JPH11123869A - Sheet for printing with water-based ink - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a sheet for printing with water-based ink which is excellent in printability, water resistance, shelf stability, etc., by a method wherein a water-based ink receiving layer constituted of a composition having hydrophilic resin and an acrylamide copolymer as indispensable constituents and a base layer are laminated with an adhesive layer containing specific carbimide resin interlaid. SOLUTION: An adhesive is prepared from single carbodiimide resin expressed by the formula (wherein R denotes C1 -C12 alkyl or C3 -C10 cycloalky, Z C1 -C12 alkylene, C3 -C10 cycloalkylene, C4 -C16 alkylene having a cyclic or noncyclic structure, or the like, (n) an integer of 1-50 and (m) an integer of 1 or 2) or from a composition constituted mainly of the carbodiimide resin of 0.1-99.9 wt.% and adhesive resin of 99.9-0.1 wt.% A sheet for printing with water based ink is prepared by laminating a water based ink receiving layer containing a cationic copolymer and a substrate base layer with an adhesive layer constituted of the adhesive interlaid.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a sheet for printing an aqueous ink. More specifically, a sheet (including a film) printed with an aqueous ink using, for example, an ink-jet printer, a pen plotter, or the like, when wet with water, peels off the ink receiving layer (A), swells white, drops off the ink. The present invention relates to the provision of a water-based ink printing sheet having excellent printability, water resistance, and storability without stickiness, blocking, deterioration in physical properties, and ink bleeding when stored under high temperature and high humidity. .

[0002]

2. Description of the Related Art Conventionally, aqueous inks can be printed, images printed, and fixed using, for example, an ink jet printer, a pen plotter, or the like, and used as a base material for, for example, an overhead projector (OHP). Sheets (including films) made of various plastics are used as ink printing sheets. Examples of such a water-based ink printing sheet include, for example, a hydrophilic or water-absorbing resin (hereinafter referred to as a “hydrophilic resin”) such as polyethylene oxide (PEO) on the surface of a sheet or film made of a polyester resin. , Polyvinyl alcohol (PVA), polyvinyl pyrrolidone (P
Aqueous ink printing sheets and the like obtained by laminating or coating a composition mainly containing a cationic component or any one or a mixture of VP) and carboxymethyl cellulose (CMC) are known.

However, such a water-based ink printing sheet generally tends to elute the hydrophilic resin constituting the water-based ink receiving layer (A) when wet with water or stored under high temperature and high humidity. There is. Therefore, in such a water-based ink printing sheet, the adhesion between the water-based ink-receiving layer (A) and the support base material layer (C) is reduced, and the water-based ink-receiving layer (A) is peeled, dissolved, swelled and turbid, and water-based. There was a tendency for ink to fall off, bleeding of the aqueous ink, stickiness, blocking, and deterioration in physical properties (for example, strength), and the like, resulting in poor printability, water resistance, and storage stability.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above situation. The purpose of the present invention is
By using a carbodiimide-based resin alone or a composition containing a carbodiimide-based resin and an adhesive resin as main components for the adhesive layer (B), it has printability, water resistance, storage stability, and mechanical strength. An object of the present invention is to provide a water-based ink printing sheet having excellent properties.

[0005]

The feature of the present invention is as follows.
A hydrophilic resin and an acrylamide-based cationic copolymer are bonded through an adhesive layer (B) composed of a carbodiimide-based resin alone or a composition containing a carbodiimide-based resin and an adhesive resin as main components. The present invention is to provide a water-based ink printing sheet obtained by laminating a water-based ink receiving layer (A) composed of a composition containing a copolymer as an essential component and a support base layer (C).

[0006]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The adhesive layer (B) constituting the aqueous ink printing sheet according to the present invention is made of a carbodiimide resin having a highly reactive carbodiimide group in the main chain and a reactive isocyanate group in the terminal. It is composed solely or of a composition mainly composed of a carbodiimide-based resin and an adhesive resin. At this time, the carbodiimide-based resin can improve the compatibility with the aqueous ink-receiving layer (A) and the support base layer (C) by, for example, introducing a urea bond into a reactive isocyanate group at the terminal of the carbodiimide-based resin. Tends to improve. Examples of the carbodiimide resin into which a urea bond is introduced include organic aliphatic diisocyanates (for example, isophorone diisocyanate,
4'-dicyclohexylmethane diisocyanate, tetramethylxylylene isocyanate and the like can be mentioned. With a primary or secondary organic aliphatic amine (for example, n-butylamine, cyclohexylamine, dicyclohexylamine, etc.), and
After introducing, for example, a urea bond into the organic aliphatic diisocyanate, a carbodiimidation catalyst (for example, 3-methyl-
1-phenyl-2-phospholene-1-oxide is preferred) and a carbodiimidization catalyst having a highly reactive carbodiimide group in the main chain obtained by carbodiimidization in the presence of an organic aliphatic diisocyanate or a carbodiimidization catalyst In the presence of, after at least a part thereof is carbodiimidated, for example, by reacting a primary or secondary organic aliphatic amine, a carbodiimide is introduced with, for example, a urea bond, and only a carbodiimide group having high reactivity in the main chain is formed. Can be exemplified, but there is no particular limitation, and it is not necessary to introduce an imide bond.

[0007]

Wherein R is a C ₁ -C ₁₂ alkyl group or C ₃ -C
The cycloalkyl group C _10, Z is a bond of an alkylene group or an aromatic C ₄ -C ₁₆ having C ₁ -C ₁₂ alkylene group, a cycloalkylene group of C ₃ -C _10, cyclic or acyclic structure the alkylene group of C ₈ -C ₁₆ that, n represents 1 to 5
M represents an integer of 1 or 2; )

The water-based ink printing sheet according to the present invention comprises:
It has a highly reactive carbodiimide group in the main chain and is composed of a carbodiimide-based resin alone or having a compatibility with the aqueous ink-receiving layer, or a composition mainly composed of the carbodiimide-based resin and the adhesive resin. The aqueous ink receiving layer (A) composed of a composition mainly composed of a hydrophilic resin and an acrylamide copolymer and a supporting substrate layer (C) are laminated via an adhesive layer (B). At this time, the carbodiimide group having a main chain of the carbodiimide-based resin is a hydroxyl group, acrylic acid, amine (primary amine, secondary amine, tertiary amine, quaternary amine) contained in the aqueous ink receiving layer (A). It is presumed that it chemically reacts with an amine), a carbonyl group, a carboxyl group, an ester group, etc., and strongly adheres the aqueous ink receiving layer (A) to the adhesive layer (B). On the other hand, the supporting base material layer (C) is also composed of the carbodiimide-based resin constituting the adhesive layer (B) alone or the adhesive layer (B) composed of a composition containing the carbodiimide-based resin and the adhesive resin as main components. Adheres firmly. Therefore, it is possible to provide a water-based ink printing sheet in which the water-based ink receiving layer (A) and the supporting base material layer (C) are firmly laminated via the adhesive layer (B).

