JP2002301861A - Sheet for ink-jet recording - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a sheet for ink-jet recording with less blotting of ink-jet recording parts and excellent water resistance of an ink receiving layer. SOLUTION: In the sheet for ink-jet recording with the ink receiving layer in which a pigment and an adhesive are main ingredients and a cationic resin which is a polycondensate of dialkylamine-epichlorohydrin is incorporated on at least one face of a substrate, the adhesive comprises 5-60 wt.% silicon- modified polyvinyl alcohol to 100 parts of the pigment and 2-25 wt.% cationic resin and 5-30 wt.% polyamideamine-epichlorohydrin resin are incorporated as a crosslinking agent in the ink receiving agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ink jet recording sheet, and more particularly to an ink jet recording sheet having excellent water resistance.

[0002]

2. Description of the Related Art In recent years, with the technical progress of an ink jet printer for producing a hard copy at high speed, it has become possible to obtain a clear image and excellent print quality. However, on the other hand, in order to further improve the print quality and image, a recording material having higher characteristics has been required. In particular, due to improvements in printing speed, resolution, etc., more advanced characteristics such as high absorbency, high absorption capacity, and regular ink bleeding are required for recording materials. Various types of recording sheets provided in the company have been developed.

The ink-jet recording system is capable of printing variable information at a high speed, and is therefore used for ticket paper, lottery tickets, and the like, and is about to be used for identification of each ticket. In addition, heat-sensitive recording media are used as recording media for tickets, lotteries, and the like from a maintenance-free viewpoint. However, since the variable information recorded on the surface of the thermosensitive recording layer of the thermosensitive recording medium may be lost by a chemical such as a plasticizer or oil, a cationic resin, a pigment and silicon-modified polyvinyl JP-A-2000-203 discloses a heat-sensitive recording medium provided with an ink receiving layer containing alcohol.
As described in JP-A-163-163, improvement of the water resistance of the ink receiving layer is demanded.

Japanese Patent Application Laid-Open No. 9-99629 discloses that
It is described that the water resistance of the ink receiving layer can be enhanced by including 40 to 90% by weight of a polyamide polyamine epichlorohydrin as a crosslinking agent in the ink receiving layer of the ink jet recording sheet. However, there is a problem in the print quality (bleeding) of the ink jet recording unit.

[0005]

SUMMARY OF THE INVENTION The present invention is to provide an ink jet recording sheet which has less blurring in an ink jet recording portion and has excellent water resistance of an ink receiving layer.

[0006]

Means for Solving the Problems In an ink jet recording sheet having a pigment-containing ink receiving layer on at least one surface of a support, one of the means for solving the above-mentioned problems is as follows. And pigment 100
5 parts by weight of silicon-modified polyvinyl alcohol
６０60 parts by weight, 2-25 parts by weight of a dialkylamine / epichlorohydrin polycondensate, and
It contains 5 to 30 parts by weight of epichlorohydrin resin.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The degree of polymerization of silicon-modified polyvinyl alcohol used as an adhesive for an ink receiving layer is preferably about 500 to 2500, more preferably 1 to 2500.
It is about 2,000 to 2,000. Further, the saponification degree is preferably at least 85 mol%.

The silicon-modified polyvinyl alcohol can be obtained, for example, by saponifying a copolymer of a vinyl ester and an olefinically unsaturated monomer containing silicon in the molecule. As silicon-containing olefinically unsaturated monomers,
For example, vinyltrimethoxysilane, vinylmethoxylauroxysilane, 3- (meth) acrylamide-propyltrimethoxysilane, 3- (meth) acrylamide-
Propyldimethylmethoxysilane and the like.

The amount of the silicon-modified polyvinyl alcohol to be used is preferably about 5 to 60 parts by weight based on 100 parts by weight of the pigment in the ink receiving layer. When the amount used is less than 5 parts by weight, when offset printing is performed on the ink receiving layer, the surface strength is weak and the receiving layer is transferred to the printing plate, and there is a possibility that plate smearing occurs, and more than 60 parts by weight. In addition, the permeability of the ink for ink jet recording into the ink receiving layer may be reduced, and blurring may occur in ink jet recording.

