JP2001162929A - Resin composition for ink jet recording and recording sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a useful recording sheet which shows outstanding fingerprint resistance, high glossiness, ink absorption and water resistance and is free from an image quality failure such as beading as an ink jet recording sheet as well as a resin composition for the ink jet recording sheet. SOLUTION: The resin composition for an ink jet recording sheet is composed of (A) 0-100 wt.% cationic acrylic copolymer containing a crosslinkable group, (B) 0-70 wt.% saponified product of a vinylacetate copolymer and (C) 0-80 wt.% modifier (total of these three is 100 wt.%) and further, contains 0.1-15 pts.wt. ether nonionic surfactant with 12 or more HLB to 100 pts.wt. composition in which (A)+(B) is >5 wt.%. In addition, the ink jet recording sheet uses the resin composition and has an image receiving layer formed at least on one of the faces of a base material for the ink jet recording sheet.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition for an ink jet recording sheet and an ink jet recording sheet using the same. More particularly, the present invention relates to a resin composition having excellent fingerprint resistance, high glossiness, ink absorption and water resistance, and BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a recording sheet useful for ink jet recording in which image quality defects such as ding do not occur, and a resin composition for an ink jet recording sheet that provides the same.

[0002]

2. Description of the Related Art Ink jet recording systems have been rapidly spreading in recent years because they are inexpensive, can be easily made full color, have low noise, and have excellent print quality. In the inkjet recording, a water-based ink is mainly used from the viewpoint of safety and recording suitability, and recording is performed by flying small ink droplets from a nozzle toward a recording sheet. Therefore, the recording sheet is required to quickly absorb the ink. That is, in a recording sheet having a low ink absorption, the ink remains on the surface of the recording sheet for a long time even after the recording is completed, and the recording is performed due to contact with a part of the apparatus, contact of an operator, or superposition of the recording sheet. The part gets dirty. In the high-density image portion, a large amount of supplied ink is mixed and flows out without being absorbed, resulting in an unclear image.

JP-A-57-36692 discloses an ink jet recording sheet coated with a basic latex polymer in order to improve water resistance, resolution and the like. This document describes that a water-soluble polymer or a pigment may be used in combination. JP-A-63-115
No. 780 discloses an ink jet recording sheet in which a polymer containing a quaternary ammonium salt is applied to a support, and also describes the use of synthetic silica in combination and the use of polyvinyl alcohol or the like as a binder. JP-A-7-61113 discloses an ink jet recording medium in which an ink receiving layer is composed of a polyvinyl acetal resin and a cationic compound.
No. 27114 discloses an ink jet recording sheet in which an ink receiving layer is composed of a pigment such as fine silica and an amphoteric ion latex. In these recording sheets, the fixability and water resistance of the ink can be improved to some extent. However, there is a contradictory relationship between the ink fixability and water resistance and the ink absorbency, and if the water resistance is improved, the ink absorbency decreases. Therefore, the water resistance and the ink absorbency cannot be maintained at high levels.

Japanese Patent Application Laid-Open No. 1-174484 discloses an ink jet recording sheet in which a coating layer containing a pigment and a copolymer of a fatty acid vinyl ester such as vinyl acetate and a cationic monomer is formed on a sheet-like support. It has been disclosed. According to this document, the cationic copolymer may be a copolymer with a nonionic monomer or a graft copolymer with polyvinyl alcohol, and may further contain a water-soluble polymer binder. Is described. JP-A-62-83178 proposes an ink jet recording sheet provided with a coating layer containing finely divided silicic acid and a cationic polymer emulsion.
This document also describes that it is preferable to use a self-crosslinkable acrylic emulsion having a glass transition temperature of 0 ° C. or lower as an adhesive. With these recording sheets, the water resistance can be improved. However, the water resistance is still low, and if water droplets adhere, the recording part elutes and bleeding occurs in the printed part or image part, and in severe cases, the printed part or image part elutes and disappears, reducing the recording quality. Greatly lower. Therefore, it is difficult to improve the water resistance and ink absorbency to a high degree while improving the printing quality.

[0005] In addition, in recent printers, in order to realize printing with photographic quality, recording sheets are becoming more and more severe, such as high-resolution printing of 1000 dpi or more, overprinting of light-color ink, and high-speed printing several times faster than the conventional printer. It is becoming increasingly used, and it is difficult to improve image quality problems such as beading that occur during printing in the printer's highest quality image quality mode. High glossiness comparable to that of photographic paper has been required, and the problem of fingerprints adhering to the surface of high glossy recording sheets has newly emerged.

[0006]

Therefore, according to the present invention, excellent printing characteristics, water resistance and high gloss can be obtained by using a water-soluble polymer compound without using any inorganic component. It is an object of the present invention to provide a recording medium suitable for a photographic ink jet recording system, in which the fingerprint does not appear after printing due to the adhesion of the fingerprint even if the finger is touched by hand.

[0007]

Means for Solving the Problems Accordingly, the inventors of the present invention have proposed water
Soluble polymer compound and at least one specific surfactant
Found that combining with
Completed the invention. That is, the first of the present invention is (A) crosslinking
-Containing cationic acrylic copolymer 0-100 weight
%, (B) saponified vinyl acetate copolymer 0 to 70 times
% And (C) 0-80% by weight of the modifier.
(Where the sum of the three is 100% by weight) and (A) +
(B) For 100 parts by weight of a composition having> 5% by weight,
(D) Surface activity of ether-based nonionic with HLB of 12 or more
Containing 0.1 to 15 parts by weight of an agent.
The present invention relates to a recording sheet resin composition. The second aspect of the present invention
Means that (D) the lipophilic group of the surfactant is C_14-20Fatty acid skeleton of
The first resin for ink jet recording sheet of the present invention
Composition. The third aspect of the present invention is that (D) surface activity
The first ink of the present invention, wherein the lipophilic group of the agent is a lanolin skeleton
The present invention relates to a resin composition for a jet recording sheet. The present invention
The fourth is that (D) the hydrophilic group of the surfactant is polyoxyalkanol.
Kiren (C _1-4) Any of the first to third aspects of the present invention which is a skeleton
Such a resin composition for an ink jet recording sheet.
Also, the fifth aspect of the present invention is the case of (B) vinyl acetate copolymer.
The saponification degree of the compound of the present invention is 70 to 95 mol%.
The resin for an ink jet recording sheet according to any one of the first to fourth aspects.
Composition. In the sixth aspect of the present invention, (A) a crosslinkable group
Containing cationic acrylic copolymer, the following (1) or
The second aspect of the present invention, which is a copolymer of a monomer containing the component (2)
1 relates to a resin composition for an ink jet recording sheet. (1) Cationic monomer (a), crosslinkable group-containing monomer
(B) and a hydrophilic monomer (d). (2) Cationic monomer (a), crosslinkable group-containing monomer
(B), the hydrophilic-containing monomer (d) and the compound represented by the formula (1)
Monomer (c) having a polyalkylene oxide unit. Formula (1)-[(CHR₁)_n-O]_m-R_Two [However, R in the formula₁Represents a hydrogen atom, a methyl group or a hydroxyl group
And R_TwoRepresents a hydrogen atom or a methyl group, and n is 1 to
5, m shows the number of 1-20. In a seventh aspect of the present invention, the crosslinking group-containing monomer is an alkoxy group.
Sixth inkjet recording system of the present invention having a silyl group
The present invention relates to a resin composition for coating. In the eighth aspect of the present invention, the present invention
For ink jet recording sheets according to any one of the first to eighth aspects of the present invention.
A resin composition is used,
It is characterized in that an image receiving layer is formed on at least one surface of the material.
The present invention relates to an ink jet recording sheet. Again
The ninth is the gloss of the image receiving layer surface (JIS Z8741.
Therefore, the measured (60 ° gloss) is 60% or more.
An eighth inkjet recording sheet according to the present invention, characterized in that:
G.