The adhesive resin to be added to the carbodiimide resin constituting the adhesive layer (B) according to the present invention is not particularly limited. For example, maleic acid, acrylic acid, methacrylic acid, fumaric acid may be used in the polyolefin resin. , Unsaturated carboxylic acids such as itaconic acid and / or their esters,
Modified polymers obtained by copolymerizing acid anhydrides, metal salts and derivatives thereof, for example, by graft copolymerization, can be exemplified as typical examples.

The adhesive resin other than the above-mentioned modified polymer includes an olefin polymer of the same kind as the above-mentioned modified polymer or other components, for example, a mixture with another olefin polymer,
Ionomer resin, ethylene-ethyl acrylate resin (EEA), ethylene-vinyl alcohol copolymer (P
VA), ethylene-vinyl acetate copolymer (EVA), saponified ethylene-vinyl acetate copolymer, and the like. Further, the adhesive resin is not limited to these, and conventionally known hot melt adhesives, modified epoxy resins, aqueous urethane resins, aqueous acrylic resins, acrylic resins
Silicon-based resins, ultraviolet-curable resins, reactive polyolefin-based oligomers, and water-based polyester resins can also be exemplified. Further, these adhesive resins can be used alone or in combination of at least two kinds.

In the aqueous ink printing sheet according to the present invention, the composition comprising the adhesive resin constituting the adhesive layer (B) and the carbodiimide-based resin is 0.1 to 0.1%.
99.9% by weight and 99.9% by weight of carbodiimide-based resin
Compositions comprising 0.1% by weight are preferred. When the carbodiimide-based resin is less than 0.1% by weight, the reactivity with the hydrophilic resin contained in the ink-receiving layer (A) and the reactive group of the acrylamide-based copolymer is reduced, so that the adhesion tends to be weak. If it exceeds 99.9% by weight, the equivalent number of reactive groups of the carbodiimide-based resin exceeds the equivalent number of reactive groups of the hydrophilic resin and the acrylamide-based copolymer contained in the aqueous ink receiving layer (A). Therefore, it is not necessary to exceed 99.9% by weight, and it is not economical.

The hydrophilic resin constituting the aqueous ink receiving layer (A) of the aqueous ink printing sheet according to the present invention includes:
A hydroxyl group (-OH group) and a carboxyl group (-CO
OH group), an ester group (-COOR group) and an amine (primary amine, secondary amine, tertiary amine, quaternary amine), etc., for example, a polyalkylene oxide compound. And a derivative thereof, a cross-linked polyalkylene oxide compound and a derivative thereof, a polyacrylic resin, a polyvinyl alcohol resin, a polyether polyol resin, a polyvinyl acetal resin, a polyvinylpyrrolidone resin, a polydioxolane resin, and a cellulose derivative. At least one or two
Mixtures of more than one species can be mentioned.

Specifically, the polyalkylene oxide compound includes a polyalkylene oxide compound obtained by addition polymerization of ethylene oxide and / or propylene oxide. Examples of the derivative of the polyalkylene oxide compound include polyalkylene obtained by addition polymerization of ethylene oxide and / or propylene oxide to a polyhydric alcohol such as ethylene glycol, diethylene glycol, 1,4-butanediol, and 1,3-butanediol. Oxide derivatives are mentioned. The molecular weight of these polyalkylene oxide compounds or their derivatives is
There is no particular limitation, and usually 20,000 or more is desirable.

As the cross-linked polyalkylene oxide compound and its derivative, an electron beam is applied to the above-mentioned polyalkylene oxide compound and its derivative, for example, 5 to 40 Mrad.
Irradiated ones, or cross-linked ones by adding a conventionally known crosslinking agent to the above-mentioned polyalkylene oxide compound and its derivative and reacting them can be exemplified.

As the above-mentioned polyalkylene oxide compound and a crosslinking agent which reacts with the compound and crosslinks, a conventionally known isocyanate compound having at least one nitrile group (—N ＝ C ＝ O group) in the molecule. Can be widely used. Specific isocyanate compounds include n-
Examples thereof include propyl isocyanate, n-hexyl isocyanate, cyclohexyl isocyanate, phenyl isocyanate, hexane diisocyanate, and hexamethylene diisocyanate.

Examples of the acrylic resin include, but are not limited to, a copolymer of ethylene and acrylonitrile, a saponified acrylate, and the like, but are not particularly limited.

As the polyvinyl alcohol resin, for example, a vinyl acetate polymer or a copolymer of vinyl acetate and another copolymerizable monomer (eg, ethylene, propylene, vinyl chloride, methacrylic acid and esters thereof) is used. Can be exemplified by those obtained by an alkali saponification method, but there is no particular limitation.

As the polyether polyol-based resin,
For example, 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 can be exemplified, but there is no particular limitation.

Examples of the polyvinyl acetal resin include compounds having reactivity with a hydroxyl group (—OH group) in polyvinyl alcohol (for example, aldehyde compound, carboxyl compound, epoxy compound, isocyanate compound, acid anhydride, N-methylol compound, Activated vinyl compounds, polyvalent metal L compounds, etc.) and polyvinyl alcohol, and / or condensation reaction products, and are not particularly limited.

As the polyvinylpyrrolidone resin, N-
A polymer having a molecular weight of 2,000 to 250,000 obtained by radical polymerization of vinyl-2-pyrrolidone is used. As a polydioxolane resin, a 1,3-dioxolane monomer is used.
An appropriate catalyst, for example, polymerized using a composite catalyst comprising a heteropolyacid and a carbonyl compound, and the like, and cellulose derivatives such as carboxymethylcellulose,
Examples thereof include methylcellulose and cationized carboxymethylcellulose.

In the aqueous ink printing sheet according to the present invention, the acrylamide copolymer of the cationic copolymer blended with the hydrophilic resin constituting the aqueous ink receiving layer (A) is represented by the following general formula (2). Ethylene structural unit 6 represented
5 to 98.9 mol%, preferably 85 to 97 mol%, 0.1 to 15 acrylate structural unit represented by the general formula 3
Mol%, preferably 3 to 7 mol%, and 1 to 35 mol%, preferably 3 to 15 mol%, of the acrylamide structural unit represented by the general formula 4, having a weight average molecular weight of 1, 1 which is linearly and irregularly arranged. 000-50,000, preferably 3,000
0 to 35,000 acrylamide copolymers.