[0010] Other adhesives can be used in combination as long as the desired effects of the present invention are not impaired. Examples of such other adhesives include water-soluble adhesives such as partially saponified (fully saponified) polyvinyl alcohol, diacetone acrylamide-modified polyvinyl alcohol, casein, starch, oxidized starch, and carboxymethyl cellulose.
And hydrophobic adhesives such as acrylic resins, styrene-butadiene resins, urethane resins, and vinyl acetate resins. The hydrophobic adhesive is used in the form of a latex.

The amount of the polyamidoamine / epichlorohydrin resin is preferably about 5 to 30% by weight.
If the amount is less than 5% by weight, the effect of increasing the water resistance of the ink receiving layer is reduced. If the amount is more than 30% by weight, bleeding of printing may occur.

The polyamidoamine / epichlorohydrin resin is obtained, for example, by reacting epichlorohydrin with a dehydrated condensate of a dicarboxylic acid such as glutaric acid, adipic acid, pimelic acid and diethylenetriamine.

The dialkylamine used for the ink receiving layer
The amount of the cationic resin which is an epichlorohydrin polycondensate is preferably about 2 to 25% by weight based on 100 of the pigment. If the amount is less than 2% by weight, the water resistance of the ink jet recording part is reduced. If the amount is more than 25% by weight, the water resistance of the ink receiving layer is reduced, and print blurring may occur. As the alkyl group of the dialkylamine in such a cationic resin, for example, an alkyl group having 1 to 5 carbon atoms is preferable.

Other cationic resins can be used in combination as long as the desired effects of the present invention are not impaired. Such cationic resins include polyethyleneimine, polyvinylpyridine, dialkylamine / ammonia / epichlorohydrin polycondensate, polydialkylaminoethyl methacrylate, polydialkylaminoethyl acrylate, polydialkylaminoethyl methacrylamide, polydialkylaminoethyl acrylamide, Compounds such as polyepoxyamine, polyamidoamine, dicyandiamide / formalin polycondensate, dicyandiamide polyalkyl / polyalkylenepolyamine condensate, polydimethyldiallylammonium chloride, polyvinylamine, polyallylamine and the like, and modified products thereof can be exemplified.

Examples of the pigment used in the ink receiving layer of the present invention include amorphous silica, aluminum silicate, magnesium silicate, precipitated calcium carbonate, heavy calcium carbonate, calcium silicate, aluminum hydroxide, zeolite, and calcined. Examples include kaolin, kaolin, talc, alumina, hydrated alumina sol, and urea-formalin resin. Two or more of such pigments can be used in combination. Among these, amorphous silica, alumina, and hydrated alumina sol are preferable because of their good ink absorbency and high color density of the ink. The use ratio of the pigment is preferably about 40 to 90% by weight based on the ink receiving layer.

The ink receiving layer is formed by using water as a medium, for example, a silicon-modified polyvinyl alcohol aqueous solution, a pigment, a cationic resin which is a dialkylamine / epichlorohydrin polycondensate, a polyamidoamine / epichlorohydrin resin aqueous solution, and A surfactant, a pigment dispersant, an antifoaming agent, a coloring agent, an antioxidant, an ultraviolet absorber, a viscosity adjusting agent and the like are mixed and stirred to prepare a coating liquid for an ink receiving layer, which is neutral or neutral. The coating amount after drying on at least one surface of a support such as acidic woodfree paper, synthetic paper, or film is 1 to 3
It is formed by coating and drying so as to have a concentration of 0 g / m ² , preferably about ² to ²⁰ g / m ² .

The coating liquid for the ink receiving layer is applied by a known coating equipment such as a bar coater, an air knife coater, a blade coater, and a gravure coater. After coating and drying, the ink jet recording sheet may be treated with, for example, a super calender or a gloss calender to impart smoothness to the surface of the ink receiving layer.

Such an ink jet recording sheet has an ink receiving layer having excellent water resistance, and a thermosensitive recording containing a leuco dye and a coloring agent between the support and the ink receiving layer or on the other surface of the support. Even if the layer is provided, an effect without sticking between the surface of the heat-sensitive recording layer and the surface of the ink-receiving layer or a desensitizing effect on the heat-sensitive recording layer can be obtained.

