WO1997032734A1

WO1997032734A1 - Raw fabric for printing

Info

Publication number: WO1997032734A1
Application number: PCT/JP1996/003031
Authority: WO
Inventors: Junichi Hirose; Kazuhiro Fukudome
Original assignee: Asahi Kasei Kogyo Kabushiki Kaisha
Priority date: 1996-03-07
Filing date: 1996-10-18
Publication date: 1997-09-12
Also published as: JP3719763B2; JPH09244224A; AU7333896A

Abstract

A raw fabric for printing prepared by coating at least one surface of a support with a binder comprising 3 to 80 % by weight of carboxyalkylcellulose nitrates having a degree of replacement by nitrate ester groups of 0.2 to 2.95 and a degree of replacement by carboxyalkyl ether groups of 0.05 to 2.8 each per anhydrous glucose unit and 97 to 20 parts by weight of a cationically modified polyvinyl alcohol, or a ternary binder comprising the two components and 1 to 20 % by weight of a cationic polymer in a total amount of the nitrates, the polyvinyl alcohol and the cationic polymer of 100 % by weight. This fabric is excellent in thermal blocking resistance, water resistance of coating, sharpness of print, drying characteristics of print, and water resistance of print.

Description

Description Printing stock

The present invention relates to a raw material for printing. More specifically, it relates to a printing material excellent in the balance of coating film water resistance, heat blocking resistance, print clarity, print dryness, and print water resistance. Background art

Various recording methods conventionally used include a wire dot recording method, a thermal coloring recording method, a thermal melting thermal transfer recording method, a thermal sublimation transfer recording method, an electrophotographic recording method, and an ink jet recording method. There is a recording method. Among these, the ink jet system can use plain paper as a recording sheet, the print cost is low, the device is compact, there is no noise, high-speed recording is possible, and color printing is possible. There is a special feature that it can be used. For this reason, attention has been paid to use as a printer for quickly and accurately outputting image information such as characters and figures created by a computer or the like. In addition, because it is easy to colorize and the pattern is clear, computer-generated image information is recorded on a transparent recording sheet by an ink jet printer, and this is recorded on an overhead projector (OHP). There is an increasing demand to use manuscripts for manuscripts at conferences and presentations at various conferences, and to use printed materials for design purposes.

The recording method of the ink jet printer is roughly classified into a continuous method in which continuously ejected ink is selectively landed on the paper, and a drop-on demand in which ink is selectively ejected. There is a method. At present, the drop-on-demand method is the mainstream. In the drop-on-demand method, the recording ink is ejected by the pressure of a fine piezoelectric element (piezo element), or by the pressure of air generated by heating the thermal head. A bubble jet method is generally used in which recording is performed by ejecting from a nozzle and attaching the recording sheet to a recording sheet. Ink jet recording is a simple mechanism in which the process is completed simply by discharging the ink, which is a color material, directly onto the recording paper, so that the recording head and ink are large. Challenges are imposed. For ink, it is required to improve poor ink jetting caused by viscosity increase due to ink drying. Normally, this ink component is generally obtained by dissolving a dye, a resin, an additive, and the like in water and alcohol.

In addition, for recording materials recorded with an ink jet printer, not only the clarity of the printed image, but also the dryness of the printed ink and the water resistance of the ink after printing are improved. Has been requested. In addition, if the heat blocking property is poor, the productivity during coating becomes poor. If the water resistance of the recording material coating film is poor, not only does the water resistance after printing deteriorate, but also if the recording material is exposed to water before use, the coating film will flow out and be used as the recording material. Because of the drawback of being unable to do so, heat blocking resistance and coating water resistance are also required.

From this point of view, the following is known as a record sheet for ink jets that has increased ink absorbency by forming an ink receiving job on the recording material. .

Ink jet recording materials with improved ink absorption include water-soluble resins such as polyvinyl pyrrolidone and polyvinyl alcohol on a support such as paper, plastic film, or glass plate. There is known a recording sheet provided with an ink-receiving layer, or a recording sheet provided with an ink-receiving layer containing a filler such as varnish (see, for example, JP-A-55-146786). JP-A-56-99692, JP-A-59-174381, JP-A-2-276670).