[0022]

Embedded image

[0023]

(Wherein R ¹ has 1 to 4 carbon atoms, preferably 1 to 4 carbon atoms)
2 represents an alkyl group. )

[0024]

(Wherein R ² has 2 to 8 carbon atoms, preferably 2 to 2 carbon atoms)
3 alkylene groups, R ³ and R ⁴ each have 1 to 1 carbon atoms
4, preferably 1 to 2 alkyl groups, and R ⁵ has 1 to 1 carbon atoms
12, preferably 1-2 alkyl groups, 1-12 carbon atoms
An arylalkyl group or an alicyclic alkyl group having 1 to 12 carbon atoms, X ⁻ is a halogen ion, preferably Cl ⁻ , CH ₃ O
SO ₂ ^- or C ₂ H ₅ OSO ₃ ^- shows the. )

The aqueous ink printing sheet according to the present invention comprises:
When the acrylamide-based copolymer of the cationic copolymer blended with the hydrophilic resin constituting the aqueous ink receiving layer (A) has an ethylene structural unit, the ethylene structural unit has 65 ethylene structural units.
When the amount is less than mol%, the softening point of the acrylamide-based copolymer becomes low, so that the aqueous ink receiving layer (A) tends to stick and stick, and the compatibility with the hydrophilic resin becomes poor, and the aqueous ink becomes poor. The transparency, glossiness, and mechanical strength of the receiving layer (A) tend to decrease. Further, when the ethylene structural unit exceeds 98.9 mol%, the fixability of the dye contained in the aqueous ink tends to decrease, so that the aqueous ink receiving layer (A) printed with the aqueous ink is exposed to water. If the water-based ink drops off or is stored for a long period of time, the water-based ink tends to bleed over time.

In the aqueous ink printing sheet, when the cationic copolymer blended with the hydrophilic resin constituting the aqueous ink receiving layer (A) is an acrylamide copolymer having an acrylate structural unit, When the unit is less than 0.1 mol%, the aqueous ink receiving layer (A)
Tends to be inferior in impact resistance, flexibility and the like. Further, when the aqueous ink receiving layer is produced by coating with a coating agent comprising a composition constituting the aqueous ink receiving layer,
There is a tendency that the adhesion of the coating film is deteriorated. When the acrylate structural unit exceeds 15 mol%, the softening point of the acrylamide-based copolymer becomes low, and the aqueous ink receiving layer (A) tends to have tackiness and stickiness. Further, the humidity dependency becomes large, and when stored under high temperature and high humidity, there is a tendency that water-based ink bleeds.

In the present invention, the aqueous ink printing sheet comprises: a hydrophilic resin constituting the aqueous ink receiving layer (A);
An acrylamide copolymer having an acrylate structural unit as a cationic polymer is blended, and a reactive group contained in the acrylate structural unit and the hydrophilic resin, and a carbodiimide contained in the carbodiimide resin constituting the adhesive layer (B) The group chemically reacts and is firmly adhered to the adhesive layer (B). Further, the adhesive layer (B) composed of a carbodiimide-based resin alone or a composition composed of the carbodiimide-based resin and the adhesive resin is firmly bonded to the support base material layer (C). Therefore, for example, (A) / (B) /
The aqueous ink printing sheet having the laminated structure (C) tends to have toughness, impact resistance, flexibility and the like.

In the aqueous ink printing sheet, when the aqueous ink receiving layer (A) comprises a hydrophilic resin and an acrylamide copolymer containing an acrylamide structural unit as a cationic polymer, the acrylamide structure If the unit is less than 1 mol%, the fixability and the water resistance of the dye contained in the aqueous ink deteriorate, so that the aqueous ink bleeding of a printed or printed image or the like tends to occur over time. The content of the acrylamide structural unit is 35
If it exceeds mol%, the compatibility with the hydrophilic resin constituting the aqueous ink receiving layer (A) is poor, the hygroscopicity is increased, and the water absorption exceeds 2 mg / cm ² / μm. When stored for a period of time, the aqueous ink tends to bleed, and when printing or printing an image, workability tends to deteriorate.

In the aqueous ink printing sheet according to the present invention, the mixing amount of the hydrophilic resin and the acrylamide copolymer constituting the aqueous ink receiving layer (A) is as follows.
Acrylamide copolymer 1 to 15 parts by weight
0 parts by weight, more preferably 5 to 75 parts by weight, further preferably 10 to 50 parts by weight.

When the amount of the acrylamide copolymer is less than 1 part by weight, the reactivity with the polycarbodiimide group of the polycarbodiimide resin constituting the adhesive layer (B) tends to be inferior, and the supporting base material layer (C) Adhesive strength is also inferior, so the adhesive strength is reduced, and the fixability of the anionic dye contained in the aqueous ink also tends to be poor.When wet with water, the aqueous ink such as a print and a printed image easily flows, In addition, there is a tendency that bleeding of the aqueous ink occurs over time. Further, when the acrylamide-based copolymer exceeds 150 parts by weight, the hygroscopicity becomes large, and the tackiness and stickiness tend to occur, and the water absorption tends to be 0.05 mg / cm ² / μm or less,
The aqueous ink printing sheet of the present invention tends to have reduced aqueous ink absorbability, and tends to be unable to expect improvements in printability, aqueous ink fixability, water resistance, and storage stability.

The aqueous ink receiving layer (A) constituting the aqueous ink printing sheet according to the present invention comprises a hydrophilic resin,
Along with the acrylamide copolymer as a cationic component, the aqueous ink receiving layer (A) has a film strength, a scratch resistance,
In order to impart tack resistance, stickiness resistance, blocking resistance, lubricity and the like, it is preferable to incorporate fine particles.

Examples of the fine particles include inorganic substances such as cerium oxide, silicate oxide, silica sol, alumina sol, alumina hydrate, acrylic emulsion, acryl-silicone emulsion, polyurethane emulsion, polyester fine particles, and acrylate-coated polyester fine particles. And a mixture obtained by using at least one kind or two or more kinds selected from the group of organic substances.

The fine particles have a particle size of 2 to 750 nm, preferably 5 to 500 nm, and more preferably 10 to 25 nm.
0 nm can be exemplified. If the particle size is less than 2 nm, the effect of improving the film strength of the aqueous ink receiving layer (A) cannot be obtained, and
When it exceeds nm, the aqueous ink receiving layer (A) has transparency,
There is a tendency that optical characteristics such as glossiness are deteriorated and surface smoothness is impaired.

The amount of the fine particles is, for example, 1 to 180 parts by weight, preferably 5 to 160 parts by weight, and more preferably 10 to 150 parts by weight, per 100 parts by weight of the hydrophilic resin. If the compounding ratio of the fine particles is less than 1 part by weight, the aqueous ink receiving layer (A) tends to be unable to impart mechanical strength improvement, adhesion resistance, stickiness resistance, blocking resistance, etc., and if it exceeds 180 parts by weight. There is a tendency that the absorption performance of the water-based ink is reduced and the printability and printability are deteriorated.

Further, other fine particles include positively charged silica sol, alumina sol, cerium oxide, and the like in order to improve the compatibility between the hydrophilic resin and the acrylamide copolymer and to improve the fixability of the anionic dye. A cationically modified acrylic emulsion or a cationically modified acrylic-silicone emulsion may be used, and there is no particular limitation.

The support base material layer (C) constituting the aqueous ink printing sheet according to the present invention is at least one selected from the group consisting of a sheet (including a film) made of a thermoplastic resin, paper, nonwoven fabric and woven fabric. One is preferred.