The heat-sensitive recording layer is prepared by, for example, using water as a medium, and pulverizing a leuco dye dispersion and a colorant dispersion finely pulverized to an average particle size of about 0.1 to 2.0 μm, partially saponified (completely saponified). Adhesives such as polyvinyl alcohol, silicon-modified polyvinyl alcohol, acetoacetyl-modified polyvinyl alcohol, carboxy-modified polyvinyl alcohol, casein, starch, oxidized starch, carboxymethylcellulose, acrylic latex, styrene-butadiene latex, urethane latex, etc. A coating amount after drying of a thermosensitive recording layer coating solution prepared by mixing and stirring amorphous pigments such as silica, calcium carbonate, aluminum hydroxide, and magnesium carbonate, and an auxiliary agent that can be contained in the ink receiving layer. forming but by coating and drying so that 2 to 8 g / ^{m 2} approximately It is.

The leuco dye contained in the heat-sensitive recording layer includes, for example, 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide, 3-cyclohexylamino-6-chlorofluoran, Diethylamino-6-methyl-7-chlorofluoran, 3- (N-ethyl-N-isoamyl) amino-6-methyl-7-anilinofluoran, 3-di (n-butyl) amino-6-methyl- 7-anilinofluoran, 3-di (n-pentyl)
Amino-6-methyl-7-anilinofluoran and the like.

Specific examples of the coloring agent include, for example, 4,4'-cyclohexylidenediphenol, 2,2-
Bis (4-hydroxyphenyl) -4-methylpentane, 2,4′-dihydroxydiphenylsulfone, 4,
4'-dihydroxydiphenylsulfone, 4-hydroxy-4'-isopropoxydiphenylsulfone, bis (3-allyl-4-hydroxyphenyl) sulfone,
-Hydroxy-4'-methyldiphenylsulfone and the like.

Further, in the heat-sensitive recording layer, for example, stearic acid amide, 2-naphthylbenzyl ether, m-terphenyl, 1,2-diphenoxyethane, 1,2-di (3 -Methylphenoxy) ethane, 1,2-di (4-methylphenoxy) ethane, di-p-chlorobenzyl oxalate, di-p oxalate
-Methylbenzyl ester, oxalic acid dibenzyl ester In order to contain a sensitizer and to improve the storage stability of the recording portion, for example, 1,1,3-tris (2-methyl-4-
(Hydroxy-5-cyclohexyl) butane, 1,1,3
-Tris (2-methyl-4-hydroxy-5-tert-butyl) butane, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanuric acid, 2,2 '-Methylenebis (4-methyl-6-
tert-butylphenol), 4-benzyloxy-4 ′
A preservative improving agent such as-(2-methylglycidyloxy) diphenylsulfone may be contained.

An undercoating layer containing an oil-absorbing pigment and organic hollow particles may be provided between the heat-sensitive recording layer and the support in order to improve the recording sensitivity, recording quality and recording runnability. It is also possible to provide a protective layer containing an adhesive having a film-forming property and a pigment in order to improve printability and recording running property. As for the heat-sensitive recording layer, the undercoat layer and the protective layer, the conventional techniques for heat-sensitive recording sheets can be used.

[0024]

EXAMPLES The present invention will be described more specifically with reference to the following examples, but it should be understood that the present invention is not limited by these examples. In the following, “parts” and “%” indicate “parts by weight” and “% by weight” of a solid content (non-volatile content).

Example 1 Preparation of a support 20 parts of light calcium carbonate was added to a slurry of 100 parts of chlorine-free bleached bleached kraft pulp.
8 parts, alkenyl succinic anhydride-based neutral sizing agent 0.11
The papermaking slurry having a concentration of 2% was dried to 10% moisture using a fourdrinier multi-cylinder paper machine, and a 6% solution of oxidized starch was applied at 5 g / m ² on both sides by a size press and dried. , dried to 6% moisture to obtain a high quality paper of calender processed rice basis 82 g / m ² neutral.