(Substrate) The substrate may be opaque, translucent or transparent depending on the application. The substrate used in an overhead projector (OHP) or the like is usually transparent. There is no particular limitation on the material of the substrate, and examples of the substrate include paper, coated paper, nonwoven fabric, plastic film, and synthetic paper. As the polymer constituting the plastic film and the synthetic paper, for example, polyethylene,
Polyolefins such as polypropylene, polyvinyl chloride, poly (meth) acrylate, polystyrene,
Cellulose derivatives such as cellulose acetate, polyesters (such as polyalkylene terephthalate such as polyethylene terephthalate, and polyalkylene naphthalate such as polyethylene naphthalate), polycarbonates, polyamides (such as polyamide 6, polyamide 6/6), and the like. May be used.

Of these films and synthetic papers, polyolefins (especially polypropylene), polyesters (especially polyethylene terephthalate, etc.) are usually used, and polyesters (especially polyethylene terephthalate) are particularly preferred in terms of mechanical strength, workability and cost. Is preferred. As paper and coated paper, for example, high-quality paper, art paper, RC paper and the like can be used.

[0010] The thickness of the substrate can be selected according to the application, and is usually 5 to 500 µm, preferably about 10 to 300 µm. If necessary, conventional additives such as a sizing agent, an antioxidant, an ultraviolet absorber, a heat stabilizer, a lubricant, and a pigment may be added to the substrate. Further, in order to improve the adhesion to the image receiving layer, a surface treatment such as a corona discharge treatment or an undercoat treatment may be performed.

(Image receiving layer) On at least one surface of the substrate, (A) a crosslinkable group-containing cationic acrylic copolymer, (B) a saponified vinyl acetate copolymer,
An image receiving layer formed of a resin composition for an ink jet recording sheet (also referred to as a recording resin composition) containing (C) a modifier and (D) an ether-based nonionic surfactant having an HLB of 12 or more is formed. Have been.

(Recording Resin Composition) A preferred image receiving layer is
On at least one surface of the substrate, (A) a crosslinkable group-containing cationic acrylic copolymer is 0 to 100% by weight,
(B) 0-70% by weight of a saponified vinyl acetate copolymer, (C) 0-80% by weight of a modifier (total 100% by weight of the three), and (A) + (B)>
(D) H based on 100 parts by weight of the composition which is 5% by weight
An ether-based nonionic surfactant having an LB of 12 or more is used in 0.1.
The recording resin composition is contained in the range of 1 to 15 parts by weight. Here, the constituent ratio of each component is expressed in terms of solid content.

The ratio of each component constituting the recording resin composition can be selected within a range that does not impair ink absorption, water resistance, print quality, gloss, fingerprint resistance, and the like. The cationic acrylic copolymer containing a crosslinkable group affects ink fixability, water resistance, and print quality. The saponified vinyl acetate copolymer has an ink absorbency, and the degree of polymerization of the saponified vinyl acetate copolymer is low. In addition, the modifier affects the print quality such as printing, the modifier affects water resistance, adhesion to a substrate, and the like, and the surfactant affects fingerprint resistance, glossiness, and ink absorption. It is a feature of the recording resin composition of the present invention that each performance is balanced at a high level in consideration of these.

Further, the quantitative ratio of each component which makes the above-mentioned performances more preferable is as follows: cationic monomer (a), crosslinkable group-containing monomer (b), monomer having polyalkylene oxide unit (c) ) And a hydrophilic group-containing monomer (d), (A) a crosslinkable group-containing cationic acrylic copolymer obtained by copolymerizing 0 to 20% by weight, and (B) a vinyl acetate copolymer 50-70% by weight of the compound (C)
The range is 30% by weight (the total of the three is 100% by weight).

Each component constituting the recording resin composition of the present invention will be described. (A) Crosslinkable group-containing cationic acrylic copolymer (A) The cationic monomer (a) constituting the crosslinkable group-containing cationic acrylic copolymer has a tertiary amino group or a base thereof. In addition to various monomers, various monomers having a quaternary ammonium base or capable of forming a quaternary ammonium base can be used. Examples of the cationic monomer include di C _1-4 alkylamino-
C _2-3 alkyl (meth) acrylamide or a salt thereof [dimethylaminoethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, diethylaminopropyl (meth) acrylamide or a salt thereof, etc. C _1-4 alkylamino -C _{2 -3} alkyl (meth) acrylate or a salt thereof [dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate,
Dimethylaminopropyl (meth) acrylate, diethylaminopropyl (meth) acrylate or salts thereof], di C _1-4 alkylamino-C _2-3 alkyl group-substituted aromatic vinyl or a salt thereof [4- (2-dimethylamino) Ethyl) styrene, 4- (2-dimethylaminopropyl)
Styrene and the like and salts thereof], a nitrogen-containing heterocyclic monomer or a salt thereof [vinylpyridine, vinylimidazole, vinylpyrrolidone or a salt thereof] and the like. Salts include hydrohalides (hydrochlorides, hydrobromides, etc.), sulfates, alkyl sulfates (methyl sulfate, ethyl sulfate, etc.), alkyl sulfonates, aryl sulfonates, carboxylic acids Salts (such as acetates) can be exemplified. The quaternary ammonium base may be generated by reacting an alkylating agent (epichlorohydrin, methyl chloride, benzyl chloride, etc.) with the tertiary amino group.

The crosslinkable group-containing monomer (b) includes various monomers having a self-crosslinkable or reactive functional group, for example, an epoxy group-containing monomer [glycidyl (meth) methacrylate, (meth) ) Allyl glycidyl ether, 1-allyloxy-3,4-epoxybutane, 1- (3-butenyloxy) -2,3-epoxypropane, 4-vinyl-1-
Cyclohexene-1,2-epoxide and the like], a methylol group-containing monomer or a derivative thereof [N-C _1-4 alkoxymethyl (meth) such as N-methylol (meth) acrylamide and N-methoxymethyl (meth) acrylamide]
Acrylamide, N-butyrol (meth) acrylamide, etc.], a monomer containing a hydrolyzable condensable group such as a silyl group [vinyltrimethoxysilane, vinyltriethoxysilane, vinyltributoxysilane, vinylmethoxydimethylsilane, vinylethoxydimethylsilane , Vinylisobutoxydimethylsilane, vinyldimethoxymethylsilane, vinyldiethoxymethylsilane, vinyltris (β
-Methoxyethoxy) silane, vinyldiphenylethoxysilane, vinyltriphenoxysilane, γ- (vinylphenylaminopropyl) trimethoxysilane, γ-
(Vinylbenzylaminopropyl) trimethoxysilane, γ- (vinylphenylaminopropyl) triethoxysilane, γ- (vinylbenzylaminopropyl) triethoxysilane, divinyldimethoxysilane, divinyldiethoxysilane, divinyldi (β-methoxyethoxy) Silane, vinyldiacetoxymethylsilane, vinyltriacetoxysilane, vinylbis (dimethylamino)
Methylsilane, vinylmethyldichlorosilane, vinyldimethylchlorosilane, vinyltrichlorosilane, vinylmethylphenylchlorosilane, allyltriethoxysilane, 3-allylaminopropyltrimethoxysilane, allyldiacetoxymethylsilane, allyltriacetoxysilane, allylbis (dimethylamino) Methylsilane,
Allylmethyldichlorosilane, allyldimethylchlorosilane, allyltrichlorosilane, methallylphenyldichlorosilane, β- (meth) acryloxyethyltrimethoxysilane, β- (meth) acryloxyethyltriethoxysilane, γ- (meth) acryloxy Propyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane, γ- (meth) acryloxypropylmethyldichlorosilane, γ- (meth) acryloxypropyltris (Β-methoxyethoxy) silane etc.), aziridinyl group-containing monomer [2- (1-aziridinyl) ethyl (meth) acrylate, 2- (1-aziridinyl) propyl (meth) acrylate, (meth) acrylic acid 3- (1-aziridinyl) Propyl and the like]. These crosslinkable monomers can be used alone or in combination of two or more. Preferred crosslinkable monomers have a hydrolytic condensable group, particularly an alkoxysilyl group (such as a C _1-4 alkoxysilyl group such as a methoxysilyl group or an ethoxysilyl group).