The thermoplastic resin is not particularly restricted but includes, for example, polyester resins, polyolefin resins, polyamide resins, polystyrene resins, cyclic polyolefin resins, norbornene resins, polycarbonate resins and the like. . Among them, polyester resins and norbornene resins are particularly preferred because of their excellent gloss, mechanical suitability, rigidity and the like. In this case, a polyester-based resin mixed with a white inorganic pigment, for example, titanium oxide, barium sulfate, magnesium carbonate, silica or the like may be used.

As the norbornene resin, for example, a ring-opened (co) polymer of a norbornene-based monomer may be modified with a polymer such as maleic acid if necessary, and then a hydrogenated resin or a norbornene-based resin may be used. Resins obtained by subjecting monomers to addition copolymerization with olefinic monomers such as ethylene and α-olefins can be used. Examples of commercially available products include ARTON [manufactured by Nippon Synthetic Rubber Co., Ltd.] and ZEONEX [Nippon Zeon Co., Ltd.] )), And Arl [manufactured by Mitsui Petrochemical Industry Co., Ltd.], and the like are not particularly limited.

As paper, art paper, coated paper, Japanese paper,
Examples include neutral paper, synthetic paper and the like, sheets obtained by laminating paper with an appropriate plastic film, and sheets obtained by impregnating paper with a synthetic resin, and are not particularly limited.
As the nonwoven fabric, for example, a fiber obtained by melt-spinning an appropriate thermoplastic resin (polyolefin resin such as polyethylene or polypropylene, polyester resin, polyamide resin, etc.) is used, for example, a binder bonding method, a mechanical bonding method, a heat bonding method. For example, a spun bond method, a melt blow method, a water jet bonding method, or the like having a basis weight of 10 to 250 g / m ² can be exemplified. Further, a woven fabric or the like made of natural fibers or synthetic fibers may be used as the support base material layer (C). At this time, such a paper, a nonwoven fabric, a woven fabric, or the like can be impregnated with the aqueous ink receiving layer (A) in the support base material layer to form an aqueous ink printing sheet.

Further, the supporting base material layer (C) according to the present invention comprises:
Depending on the use (for example, a color filter or the like), a thin plate made of, for example, glass or wood (for example, a plywood or a plywood) may be used as a supporting substrate other than these.

The aqueous ink sheet according to the present invention includes an aqueous ink receiving layer (A) comprising a composition comprising a hydrophilic resin, an acrylamide copolymer and, if necessary, fine particles. An adhesive layer (B) composed of a carbodiimide-based resin alone or having a carbodiimide-based resin having a highly reactive carbodiimide group in the main chain and having compatibility with the aqueous ink-receiving layer, and an adhesive layer (B) comprising a composition of an adhesive resin and a support A two-layer structure (A) / (B) comprising a base material layer (C),
Three layers of (A) / (B) / (A) and (A) / (B) / (C), five layers of (A) / (B) / (C) / (B) / (A) The configuration and the like are preferable.

In the water-based ink printing sheet having such a constitution, the acrylamide copolymer which is a cationic component of the water-based ink-receiving layer (A) is contained in the water-based ink-receiving layer of a conventional water-based ink printing sheet. It has a higher molecular weight than a hydrophilic cationic component having a hydrophilic property (for example, a cationized polymer composed of a quaternary ammonium salt, polyalkyleneamine, polyvinyl alcohol, starch, or the like), and is relatively hardly soluble in water. Moreover, ethylene structural units,
It is considered that the acrylate structural unit and the amide structural unit are constituted from the specified range and chemically react with the carbodiimide group of the carbodiimide-based resin contained in the adhesive layer (B). Further, the adhesive layer (B) is strongly bonded to the supporting base material layer (C) by a single carbodiimide-based resin constituting the adhesive layer (B) or a composition comprising the carbodiimide-based resin and the adhesive resin. Has a tendency to adhere.

Accordingly, the water-based ink printing sheet having the water-based ink receiving layer (A) is excellent in water resistance, moisture resistance, adhesion resistance, stickiness resistance, blocking resistance, and reproducibility of printing and printed images. It can be expected to impart the properties and fixing properties. Further, even if the aqueous ink printing sheet is immersed in water, the aqueous ink receiving layer (A) and the supporting base material layer (C)
Are firmly laminated via an adhesive layer (B) composed of a carbodiimide-based resin alone or a carbodiimide-based resin and an adhesive resin, so that the aqueous ink-receiving layer (A) falls off, dissolves, and swells. No deterioration in strength and the like, and excellent storage stability that does not cause water-based ink bleeding even when a sheet on which prints and images are printed for a long period of time under high temperature and high humidity. Further, the aqueous ink printing sheet tends to have excellent light fastness and low surface specific electric resistance.

The aqueous ink receiving layer (A) constituting the aqueous ink printing sheet according to the present invention has a water absorption of 0.05 to 0.05.
2 mg / cm ² / μm is preferred. 0.05m water absorption
If it is less than g / cm ² / μm, the amount of water-based ink absorbed will be small, and the printability tends to be poor. Furthermore, since the water-based ink printing sheet is immersed in water, the mechanical strength of the water-based ink receiving layer (A) tends to be unable to be maintained for a long time because the water-based ink printing sheet is immersed in water. 2 mg / cm ² /
If it exceeds μm, when the aqueous ink printing sheet is immersed in water, the receiving layer (A) tends to swell, and the reproducibility of printing, printed images, and the like tends to be poor. When stored, water-based ink bleeding tends to occur.

Further, as another embodiment of the present invention, an aqueous ink receiving layer (A) comprising a composition mainly composed of a hydrophilic resin, an acrylamide copolymer and, if necessary, fine particles; A two-layer structure of, for example, (A) / (C), comprising a supporting base material layer (C) containing a resin,
An aqueous ink printing sheet having a three-layer structure of (A) / (C) / (A) can be exemplified.

In this case, the content of the carbodiimide resin is 99.9 to 50% by weight of the thermoplastic resin and 0.1 to 50% by weight of the carbodiimide resin when the supporting base material layer (C) is molded from a thermoplastic resin. Compositions consisting of% by weight are preferred. When the support base layer (C) is paper, nonwoven fabric, woven fabric, or the like, the support substrate layer (C) may be impregnated or coated so that the content of the carbodiimide-based resin is 0.1 to 50% by weight.
When the content of the carbodiimide-based resin is less than 0.1% by weight, the adhesion to the hydrophilic resin and / or the acrylamide-based copolymer constituting the aqueous ink-receiving layer (A) tends to be weak, and the water resistance When the aqueous ink printing sheet is immersed in water, the aqueous ink receiving layer (A) tends to fall off, dissolve, swell, become cloudy, and have reduced strength. There is a tendency that bleeding of the aqueous ink is generated. When the content of the carbodiimide-based resin exceeds 50% by weight, the original mechanical strength of the supporting base material layer (C) tends to be lost.

The aqueous ink printing sheet according to the present invention comprises:
If necessary, the surface of the layer (B) and / or the layer (C) or the layer (A) as long as the water resistance, printability, fixability, aqueous ink bleeding prevention (storability), etc. are not impaired. A layer made of one or more resins may be laminated between the layer between the layer (B) and the layer (A) and between the layer (A) and the layer (C). As such a resin,
Although there is no particular limitation, a resin of the same type or a resin of a different type from any of the layer (A), the layer (B) and the layer (C) may be used. The different resin may be any hydrophilic resin other than the hydrophilic resin contained in the layer (A), and is not particularly limited.

