JPH10129109A - Recorded material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a recorded material, improved in drying property of ink, a resistance to moisture and heat blocking property while retaining printing property as it is. SOLUTION: Binder, consisting of 3-80wt.% of ethyl ether group of carboxy alkylcellulose, whose degree of substitution of ethyl ether group per one unit of anhydrous glucose is 0.2-2.95 and whose degree of substitution of carboxy alkyl ether group is 0.05-2.8, and 97-20wt.% of cation modified polyvinyl alcohol, is applied on at least one side of a substrate (paper, film or the like) of a recorded material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a recording material. More specifically, the present invention relates to a recording material having improved ink drying property, water resistance and heat blocking property while maintaining printability.

[0002]

2. Description of the Related Art Conventionally, various recording methods such as a wire dot recording method, a thermosensitive coloring recording method, a thermosensitive thermal transfer recording method, a thermosensitive sublimation transfer recording method, an electrophotographic recording method and an ink jet recording method have been used. There is. Among them, the ink jet system can use plain paper as a recording sheet, the printing cost is low, the device is compact, there is no noise, and high-speed recording is possible.
It has features such as colorization. For this reason, attention has been paid to the use as a printer for outputting image information such as characters and figures created by a computer or the like at high speed and accurately. In addition, since it is easy to colorize and the picture pattern is clear, image information created by a computer is recorded on a transparent recording sheet by an ink jet printer, and this is used as a manuscript for an overhead projector (OHP), and is used for conferences and various conferences. There has been an increasing demand for use in presentations and the like, and for use of printed matter for design purposes.

[0003] It is required for a recording material to be recorded by an ink jet printer to absorb the moisture of the attached ink and dry and solidify the ink. From such a viewpoint, the following is known as a recording sheet for ink jet in which an ink receiving layer is formed on a recording material to enhance the ink absorbency. Examples of the inkjet recording material having improved ink absorption include a recording sheet in which an ink receiving layer made of a water-soluble resin such as polyvinylpyrrolidone and polyvinyl alcohol is provided on a support such as paper, a plastic film, and a glass plate, or silica. Recording sheets provided with an ink receiving layer containing a filler (for example, JP-A-55-146786, JP-A-56-99692, and JP-A-59-17)
No. 4381, JP-A-2-276670).

[0004] This type of recording sheet has good absorbability and fixability of aqueous ink, but has the disadvantage that the ink receiving layer has poor water resistance and the ink receiving layer is easily peeled off when exposed to water. Furthermore, when a filler such as silica is contained, if the content of the filler is high, the ink adsorbing force is too strong, so that an appropriate dot spread cannot be obtained and a thin image is formed. That is, the required image cannot be obtained. On the other hand, if the content of the filler is low, there is a problem that the ink cannot be sufficiently dried, and blocking or image disorder occurs. Further, the addition of the filler causes a problem that a fine crack is generated on the surface of the recording sheet, thereby sharpening an image or impairing the flexibility of the ink receiving layer.

[0005] In some cases, use of a cationic resin has been proposed for the purpose of improving the adsorptivity of the dye (for example, Japanese Patent Application Laid-Open No. 4-263984). In this case,
Although the adsorptivity between the ink receiving layer and the dye is improved, there is a problem that water resistance is insufficient and the ink receiving layer easily flows with water.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a recording material having improved ink absorbency, water resistance and blocking resistance while maintaining printability.

[0007]

Means for Solving the Problems In order to solve the above problems, the present inventors have found that ethyl ethers of carboxyalkyl cellulose and cation-modified polyvinyl alcohol are useful as binders and complete the present invention. Reached. That is, in the present invention, the degree of substitution of ethyl ether groups per anhydroglucose unit is 0.2 to 2.95 and the degree of substitution of carboxyalkyl ether groups is 0.05 to 2.8 per at least one surface of the support. Ethyl ethers of carboxyalkyl cellulose 3 to 80% by weight
And a binder comprising 97 to 20% by weight of a cation-modified polyvinyl alcohol.

As the support used in the present invention, a synthetic resin film, paper, synthetic paper, coated paper, metal, glass, cloth and the like can be used. Examples of the synthetic resin film include polyester, polyolefin, polyamide, polyester amide, polyether, polyimide, polyamide imide, polystyrene, polycarbonate, poly-P
-Phenylene sulfide, polyetherester, polyvinyl chloride, poly (meth) acrylate and the like can be used. Further, copolymers, blends, crosslinked products, kneaded pigments, glossy products, and the like can also be used. Among the above plastic films, polyester, preferably polyethylene terephthalate, is preferred in terms of mechanical properties, workability, and the like.