The monomer (c) having a polyalkylene oxide unit represented by the formula (1) includes diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, Propylene glycol
(Meth) acrylate, tripropylene glycol (meth)
Acrylate, polypropylene glycol (meth) acrylate, polyethylene glycol polypropylene glycol (meth) acrylate, hydroxypropyl (meth)
Examples include acrylate, polyethylene glycol polytetramethylene glycol (meth) acrylate, polypropylene glycol polytetramethylene glycol (meth) acrylate, and glycerol (meth) acrylate.

(D) The hydrophilic monomer includes, for example, carboxyl group-containing monomers [(meth) acrylic acid, itaconic acid, maleic acid, maleic anhydride, fumaric acid, crotonic acid, etc. Or a monomer having an acid anhydride group, and a salt thereof (eg, an alkali metal salt, an alkaline earth metal salt, an ammonium salt, or an amine salt)], an unsaturated polycarboxylic acid or an acid anhydride thereof, and 1 carbon atom. Half-esters of about 20 to about 20 linear or branched alcohols [monomethyl maleate, monoethyl maleate, monobutyl maleate, monooctyl maleate, mono-2-ethylhexyl maleate, etc.], hydroxyl group-containing monomer [(meth) 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, 3- (meth) acrylate
Hydroxypropyl, (meth) acrylic acid hydroxy C _2-6 alkyl ester such as 4-hydroxybutyl (meth) acrylate], amide group-containing monomer [(meth)
Acrylamide, α-ethyl (meth) acrylamide,
N-methyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, diacetone (meth) acrylamide, etc.], sulfonic acid group-containing monomers [styrene sulfonic acid, vinyl sulfonic acid, etc.], ether group-containing monomers [ Vinyl methyl ether, vinyl ethyl ether,
Vinyl ethers such as vinyl isobutyl ether]. These hydrophilic monomers can be used alone or in combination of two or more. Preferred hydrophilic monomers include carboxyl group-containing monomers [such as (meth) acrylic acid] and hydroxyl group-containing monomers [such as 2-hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate]. included.

These monomers are usually used in combination with a nonionic monomer in order to adjust film formability and film properties. Nonionic monomers (e) include, for example, alkyl esters [eg, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate,
Isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, (meth)
T-butyl acrylate, hexyl (meth) acrylate,
Octyl (meth) acrylate, 2- (meth) acrylate
(Meth) acrylic acid C such as ethylhexyl, lauryl (meth) acrylate, and stearyl (meth) acrylate
_1-18 alkyl esters, etc.], cycloalkyl esters [cyclohexyl (meth) acrylate, etc.], aryl esters [phenyl (meth) acrylate, etc.], aralkyl esters [benzyl (meth) acrylate, etc.], aromatic vinyls [ Styrene, vinyltoluene, α-methylstyrene, etc.], vinyl esters [vinyl acetate, vinyl propionate, vinyl versatate, etc.], allyl esters [allyl acetate, etc.], halogen-containing monomers [vinylidene chloride, vinyl chloride, etc.] ], Vinyl cyanide [such as (meth) acrylonitrile], and olefins [such as ethylene and propylene]. These nonionic monomers can be used alone or in combination of two or more.

As the nonionic monomer (e), usually,
(Meth) acrylic acid C _1-18 alkyl esters [especially C _2-10 alkyl acrylates and C _1-6 alkyl methacrylates], aromatic vinyls [especially styrene],
Vinyl esters [especially vinyl acetate] are used.

The amounts of the cationic monomer (a) and the crosslinkable group-containing monomer (b) can be selected within a range that does not impair the water resistance and ink absorbency. a) is from 0.1 to 50 mol% (e.g., from 1 to 45 mol%) of the entire monomer from the viewpoint of the ink fixing property (the dye ink is not fixed when the amount is too small, and the coloring is deteriorated when the amount is too large)
%), Preferably 0.5 to 40 mol% (for example, 2 to 40 mol%).
35 mol%), more preferably 1 to 30 mol%
(For example, 3 to 25 mol%), and usually 2 to 25 mol%.
It is about 25 mol%. The amount of the crosslinkable group-containing monomer (b) is, for example, 0.1 to 25 mol%, preferably 0.2 to 20 mol% of the whole monomer from the viewpoint of water resistance.
%, More preferably about 0.5 to 15 mol%, and usually about 0.3 to 10 mol%.

The glass transition temperature of (A) the crosslinkable group-containing cationic acrylic copolymer can be selected within a range that does not impair the film-forming properties and the like.
The temperature is about 10 to 40C, more preferably about 0 to 30C. If the glass transition temperature is lower than -20 ° C, it becomes sticky, and if it exceeds 50 ° C, the film-forming property tends to decrease.
The polymer having such a glass transition temperature can be adjusted by appropriately combining the above-mentioned cationic monomer, crosslinkable monomer and other monomers. The monomer is usually a hard monomer [for example, a monomer that forms a homopolymer having a glass transition temperature of about 80 to 120 ° C (particularly 90 to 105 ° C) such as methyl (meth) acrylate, styrene, etc.], glass transition temperature -85-10 ° C., such as soft monomer [acrylic acid C _2-10 alkyl esters (in particular -8
Monomer which forms a homopolymer of about 5 to −20 ° C.) in many cases. When combining each of the monomers, the ratio of each monomer, for example,
You can select from the following range. In terms of weight, monomers (c) having a polyalkylene oxide unit (1 to 40)
% By weight (preferably 3 to 35% by weight, especially 5 to 30% by weight), (d) 0 to 50% by weight of hydrophilic monomer (preferably 2 to 45% by weight, particularly 5 to 40% by weight), ( b) 0.1 to 20% by weight (preferably 0.2 to 15% by weight, particularly 0.5 to 10% by weight) of a crosslinkable monomer, (a) 1 to 40% by weight of a cationic monomer (preferably Is 3 to 35% by weight, particularly 5 to 30% by weight), (e-1) hard monomer 10 to 6
0% by weight (preferably 20-55% by weight, especially 25-5%
0% by weight) and (e-2) 10 to 60% by weight (preferably 15 to 50% by weight, particularly 20 to 45% by weight) of a soft monomer. The weight average molecular weight of (A) the cationic polymer can be selected, for example, from the range of about 0.2 × 10 ^{4 to} 100 × 10 ⁴ , preferably about 1 × 10 ⁴ to 50 × 10 ⁴ . When the weight-average molecular weight is less than 0.2 × 10 ⁴ , if the low-molecular-weight component increases, stickiness may be caused, and 100 × 10 ⁴
If it exceeds, the viscosity becomes high, which causes inconvenience in production.

