JPH10147057A - Additive for ink-jet recording paper - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an additive for ink-jet recording papers which forms characters and images with high resolution and less change in hue, by preparing the additive from a resin having essential components of a secondary amine, ammonia and epihalohydrin as monomers. SOLUTION: An additive for ink-jet recording papers is prepared from a resin having essential components of a secondary amine, ammonia and epihalohydrin. The ink-jet recording papers can accordingly be produced whereby waterproof properties of ink are improved, characters and images described on the recording papers show high resolution as formed by photographic printing, with less change in hue and without yellowing. The secondary amine used in dimethyl amine, diethyl amine, methyl ethyl amine, methyl propyl amine, methyl butyl amine, piperidine, etc. A mol ratio of the resin obtained from a reaction of the secondary amine, ammonia and epihalohydrin is preferably set to be 1:0.02-1:0.8-2.2.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an additive for ink jet recording paper, and more particularly, to a character or image described on the recording paper which has high resolution and water resistance, has little change in hue, and has a yellow color. The present invention relates to an additive for obtaining an ink jet recording sheet suitable for multicolor recording without changing.

[0002]

2. Description of the Related Art In recent years, the ink jet recording system has low noise, easy multi-color printing, development and fixing are unnecessary, and the like.
It is rapidly spreading as costs decrease. High quality paper, coated paper, art paper, etc. used for general printing have extremely poor ink absorbency, so when used for ink jet recording, the ink remains on the surface for a long time, The paper gets dirty. In particular, when ink dots overlap each other in multicolor recording, there is a disadvantage that ink is washed away or bleeds by ink dots attached later, and the resolution of printed characters and images becomes unclear. To prevent them, the type and amount of pigments such as silica, clay and talc are changed, and the type and amount of adhesives such as starch, gum arabic and carboxymethyl cellulose are changed, but the effect is not sufficient .

[0003] Further, as a water-proofing agent, for example, dicyandiamide-formaldehyde resin, diethylenetriamine.
Dicyandiamide / ammonium chloride condensate, (di) alkylaminoalkyl (meth) acrylate / acid salt polymer, (meth) acryloyloxyalkyltrialkylammonium chloride polymer, dimethyldiallylammonium chloride polymer, vinylpyridine acid There is an example in which a water-soluble cationic resin such as a salt polymer, an ethyleneimine polymer, a diallylamine polymer, and a shrimp chlorohydrin / dimethylamine polymer is added to a paper coating composition (Japanese Patent Application Laid-Open No. Hei 1-1-1). 214471).

When printing with an aqueous ink containing a direct dye, an acid dye, a reactive dye or the like having a water-soluble anionic group, a water-soluble cationic resin forms a complex by ionic bonding to improve the water resistance of the ink. Many resins have poor light fastness, for example, dicyandiamide / formaldehyde resin, diethylenetriamine / dicyandiamide / ammonium chloride condensate, ethyleneimine polymer, diallylamine polymer, etc. It is impossible to achieve both water resistance and light resistance. Polymers of (meth) acryloyloxyalkyltrialkylammonium chloride, polymers of dimethyldiallylammonium chloride, etc., which have relatively good lightfastness, have insufficient water resistance or change the color of the ink. Cannot be put to practical use. Epichlorohydrin / dimethylamine polymer has been proposed as a resin having excellent light resistance and water resistance (Japanese Patent Application Laid-Open No. 6-92012), but sufficient water resistance has not been obtained in practical use.

[0005]

SUMMARY OF THE INVENTION The present invention improves the water resistance of ink, which is a drawback of the conventional ink jet recording paper, so that characters and images written on the recording paper have high resolution and hue like photographic printing. It is an object of the present invention to provide an additive for obtaining an ink jet recording sheet having little change and not causing yellowing of the recording sheet.

[0006]

SUMMARY OF THE INVENTION An ink jet recording paper is provided which achieves the above objects by the additive according to the present invention. That is, the present invention relates to an additive for ink jet recording paper comprising a resin containing a secondary amine, ammonia and epihalohydrin as essential components.

The present inventors have found that a resin obtained by reacting a secondary amine with ammonia and epihalohydrin, to which ammonia is added, is much more effective than a resin obtained by reacting a secondary amine with epihalohydrin as a monomer. Ink has good water resistance and high resolution like photo printing,
Moreover, they found no change in hue.