Preparation of Coating Solution for Ink Receiving Layer 100 parts of amorphous silica (trade name: Mizukasil P-603, manufactured by Mizusawa Chemical Industry Co., Ltd.), silicon-modified polyvinyl alcohol having a saponification degree of 98 mol% (trade name: R-1130) 350% 10% aqueous solution of polyamideamine
40 parts of a 25% aqueous solution of an epichlorohydrin resin (trade name: WS-547, manufactured by PMC Japan), and a dialkylamine / ammonia / epichlorohydrin polycondensate (trade name: Sambright KH-65) as a cationic resin (Manufactured by Daiwa Chemical Industry Co., Ltd.) and 12 parts of a 60% aqueous solution and 200 parts of water were mixed and stirred to obtain a coating liquid for an ink receiving layer.

Preparation of Ink-Jet Recording Sheet On one side of the obtained high-quality paper, the following coating liquid for an ink-receiving layer was applied using a bar coater so that the coating amount after drying was 6 g / m ^2, and then dried. An inkjet recording sheet was obtained.

Example 2 In the preparation of the ink receiving layer coating liquid of Example 1, a dialkylamine / ammonia / epichlorohydrin polycondensate (trade name: Sunbright KH-65, manufactured by Daiwa Chemical Industry Co., Ltd.) was used. Sheet for inkjet recording in the same manner as in Example 1 except that 12 parts of a 50% aqueous solution of a dialkylamine / ammonia / epichlorohydrin polycondensation product (trade name: Jetfix 36N, manufactured by Satoda Kako Co., Ltd.) was used. I got

Example 3 In the preparation of the ink receiving layer coating liquid of Example 1, a dialkylamine / ammonia / epichlorohydrin polycondensate (trade name: Sunbright KH-65, manufactured by Daiwa Chemical Industry Co., Ltd.) was used. Example 1 was repeated except that 12 parts of a 60% aqueous solution of a dialkylamine / ammonia / epichlorohydrin polycondensate (trade name: HP-37A, manufactured by SENKA) was used.
In the same manner as in the above, an ink jet recording sheet was obtained.

Example 4 In the preparation of the ink receiving layer coating liquid of Example 1, silicon-modified polyvinyl alcohol (trade name: R-) was used instead of 300 parts of a 10% aqueous solution of silicon-modified polyvinyl alcohol.
2105, manufactured by Kuraray Co., Ltd.), except that 500 parts of a 10% aqueous solution was used in the same manner as in Example 1 to obtain an ink jet recording sheet.

Example 5 In the preparation of the coating liquid for the ink receiving layer of Example 1, talc (trade name: Himicron HE) was used instead of amorphous silica (trade name: Mizukasil P-603, manufactured by Mizusawa Chemical Industry Co., Ltd.).
-5, manufactured by Takehara Chemical Co., Ltd.), to obtain an ink jet recording sheet in the same manner as in Example 1.

Example 6 The procedure of Example 1 was repeated, except that the coating liquid for the ink-receiving layer was applied and dried so that the coating amount after drying was 10 g / m ^{2 in} the preparation of the coating liquid for the ink-receiving layer. In the same manner as in the above, an ink jet recording sheet was obtained.

Example 7 On the other side of the ink jet recording sheet obtained in Example 1, the following coating liquid for undercoat layer, coating liquid for heat-sensitive recording layer and coating liquid for protective layer were applied after drying. 8 g / m ² , 4 g / m
^An undercoat layer and a heat-sensitive recording layer were formed by coating and drying in order to obtain an undercoat layer and a heat-sensitive recording layer of ² , 2 g / m ² .

Preparation of Coating Solution for Undercoat Layer Calcined Kaolin (trade name; Ansilex, EC) 1
5 parts, 100 parts of a 30% dispersion liquid of organic hollow particles of an acrylic resin having an average particle diameter of 1.0 μm (film thickness: 0.3 μm),
Styrene-butadiene latex 2 having a solid concentration of 50%
0 parts, 150 parts of a 30% acid solution of paraffin wax (melting point 75 ° C.), 40 aqueous solution of sodium polyacrylate 1
Parts and 20 parts of water were mixed and stirred to obtain a coating solution for an undercoat layer.