The form of the cationic polymer (A) may be a solution such as an organic solvent solution or an aqueous solution, but is usually a form of a cationic emulsion (particularly an aqueous emulsion). The surface potential (ζ potential) of the polymer particles contained in the cationic emulsion is, for example, +10 to +60 m
V, preferably +12 to +55 mV (for example, +15 to +55 mV
+55 mV), and more preferably about +20 to +55 mV. As the surface potential of the polymer particles decreases, the fixability and water resistance of the ink decrease, and as the surface potential increases, the ink absorbency decreases. In the range of +10 to +60 mV, the balance between the two is excellent. The surface potential (ζ potential) of the polymer particles can be measured, for example, under the following conditions. Measurement device: Otsuka Electronics Co., Ltd., electrophoretic light scattering photometer (ELS-800) Measurement temperature: 25 ° C., concentration: solid content concentration 0.01 to 0.05
Dilution of the emulsion with distilled water to weight% Distance between electrodes: 32
mm applied electric field: 50 V / cm

The average particle size of the polymer particles in the cationic emulsion is, for example, 1 to 200 nm, preferably 3 to 200 nm.
To 100 nm, more preferably about 5 to 50 nm. The cationic emulsion containing the (A) crosslinkable group-containing cationic polymer can be prepared by a conventional method, for example,
A method of emulsion-polymerizing the monomer in an emulsion polymerization system containing a nonionic surfactant and / or a cationic surfactant,
After polymerization of the monomer, a tertiary amine salt or a quaternary ammonium salt is formed to obtain an aqueous emulsion.

(B) Saponified Vinyl Acetate Copolymer When the recording resin composition of the present invention is composed of a combination of a saponified vinyl acetate copolymer and other components, the ink absorbency is remarkably improved. The water resistance and print quality can be improved without impairment. The saponified vinyl acetate copolymer is a partially saponified vinyl acetate homopolymer and a copolymer of vinyl acetate and another copolymerizable monomer,
Degree of saponification of 7 from the viewpoint of balance between water resistance and ink absorption
0 to 95%, preferably a saponification degree of 75 to 92%, more preferably 79 to 89%, and a polymerization degree of 20.
It is 0-1000, preferably 300-800. When the polymerization degree is 200 or less, the effect of improving the water resistance may not be exhibited, and when it is 1000 or more, the uniformity of the image may be impaired.

Preferred copolymerizable monomers include hydrophilic groups having a hydrophilic group (for example, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, an acid anhydride group, an amide group, a hydroxyl group, an ether group, etc.). Contains monomers, especially vinyl monomers having ether groups, especially alkylene oxide units, diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, dipropylene glycol (meth) acrylate , Tripropylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, polyethylene glycol polypropylene glycol (meth) acrylate, hydroxypropyl (meth) acrylate, polyethylene glycol poly Tiger glycol (meth)
Acrylate, polypropylene glycol polytetramethylene glycol (meth) acrylate, glycerol
(Meth) acrylates. These vinyl monomers can be used alone or in combination of two or more. Preferred monomers include (meth) acrylates, which are vinyl monomers whose oxyalkylene units are oxyethylene units, especially polyoxyalkylene (meth) allyl ethers (among others, polyoxyethylene allyl ethers). In the vinyl acetate-based copolymer, the proportion of the copolymerizable monomer can be selected within a range that does not impair image clarity, water resistance, and the like.
mol%, preferably 1 to 30 mol%, more preferably 2.5 to 25 mol% (for example, 3 to 20 mol%).
%).

Depending on the purpose, the saponified vinyl acetate copolymer may be used alone, a plurality of saponified vinyl acetate copolymers may be used, or other hydrophilic polymers may be used. You may mix.

Examples of the hydrophilic polymer (a water-soluble polymer or a water-insoluble and water-absorbing polymer) that can be used in combination with a saponified vinyl acetate copolymer include, for example, a hydrophilic natural polymer and a hydrophilic polymer. Its derivatives (starch, corn starch, sodium alginate, gum arabic, gelatin,
Casein, dextrin, etc.), cellulose derivatives (methylcellulose, ethylcellulose, hydroxyethylcellulose, carboxymethylcellulose, cellulose sulfate, cyanoethylcellulose, etc.), vinyl alcohol polymers (polyvinyl alcohol, ethylene-vinyl alcohol copolymer, etc.), ethylene polymer Copolymer (ethylene-maleic anhydride copolymer, etc.), vinyl acetate copolymer (vinyl acetate-methyl acrylate copolymer, etc.), polyalkylene oxide (polyethylene oxide, ethylene oxide-propylene oxide block copolymer, etc.) , A polymer having a carboxyl group or a sulfonic acid group or a salt thereof [acrylic polymer (poly (meth) acrylic acid or a salt thereof (alkaline such as ammonium, sodium, etc.) Metal salts), methyl methacrylate -
(Meth) acrylic acid copolymers, acrylic acid-polyvinyl alcohol copolymers, etc.), vinyl ether polymers (polyvinyl alkyl ethers such as polyvinyl methyl ether and polyvinyl isobutyl ether, methyl vinyl ether-maleic anhydride copolymers, etc.), Styrene-based polymers (styrene-maleic anhydride copolymer, styrene- (meth) acrylic acid copolymer, sodium polystyrenesulfonate, etc.), sodium polyvinylsulfonate, etc.], nitrogen-containing polymers (or cationic polymers)
Or salts thereof (quaternary ammonium salts such as polyvinylbenzyltrimethylammonium chloride and polydiallyldimethylammonium chloride, polydimethylaminoethyl (meth) acrylate hydrochloride, polyvinylpyridine, polyvinylimidazole, polyethyleneimine, polyamidepolyamine, polyacrylamide, polyvinylpyrrolidone) Etc.). These hydrophilic polymers can be used alone or in combination of two or more. Among these hydrophilic polymers, a cellulose derivative (particularly, hydroxyethyl cellulose, etc.), a vinyl alcohol-based polymer, a vinyl ester-based polymer, and polyvinyl pyrrolidone are preferred. A polyoxyalkylene unit,
A hydrophilic polymer having at least one functional group selected from an acetoacetyl group, a carboxyl group, an acid anhydride group and an amino group is also preferable.

(C) Modifier The modifier used in the present invention is an aqueous polyurethane resin or an aqueous polyester resin.

(C-1) Aqueous polyurethane resin An aqueous polyurethane resin is a polyurethane resin synthesized from a polyol component, a polyisocyanate component, and a low molecular weight chain extender containing at least two hydrogen atoms that react with the polyisocyanate component. Is obtained by dissolving or dispersing in water and synthesized by a known method.
That is, after a relatively high-molecular-weight polyurethane is synthesized in a solvent that does not react with isocyanate, water is added little by little to perform phase inversion emulsification. Or a method of dissolving or dispersing a urethane prepolymer in which a hydrophilic group such as a polyethylene glycol or a carboxyl group or the like is introduced in water into a polymer, and then adding a chain extender to react. is there.