Hereinafter, the present invention will be described in more detail. The secondary amine used as a monomer in a resin obtained by reacting secondary amine, ammonia and epihalohydrin as essential components is dimethylamine, diethylamine, methylethylamine, methylpropylamine, methylbutylamine, piperidine, pyrrole, and the like. Carbazole and the like. In addition, as a monomer, a secondary amine, ammonia and epihalohydrin are essential components, and epihalohydrin used in a resin obtained by reacting them is epichlorohydrin, epiiodohydrin, epibromohydrin, and the like. Epichlorohydrin is preferred.

The molar ratio of the resin obtained by reacting the secondary amine, ammonia and epihalohydrin is 1:
The ratio is from 0.01 to 2: 0.5 to 2.5, particularly preferably from 1: 0.02 to 1: 0.8 to 2.2. Even if the amount of ammonia is further increased, the reactivity with epichlorohydrin is poor, and there is a disadvantage that gelation easily occurs.

The resin used in the present invention can be easily reacted by dissolving a secondary amine and ammonia in a water-soluble solvent such as water, adding epihalohydrin dropwise, and further heating at 30 to 100 ° C. I can do it. The weight average molecular weight of the resin obtained by the reaction is 1,000 to 20
000, preferably 3,000 to 100,000.

As a substrate of the ink jet recording paper used for the additive of the present invention, paper is representative, but cloth, resin,
Films, synthetic papers and the like can also be used.

The method for producing an ink jet recording paper containing the additive of the present invention includes a method of dipping a substrate in an impregnating liquid containing the additive of the present invention (post-treatment method), and a method of adding the present invention in a papermaking process. And a method in which the additive of the present invention is contained in a coating liquid, a substrate is coated with the coating liquid, and then dried, and the like.

The coating liquid includes synthetic silica, clay, talc,
Diatomaceous earth, calcium carbonate, calcium sulfate, barium sulfate, zinc oxide, titanium oxide, titanium white, inorganic pigments such as aluminum silicate, styrene-based polymer,
Organic pigments such as urea polymers, oxidized starch,
Water-soluble polymers such as cationic starch, esterified starch, pregelatinized starch, ether starch, gelatin, casein, carboxymethylcellulose, hydroxyethylcellulose, methylcellulose, polyvinyl alcohol, polyacrylamide, polyethylene oxide, polyvinylpyrrolidone, etc. Polymer latex, methyl methacrylate-butadiene copolymer latex, synthetic resin latex such as ethylene vinyl acetate copolymer latex, polyvinyl butyral, organic solvent-soluble resin such as phenylguanamine resin, dye, water retention agent, Waterproofing agent, optical brightener,
It may contain commonly used chemicals such as a pH adjuster, an antifoaming agent, a lubricant, a preservative, a surfactant, and a conductive agent, and is not particularly limited.

The concentration of the additive of the present invention in the impregnating solution or aqueous solution can be varied, but is usually 0.01 to 10% by weight, preferably 0.05 to 5% by weight. The bath ratio in this case is usually from 1: 5 to 200, preferably from 1:10 to 1
00. The aperture ratio is usually 30 to 150%, preferably 50 to 100%.

The concentration of the additive of the present invention in the coating liquid can be variously changed, but is usually 0.01 to 10% by weight, preferably 0.05 to 5% by weight. The water-soluble polymer is usually 1 to
Usually, 15 to 15% and 3 to 15% of inorganic pigment are used. The coating amount is usually 1 to 60 g / m ² (dry coating amount), preferably ² to 50 g / m ² . As a coating method, a known method such as a roll coater method, an air knife coater method, and a blade coater method can be used.

As the drying method, for example, a normal method such as a steam heating heater, a gas heater, an infrared heater, an electric heater, and a hot air heating is performed. ,
It is possible to impart gloss by a finishing process such as a gloss calendar. In addition, any general processing means is possible.

As a water-based ink for ink jet, a water-soluble direct dye, an acid dye, a basic dye, a reactive dye, or the like is usually used as a colorant. The solvent of the water-based ink is water and a water-soluble organic solvent, for example, Polyhydric alcohols such as monoethylene glycol, diethylene glycol, triethylene glycol and glycerin, and lower alkyl ethers of polyhydric alcohols such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether and triethylene glycol monomethyl ether are used. Examples of other additives include a fungicide, a bactericide, an antioxidant, a pH adjuster, a dispersant, a rust preventive, a chelating agent, a surfactant, and a viscosity adjuster.

