sheet was obtained in the same manner as in Example 6. Table 2 shows the results of the water absorption, water resistance, storability, recording properties, printability, transparency, quick drying, stickiness and surface electrical resistance of the aqueous ink recording sheet.

As is evident from Table 1, the aqueous ink recording sheets of Examples 1 to 6 had the aqueous ink receiving layer (A).
, A crosslinking agent or a thermosetting resin, and if necessary, a crosslinking aid, and a heat treatment or an electron beam irradiation treatment to carry out crosslinking and curing, whereby the water absorption of the aqueous ink receiving layer (A) is 0.5 to 20. 0 mg / mm2 / μm,
Even if the aqueous ink recording sheet on which printing, images, etc. are recorded under high temperature and high humidity is stored for a long period of time, there is no bleeding of the aqueous ink, and water resistance, recording properties, printability, transparency, quick drying and stickiness are resistant. It has excellent properties. On the other hand, Comparative Examples 1-4
Is because the aqueous ink receiving layer (A) does not contain a crosslinking agent, a thermosetting resin, or a crosslinking auxiliary, and is not subjected to a heat treatment or an electron beam irradiation treatment. When stored for a period of time, the water resistance is poor, and bleeding of the aqueous ink such as recorded prints and images tends to occur.

[0087]

The water-based ink recording sheet according to the present invention has excellent water resistance, recording properties, printability and transparency, and does not decrease the strength of the ink-receiving layer even when immersed in water or the like. The sheet has excellent reproducibility, such as printing, images and the like, and does not tend to cause aqueous ink bleeding even when stored for a long period of time under high temperature and high humidity. Accordingly, the water-based ink recording sheet according to the present invention includes an overhead projector sheet, a glossy film, a poster, an advertisement sheet, an illumination sheet and a color filter substrate, a gravure or offset printing substrate, and an adhesive label. It can be suitably used as a base material or the like.

Claims (8)

[Claims] 1. 100 parts by weight of a water-absorbent resin, 1 to 250 parts by weight of a cationic component and a crosslinking agent or a thermosetting resin 1
Aqueous ink receiving layer (A) comprising a composition containing 10 to 10 parts by weight as an essential component, crosslinked and cured by heat treatment or electron beam irradiation treatment, and having a water absorption of 0.05 to 2.0 mg / cm ² / μm. A) a water-based ink recording sheet having at least one outer layer. 2. The aqueous ink recording sheet according to claim 1, which has a multilayer structure comprising an aqueous ink receiving layer (A), an adhesive layer (B) made of an adhesive resin, and a support base material layer (C). . 3. The two of (A) / (B) and (A) / (C)
Layers, (A) / (B) / (A), (A) / (B) /
(C), (A) / (C) / (A), (A) / (C) /
(B) three layers, (A) / (B) / (C) / (B),
(A) / (B) / (C) / (A) four layers, (A) /
The aqueous ink recording sheet according to any one of claims 1 to 2, wherein the sheet has a multilayer structure having five layers (B) / (C) / (B) / (A). 4. A water-absorbing resin comprising: a polyalkylene oxide compound and a derivative thereof; a crosslinked polyalkylene oxide compound and a derivative thereof; a reaction product of a polyalkylene oxide compound or a derivative thereof with an isocyanate compound; a polyacrylic resin; 4. The method according to claim 1, wherein the resin is at least one or more selected from a polyvinyl alcohol resin, a polyether resin, a polyvinyl acetal resin, a polyvinyl pyrrolidone resin, and a cellulose derivative.
4. The aqueous ink recording sheet according to any one of 3. 5. The cationic component is a secondary ammonium salt, a tertiary ammonium salt, a quaternary ammonium salt, a secondary ammonium salt type cationic surfactant, a tertiary ammonium salt type cationic surfactant, The quaternary ammonium salt type cationic surfactant, amine type or amine salt type cationic surfactant, at least one selected from the group consisting of positively charged fine particles and cationic polymer. The aqueous ink recording sheet according to any one of the above. 6. The aqueous ink recording sheet according to claim 1, wherein the crosslinking agent is at least one selected from organic peroxides. 7. The thermosetting resin may be a melamine-formalin resin, a urea-formalin resin, a glyoxal resin, a urethane-acrylic acid copolymer, a vinyl ether resin, an acrylate resin, or any of the above monomers ( At least one selected from the group consisting of a monomer), a low polymer (oligomer) and an epoxy resin.
The aqueous ink recording sheet according to any one of Items 1 to 3, wherein 8. The support base material layer (C) is made of plastics,
The aqueous ink recording sheet according to any one of claims 1 to 7, comprising one of paper and a nonwoven fabric.