The carboxyalkyl cellulose ethyl ether used in the present invention has an ethyl ether group substitution degree of 0.2 to 2.95 and a carboxyalkyl ether group substitution degree of 0.05 to 2.8. If the degree of ethyl ether group substitution of the carboxyalkyl cellulose is less than 0.2, the water resistance is insufficient, and if it exceeds 2.95, the hydrophilicity becomes insufficient. The preferred range of the degree of substitution of the ethyl ether group is 0.2 or more and 2.2 or less.

If the degree of substitution of the carboxyalkyl ether group is less than 0.05, the solubility in water becomes insufficient,
If the ink absorbency becomes insufficient, and if it exceeds 2.8, the water resistance of the coated surface becomes insufficient. The preferred range of the degree of carboxyalkyl ether group substitution is 0.05 or more and 1.5 or less. The cation-modified polyvinyl alcohol used in the present invention refers to an amide-modified group, an imide group, a primary amino group, a secondary amino group, a tertiary amino group,
Preferred are those containing at least one cationic group selected from quaternary ammonium bases, secondary ammonium bases, tertiary ammonium bases, and quaternary ammonium bases. Further, a primary amino group, a secondary amino group, a primary ammonium base, and a secondary ammonium base are preferred. The preferred content of the cation modifying group is 0.01 mol% or more. More preferably, 0.1 to 30 mol%, further preferably 0.1 to 15 mol%.
Molar% is preferred. If the amount of modification of the cationic group is less than 0.01 mol%, the water resistance of the ink absorbing layer is not always sufficient. The average degree of saponification is preferably from 40 to 100 mol%. If the saponification degree is less than 40 mol%, the ink absorbency tends to decrease. The average degree of polymerization is 100 to 5
000 is preferable, and 200 to 3000 is more preferable. If the average degree of polymerization is less than 100, the water resistance of the ink absorbing layer tends to decrease, and if it exceeds 5,000, the viscosity of the solution becomes high, which may hinder workability.

The mixing ratio of the carboxyalkyl cellulose ethyl ethers and the cation-modified polyvinyl alcohol used in the present invention is 3 to 80% by weight of the carboxyalkyl cellulose ethyl ethers to the cation-modified polyvinyl alcohol 20 to 20% by weight based on the solid content. 97% by weight is preferred. If the content of ethyl ethers of carboxyalkyl cellulose is less than 3% by weight, water resistance becomes insufficient, and if it is 80% by weight or more, ink absorbency becomes insufficient.

The thickness of the coating layer provided on the support of the recording material of the present invention is 1 to 100 μm, preferably 1 to 50 μm.
μm, and more preferably 5 to 30 μm. 1μ thick
If it is less than m, the ink absorbency is not sufficient, and it takes time to dry. If it exceeds 100 μm, the workability during coating may be reduced. The ethyl ethers of carboxyalkylcellulose and the cation-modified polyvinyl alcohol used in the present invention may be mixed with an aqueous polymer for the purpose of improving ink drying properties, film properties of the ink receiving layer, gloss, and image clarity. good. For example, gelatin derivatives such as lime-processed gelatin, acid-processed gelatin, and enzyme-processed gelatin, for example, various gelatins such as gelatin reacted with anhydrides of dibasic acids such as phthalic acid, maleic acid, and fumaric acid, oxidized starch, and cationized gelatin Starch such as starch, etherified starch, cellulose derivatives such as methylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, carboxymethylcellulose, hydroxyethylcellulose, cationized hydroxyethylcellulose, polyalkylene oxides and derivatives thereof, polyacrylic acid, polymethacrylic Acids or their esters, salts and their copolymers, polyhydroxyethyl methacrylate and its copolymers, polyvinylpyrrolidone, polyvinylpyridyl Muhalide, polyvinyl alcohol of various degrees of saponification, carboxy-modified, amphoteric polyvinyl alcohol, polyethylene glycol, polypropylene glycol, polyvinyl ether, alkyl vinyl ether / maleic anhydride copolymer, styrene / maleic anhydride copolymer, and salts thereof, Synthetic polymers such as polyethyleneimine, conjugated diene copolymer latex such as styrene / butadiene copolymer, methyl methacrylate / butadiene copolymer, polyvinyl acetate, vinyl acetate / maleic ester copolymer, vinyl acetate / acryl Acid ester copolymer,
Acrylic polymers such as vinyl acetate copolymer latex such as ethylene-vinyl acetate copolymer, acrylic ester polymer, methacrylic ester polymer, ethylene-acrylic ester copolymer, and styrene-acrylic ester copolymer Thermosetting properties of latex of copolymer or copolymer, latex of vinylidene chloride-based copolymer or functional group-modified polymer latex with functional group-containing monomer such as carboxyl group of these polymers, melamine resin, urea resin, etc. Aqueous adhesive such as synthetic resin, polymethyl methacrylate, polyurethane resin, unsaturated polyester resin, vinyl chloride / vinyl acetate copolymer, polyvinyl butyral, alkyd resin, dimethyldiallylammonium salt polymer, dimethyldiallylammonium salt and acrylamide It may be mentioned synthetic resins such as copolymers of. These can be used alone or in combination.