[0018] Ink jet printers are used in the usual manner,
For example, a drop-on-demand method, a continuous method, an intermittent ejection method, an ink mist method, or the like can be used.

Until now, there has been no ink jet recording paper which satisfies all of the pattern, hue change, water resistance, etc. of the ink at once, but the secondary amine, ammonia, epihalohydrin, etc. as the monomer of the present invention. This has been made possible by using an additive for ink jet recording paper comprising a resin having as an essential component.

[0020]

EXAMPLES The characteristics of the present invention will be further clarified by giving examples and comparative examples, but the present invention is not limited to the following examples. Part in the examples,
The percentages are by weight unless otherwise specified.

Synthesis of dimethylamine-ammonia-epichlorohydrin resin

Synthesis Example 1 (1: 0.1: 1.1 mol ratio) 90.2 aqueous dimethylamine solution (50%) was placed in a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer.
g, ammonia water (25%) 6.8 g and water 172.6 g
Was added and stirred to dissolve uniformly, and 101.8 g of epichlorohydrin was dropped into the mixture over about 3 hours from a dropping funnel. After completion of the dropwise addition, the reaction was continued at 80 ° C. for 6 hours to obtain a colorless to pale yellow liquid aqueous solution having a resin content of 39%.
The weight average molecular weight of the obtained polymer determined by GPC (liquid chromatography) was 20,000.

Synthesis Example 2 (1: 0.5: 1.5 mol ratio) A dimethylamine aqueous solution (50%) 90.2 was placed in a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer.
g and ammonia water (25%) 34.0 g and water 217.9
g, and stirred to dissolve uniformly, and then 138.8 g of epichlorohydrin is added to the mixture from a dropping funnel in an amount of about 38.8 g.
It was dropped over time. After completion of the dropwise addition, the reaction was continued at 80 ° C. for 8 hours to obtain a colorless to pale yellow liquid aqueous solution having a resin content of 39%. The weight average molecular weight of the obtained polymer obtained by GPC was 25,000.

Synthesis Example 3 (1: 1: 2 molar ratio) 90.2 aqueous dimethylamine (50%) solution was placed in a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer.
g, 68 g of aqueous ammonia (25%) and 2746 g of water were added and stirred to dissolve uniformly, and 185 g of epichlorohydrin was added dropwise to the mixture over about 3 hours from a dropping funnel. After completion of the dropwise addition, the reaction was continued at 80 ° C. for 10 hours to obtain a colorless to pale yellow liquid aqueous solution having a resin content of 39%. The weight average molecular weight of the obtained polymer obtained by GPC was 300000.

Synthesis Example 4 (1: 1: 2.2 mol ratio) A dimethylamine aqueous solution (50%) 90.2 was placed in a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer.
g, ammonia water (25%) 68g and water 81g,
After stirring and dissolving uniformly, 203.5 g of epichlorohydrin was dropped into this mixture from the dropping funnel over about 3 hours. After completion of the dropwise addition, the reaction was continued at 90 ° C. for 10 hours to obtain a colorless to pale yellow liquid aqueous solution having a resin content of 57%. The weight average molecular weight of the obtained polymer determined by GPC was 80,000.

Synthesis Example 5 (1: 0.5: 1.5 molar ratio) Diethylamine aqueous solution (50%) in a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer.
2 g, 34.0 g of aqueous ammonia (25%) and water 231.
After adding 9 g and stirring to dissolve uniformly, 138.8 g of epichlorohydrin was dropped into the mixture over about 3 hours from a dropping funnel. After completion of the dropwise addition, the reaction was continued at 80 ° C. for 10 hours to obtain a colorless to pale yellow liquid aqueous solution having a resin content of 39%. The weight average molecular weight of the obtained polymer obtained by GPC was 300000.