This type of recording sheet has good water-absorbent ink absorption and fixation properties, but has the disadvantage that the ink-receiving surface is poorly water-resistant, and that the ink-receiving employees can easily come off when exposed to water. . Furthermore, when a filler such as silica is contained, if the content of the filler is too high, the ink adsorption power is too strong, so that an appropriate dot spread cannot be obtained and the line is thin. The image becomes the image and the required image is obtained. Not. On the other hand, if the content of the filler is low, there is a problem that the ink cannot be sufficiently dried, so that blocking and image disorder may occur. In addition, the addition of the filler also caused a problem that fine cracks were generated on the surface of the recording sheet, which caused the image to be clear and the flexibility of the ink receiving layer to be impaired.

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, the adsorptivity between the ink receiving layer and the dye is improved, but the water resistance is insufficient, and there is a problem that the ink receiving layer easily flows with water. On the other hand, if the added amount of the water-proofing agent is too large, the printability deteriorates. If a composition that balances printability and water resistance is used, both printability and water resistance will not reach satisfactory levels.

It has been proposed to use a combination of cation-modified polyvinyl alcohol and anion-modified polyvinyl alcohol for the purpose of improving water resistance (see, for example,

3-1 8 3 8 7 4 publication). In this case, a polyion complex is formed to improve the water resistance of the coating film.However, since the printability of each of the polyvinyl alcohols alone is insufficient, the printability of the system used in combination is sufficient. It does not reach the level. Further, even if the water resistance of the coating film is improved, the water resistance of the printed portion cannot be satisfied due to insufficient absorption of the dye in the coating film.

Further, it has been proposed to use an aluminum hydrate having a pseudo-boehmite structure as a receiving layer having excellent print clarity and water resistance (for example, see US Pat. No. 4,879,16). No. 6, U.S. Pat. No. 5,104,730, JP-A-2-276670, JP-A-5-32037). Further, it has been proposed to form an ink-receiving layer having a laminated structure using the alumina material or the silicon material (for example, US Pat. No. 5,104,730, US Pat. Statement

No. 4,780,356, Japanese Unexamined Patent Publication No. Hei 4-37,376, Japanese Unexamined Patent Publication No. Hei 4-37576, Japanese Unexamined Patent Publication No. Hei 3-28,384). However, when the number of inks increases, the ink cannot be absorbed sufficiently and bleeding occurs. In addition, since voids such as an alumina material are used, if the voids are blocked by moisture or the like, there is a problem that the absorption of ink becomes insufficient. In addition, there is another inconvenience such as a decrease in workability due to a viscosity increase of the coating solution over time.

An object of the present invention is to provide a printing material having a good balance of coating film water resistance, heat blocking resistance, print clarity, print drying property, and print water resistance. Disclosure of the invention

In order to solve the above problems, the present inventor has proposed that a carboxyalkylcellulose nitrate and a cation-modified polyvinyl alcohol, or a three-component system in which the above two components are used in combination with a cationic polymer are useful as a binder. The inventors have found that the present invention has been completed.

That is, in the present invention, at least one surface of the support has a nitrate ester substitution degree of 0.2 to 2.95 and a carboxyalkyl ether group substitution degree of 0.05 to 2.8 per anhydroglucose unit. 3 to 80% by weight of a carboxyalkyl cellulose nitrate ester and 97 to 20% by weight of a thiothion-modified polyvinyl alcohol, or 1 to 20% by weight of the two components and a cationic polymer, and The present invention relates to a printing material characterized by applying a binder having a total of 100% by weight of nitrates, cationically modified polyvinyl alcohol, and cationic polymer. BEST MODE FOR CARRYING OUT THE INVENTION

Examples of the support used in the present invention include a synthetic resin film or paper. Examples of the synthetic resin film include polyester, polyolefin, polyamide, polyesteramide, polyether, polyamide, polyamideamide, polystyrene, polycarbonate, and poly-P. —Phenylene sulfide, polyetherester, polyvinyl chloride, polyvinyl acetate, poly (meth) acrylic acid ester, etc. can be used. In addition, these copolymers, blends, and further crosslinked products, or pigments are kneaded and opaque. Films, foamed films, glossy films, etc. can also be used. Among the above supports, polyester and preferably polyethylene terephthalate are preferred in terms of mechanical properties, workability and the like. Examples of paper include high quality paper, medium quality paper, art paper, bond paper, copy paper, baryta paper, cast paper, corrugated paper, coated paper, synthetic paper, glossy paper. And resin-coated paper can be used. In addition to synthetic resin film and paper, cloth such as cotton, rayon, acryl, and polyester, glass plate, metal, etc. can be used according to the application.