The polyisocyanate component used for producing the above-mentioned aqueous polyurethane resin includes, for example, aromatic polyisocyanates (for example, m-phenylene diisocyanate, p-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6- Diisocyanates such as tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate and 1,5-naphthalene diisocyanate, polyisocyanates such as triphenylmethane triisocyanate, etc., and araliphatic polyisocyanates (for example, 1,3-xylylene diisocyanate) Diisocyanates such as 1,4-xylylene diisocyanate and tetramethyl xylylene diisocyanate; polyisocyanates such as 1,3,5-triisocyanate methylbenzene Alicyclic polyisocyanates (for example, diisocyanates such as isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate and cyclohexane-1,4-diisocyanate, and polyisocyanates such as 1,3,5-triisocyanate cyclohexane) ), Aliphatic polyisocyanates (for example, aliphatic diisocyanates such as 1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, and aliphatic such as 1,3,6-hexamethylene triisocyanate) Polyisocyanate). The polyisocyanate component can be used alone or in combination of two or more. In many cases, a diisocyanate component is used as the polyisocyanate component.
Further, the polyisocyanate component may be an adduct having a polyisocyanate compound added to a polyhydric alcohol and having an isocyanate group at a terminal, a cyanurate, a dimer, or a trimer generated by a Burette reaction. The polyisocyanate component can be used alone or in combination of two or more.

Examples of the aqueous polyol component constituting the aqueous polyurethane resin according to the present invention include polyester polyols and polyether polyols (for example, oxy-C _2-4 such as polyoxytetramethylene glycol).
A polyether diol having an alkylene unit),
Polycarbonate polyol (for example, polycarbonate diol and the like) and the like can be mentioned. The polyester polyol is a polyester having a hydroxyl group obtained by reacting a polyhydric alcohol with a polyhydric carboxylic acid or a lower alkyl ester or an acid anhydride thereof, and may be derived from a lactone. The polyol components can be used alone or in combination of two or more. As the polyol component, a diol component (for example, polyester diol or the like) is often used.

The polyhydric alcohol for preparing the polyester polyol as the polyol component includes, for example,
Aliphatic polyhydric alcohols (eg, ethylene glycol,
Trimethylene glycol, propylene glycol, 1,
_C2-10 alkylene diols such as 3-butanediol, tetramethylene glycol, hexamethylene glycol and neopentyl glycol; polyoxy- _C2-4 alkylene glycols such as diethylene glycol and triethylene glycol; polyols such as trimethylolpropane and pentaerythritol Alicyclic polyhydric alcohols (e.g., 1,4-cyclohexane dimethylol,
Alicyclic diols such as hydrogenated bisphenol A),
Aromatic polyhydric alcohols [for example, aromatic diols such as 2,2-bis (2-hydroxyethylphenyl) propane and the like] are included. Polyhydric alcohols can be used alone or in combination of two or more. The polyhydric alcohol is usually an aliphatic diol.

Examples of the polycarboxylic acid for producing the polyester polyol include aliphatic polycarboxylic acids (for example, saturated aliphatic dicarboxylic acids such as adipic acid, suberic acid, azelaic acid, sebacic acid and dodecanedicarboxylic acid). Acids, unsaturated aliphatic dicarboxylic acids such as maleic acid, etc.), and alicyclic polycarboxylic acids (eg, 1,4
Alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid), aromatic polycarboxylic acids (e.g., phthalic acid,
Examples thereof include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid and 1,5-naphthalenedicarboxylic acid, and aromatic polycarboxylic acids such as trimellitic acid. Polycarboxylic acids can be used alone or in combination of two or more.

Further, the above polyester polyol can be derived from lactone. The lactone includes, for example, butyrolactone, valerolactone, caprolactone and the like, and they may be used alone or in combination of two or more. In addition, if necessary, a short-chain polyol (for example,
The above-mentioned aliphatic polyhydric alcohol) may be used as a part of the polyol component.

(C-1) As a chain extender used in the production of an aqueous polyurethane resin, there is a polyamine component, and ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, 1,7-
Diamines such as diaminoheptane, 1,8-diaminooctane, xylylenediamine, 1,4-diaminocyclohexaneisophoronediamine, and phenylenediamine;
And polyamines such as triaminopropane.
The polyurethane resin thus obtained may be used alone, or a plurality of types of polyurethane resins may be used. Further, if necessary, other resins and additives can be blended.

(C-2) Aqueous polyester resin As the aqueous polyester used for the modifier of the present invention, a polyester resin having an average molecular weight of 4000 to 30,000 is used. The aqueous polyester of the present invention is produced by esterification (ester exchange) and polycondensation of a dicarboxylic acid and a diol by a known production technique, but the production method is not limited at all.

As the dicarboxylic acid component, an aromatic dicarboxylic acid such as terephthalic acid, isophthalic acid, phthalic acid or naphthalene dicarboxylic acid or an ester thereof is preferably used. This is because the aromatic nucleus of the aromatic dicarboxylic acid has a high affinity for hydrophobic plastics and thus has an advantage of improving the adhesion. In particular, an aqueous polyester using terephthalic acid has high adhesion to a molded article of polyethylene terephthalate-based polyester, and is a preferred aqueous polyester.

As the dicarboxylic acid component constituting the aqueous polyester, it is preferable to use the above-mentioned aromatic dicarboxylic acids or esters thereof. In addition to these, adipic acid, succinic acid, sebacic acid and dodecane diacid are preferred. Such as an aliphatic dicarboxylic acid, a hydroxycarboxylic acid such as hydroxybenzoic acid or an ester thereof,
It can also be used as a dicarboxylic acid component or as a part thereof. When an ester is used, a lower alkyl ester such as a methyl ester or an ethyl ester is used. These esters can be monoesters or diesters.

On the other hand, as the diol component, ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, cyclohexanedimethanol, and bisphenols are used.

The aqueous polyester resin used in the present invention is polymerized so as to contain a sulfonic acid group or a carboxylic acid group as a hydrophilic group in the molecule in order to impart water solubility or water dispersibility. As a specific example for containing a sulfonic acid salt, there is a method in which a dicarboxylic acid component such as 5-sodium sulfoisophthalic acid is used as a part of the dicarboxylic acid component. The use amount thereof is preferably 2 to 15 mol% in the dicarboxylic acid component. Specific examples for containing a carboxylate include a method of using a trifunctional or higher polycarboxylic acid as a condensed acid component during the production of a polyester resin, and a method of grafting a polymerizable unsaturated carboxylic acid to the polyester resin. To produce a carboxylic acid-containing polyester, which is then converted to a salt with a substance that forms a water-soluble salt together with an alkali metal, various amines, an ammonium compound, and the like. The amount of the carboxylate in the polyester resin is preferably such that the acid value of the produced polyester resin is between 15 and 250 KOH mg / g.

The polyester used for the aqueous polyester resin has a molecular weight of 4,000 to 30,000. If the molecular weight is less than 4,000, the resin physical properties such as water resistance, blocking resistance and adhesion will be reduced. Uniform dissolution or dispersion in water is difficult, and it tends to gel over time. Especially when the molecular weight is 50
The thing of 00-25000 is preferable.