In the aqueous ink printing sheet according to the present invention, each of the compositions for forming the aqueous ink receiving layer (A), the adhesive layer (B) and the supporting substrate layer (C) is prepared by a conventional polyolefin. What is necessary is just to carry out by the well-known method used for preparation of a system composition. Specifically, a method of blending using a ribbon blender, a Hensel mixer, a tumbler, or the like, a method of kneading using a kneader blender, a Banbury mixer, a roll mixer, or the like, melting using a single-screw or twin-screw extruder, After kneading and extruding, a method of producing pellets by granulation can be exemplified, and there is no particular limitation.

The aqueous ink receiving sheet (A), the adhesive layer (B) and the supporting substrate layer (C) constituting the aqueous ink printing sheet according to the present invention are provided with the properties of the aqueous ink printing sheet (adhesion resistance). , Water resistance, printability, fixability, storage stability, etc.), as necessary, various additives, fillers,
Other thermoplastic resins and the like may be blended. For example, as additives, heat stabilizers, light stabilizers, antioxidants, antistatic agents, lubricants, antibacterial agents, ultraviolet inhibitors, deodorants, film forming aids, dyes or pigments, as fillers, Examples thereof include calcium carbonate, barium sulfate, calcium hydroxide, talc, silica, titanium oxide, zirconia, and metal-based fine particles (such as antimony). Examples of other thermoplastic resins include, for example, ionomers and thermoplastic elastomers, but are not particularly limited and may not be added.

The aqueous ink printing sheet according to the present invention comprises:
In the case of a laminated structure including at least the aqueous ink receiving layer (A), the adhesive layer (B), and the supporting base material layer (C), the laminating method is, for example, (A) / (B) / (C). And a co-extrusion method of laminating using a co-extrusion machine, or (A)
(B) and (C) on the surface of (C) or (B) and (A) on the surface of (C) by melt extrusion, for example, (A) / (B)
/ (C) a melt extrusion lamination method for laminating so that
(A), (B), and (C) are connected via an adhesive to (A) /
(B) / dry lamination method of laminating so that (C) or (A), (B) and (C) are separately formed into a film,
(A) / (B) / (C), thermocompression bonding method of laminating by heating and pressing, and coating (A) on one surface of (B) or (C) Methods and the like can be exemplified, and there is no particular limitation.

Further, at least the aqueous ink receiving layer (A)
(A) / (B), (A) /
(A) / (C) comprising an aqueous ink printing sheet having a (B) / (A) configuration, or an aqueous ink receiving layer (A) and a supporting base material layer (C) containing a carbodiimide resin.
As a method of laminating the aqueous ink printing sheet having the constitution (A) / (C) / (A), a coextrusion method, a melt extrusion lamination method, a dry lamination method, a thermocompression bonding method, and a coating method in which the sheets are laminated by the same method as described above. The method can be exemplified, and there is no particular limitation.

The method for producing the aqueous ink printing sheet according to the present invention is not particularly limited, but is preferably, for example, co-extruded and laminated by a T-die method capable of melt lamination. Specifically, 100 parts by weight of the hydrophilic resin, 1 to 100 parts by weight of the alkyl amide copolymer and, if necessary, fine particles 1
~ 180 parts of the composition, barrel temperature 80 ~
The mixture is melt-kneaded in a twin-screw extruder set at 150 ° C and a die temperature of 100 to 130 ° C, extruded into strands, water-cooled and / or
Or after air cooling, form an aqueous ink receiving layer (A);
For example, pellets having a particle size of 3 mm and a length of 4 mm are granulated.
When the adhesive layer (B) is a composition comprising a carbodiimide-based resin and an adhesive resin, similarly, 0.1 to 99.9% by weight of the carbodiimide-based resin and the adhesive resin 9 are used.
The composition comprising 9.9 to 0.1% by weight is charged into a twin-screw extruder set at a barrel temperature of 30 to 180 ° C. and a die temperature of 50 to 150 ° C. to form a pellet for forming an adhesive layer (B). Granulate.

Next, the pellets forming the aqueous ink receiving layer (A) are placed in one of at least three independent extruders sharing a co-extrusion T-die, and the pellets are placed in another extruder. The pellets forming the adhesive layer (B) are further supplied to another extruder, for example, a polyester resin (preferably pellets) forming the support base material layer (C). Each of the supplied pellets is not particularly limited.
It is melt-extruded by an extruder heated to 0 to 130 ° C. and solidified by cooling with a cooling roll, underwater or air cooling.
A water-based ink printing sheet having a configuration of / (B) / (C) can be formed.

Further, as another configuration, for example, (A) / (B) /
A water-based ink printing sheet having a five-layer structure such as (C) / (B) / (A) can be formed. (A) / (B), (A)
/ (B) / (A) The composition or (A) and the supporting base material layer (C) in which the carbodiimide-based resin is blended are (A) /
In the case of laminating (C), (A) / (C) / (A), it may be molded in the same manner as above.

As another manufacturing method, a hydrophilic ink is formed as an aqueous ink receiving layer (A) on at least one surface of a sheet forming an adhesive layer (B) or a support base material layer (C) according to the present invention. A method of forming a water-based ink printing sheet by coating a coating agent obtained by dissolving a composition containing a resin, an acrylamide-based copolymer and, if necessary, fine particles, with an appropriate solvent can be exemplified.

The coating method is not particularly limited, and examples of the coating method include a gravure coating, a reverse roll coating, a dip coating, an air knife coating, and a bar coating. As the coating agent, a composition constituting the aqueous ink receiving layer (A) may be prepared by adding an organic solvent such as methyl alcohol, ethyl alcohol, isopropyl alcohol, chloroform, or ethyl acetate, or an organic solvent (for example, 70 parts by weight) to water. For example, a solution having a concentration of 3 to 35% by weight dissolved in a mixed solvent can be exemplified. If the concentration is less than 3% by weight, the thickness of the aqueous ink-receiving layer (A) to be coated tends to be thin, and the printability of a printed image or a printed image tends to decrease. The agent tends to have a high viscosity, and the accuracy of the thickness of the aqueous ink receiving layer (A) and the workability tend to decrease.

The aqueous ink printing sheet according to the present invention comprises:
The total thickness can be, for example, 5 to 750 μm. If it is less than 5 μm, the mechanical strength is weak, so that printability with aqueous ink tends to be poor. If it exceeds 750 μm, it becomes rigid, and its practicality as a water-based ink printing sheet tends to be limited. However, it can be used depending on the application, and the thickness is not particularly limited.