The carboxyalkyl cellulose nitrate used in the present invention is a carboxyalkyl cellulose having a nitrate ester substitution degree of 0.2 to 2.95 and a carboxyalkyl ether group substitution degree of 0.05 to 2 And specifically refers to an aqueous cellulose derivative disclosed in JP-A-5-39301 and JP-A-5-39302.

In the present invention, the preferred range of the degree of substitution of the nitrate group of the nitrates of the carboxyalkyl cellulose is 0.2 or more and 2.2 or less, and the preferred range of the degree of substitution of the carboxyalkyl ether group is 0.05. As mentioned above, it is 1.5 or less. If the degree of substitution of the nitrate ester group is less than 0.2, the water resistance of the coating film is insufficient.If the degree of substitution of the carboxyalkyl ether group is less than 0.05, the solubility in water becomes insufficient, and Ink absorption becomes insufficient. On the other hand, if the degree of ester nitrate substitution exceeds 2.95, the hydrophilicity becomes insufficient. If the degree of substitution of the carboxyalkyl ether group exceeds 2.8, the water resistance of the coating film becomes insufficient.

The cation-modified polyvinyl alcohol used in the present invention includes an amide group, an imido group, a primary amino group, a secondary amino group, a tertiary amino group, a primary ammonium salt group, Polyvinyl alcohol containing at least one cationic group selected from a secondary ammonium base, a tertiary ammonium base and a quaternary ammonium base is preferred. Further, the amount of cation conversion refers to polyvinyl alcohol containing at least 0.01 mol%. The preferred range of the amount of metamorphosis is 0.1 to 30 mol%. Further, 0.1 to 15 mol% is preferable. Modification amount of cationic group If it is less than 0.01 mol%, the water resistance of the coating film is insufficient, which is not preferable. The average degree of oxidation is preferably from 40 to 100 mol%. If the degree of oxidation is less than 40 mol%, the ink absorbency becomes insufficient. The average degree of polymerization is preferably from 100 to 500. Further, 2000 to 300 is preferable. If the average degree of polymerization is less than 100, the water resistance of the coating film is reduced.If it exceeds 500, the solution viscosity is too high, and workability such as resin mixing and coating on a support is poor. Become.

The mixing ratio of the carboxyalkyl cellulose nitrate and the cation-modified polyvinyl alcohol used in the present invention is 3 to 80% by weight of the carboxyalkylcellulose nitrate with respect to the carboxyalkyl cellulose nitrate. Alcohol 20 to 97% i% is preferred. When the amount of nitrates in the mouth of the rutile cell is less than 3% by weight or more than 80% by weight, the water resistance of the coating film becomes insufficient.

The cation polymer used in the present invention is a water-soluble cationized polymer other than the above-mentioned cation-modified polyvinyl alcohol, and is a cationized cellulose derivative, cationized starch, cationized guar gum, diaryl quaternary ammonium salt polymer. And copolymers of diaryl quaternary ammonium salts with acrylamide, aniline resins, polythioureas, polyethyleneimines, polyvinyl pyridines and the like.

The mixing ratio of the cationic polymer used in the present invention is 3 to 80% by weight of carboxylalkylcellulose nitrates, 96 to 10% by weight of cation-modified polyvinyl alcohol, and 96 to 10% by weight of cationic polymer. Preferably, it is 20% by weight, and the total of the three components of nitrates, cationically modified polyvinyl alcohol, and cationic polymer is 100% by weight i%.

The thickness of the coating applied on the support of the printing material of the present invention is 1 to 100 rn, preferably 1 to 50 m, and more preferably 5 to 30 m. is there. When the thickness is less than 1 m, the ink absorbency is insufficient and drying takes a long time. When the thickness exceeds 100, the drying property and the coating property during coating are insufficient.