The aqueous polyester is converted into an aqueous solution or aqueous dispersion. In the case of a sulfonate-containing polyester resin, the aqueous polyester is dissolved or dispersed in warm water, preferably at 50 to 90 ° C., with stirring. In this case, a water-soluble organic solvent may be used in combination to facilitate dissolution or dispersion of the resin. Examples of the water-soluble organic solvent include lower alcohols, polyhydric alcohols and alkyl ethers or alkyl esters thereof, and specifically, lower alcohols such as methanol, ethanol, normal propanol and isopropanol, ethylene glycol,
Polyhydric alcohols such as propylene glycol, diethylene glycol, dipropylene glycol, glycerin, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol acetate, diethylene glycol monomethyl ether, dipropylene glycol monomethyl Ether and the like can be used. In the case of a carboxylate-containing polyester resin, ammonia water, sodium hydroxide, potassium hydroxide, preferably 50 to 90 ° C warm water to which an alkaline compound such as various amines is added,
Dissolve or disperse with stirring. In this case, the water-soluble organic solvent may be used in combination. The polyester resin thus obtained may be used alone, or a plurality of polyester resins may be used. If necessary, other resins and additives can be blended.

(D) Surfactant The surfactant used in the present invention has an HLB value (Griffin method: WCG) based on compatibility with a water-soluble resin and ink absorption.
riffin, Kirk-Othmer Encyclopedia of Chemical Techn
ology, 3rd.ed, Vol. 8, Weiley Interscience, New Yo
rk 1979, pp. 900-930) requires 12 or more. HL
If B is less than 12, the printed image tends to be poor. HL
B is preferably 14 or more, more preferably 16 or more. Further, the surfactant used in the present invention is an ether-based nonionic surfactant. When an ether-based nonionic surfactant is used, it has the effect of improving fingerprint resistance, and has excellent ink absorbency and can provide good image quality without beading. Although the reason is not yet clear, beading occurs when an ester surfactant is used, which adversely affects the image quality.

Examples of the ether nonionic surfactant having an HLB of 12 or more include polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monooleate, and polyoxyethylene sorbitan monooleate. Oxyethylene sorbitan trioleate, polyoxyethylene sorbite tetraoleate, polyoxyethylene monopalmitate, polyoxyethylene monostearate, polyoxyethylene monolaurate, polyoxyethylene monooleate, polyoxyethylene oleyl ether, polyoxy Ethylene lanolin ether,
Decaglycerin monostearate, hexaglycerin monostearate, decaglycerin monooleate, hexaglycerin monooleate, decaglycerin monolaurate, hexaglycerin monolaurate, decaglycerin monocaprylate or hexaglycerin monoester And caprylic acid esters. These surfactants can be used alone or in a mixture of two or more.
Among these surfactants, particularly, polyoxyethylene oleyl ether having an ethylene oxide addition mole number of 40 moles or more, polyoxyethylene lanolin ether,
It is preferable for improving fingerprint resistance and ink absorption. This is because nearly 20% of the sweat component is composed of oleic acid, which is an unsaturated fatty acid having 18 carbon atoms. Lanolin is an ester of various complex fatty acids and monohydric higher alcohols, and is easily absorbed by the skin and adheres well to mucous membranes. Therefore, it is desirable to use an ether type nonionic surfactant having a lanolin skeleton.

The compounding amount of the ether nonionic surfactant having an HLB of 12 or more in the ink absorbing layer is, in terms of solid content, a crosslinked group-containing cationic acrylic copolymer, a saponified vinyl acetate copolymer and The amount is 0.1 to 15 parts by weight, preferably 2 to 10 parts by weight, based on 100 parts by weight of the resin composition composed of a modifier. When the amount of the surfactant is less than 0.1 part by weight, the effect of the surfactant is not exhibited, which is not preferable. When the amount is more than 15 parts by weight, the compatibility with the dope becomes poor, and the obtained recording sheet is obtained. Is unfavorable because the glossiness of the film decreases.

(Blending of Recording Resin Composition) A curing agent (curing catalyst or curing accelerator) may be added to the recording resin composition of the present invention in order to accelerate the curing reaction. As the curing agent, for example, organotin compounds (dibutyltin dilaurate, dibutyltin dimaleate, dioctyltin dilaurate, dioctyltin dimaleate, dibutyltin diacetate, dibutyltin dimethoxide, tributyltin sulphite, dibutyltin thioglycolate, tin octylate, etc. ), Organoaluminum compounds (aluminum isopropylate, aluminum tris (ethyl acetoacetate), aluminum tris (acetylacetonate), ethyl acetoacetate aluminum diisopropylate, etc.), and organic titanium compounds (isopropyl tristearoyl titanate, tetraisopropyl bis ( Dioctyl phosphite) titanate, bis (dioctyl pyrophosphate) oxyacetate titanate ), Organic zirconium compounds (tetra-n-butoxyzirconium, zirconyl octylate, reaction products of alkoxy zirconium with acetylacetone or acetoacetic ester), acidic compounds (organic acids such as aliphatic acids such as acetic acid and propionic acid) Aromatic carboxylic acids such as carboxylic acids, oxycarboxylic acids, and benzoic acids; sulfonic acids such as benzenesulfonic acid, p-toluenesulfonic acid, and dodecylbenzenesulfonic acid; and basic compounds (bases, for example, organic bases such as triethylamine) , Sodium hydroxide, inorganic hydroxides such as potassium hydroxide), acidic phosphates (monobutyl phosphate, dibutyl phosphate, isopropyl acid phosphate, butyl acid phosphate, octyl acid phosphate, trideciate) Acid phosphate, etc.), the acid phosphoric acid ester with an amine (hexylamine, triethylamine, N, N-dimethyldodecylamine, mixture or reaction product of 3-propanolamine, etc.). These curing agents can be used alone or
A mixture of more than one species can be used.

The amount of the curing agent used is within a range capable of promoting the curability, for example, in terms of solid content, it is composed of a crosslinkable group-containing cationic polymer, a saponified vinyl acetate copolymer, and a modifier. 0.01 to 1 part by weight per 100 parts by weight of the resin composition (hereinafter simply referred to as “resin composition” unless otherwise noted).
0 parts by weight, preferably about 0.1 to 5 parts by weight.

Further, in order to improve the fixability of the colorant (dye), it is advantageous to use a dye fixing agent, in particular, a high molecular dye fixing agent. The dye fixing agent (polymer dye fixing agent)
Usually, a cationic group (particularly, guanidyl group or
Quaternary ammonium salt type strong cation group).
The dye fixative may be water-soluble. Examples of the dye fixing agent include a dicyan fixing agent (such as a dicyandiamide-formalin polycondensate) and a polyamine fixing agent (eg, aliphatic polyamines such as diethylenetriamine, triethylenetetramine, dipropylenetriamine, and polyallylamine, and aromatic compounds such as phenylenediamine). Group polyamines, condensates of dicyandiamide with (poly) C _2-4 alkylene polyamines (such as dicyandiamide-diethylenetriamine polycondensates)], and polycationic fixing agents. Examples of the polycationic fixing agent include an epichlorohydrin-di C _1-4 alkylamine addition polymer (e.g., epichlorohydrin-dimethylamine addition polymer), a polymer of allylamine or a salt thereof (a polymer of polyallylamine or a hydrochloride thereof) For example, Nitto Boseki Co., Ltd., PAA-10
C, PAA-HCl-3L, PAA-HCl-10L, etc.), a polymer of diallyl C _1-4 alkylamine or a salt thereof (a polymer of diallylmethylamine or a hydrochloride thereof, for example, Nitto Boseki Co., Ltd.)
PAS-M-1), a polymer of diallyl di C _1-4 alkyl ammonium salt (a polymer of diallyl dimethyl ammonium chloride, for example, Nitto Boseki Co., Ltd., PAS-H-5L, PAS-H-
10L), a copolymer of diallylamine or a salt thereof and sulfur dioxide (diallylamine hydrochloride-sulfur dioxide copolymer, for example, Nitto Boseki Co., Ltd., PAS-92, etc.), diallyldi C _1-4 alkylammonium salt— Sulfur dioxide copolymer (diallyldimethylammonium chloride-sulfur dioxide copolymer, for example, Nitto Boseki Co., Ltd., PAS-A-
1, PAS-A-5, PAS-A-120L, PAS-A-120A, etc.), a copolymer of diallyldi C _1-4 alkylammonium salt and diallylamine or a salt or derivative thereof (diallyldimethylammonium chloride-diallylamine hydrochloride) copolymers of salt derivatives, for example, Nitto Boseki Co., such as PAS-880), Jiariruji C _1-4 alkylammonium salt polymers, di C _1-4 alkylamino ethyl (meth) acrylate quaternary salt polymer Diallyl di C _1-4 alkyl ammonium salt-acrylamide copolymer (diallyl dimethyl ammonium chloride-acrylamide copolymer, such as Nitto Boseki Co., Ltd., PAS-J-81, etc.), amine-carboxylic acid copolymer (for example, , Nitto Boseki Co., Ltd., PAS-410, etc.). These dye fixing agents may be used alone or in combination of two or more.