The aqueous ink printing sheet according to the present invention comprises:
An aqueous ink receiving layer (A) comprising a composition comprising a hydrophilic resin, an acrylamide copolymer and, if necessary, a microparticle, and a carbodiimide resin compatible with the aqueous ink receiving layer (A). A single layer or an adhesive layer (B) composed of a carbodiimide resin and an adhesive resin (A)
/ (B) two-layer constitution, and the aqueous ink receiving layer (A)
And a supporting substrate layer (C) containing a carbodiimide-based resin
In the case of a two-layer configuration of (A) / (C), the total thickness is 5 to 750 μm, the thickness of (A) is 2 to 150 μm,
The preferred thickness of (B) or (C) is 3 to 600 μm, and there is no particular limitation.

At this time, if the thickness of (A) is less than 2 μm,
The water absorption tends to be less than 0.05 mg / cm ² / μm, which tends to reduce printing and printability.
If it exceeds m, the transparency of the aqueous ink receiving layer (A) will be impaired, which is not suitable for applications requiring transparency. Generally, the thickness of the aqueous ink receiving layer (A) is determined by the thickness of the adhesive layer (B),
When the thickness is larger than the thickness of the supporting base material layer (C), when immersed in water, swelling cloudiness, softening and elution of the receiving layer are liable to occur, and the mechanical strength tends to decrease. In addition, water absorption is 2mg
/ Cm ² / μm, and when stored for a long time under high temperature and high humidity, changes in physical properties (printability and transparency) due to moisture absorption of the aqueous ink receiving layer (A), Bleeding is likely to occur, and storage stability tends to decrease.

Further, in the aqueous ink printing sheet according to the present invention, an aqueous ink receiving layer (A) formed from a composition comprising a hydrophilic resin, an acrylamide copolymer and, if necessary, fine particles, A carbodiimide-based resin compatible with the aqueous ink-receiving layer (A), or an adhesive layer (B) composed of a carbodiimide-based resin and an adhesive resin
And (A) / (B) /
(A), three-layer structure of (A) / (B) / (C) and (A)
/ (B) / (C) / (B) / (A)
The thickness of (A) can be exemplified by 2 to 150 μm. When the thickness of (A) is less than 2 μm, the water absorption is 0.05 mg / c.
When the amount is less than m ² / μm, the amount of water-based ink absorbed decreases, and the printability and printability tend to deteriorate. When the thickness of (A) exceeds 150 μm, the water resistance is poor, and when the aqueous ink printing sheet is immersed in water, it swells and becomes cloudy, and the receiving layer (A) drops and dissolves, resulting in a mechanical problem. The strength tends to decrease. The thickness of the adhesive layer (B) is not particularly limited as long as (A) and (A) and (A) and (C) can be firmly bonded, and there is no particular limitation, and the thickness is 10 μm or less, preferably 1 to 3 μm. Can be exemplified. The thickness of the support substrate (C) may be appropriately set depending on the application, and is not particularly limited. If it is less than 3 μm, the mechanical strength tends to decrease, and if it exceeds 600 μm, the rigidity is high and the flexibility is inferior, so the use tends to be limited.

Further, the aqueous ink printing sheet according to the present invention comprises an aqueous ink receiving layer (A) and a carbodiimide-based ink having compatibility with the aqueous ink receiving layer (A) without an adhesive layer (B). In the case of a three-layer structure of (A) / (C) / (A) obtained by laminating a supporting base material layer (C) containing a resin, the thickness of (A) can be exemplified by 2 to 150 μm. . When the thickness of (A) is less than 2 μm, the absorbability of the aqueous ink is inferior, and the printability and printability tend to decrease. When the thickness exceeds 150 μm, the water absorption is 2 mg / cm ² /
When the thickness exceeds μm, and the aqueous ink printing sheet is immersed in water, the aqueous ink receiving layer (A) tends to have swelling cloudiness and a decrease in mechanical strength. The total thickness of the supporting base material layer (C) containing the carbodiimide-based resin is 5
The distance may be appropriately set depending on the application as long as it is up to 750 μm, and there is no particular limitation.

The aqueous ink printing sheet according to the present invention comprises:
A coating material comprising the composition constituting the aqueous ink receiving layer (A) is coated on at least one surface of the adhesive layer (B) and the support base layer (C), for example, (A) /
(B), (A) / (C), (A) / (B) / (C),
In the case of (A) / (B) / (A), (A) / (C) / (A) configurations, the total thickness is 5 to 750 μm, and the thickness of (A) is 2 to
The thickness is 150 μm, and the thickness of (B) or (C) is 3 to 600 μm, and there is no particular limitation.

At this time, if the thickness of (A) is less than 2 μm,
The absorption of the aqueous ink is poor, the tendency of the printability and printability of images, etc., to decrease, when it exceeds 150 μm, the water absorption decreases and the water resistance decreases, and when the aqueous ink printing sheet is immersed in water, The aqueous ink receiving layer (A) has a tendency to cause swelling white turbidity, peeling of the film, elution, and the like, and storage at high temperature and high humidity tends to cause a decrease in transparency due to moisture absorption. If the thickness of (B) and (C) is less than 3 μm, the mechanical strength tends to decrease, and if it exceeds 600 μm, the rigidity is high, the flexibility is poor, and the printability tends to deteriorate. However, it can be used for applications other than the aqueous ink printing sheet.

The aqueous ink printing sheet according to the present invention comprises:
Surface electric resistivity is 10 ¹³ Ω / cm or less, 10 ⁸ Ω / cm
It is preferable to make the above. Surface electric resistivity is 10 ¹³ Ω
/ Cm, static electricity is likely to occur due to static electricity, for example, when printing or printing and transporting the aqueous ink printing sheet using a printer, especially when printing under dry conditions, and troubles occur frequently, and paper jams occur. Also, the printing performance tends to decrease.

The aqueous ink printing sheet according to the present invention comprises:
For example, a sheet for an overhead projector (OHP) formed by printing and / or printing an image with an aqueous ink using an aqueous inkjet printer or the like, a poster printed with the aqueous ink, a substrate for advertisement, a substrate for print lamination , Barcode printing base material, illumination decoration base material (sheet and film), color filter base material, various cards printed with aqueous ink (for example, prepaid card, ID
Card, cash card, credit card, etc.) and a substrate for gravure or offset printing. In addition to the above-mentioned printing applications, it can be used, for example, for packaging films, gloss films, agricultural sheets, dew condensation prevention sheets, humidity control sheets, adhesive sheets, etc., and there is no particular limitation.

[0066]

The present invention will be described below with reference to examples.
The present invention is not limited by the following Examples and Comparative Examples.

In the following examples and comparative examples, measurement and evaluation of each inspection item were performed by the following methods.

[Water resistance]: A pattern was printed with an aqueous ink using an aqueous ink BJ printer [BJ-620J manufactured by Canon Inc.], immersed in water for 5 days, and then bleeding of the ink and the degree of dropping of the ink. The coating strength was evaluated visually and by touch. 5: No ink bleeding or ink dropout was recognized, and the ink was not peeled off by touch. 4: Although slight ink peeling is observed in some colors,
It has clear images and film strength. 3: Ink bleeding and dropping of ink were observed in all colors, and a part of the coating was peeled off by the touch finger, but the printed image could be recognized. 2: A part of the printed image could not be recognized, and the coating was easily peeled off by a touch finger. 1: Image recognition cannot be performed at all due to dropout of ink and peeling of the film.

[Printability]: Using a water-based ink BJ printer [BJ-620J manufactured by Canon Inc.], cyan (indigo), magenta (red), yellow (yellow), black (black), red, green, Printing was performed using a square solid printing test pattern so that the blue colors were adjacent to each other, and the color mixing (beading) at the boundary between the colors, the color developability of the aqueous ink, and the sharpness were evaluated. 5: There was no beading, and the printed water-based ink had good color developability and sharpness. 4: Although beading occurs slightly, the water-based ink has good color developability and sharpness. 3: Beading occurs and the aqueous ink lacks sharpness, but can be used practically. 2: Severe beading, poor coloring and sharpness of aqueous ink, no practicality. 1: lacks sharpness and is not practical.

[Storability]: Printing and printing with an aqueous ink using an aqueous ink BJ printer [BJ-420J manufactured by Canon Inc.], and after standing at 35 ° C. and 95% RH for 168 hours (7 days) The ink was visually evaluated for bleeding. 5: No bleeding of the aqueous ink is observed. 4: Slight bleeding was observed in some colors in the outline of the print pattern, but the sharpness of the printed image was maintained. 3: The ink bleeding of each color was observed at the contour of the water-based ink, and the printed image lacked sharpness. 2: The bleeding of the aqueous ink was so severe that a part of the printed image could not be recognized. 1: The printed image cannot be recognized.

[Sticking resistance]: Printing and printing of images, etc. were performed with an aqueous ink using an aqueous ink BJ printer [BJ-600J manufactured by Canon Inc.], and left at 40 ° C. and 90% RH for 24 hours. After the evaluation, the fingerprint adhesion resistance was evaluated. ：: No stickiness. Δ: Fingerprint easily adheres when touched. ×: Very sticky.

[Water absorption]: The water absorption per area was measured according to JIS K-7209, and the value was divided by the thickness (mg / cm ² / μm) to evaluate.

[Surface electric resistivity]: JIS K-691
It measured according to 1.

Example 1 (1) Preparation of a pellet constituting the aqueous ink receiving layer (A). A composition comprising 80 parts by weight of a polyethylene oxide-based crosslinked product, 10 parts by weight of an acrylamide-based copolymer, and 10 parts by weight of an alumina sol was supplied to a vented twin-screw extruder set at a cylinder temperature of 170 ° C. and a die temperature of 160 ° C.,
After melt-kneading, extruding into strands and cooling and solidifying,
After cutting, pellets having a particle size of 3 mm and a length of 4 mm were granulated. (2) Production of pellets constituting the adhesive layer (B). Maleic acid-modified polyolefin adhesive resin 60% by weight
And a carbodiimide-based resin in an amount of 40% by weight, and a cylinder temperature of 170 ° C. and a die temperature of 150 ° C.
Is supplied to a twin-screw extruder set to a temperature of 2,000 kPa, melt-kneaded, extruded into strands, cooled and solidified, and then cut to a particle size of 3.5.
A pellet having a length of 4.5 mm and a length of 4.5 mm was granulated. (3) A resin constituting the supporting base material layer (C). Norbornene resin ("ARTON" Japan Synthetic Rubber Co., Ltd.)
Pellets). (4) Forming a sheet for aqueous ink printing. One of three independent extruders connected to a co-extrusion die
The pellets forming the aqueous ink receiving layer (A) are placed on another base, the pellets forming the adhesive layer (B) are placed on another extruder, and the pellets forming the adhesive layer (B) are placed on another extruder. Pellets forming the above-mentioned supporting base material layer (C) were supplied.
Then, the extruder for forming the aqueous ink receiving layer (A) has a cylinder temperature of 160 ° C., and the extruder for forming the adhesive layer (B) has a cylinder temperature of 180 ° C. The mixture was heated to a cylinder temperature of 280 ° C. and a co-extrusion die temperature of 260 ° C., melt-kneaded and co-extruded the respective pellets, cooled and solidified, and (A) / (B) / (C) = 20 /
An aqueous ink printing sheet of 2/100 = 122 μm was obtained. Table 1 shows the water resistance, printability, storability, stickiness, water absorption and surface resistivity of the aqueous ink printing sheet.

[0075]

[Table 1]

Example 2 (1) Coating agent for forming aqueous ink receiving layer (A) Polyale polyol (number average molecular weight Mn = 8,000
0, 20% aqueous solution) 70 parts by weight, acrylamide copolymer (19.4% solids emulsion) 20 parts by weight,
A composition comprising 10 parts by weight of alumina sol (21% aqueous solution) and 0.02 parts by weight of porous silica was used. (2) As the adhesive layer (B), a carbodiimide-based resin (1
(0% aqueous solution) 100 parts by weight of a single solution was used. (3) As a supporting base material layer (C), a transparent biaxially stretched polyester film (100 μ
m) (“Melinex 705” manufactured by ICI) was used. (4) Forming a sheet for aqueous ink printing. An aqueous solution of carbodiimide is coated on the surface of the polyester-based film forming the support base material layer (C) using a wire bar, and then dried with hot air at 100 ° C. for 1 minute to form an adhesive layer (B). did. Next, the coating agent for forming the aqueous ink-receiving layer (A) is coated on the surface of the layer (B) using a wire bar, and then dried with hot air at 110 ° C. for 2 minutes to obtain (A) / ( B) /
(C) = Aqueous ink printing sheet of 20/2/100 = 122 μm was obtained. Table 1 shows the water resistance, printability, storability, stickiness, water absorption and surface electrical resistivity of the aqueous ink printing sheet.

Example 3 (1) As a composition for forming the aqueous ink receiving layer (A), 80 parts by weight of a crosslinked polyethylene oxide, 10 parts by weight of an acrylamide copolymer, and 10 parts by weight of silica sol as fine particles were blended. Was used. (2) As a composition for forming the adhesive layer (B), a urethane-based adhesive resin 30 parts by weight and a carbodiimide-based resin 70
A composition obtained by blending with parts by weight was used. (3) As a supporting base material layer (C), a milky white biaxially stretched polyester film (10
0 μm) (“Crisper G121” manufactured by Toyobo Co., Ltd.)
2 ") was used. (4) Forming a sheet for aqueous ink printing. The composition for forming the adhesive layer (B) on the corona discharge treated surface of the support base material layer (C) was subjected to a cylinder temperature of 160 ° C. and a T-die temperature of 1
Using an extruder equipped with a T-die set at 50 ° C., it was melt-extruded and extrusion-laminated to a thickness of 2 μm. Next, the composition for forming the aqueous ink receiving layer (A) on the surface of the layer (B) was applied at a cylinder temperature of 17 ° C.
Using an extruder equipped with a T-die set at 0 ° C. and a die temperature of 160 ° C., melt-extruded, extrusion-laminated to a thickness of 20 μm, and (A) / (B) / (C) =
An aqueous ink printing sheet having a thickness of 20/2/100 = 122 μm was obtained. Table 1 shows the water resistance, printability, storability, stickiness, water absorption and surface electrical resistivity of the aqueous ink printing sheet.