The nitric acid ester of the lipoxyalkyl cellulose used in the present invention Aqueous polymer is used for the purpose of improving ink drying properties, coating film physical properties, gloss, image clarity, etc. to on-modified polyvinyl alcohol or a three-component system combining the above two components and a cationized polymer. You may mix. For example, gelatin derivatives such as lime-treated gelatin, acid-treated gelatin, and enzyme-treated gelatin; various gelatins such as gelatin reacted with anhydrides of dibasic acids such as phthalic acid, maleic acid, and fumaric acid; and oxidized starch. , Cellulose derivatives such as methylcellulose, hydroxypropylcellulose, hydroxypropyl propylmethylcellulose, carboxymethylcellulose, hydroxyshethylcellulose, polyalkylene oxides and derivatives thereof, polyacrylyl Acids, polymethacrylic acid or its esters, salts and their copolymers, polyhydroxyshethyl methacrylate and its copolymers, polyvinylpyrrolidone, polyvinylpyridyl halide, various types化 Degree of conversion Polyvinyl alcohol, carboxy-modified, amphoteric polyvinyl alcohol, polyethylene glycol, polyvinyl alcohol, polyvinyl ether, alkyl vinyl ether, maleic anhydride copolymer, styrene, maleic anhydride copolymer, and their copolymers Salts, synthetic polymers such as polyethyleneimine, conjugated copolymers such as styrene 'butadiene copolymer, methylmethacrylate' butadiene copolymer latex, polyvinyl acetate, vinyl acetate 'male Vinyl acetate copolymer latex such as acid ester copolymer, vinyl acetate / acrylic acid ester copolymer, ethylene / vinyl acetate copolymer, acrylic acid ester polymer, metaacrylic acid ester polymer , Ethylene acrylate copolymerization Styrene-acrylic acid ester copolymers and other acrylate polymers or copolymer latex, vinylidene chloride copolymer latex or functional groups such as carboxyl groups of these various polymers Aqueous adhesives such as thermosetting synthetic resins such as functional group-modified polymer latex, monomer resin, and urea resin with monomers, and polymethylmethacrylate, polyurethane resin, and unsaturated polyester resin Synthetic resins such as vinyl chloride, vinyl acetate copolymer, polyvinyl butyral, and alkyd resin. Can be. These can be used alone or in combination.

Known additives can be used for the binder of the printing material used in the present invention as long as the properties of the present invention are not impaired. For example, matting agents such as calcium carbonate, basic magnesium carbonate, and crystalline cellulose, antifoaming agents, coating improvers, thickeners, antistatic agents, antioxidants, ultraviolet absorbers, dyes, water-resistant agents, Examples include lightfastness improvers, storability improvers, printability improvers such as colloidal silica, and aluminum sol.

The nitric acid esters of carboxyalkyl cellulose used in the present invention can be dissolved in water and / or an organic solvent containing water as a main component. In order to increase the solubility in these solvents, the carboxyl group contained in the ester nitrates of carboxyalkyl cellulose may be partially or entirely neutralized. For neutralization, one or more kinds of cations such as alkali metal ions, 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 organic solvent, but generally, 50% or more of the carboxyl groups contained are neutralized. Is preferred. Neutralizing the nitrates of the propyloxyalkyl cellulose lowers the viscosity of the solution and improves the coatability of the support.

Examples of the organic solvent that can be used for dissolving the carboxyalkyl cellulose nitrate used in the present invention include alcohols, polyhydric alcohols, derivatives of polyhydric alcohols, ketones, esters, and carbonates. And a solvent composed of one kind or a combination of two or more kinds selected from the above-mentioned kinds.

Alcohols include methanol, ethanol, n-propanol, n-butanol, n-pentanol, n-hexanol, n-heptanol, n-butanol, n-nonyl alcohol, n-decanol, n —Polyethylene or their isomers, cyclopentanol, cyclohexanol and the like. Preferably, they are alcohols having 1 to 6 alkyl carbon atoms. Polyhydric alcohols include ethylene glycol and propylene Glycol, 1,3-butylene glycol, 1,4-butylene glycol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1.2-cyclohexanediol, 1 7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decandyl, 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, and ethylene glycol monobutyl ether. Sobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, cellosolve acetate, etc., or a solvent pocketbook (edited by the Society of Synthetic Organic Chemistry) ρ479-ρ5754>. (September 19, 1990, published by Form) and polyhydric alcohols and their derivatives.

Examples of ketones include acetone, methylethylketone, methylbutylketone, methylisobutylketone, diisoprovirketone, cyclopentanone, cyclohexanone and the like.

Esters include methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isoptyl acetate, ammonium acetate, lactate ester, butyrate ester, dibutyl phthalate, octyl phthalate, and ε -Caprolactone, ε-Cyclic esters such as caprolactam.

Examples of ethers include getyl ether, isopropyl ether, η-butyl ether, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, and the like.

Examples of the carbonates include dimethyl carbonate, getyl carbonate, ethyl methyl carbonate, and ethylene carbonate.

The method of forming a coating film that absorbs the ink of the printing material of the present invention is as follows: Air Doctor Co., Ltd., Rod Coater, Knife Coater, River's Roll Coater, Tiger Overseas Coater, Kisco Overnight, Cast Coating, Spray Coat Overnight, Slot Orifice Coater, Calender Coater, Blade Coater, Gravure Coat Overnight A known method such as a force coater or a roll coater can be applied. At this time, before the coating on the support, a known surface treatment such as corona discharge treatment or primer treatment in air or other atmosphere is performed as necessary, so that the coatability is improved. Instead, it can be formed firmly on the film surface. If necessary, a binder may be coated on both sides of the support, or an ink absorbing member 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. However, it is preferable that the drying conditions for the coating film be performed within a range that does not adversely affect the crying characteristics of the base material.

The use of the carboxyalkylcellulose nitrates and cation-modified polyvinyl alcohol of the present invention, or a ternary binder containing the above-mentioned two components and a cationic polymer, provides heat blocking resistance, coating water resistance, and clear printing. A raw material for printing capable of forming an ink-receiving eyebrow with a good balance of printability, print drying property and print water resistance is obtained. As a result, the binder eyebrows can be made opaque and the printed image can be applied to back coating films where the printed image is viewed from the direction of the support, glossy printing stock, so-called glossy paper or glossy film.

(Example)

Hereinafter, the present invention will be further described with reference to examples. The methods for measuring various characteristics in this example are as follows.

[Evaluation method of heat-resistant blocking property] The printing surfaces of printing stocks were superimposed on each other, subjected to a load (125 g / cm ² ), allowed to stand at 60 for 30 minutes, and then printed at room temperature. The blocking state when the counter was manually spread was determined.

〇: No resistance With resistance X: Substrate rupture

After crushing immersion for 2 minutes [coating water resistance evaluation method] print raw in water of 2 5 ^e C, and dried for 30 minutes at 8 0 ° C, the reduction rate of the heavy S of the coating film before and after the test Was measured. In addition, in terms of reading the image of the printed portion after the print water resistance test, the weight reduction rate is practically 50% or less is preferred.

Weight loss rate = (weight of printing stock before test-weight of printing stock after test) x 100

(Weight of raw material for printing before test-weight of support)

[Evaluation method of printability] Solid print is applied to the printing material using an ink jet printer (BJ-600J; manufactured by Canon Inc.). After recording, the sharpness and the degree of bleeding were visually judged.

〇: good △: slightly bad X: bad

[Evaluation method of print dryness] For printing on the raw material for printing, after 60 seconds and 90 seconds, copy paper is superimposed on the printed part, and the load is applied (125 / cm ² ) to copy. 1 The degree of transfer to paper was evaluated.

〇: No transfer after 60 seconds △: No transfer after 90 seconds X: Transfer after 90 seconds [Evaluation method of print water resistance] The solid printed printing material is played in water at 25 ° C for 2 minutes. After that, it was dried at room temperature, and the degree of blurring or blurring of the printed image was visually determined.

〇: No change △: Slightly bleed X: Ink spill

(Production Example 1)

Carboxymethylcellulose (Cellogen 5A; manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd .; strength of substitution of propyloxymethyl ether group = 0.7) 100 g;

6 3/25 5/12 g of an acid mixture consisting of 12% by weight was placed in a 5 liter reaction vessel, and the nitrification reaction was continued for 60 minutes at 5 to 10 ° C while stirring. Do. The reaction product is deacidified with a centrifuge and washed immediately with plenty of water. Further, the reaction product was made into a 10% slurry in an autoclave, treated at i 40 ° C. for 30 minutes, and separated by a Buchner funnel to collect the reaction product. The reaction product was dried at 80 V for 2 hours to obtain 120 g of carboxymethylcellulose nitrate. The degree of substitution of the nitrate group per anhydroglucose unit of this nitrate was 1.9 based on the degree of substitution of the carboxymethyl ether group (0.7) of carboxymethylcellulose and the measurement of the nitrogen content by a CHN coder. I knew it. Next, the carboxymethyl cellulose nitrate ester having a degree of substitution of 1.9 per unit of anhydrous glucose unit and a degree of substitution of carboxymethyl ether group of 0.7 per unit of anhydrous glucose 100 obtained here was used. g, ion-exchanged water 59.8.6 g, and Petrice Mouth Solve 250.50 g were placed in a closed mixer and stirred. Further, 51.4 g of 10% aqueous ammonia was added as a neutralizing agent. The solution was completely dissolved while heating to obtain a solution having a solid content of 10% (this is referred to as a binder solution A).

(Production Example 2)

Using carboxymethylcellulose (cellogen 5A; manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd .; strength of propyloxymethyl ether group = 0.7), the aqueous sulfuric acid / nitric acid solution was changed to 59/20/21% by weight. in preparative click Loew 1 3 0 other subjected to 3 0-minute treatment at ^e C in the same manner as in production example 1 to obtain ί Ayakasan ester of carboxymethyl cellulose dry 9 0 g. The nitrate ester substitution degree per anhydroglucose unit of this nitrate ester was 1.2 based on the carboxymethyl ether group substitution degree (0.7) of carboxymethylcellulose and the measurement of nitrogen content by CHN coder. I understood.

Next, ion exchange with 100 g of carboxymethylcellulose nitrate having a degree of substitution of nitrate of 1.2 per unit of anhydrous glucose and a degree of substitution of carboxymethyl ether of 0.7 per unit of anhydrous glucose obtained here was performed. 842.8 g of water and 200 g of isopropyl alcohol were put into a closed mixer and stirred. Further, 57.2 g of 10% ammonia water was added as a neutralizing agent. The solution was completely dissolved while heating to obtain a solution having a solid content of 10% (this is referred to as a binder solution B). (Example 1)

100 g of cationically modified polyvinyl alcohol (CM318: Kuraray), 100 g of ion-exchanged water, and 100 g of isopropyl alcohol are placed in a mixer, and stirred until completely dissolved. As a result, a solution having a solid content of 10% was obtained (this is referred to as a binder solution C).

Binder solution A and binder solution C were mixed at a weight ratio of 20:80 to prepare a binder for a printing original material. Place the binder in a 100 m thick transparent On a polyethylene terephthalene resin (Melinex D535: ICI Jano, Inc.), the rod core is adjusted so that the film thickness after drying becomes 10 to 25 m. It was coated and dried in the evening to obtain a raw material for printing. Table 1 shows the evaluation results.

(Example 2)

A printing material similar to that of Example 1 was obtained except that the binder liquid A was changed to the binder liquid B and the mixing ratio was changed to 60 to 40. The evaluation results are shown in Table 1 ₍ [Comparative Example 1]

A printing substrate was obtained in the same manner as in Example 1 except that only the binder solution C of Example 1 was used as the binder solution. Table 1 shows the evaluation results.

(Comparative Example 2)

50 g of carboxymethylcellulose (degree of carboxymethyl ether group substitution: 0.7), 850 g of ion-exchanged water, and 100 g of isopropyl alcohol were placed in a mixer, and stirred until completely dissolved. A solution having a solid content of 5% was obtained (this is referred to as a binder solution D).

A printing material was obtained in the same manner as in Example 1 except that Binder B solution and Binder D solution were mixed at a mixing ratio of 20:80 in terms of solid content. Table 1 shows the evaluation results.

(Comparative Example 3)

A printing material was obtained in the same manner as in Comparative Example 1 except that boric acid (5% aqueous solution) was added as a water-proofing agent at a solid content of 1% by weight based on the binder liquid C. Table 1 shows the evaluation results.

(Comparative Example 4

100 g of anion-modified polyvinyl alcohol (amount of carboxyl group conversion: 1 mol%), 800 g of ion-exchanged water, and 100 g of isopropyl alcohol are put into a mixer, and stirred until completely dissolved. Thus, a solution having a solid content of 10% was obtained (this is referred to as a binder solution D).

A printing material was obtained in the same manner as in Example 1 except that the binder liquid C and the binder liquid D were mixed at a mixing ratio of 20:80. Table 1 shows the evaluation results. (Comparative Example 5)

A printing material was obtained in the same manner as in Example 1, except that Binder Solution C and Binder Solution D were mixed at a mixing ratio of 80:20. Table 1 shows the evaluation results.