The amount of the dye fixing agent used is within a range capable of improving the fixing property, for example, 0.1 to 40 parts by weight, preferably 1 to 30 parts by weight, based on 100 parts by weight of the resin composition in terms of solid content. More preferably, it can be selected from the range of about 2 to 20 parts by weight.

In the image receiving layer, if necessary, other components such as an aqueous emulsion containing a polymer having no crosslinkable group or polymer particles (for example, an acrylic resin emulsion, ethylene-vinyl acetate copolymer). Coalesced emulsion, vinyl acetate emulsion, etc.).

The image receiving layer may contain a powder (eg, a pigment). Examples of the granules include inorganic granules (white carbon, fine-particle calcium silicate, zeolite, magnesium aminosilicate, calcined silica, fine-particle magnesium carbonate, fine-particle alumina, silica, talc,
Minerals such as kaolin, delamikaolin, clay, heavy calcium carbonate, light calcium carbonate, magnesium carbonate, titanium dioxide, aluminum hydroxide, calcium hydroxide, magnesium hydroxide, magnesium silicate, calcium sulfate, sericite, bentonite, smectite And organic particles (crosslinked or non-crosslinked organic fine particles such as polystyrene resin, acrylic resin, urea resin, melamine resin, and benzoguanamine resin, and organic powdered particles such as minute hollow particles). These powders are 1
Species or two or more kinds can be appropriately selected and used in combination. In the case of using a powdery or granular material, a hydrophilic polymer such as a saponified vinyl acetate copolymer can be used as the binder resin. The ratio of the granular material to the binder resin is, for example, 0. 0 to 100 parts by weight of the binder resin.
It is about 1 to 80 parts by weight, preferably about 0.2 to 50 parts by weight. The image-receiving layer may further contain conventional additives as long as the properties are not impaired, such as an antifoaming agent, a coating improver, a thickener, a lubricant, a stabilizer (an antioxidant, an ultraviolet absorber, a heat stabilizer, etc.), You may add an antistatic agent, an anti-blocking agent, etc.

[Method of Manufacturing Recording Sheet] The recording sheet of the present invention can be manufactured by forming an image receiving layer made of a recording resin composition on at least one surface of the substrate. Each image receiving layer is formed by applying a coating solution prepared using an appropriate solvent (water, a hydrophilic solvent which may be water-soluble, a hydrophobic solvent or a mixed solvent thereof) to a substrate as a support. Can be formed. When the resin composition containing the crosslinkable group-containing cationic acrylic copolymer is in the form of an aqueous emulsion, it is used in the form of an aqueous coating solution. The coating solution is formed by a conventional casting or coating method, such as a roll coater, an air knife coater, a blade coater, a rod coater, a bar coater, a comma coater, a gravure coater, a silk screen coater method, or the like. Is cast or applied. The image receiving layer can be formed by applying a coating solution containing the above components to at least one surface of the substrate and drying the coating solution. Further, if necessary, after the coating liquid is applied, a crosslinked ink absorbing layer may be formed by heating at an appropriate temperature selected from the range of about 50 to 150 ° C. Note that a porous layer, an anti-blocking layer, a lubricating layer, an antistatic layer, and the like may be formed on the image receiving layer, if necessary.

The thickness of the image receiving layer formed of the recording resin composition can be selected according to the intended use.
m, preferably about 6 to 30 μm, usually 5 to 3 μm.
It is about 0 μm.

Since the recording sheet of the present invention has the image receiving layer, the ink absorbing property and the ink fixing property are high, and the water resistance and the print quality are remarkably improved. That is, when a printed portion or an image portion is formed with an aqueous ink by an ink-jet recording method without occurrence of image quality defects such as beading, and the dried printed portion or the image portion is immersed in water at a temperature of 30 ° C. for 1 minute, the color density is maintained. The rate is 80% or more (for example, about 85 to 100%), preferably 85% or more (for example, about 90 to 99%).

The recording sheet of the present invention is useful as a recording sheet by an ink jet system for recording by flying small ink droplets, but it is a sheet for printing such as offset printing and flexographic printing (particularly a sheet for aqueous ink). It can also be used as such.

[0057]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Unless otherwise specified, the compounding ratio represents a solid content conversion value. The methods for evaluating various characteristics of the recording sheets obtained in the examples and comparative examples are as follows.

Using an inkjet printer (manufactured by Seiko Epson Corporation, PM-770C), the recording sheets obtained in the examples and comparative examples were applied with cyan, yellow,
A color pattern using each color of magenta and black was printed in a photo glossy paper mode to form a recorded image.

(Fingerprint Resistance) After pressing a finger on the recording sheet obtained by the recording sheet manufacturing method of the present invention, a recorded image was formed as described above. The recorded image was visually observed, and the fingerprint resistance was determined based on the following criteria. ：: No fingerprint appeared at all. Δ: Fingerprints are hard to come out, and the appearance of the recorded image is not significantly impaired. ×: Fingerprints emerged clearly, impairing the appearance of the recorded image. (Gloss) The gloss of the recording sheet obtained by the recording sheet manufacturing method of the present invention was measured using a gloss meter. ○: 60 or more at 60 ° gloss Δ: 40 or more at 60 ° gloss ×: 40 or less at 60 ° gloss (water resistance) One drop of water was dropped on the printed image, and after standing for 10 seconds, the water drop was absorbed with tissue paper. . The recorded image at that time was visually observed, and the water resistance was judged based on the following criteria. ：: No dropout occurs in the image because the ink and resin do not dissolve. Δ: The ink and the resin are slightly dissolved, and a slight omission occurs in the image. X: The ink and the resin are dissolved and the image is missing. (Ink Absorption / Image Quality) The recorded image was visually observed, and the ink absorption / image quality was determined based on the following criteria. ：: The same color density portion is uniform and blurred, and there is no image quality defect such as unevenness or beading. Δ: Image quality is poor, such as partial bleeding and unevenness or beading. ×: There is poor image quality such as blurring, unevenness and beading in a wide range.