Preparation of Solution A A composition consisting of 10 parts of 3-di (n-pentyl) amino-6-methyl-7-alininofluoran, 5 parts of a 5% aqueous solution of methylcellulose and 15 parts of water was subjected to sand milling to obtain an average particle size. Was reduced to 0.8 μm to obtain a liquid A.

Solution B Preparation A composition comprising 20 parts of 2,4'-dihydroxydiphenylsulfone, 20 parts of di-p-methylbenzyl oxalate, 5 parts of a 5% aqueous solution of methylcellulose and 55 parts of water was subjected to sand milling to obtain an average particle size. Was pulverized to 1.0 μm to obtain a liquid B.

Preparation of coating solution for heat-sensitive recording layer 25 parts of solution A, 100 parts of solution B, 30 parts of 20% aqueous solution of oxidized starch, 10 parts of light calcium carbonate, 10 parts of 25% aqueous solution of polyamide resin, completely saponified polyvinyl alcohol Was mixed and stirred to obtain a coating solution for a heat-sensitive recording layer.

Preparation of Coating Solution for Protective Layer A composition comprising 300 parts of a 10% aqueous solution of acetoacetyl-modified polyvinyl alcohol, 100 parts of a 60% dispersion of kaolin, and 20 parts of a 30% dispersion of zinc stearate was mixed and stirred. A coating liquid for a protective layer was obtained.

Example 8 A part of the protective layer of the ink jet recording sheet obtained in Example 7 was coated with an ink receiving layer coating solution and dried so that the coating amount after drying was 6 g / m ² . An inkjet recording sheet was obtained.

Comparative Example 1 In the preparation of the coating liquid for the ink receiving layer of Example 1, a dialkylamine / ammonia / epichlorohydrin polycondensate (trade name: Sunbright KH-65, manufactured by Daiwa Chemical Industry Co., Ltd.) was used. And 40 of a cationic resin having a methyl sulfate as a counter ion (trade name: F-13, manufactured by SENKA).
A sheet for ink jet recording was obtained in the same manner as in Example 1 except that 18 parts of a 20% aqueous solution was used.

Comparative Example 2 In the preparation of the coating solution for the ink receiving layer of Example 1, a dialkylamine / ammonia / epichlorohydrin polycondensate (trade name: Sunbright KH-65, manufactured by Daiwa Chemical Industry Co., Ltd.) was used. In addition, an anionic polyamide resin (trade name:
A sheet for inkjet recording was obtained in the same manner as in Example 1 except that 24 parts of a 30% aqueous solution of PA-800 (manufactured by PMC Japan) was used.

Comparative Example 3 In the preparation of the coating liquid for the ink receiving layer of Example 1, 60 parts of dialkylamine / ammonia / epichlorohydrin polycondensate (trade name: Sunbright KH-65, manufactured by Daiwa Chemical Industry Co., Ltd.) were prepared. Except that 12 parts of the 20% aqueous solution was changed to 60 parts.
In the same manner as in Example 1, an ink jet recording sheet was obtained.

Comparative Example 4 In the preparation of the coating liquid for the ink receiving layer of Example 1, a dialkylamine / ammonia / epichlorohydrin polycondensate (trade name: Sunbright KH-65, manufactured by Daiwa Chemical Industry Co., Ltd.) was used. An ink jet recording sheet was obtained in the same manner as in Example 1 except that the sheet was not provided.

Comparative Example 5 In the preparation of the coating liquid for the ink receiving layer in Example 1, a polyamideamine / epichlorohydrin resin (trade name: WS-
547, manufactured by Nippon PMC Co., Ltd.)
A sheet for ink jet recording was obtained in the same manner as in Example 1 except that the number of parts was changed.

Comparative Example 6 In the preparation of the coating liquid for the ink receiving layer in Example 1, a polyamideamine / epichlorohydrin resin (trade name: WS-
547, manufactured by Nippon PMC Co., Ltd.)
An ink jet recording sheet was obtained in the same manner as in Example 1 except that the amount was changed to 0.