(Example 3)

Binder B solution, Binder C solution, and diaryl quaternary ammonium salt-based cation polymer (ADEKAI KACHIOACE PD-50; manufactured by Asahi Denka Kogyo Co., Ltd.) in a weight ratio of 47.5 to 47.5 A printing material was obtained in the same manner as in Example 1 except that the mixture was mixed in a ratio of 47.5 to 5.0. Table 1 shows the evaluation results.

(Example 4)

A printing material similar to that of Example 1 was obtained except that the support was changed to gloss film (Melinex D534: manufactured by ICI Japan). Table 1 shows the evaluation results.

Table 1: Evaluation results Heat resistance D King property Water resistance of coating film Printing property Drying property Water resistance of printing Example 1 〇 18% 〇〇〇 Example 2 〇 4 2% 〇〇例 Example 3 〇 4 2% 〇〇〇 Example 4 〇 1 8% 〇〇比 Comparative example 1 X 100% XXX

Comparative Example 2 X 100% Δ △ X

Comparative Example 3 X68% XX Δ Comparative Example 4 X32% XX △ Comparative Example 5 X71% XXX From these evaluation results, the printing material of the present invention is excellent in ink absorption and ink. It is clear that it has excellent drying properties, print clarity, water resistance, and heat blocking properties. Call Industrial applicability

At least one surface of the support according to the present invention has a nitrate ester substitution degree of 0.2 to 2.95 and a carboxyalkyl ether group substitution degree of 0.05 to 2.95 per anhydroglucose unit. 3 to 80% by weight of carboxyalkylcellulose nitrate ester of 8, and 97 to 20% by weight

%, Or a binder comprising the above two components and 1 to 20% by weight of a cationic polymer, and a total of 100% by weight of nitrates, cationically modified polyvinyl alcohol, and cationic polymer is applied. By using a printing material that is suitable for use, printed matter excellent in ink absorption, ink drying, print clarity, water resistance, and ft heat blocking can be obtained.

Therefore, it can be used for applications such as HP sheets, calendars, seals (stickers, etc.), cards (business cards, etc.) posters, and raw materials for digital camera image output. Also, by making the coating layer on the transparent support opaque, it can be used for back coat film, glossy paper, glossy film, etc., where the printed image is viewed from the support direction.

Claims

The scope of the claims

1. At least one surface of the support has a degree of substitution of ester nitrate group of 0.2 to 2.95 and a degree of substitution of carboxyalkyl ether group of 0.05 to 2.8 per i anhydroglucose units. A raw material for printing, which is coated with a binder comprising 3 to 80% by weight of nitric acid esters of carboxyalkyl cellulose and 97 to 20% by weight of modified polyvinyl alcohol.

2. At least one surface of the support has a degree of substitution of ester nitrate group per anhydroglucose unit of 0.2 to 2.95 and a degree of substitution of carboxyalkyl ether group of 0.05 to 2.8. 3 to 80% by weight of nitric acid ester of carboxyalkyl cellulose and 96 to 10% by weight of thiothion-modified polyvinyl alcohol and 1 to 20% by weight of thiothion polymer, and nitrates and cationically modified polyvinyl A printing material characterized by being coated with a binder having a total of 100% by weight of three components of an alcohol and a cationic polymer.

3. The raw material for printing according to claim 1, wherein the carboxyalkyl ether group is a carboxymethyl ether group.

4. The composition according to claim 1, which comprises at least one kind of cationic group selected from cation-modified polyvinyl alcohol and cationic polymarker, amino group, amido group, imido group, and ammonium base. Or the printing stock described in 2.

5. The raw material for printing according to claim 1 or 2, wherein the cation-modified polyvinyl alcohol has a cation-modified amount of 0.01 to 30 mol%.

6. The method according to claim 1, wherein the degree of polymerization of the cation-modified polyvinyl alcohol is 40 to 100 mol% and the average degree of polymerization is 100 to 500. Raw material for printing.

7. The printing material according to claim 1, wherein the cationic polymer is a diaryl quaternary ammonium salt polymer or a copolymer thereof.

8. The printing material according to claim 1, wherein the support is made of paper or a synthetic resin film.

9. The printing material according to claim 1 or 2, which is used for a recording material of an ink jet recording method.