As a method for producing a recording material of the present invention, for example, a binder obtained by dissolving ethyl ether of carboxyalkyl cellulose and cation-modified polyvinyl alcohol in water or water containing an organic solvent is coated on a support. Coating and drying may be mentioned. Also,
When ethyl ethers of carboxyalkyl cellulose are neutralized with a neutralizing agent, the solubility is improved and the viscosity of the binder is reduced, which is preferable from the viewpoint of workability during coating.

As the binder, known additives can be used as long as the properties of the present invention are not impaired. For example, calcium carbonate, basic magnesium carbonate, matting agents such as crystalline cellulose, defoaming agents, coating improvers, thickeners, antistatic agents, antioxidants, ultraviolet absorbers, dyes, water resistance agents,
Examples include lightfastness improvers, storage stability improvers, and printability improvers such as colloidal silica and alumina sol.

The carboxyalkylcellulose ethyl ethers used in the present invention may have some or all of the carboxyl groups contained therein neutralized. By being neutralized, the solubility in water and a water-soluble organic solvent containing water as a main component increases, the viscosity decreases, and the workability during coating improves. For neutralization, alkali metal ions,
One or more kinds of cations such as alkaline earth metal ions, ammonium ions, and organic amines can be used. In this case, the degree of neutralization is arbitrarily determined according to the composition of the target solution such as water and an organic solvent. Generally, 50% or more of the carboxyl groups contained are neutralized. This is preferred from the viewpoints of solubility and solubility, and subsequent handling of the coating liquid.

The water-soluble organic solvent which can be used for dissolving the ethyl ether of carboxyalkyl cellulose used in the present invention includes alcohols, polyhydric alcohols, derivatives of polyhydric alcohols, ketones, esters, carbonates. Or a combination of two or more solvents. As alcohols, methanol, ethanol, n-propanol, n-butanol,
Examples include n-pentanol, n-hexanol, n-heptanol, n-octanol, n-nonyl alcohol, n-decanol, n-undecanol or isomers thereof, cyclopentanol, cyclohexanol and the like. Preferred are alcohols having 1 to 6 alkyl carbon atoms.

The polyhydric alcohols include ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 2-cyclohexanediol, 1,7
-Heptanediol, 1,8-octanediol, 1,
Examples include 9-nonanediol, 1,10-decanediol, glycerin, pentaerythritol and the like.

Derivatives of polyhydric alcohols include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol isopropyl ether, ethylene glycol monobutyl ether, ethylene glycol isobutyl ether, propylene glycol monomethyl ether, propylene Glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, cellosolve acetate, or the like, or a solvent pocket book edited by Japan Society of Synthetic Organic Chemistry (p479-p574; September 20, 1990,
And polyhydric alcohols and derivatives thereof described in Ohm Co., Ltd.).

Examples of ketones include acetone, methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, diisopropyl ketone, cyclopentanone and cyclohexanone. As the esters, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, amyl acetate, lactate ester, butyrate ester, dibutyl phthalate, dioctyl phthalate, and cyclic esters such as ε-caprolactone and ε-caprolactam Esters are mentioned.

As ethers, diethyl ether,
Isopropyl ether, n-butyl ether, tetrahydrofuran, tetrahydropyran, 1,4-dioxane and the like can be mentioned. Examples of carbonates include dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ethylene carbonate and the like.