Comparative Example 7 In the preparation of the coating liquid for the ink receiving layer of Example 1, silicon-modified polyvinyl alcohol (trade name: R-1130, manufactured by Kuraray Co., Ltd.) was replaced with partially saponified polyvinyl alcohol (trade name: PVA217EE, Kuraray A sheet for ink-jet recording was obtained in the same manner as in Example 1 except that the sheet was changed to (manufactured by KK).

Comparative Example 8 The procedure of Example 1 was repeated except that 350 parts of a 10% aqueous solution of silicon-modified polyvinyl alcohol (trade name: R-1130, manufactured by Kuraray Co.) was changed to 40 parts. In the same manner as in Example 1, an ink jet recording sheet was obtained.

Comparative Example 9 Except that 350 parts of a 10% aqueous solution of silicon-modified polyvinyl alcohol (trade name: R-1130, manufactured by Kuraray Co., Ltd.) was changed to 700 parts in the preparation of the coating liquid for the ink receiving layer in Example 1. In the same manner as in Example 1, an ink jet recording sheet was obtained.

The ink-jet recording sheet thus obtained was subjected to the following evaluation tests, and the evaluation results are shown in Table 1.

(1) Printing suitability of the ink jet recording unit An ink jet recording machine (trade name: Color Image Jet IO735X, manufactured by Sharp Corporation) is loaded with black ink (trade name: Cytex # 1007, manufactured by Cytex Japan). Ink jet recording is performed on the back of each thermosensitive recording medium, and the color density of the solid recording portion is measured using a Macbeth densitometer (RD).
-914 type, manufactured by Macbeth Corporation) in the visual mode. In addition, a bar code is printed and a bar code scanner (trade name: LASER CHEK II, Fuji D)
enki Reiki Co. , Ltd.)
The legibility by rainbow was evaluated as follows. ◎ ・ ・ ・ Barcodes can be read with almost no blurring.・ ・ ・: The bar code is readable, although there is a slight blur. ×: The barcode was too blurry to read.

(2) Water resistance of the ink receiving layer The ink jet recording sheet was immersed in water at 25 ° C. for 30 seconds, and the ink receiving layer was rubbed five times with a finger. The state of the ink receiving layer was as follows. evaluated. A: The ink receiving layer is hardly peeled off.・ ・ ・: The ink receiving layer is slightly peeled off. X: The ink receiving layer is largely peeled off.

(3) Water resistance of the recording unit A black ink (trade name: Cytex # 1007, manufactured by Cytex Japan) was loaded into an ink jet recording machine (trade name: Color Image Jet IO735X, manufactured by Sharp Corporation). Inkjet recording was performed on the back surface of each thermosensitive recording medium, and the inkjet recording sheet 10 minutes after recording was immersed in water at 25 ° C. for 3 minutes, and the recording state was evaluated as follows.・ ・ ・: There is no bleeding in the recording part, and it can be clearly read. ・ ・ ・: The ink in the recording part elutes a little, but it can be read. ×: The ink in the recording part elutes and it cannot be read.

(4) Printability In accordance with JIS-P8129, an ink for print test (Red, T) was prepared using an orange proofer (manufactured by IGT).
= 13, manufactured by T & K TOKA Co., Ltd.], and the degree of surface scorching was visually evaluated, and the evaluation criteria were as follows. ◎: There is no loss at all. ：: Slightly disturbed. ×: The entire surface is distorted.

[0054]

[Table 1]

[0055]

The recording sheet for an ink jet printer according to the present invention has less bleeding in the ink jet recording section.
In addition, the ink receiving layer has an excellent effect on water resistance.

Claims (2)

[Claims] 1. An ink jet recording sheet having a pigment-containing ink receiving layer on at least one surface of a support, wherein in the ink receiving layer, silicon-modified polyvinyl alcohol is added in an amount of 5 to 100 parts by weight of the pigment. An ink jet recording sheet comprising 60 parts by weight, 2 to 25 parts by weight of a dialkylamine / epichlorohydrin polycondensate, and 5 to 30 parts by weight of a polyamidoamine / epichlorohydrin resin. 2. The ink jet recording sheet according to claim 1, further comprising a heat-sensitive recording layer containing a leuco dye and a colorant between the support and the ink receiving layer or on the other surface of the support.