Example 4 (1) Preparation of a pellet for forming the aqueous ink receiving layer (A). A composition comprising 80 parts by weight of polydioxolane (number average molecular weight: 200,000), 10 parts by weight of acrylamide copolymer and 10 parts by weight of silica sol (20% aqueous solution) was set at a cylinder temperature of 140 ° C. and a die temperature of 140 ° C. The mixture was melt-kneaded in a vented twin-screw extruder, extruded into a strand, cooled, cut, and cut to a particle size of 3.0 mm and a length of 4.0 m.
m pellets. (2) A carbodiimide-based resin was used as the adhesive layer (B). (3) As the supporting base material layer (C), a polyester nonwoven fabric having a thickness of 100 μm and a basis weight of 60 g / m ² was used. (4) Forming a sheet for aqueous ink printing. An adhesive layer (B) is formed on the surface of the supporting base material layer (C) made of the polyester-based nonwoven fabric using an extruder equipped with a T-die set at a cylinder temperature of 160 ° C and a T-die temperature of 150 ° C. The carbodiimide-based resin was melt-extruded to a thickness of 3 μm, solidified by cooling, and then pressure-bonded with a roll heated to 140 ° C. at a linear pressure of 10 kg · cm. Next, a cylinder temperature of 160 was applied to the surface of (B).
Using an extruder equipped with a T-die set at 150 ° C. and a T-die temperature, the above-mentioned pellets forming the aqueous ink-receiving layer (A) were melt-extruded to a thickness of 20 μm and a surface temperature of 5 ° C. (A) /
An aqueous ink printing sheet (B) / (C) = 20/3/100 = 123 μm was obtained. Table 1 shows the water resistance, printability, storability, stickiness, water absorption and surface electrical resistivity of the aqueous ink printing sheet.

Example 5 (1) The pellet obtained in Example 1 was used as a pellet for forming the aqueous ink receiving layer (A). (2) The support base material layer (C) is granulated from a composition comprising 20 parts by weight of the carbodiimide-based resin and 80 parts by weight of the polyester-based resin forming the support base layer used in Example 1. The pellets used were used. (3) Formation of aqueous ink printing sheet. The pellets forming the aqueous ink-receiving layer (A) are placed on two of three independent extruders connected to the co-extrusion T-die, and the supporting material layer (C) is placed on another extruder. Was supplied. Next, the extruder for forming the aqueous ink receiving layer (A) was heated to a cylinder temperature of 160 ° C., the extruder for forming the support material layer (C) was heated to a cylinder temperature of 280 ° C., and a co-extrusion T-die temperature was heated to 260 ° C. After kneading and co-extrusion, the mixture is cooled and solidified, and (A) / (C) / (A) = 20/10
An aqueous ink printing sheet of 0/20 = 140 μm was formed. Table 1 shows the water resistance, printability, storage stability, stickiness resistance, water absorption and surface electrical resistivity of the aqueous ink printing sheet.
It was shown to.

Comparative Example 1 Aqueous ink printing was performed in the same manner as in Example 1 except that the aqueous ink receiving layer (A) used an acrylamide copolymer and the adhesive layer (B) did not contain a carbodiimide resin. Sheet was formed. Table 1 shows the water resistance, printability, storability, stickiness, water absorption and surface electrical resistivity of the aqueous ink printing sheet.

Comparative Example 2 An adhesive layer (B) consisting of a carbodiimide resin alone was
An aqueous ink printing sheet was formed in the same manner as in Example 2 except that the aqueous ink receiving layer (A) and the support base material layer (C) were not interposed. Table 1 shows the water resistance, printability, storability, stickiness, water absorption and surface electrical resistivity of the aqueous ink printing sheet.

[0082]

The water-based ink printing sheet according to the present invention has excellent water resistance by using the carbodiimide-based resin alone or the composition comprising the carbodiimide-based resin and the adhesive resin for the adhesive layer (B). It has good printability, printability, and stickiness, and has little bleeding phenomenon of printed or printed aqueous ink even after long-term storage under high temperature and high humidity, and has low surface electric resistivity. It is excellent in printability, in which a printing trouble hardly occurs.

Claims (5)

[Claims] 1. A compound of the general formula (Wherein, R a cycloalkyl group alkyl Motomata is C ₃ -C ₁₀ a C ₁ ~C _12, Z is an alkylene group of C ₁ ~C _12, C ₃
Cycloalkylene -C _10, an annular or C ₄ -C ₁₆ alkylene group or an aromatic-bonded alkylene group having C ₈ -C ₁₆ in having a non-cyclic structure, n represents an integer of 1 to 50, m Represents an integer of 1 or 2. ) Alone or 0.1 to 99.9% by weight of the carbodiimide-based resin and 99.9 to
An aqueous ink receiving layer (A) containing a cationic copolymer and a support base material layer (C) via an adhesive layer (B) composed of a composition containing 0.1% by weight as a main component. Aqueous ink printing sheet formed by laminating. 2. The aqueous ink receiving layer (A) is composed of a composition obtained by mixing 1 to 100 parts by weight of a cationic copolymer and 1 to 180 parts by weight of fine particles with respect to 100 parts by weight of a hydrophilic resin. Its water absorption is 0.05 to ² mg / cm ² / μ
The aqueous ink printing sheet according to claim 1, wherein m is m. 3. The cationic copolymer blended in the aqueous ink receiving layer (A) has a general formula: 65 to 98.9 mol% of an ethylene structural unit represented by the following general formula: (Wherein, R ¹ represents an alkyl group having 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms).
~ 15 mol% and the general formula (Wherein, R ² is an alkylene group having 2 to 8 carbon atoms, preferably 2 to 3 carbon atoms, R ³ and R ⁴ are each an alkyl group having 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms, and R ⁵ is 12, preferably an alkyl group having 1 or 2, arylalkyl Motomata alicyclic alkyl group having 1 to 12 carbon atoms having 1 to 12 carbon atoms, X ^-
Halogen ions, preferably Cl ^-, CH ₃ OSO ₂ ^- or C ₂ H ₅ OSO ₃ ^- shows the. 3. The aqueous ink printing sheet according to claim 1, which is a linearly irregularly arranged acrylamide-based copolymer composed of 1 to 35 mol% of acrylamide structural units represented by the formula: 4. The hydrophilic resin constituting the aqueous ink receiving layer (A) has at least one or more hydroxyl groups (—O
(H group), a carboxyl group (-COOH group), an ester group (-COOR group), and an amine (primary amine, secondary amine, tertiary ammine, quaternary amine). The aqueous ink printing sheet according to claim 1. 5. The support base material layer (C) comprises at least one selected from the group consisting of a thermoplastic resin sheet, paper and nonwoven fabric.
The aqueous ink printing sheet according to any one of claims 1 to 4, which is a seed.