Synthesis of dimethylamine-epichlorohydrin resin

Synthesis Example 6 (1: 1 molar ratio) 90.2 aqueous dimethylamine solution (50%) was placed in a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer.
g of water and 46.6 g of water, and the mixture was stirred to dissolve uniformly, and epichlorohydrin 9 was added to this mixture from a dropping funnel.
2.5 g was added dropwise over about 3 hours. After dropping, 90
The reaction was continued at 5 ° C. for 5 hours to obtain a colorless to pale yellow liquid aqueous solution having a resin content of 59%. The weight average molecular weight of the obtained polymer obtained by GPC was 50,000.

Example 1 A 1% (in terms of resin solids) aqueous solution of the resin of Synthesis Example 1 was filtered with a filter paper No. 1 (made by Toyo Filter Paper) with a pad (1 dip 1 ni
p, Pick Up 80%).
After drying for a minute, it was used as a test recording paper. Hereinafter, all additives used are in terms of resin solid content. Tables 1 and 2 show the results of measuring the suitability for inkjet. The inkjet suitability was measured by the following method.

The bleeding was performed by printing a fine line pattern using cyan (C), magenta (M), yellow (Y), and black (BK) inks using a Canon inkjet printer (BJC-600J), and then allowed to stand for 24 hours. After that, the degree of bleeding of the ink was observed.

The hue change was carried out using the same printer, after printing with cyan (C), magenta (M), yellow (Y), and black (BK) inks, leaving it to stand for 24 hours, and then using a colorimeter (CR-200 Minolta Camera). Was used to measure the color difference ΔE from the blank.

The white paper yellowing is performed by irradiating a test recording paper to which various resin additives have been added with a carbon arc lamp (Standard Fade Meter, manufactured by Toyo Rika Kogyo Co., Ltd.) at 63 ° C. for 80 hours. Was measured for color difference ΔE.

Water resistance was determined by printing a fine line pattern using the same printer with cyan (C), magenta (M), yellow (Y), and black (BK) inks, and allowed to stand for 24 hours. Next, it was immersed in water for 1 minute and air-dried, and the state of peeling of the dye was observed.

Examples 2 to 5 The procedure of Example 1 was repeated except that the resin of Synthesis Example 1 was replaced with the resin of Synthesis Examples 2 to 5. Tables 1 and 2 show the results of measuring the suitability for inkjet.

Comparative Example 1 The procedure of Example 1 was repeated, except that the resin of Synthesis Example 1 was replaced with the resin of Synthesis Example 6. Tables 1 and 2 show the results of measuring the suitability for inkjet.

Comparative Example 2 The procedure of Example 1 was repeated except that the resin of Synthesis Example 1 was replaced by polydiallyldimethylammonium hydrochloride (molecular weight: 200,000; manufactured by Sengka). Tables 1 and 2 show the results of measuring the suitability for inkjet.

Comparative Example 3 The procedure of Example 1 was repeated except that the resin of Synthesis Example 1 was replaced with polydiallylammonium hydrochloride (molecular weight: 20,000, manufactured by Sengka). Table 1 shows the results of measuring the inkjet suitability.
It is shown in Table 2.

Comparative Example 4 A resin was treated in the same manner as in Example 1 except that the resin of Synthesis Example 1 was replaced with a dicyandiamide / diethylenetriamine condensate (molecular weight: 55,000: manufactured by Sengka). Tables 1 and 2 show the results of measuring the suitability for inkjet.

Results Tables 1 and 2 show the results of Examples 1 to 5 and Comparative Examples 1 to 4. As can be seen from Tables 1 and 2, Examples 1 to 5 of the present invention
In the case where the resin containing essential components of secondary amine, ammonia and epichlorohydrin was added, the pattern bleeding, white paper yellowing and hue change were small, and the water resistance was good. On the other hand, the products to which the resins of Comparative Examples 1 to 3 and 4 are added do not have sufficient white paper yellowing, hue change, and water resistance, and satisfies all of bleeding, white paper yellowing, hue change, water resistance, light resistance, and the like. There was nothing.

[0040]

According to the above results, the use of an additive for an ink jet recording paper comprising a resin containing a secondary amine, ammonia and epihalohydrin as essential components as monomers enables the characters and images described on the recording paper to have a high resolution. Thus, an ink jet recording paper having water resistance and less yellowing and suitable for multicolor recording can be obtained.

[Table 1]

[Table 2]

Claims (1)

[Claims] 1. An additive for an ink jet recording paper comprising a resin containing, as essential components, a secondary amine, ammonia and epihalohydrin as monomers.