[Production of Cationic Acrylic Copolymer Containing Crosslinkable Group (A)] Isopropyl alcohol (IPA) was placed in a 2000 ml reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a nitrogen inlet tube and a thermometer. 219 parts and 1.23 parts of azoisobutyronitrile (AIBN) were added and dissolved by stirring, and the mixture was heated to 80 ° C. 93.7 parts of methyl methacrylate (MMA) as a copolymer component, n
-Butyl acrylate (BA) 98.7 parts, diethylaminoethyl methacrylate (DEAEMA) 49.3
Was mixed with 4.93 parts of trimethoxysilanepropyl methacrylate (A-174, manufactured by Nippon Unicar Co., Ltd.) and added dropwise to the flask over about 4 hours. After dropping, 0.25 parts of AIBN as an additional catalyst and solvent IP
A solution consisting of 25 parts of A was added dropwise, and the reaction was continued for another 2 hours to complete the polymerization. After completion of the polymerization, 16 parts of acetic acid was added to the flask while stirring, and water 70
5 parts were added dropwise over about 2 hours to emulsify. After emulsification, use a rotary evaporator for IPA
Was evaporated to obtain an emulsion of a crosslinkable group-containing cationic acrylic copolymer (solid content: 34.7% by mass).

(Example 1) (A) obtained in the above step
10 parts of a crosslinkable group-containing cationic acrylic copolymer,
(B) PVA-405 manufactured by Kuraray Co., Ltd. (degree of saponification: 80.0 to 83.0) as a saponified product of a vinyl acetate copolymer.
%, Degree of polymerization: 500) and (C) HUX-6 manufactured by Asahi Denka Kako Co., Ltd. as an aqueous polyurethane resin as a modifier.
70 and 30 parts of (D) a polyoxyethylene lanolin ether type nonionic surfactant ES-13 (H
LB15.0) was mixed to obtain an aqueous coating liquid. Apply an aqueous coating solution to art paper (NK white tong loss 180.0) having a thickness of 190 μm,
After drying for 15 minutes, an ink absorbing layer (image receiving layer) having a thickness of 15 μm was formed, and a recording sheet 1 was obtained.

Example 2 (D) Except that a polyoxyethylene oleyl ether type nonionic surfactant EN-1540 (HLB17.4) was used in place of the polyoxyethylene lanolin ether type nonionic surfactant made by Aoki Yushi. In the same manner as in Example 1, recording sheet 2 was obtained.

Example 3 A recording sheet 3 was obtained in the same manner as in Example 1 except that (A) the cationic acrylic copolymer containing a crosslinkable group was not added.

(Example 4) (A) The amount of the polyoxyethylene oleyl ether type nonionic surfactant (A) manufactured by Aoki Yushi was changed to 5 parts without adding the crosslinkable group-containing cationic acrylic copolymer. Other than the above, in the same manner as in Example 2,
Recording sheet 4 was obtained.

Example 5 (C) H manufactured by Asahi Denka Kogyo KK
Recording sheet 5 was obtained in the same manner as in Example 1 except that UX-670 was not added.

Example 6 (A) Cationic acrylic copolymer containing a crosslinkable group and (C) HUX manufactured by Asahi Denka Kogyo KK
A recording sheet 6 was obtained in the same manner as in Example 1 except that -670 was not added.

(Comparative Example 1) Recording sheet 7 was prepared in the same manner as in Example 3 except that (D) nonionic surfactant was not added.
I got

Comparative Example 2 (D) Polyoxyethylene oleyl ether type nonionic surfactant EN-1504 (HLB = 7.9) was used in place of the polyoxyethylene lanolin ether type nonionic surfactant made by Aoki Yushi. A recording sheet 8 was obtained in the same manner as in Example 3 except for the above.

(Comparative Example 3) (D) A polyoxyethylene lanolin ether type nonionic surfactant manufactured by Aoki Oil & Fat, instead of a polyoxyethylene oleate ester type nonionic surfactant manufactured by Daiichi Kogyo Seiyaku, ES-99 (HLB = 9) A recording sheet 9 was obtained in the same manner as in Example 3 except that the above-described method was used.

Comparative Example 4 (D) Polyoxyethylene lanolin ether type nonionic surfactant ES- made by Aoki Yushi
Recording sheet 10 was obtained in the same manner as in Example 1 except that the amount of 13 was changed to 20 parts. Table 1 shows the evaluation results of the recording sheets obtained in Examples and Comparative Examples.

[0071]

[Table 1]

As is clear from Table 1, the recording sheets obtained in the examples as compared with the comparative examples have problems in water resistance depending on the composition of the resin composition, but all of them have glossiness and gloss.
Good fingerprint resistance.

[0073]

The recording sheet having the recording resin composition of the present invention and the image receiving layer formed on at least one surface thereof has high glossiness, improves fingerprint resistance,
This makes it possible to obtain print quality comparable to that of photographic image quality.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2H086 BA31 BA34 BA37 BA41 4J002 BE03X BG07W BG13W CF063 CH054 CK023 EH046 FD090 FD140 FD314 FD316 GS00 4J038 CE021 CE022 CG001 CG002 CG141 C02J01 C03 012 DG121 DG122 DG131 DG132 DG261 DG262 GA02 GA04 GA06 GA07 GA08 GA12 GA13 GA15 KA09 MA10 MA13 MA14 PB03 PC08 PC10

Claims (9)

[Claims] (A) 0-100% by weight of a crosslinkable group-containing cationic acrylic copolymer, (B) 0-70% by weight of a saponified vinyl acetate copolymer, and (C) 0% by weight of a modifier. ~ 8
Composition 1 consisting of 0% by weight (where the sum of the three is 100% by weight) and (A) + (B)> 5% by weight
(D) A resin composition for an ink jet recording sheet comprising (D) an ether nonionic surfactant having an HLB of 12 or more in an amount of 0.1 to 15 parts by weight based on 00 parts by weight. 2. The resin composition for an ink jet recording sheet according to claim 1, wherein (D) the lipophilic group of the surfactant is a C _14-20 fatty acid skeleton. 3. The resin composition for an ink jet recording sheet according to claim 1, wherein the lipophilic group of the surfactant (D) has a lanolin skeleton. 4. The resin composition for an ink jet recording sheet according to claim 1, wherein (D) the hydrophilic group of the surfactant has a polyoxyalkylene (C _1-4 ) skeleton. 5. The resin composition for an ink jet recording sheet according to claim 1, wherein the saponification degree of the saponified product of the vinyl acetate copolymer (B) is 70 to 95 mol%. 6. The ink jet recording sheet according to claim 1, wherein (A) the cationic acrylic copolymer having a crosslinkable group is a copolymer of a monomer containing the following component (1) or (2). Resin composition. (1) A cationic monomer (a), a crosslinkable group-containing monomer (b), and a hydrophilic monomer (d). (2) Cationic monomer (a), crosslinkable group-containing monomer (b), hydrophilic-containing monomer (d) and monomer (c) having a polyalkylene oxide unit represented by formula (1) ). Formula (1)-[(CHR ₁ ) _n -O] _m -R ₂ wherein R ₁ represents a hydrogen atom, a methyl group or a hydroxyl group, R ₂ represents a hydrogen atom or a methyl group, and n represents 1 to
5, m shows the number of 1-20. ] 7. The resin composition for an ink jet recording sheet according to claim 6, wherein the crosslinkable group-containing monomer has an alkoxysilyl group. 8. An ink-jet recording method, comprising using the resin composition for an ink-jet recording sheet according to claim 1, wherein an image-receiving layer is formed on at least one surface of a substrate for the ink-jet recording sheet. Recording sheet. 9. Gloss (JIS Z8741) on the surface of an image receiving layer
9. The ink jet recording sheet according to claim 8, wherein the 60 ° gloss measured according to (1) is 60% or more.