In the present invention, a known method such as an air knife coater, a blade coater, a gravure coater, a spray coater, a curtain coater, a roll coater, and an applicator can be applied for forming the coating layer. At this time, if the surface of the support is subjected to a known surface treatment such as a corona discharge treatment or a primer treatment in air or other atmospheres as necessary before application, thereby improving the applicability, And a coating film can be firmly formed on the film surface.

If necessary, a binder may be applied to both sides of the support, or ink absorbing layers having different physical properties may be laminated on the support. The concentration of the coating solution and the conditions for drying the coating film are not particularly limited, but the drying conditions for the coating film are desirably in a range that does not adversely affect the properties of the substrate. In the present invention, by using a binder containing ethyl ethers of carboxyalkylcellulose and cation-modified polyvinyl alcohol, an ink receiving layer having improved ink absorbency, water resistance and blocking resistance while maintaining printability is formed. A recordable material is obtained. Further, as a result, the binder layer is made opaque, so that the present invention can be applied to a back coat film in which a printed image is viewed from the support direction, a gloss paper having a glossy printed surface, a gloss film, and the like.

[0023]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be further described below with reference to examples. In addition, the measuring method of various characteristics in the present invention is as follows. [Evaluation method of printability] Inkjet printer (BJ
-600 J; manufactured by Canon Inc.) to print solid on the recording material. The degree of printing after recording was visually determined.

：: good, ×: poor [Evaluation method of dryness] Solid printing was performed on the recording material, and after 60 seconds and 90 seconds, copy paper was overlaid on the printed portion and a load (125 g / cm ² ) was applied. The degree of transfer to copy paper was evaluated. ：: no transfer after 90 seconds, ×: transfer after 90 seconds [Evaluation method of water resistance]
After being immersed in water for 2 minutes, the ink was naturally dried at room temperature, and the degree of outflow of ink was visually determined.

：: good, ×: complete ink loss [Method of evaluating heat-resistant blocking property] After the recording surfaces of the recording sheets are overlapped with each other and subjected to a load (125 g / cm ² ) and allowed to stand at 60 ° C. for 30 minutes. After cooling to room temperature, the recording material was peeled off by hand, and the blocking state was determined. ：: No breakage of substrate, ×: Breakage of substrate

[0026]

Example 1 Cation-modified polyvinyl alcohol (CM
318: Kuraray Co., Ltd.) 100 g, ion-exchanged water 800
g, 100 g of isopropyl alcohol in a mixer,
The solution was stirred until it was completely dissolved to obtain a solution having a solid content of 10% (this solution was referred to as a binder solution A).

100 g of carboxymethylethylcellulose (carboxymethyl group content 12.8%, ethyl ether group content 40%: manufactured by Freund Corporation), ion-exchanged water 684.1 g, isopropyl alcohol 200 g, 2 g
15.9 g of 8% aqueous ammonia was put into a mixer and stirred until completely dissolved to obtain a solution having a solid content of 10% (this is referred to as a binder liquid B).

A binder for recording material was prepared by mixing the binder liquid A and the binder liquid B at a weight ratio of 80:20. The binder was coated on a polyethylene terephthalate film with a rod coater so that the film thickness after drying was 10 to 25 μm, and dried to obtain a recording material. The evaluation results are as follows. Printability: 、, drying property: 、, water resistance; 、, heat blocking property: ○

[0029]

Comparative Example 1 A recording material was obtained in the same manner as in Example 1 except that only the binder liquid A of Example 1 was used as the binder liquid. The result is as follows. ×, drying property; ×, water resistance; ×, heat blocking property; × From the above results, the recording material of the present invention has the ink drying property, water resistance, and heat blocking property while maintaining the printing property. It can be seen that it has been improved.

[0030]

The recording material of the present invention is excellent in ink absorbency, ink drying property, print clarity, water resistance, and heat blocking property. For this reason, OHP sheets, calendars, stickers (stickers) Etc.), cards (business cards etc.)
It can be suitably used for applications such as. Further, by making the binder layer opaque, it can be used as a back coat film or the like for viewing a printed image from the direction of the support.

Claims (1)

[Claims] 1. The method according to claim 1, wherein at least one surface of the support has an ethyl ether group substitution degree of 0.2 per anhydroglucose unit.
A binder comprising 3-80% by weight of ethyl ethers of carboxyalkyl cellulose having a carboxyalkyl ether group substitution degree of 0.05-2.8 and 97-20% by weight of cation-modified polyvinyl alcohol. Recording material, characterized in that: