JPH11222588A - Waterproofing agent for recording paper - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a waterproofing agent which can give a recording paper on which characters and images not blotting even when they are wetted with water and which does not yellow by incorporating an addition polymer of and/or a salt of bisphenol A diglycidyl ether having a specified epoxy equivalent with a dialkylamine. SOLUTION: There is provided a waterproofing agent containing an addition polymer of and/or a salt of bisphenol A diglycidyl ether having an epoxy equivalent of 140-1,000 with a dialkylamine such as dimethylamine in a molar ratio of 1/(1.0-1.7). A waterproofing ink jet recording paper can be obtained by coating a recording paper with a coating fluid containing an inorganic pigment such as titanium oxide, a water-soluble polymer such as methylcellulose, an organic- solvent-soluble resin such as polyvinyl butyral, a water retentive, a fluorescent whitening agent, a pH modifier, an antifoam, a lubricant, a surfactant, etc., and the waterproofing agent in a concentration of 0.01-10 wt.% in a coating amount of the waterproofing agent of 0.01-10 g/m<2> (in terms of the amount after drying) by e.g. a roll coater process.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a waterproofing agent for recording paper, and more particularly to an ink jet recording paper which does not bleed even when water comes into contact with characters or images recorded on the recording paper and does not cause yellowing. Water-resistant agent.

[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. In the inkjet printer, a water-soluble ink is used in order to prevent clogging of a jet nozzle, and a water-soluble direct dye, an acid dye and a reactive dye are mainly used as a pigment component thereof. However, since these dyes have extremely high solubility in water, if water is applied to characters and images recorded on recording paper, they will bleed or disappear, and have little water resistance.

As an improvement method, -SO ₃ Na, -SO ₃ H, -COONa,
-Anionic groups such as -COOH form strong ionic bonds with the cationic groups of the water-soluble cationic polymer, making use of the property that the dye becomes insoluble in water, so that various cationic polymers can be treated as a waterproofing agent. Became. For example, dicyandiamide / formaldehyde resin, diethylenetriamine /
Dicyandiamide / ammonium chloride condensate, (di) alkylaminoalkyl (meth) acrylate / acid salt polymer, (meth) acryloyloxyalkyltrialkylammonium chloride polymer, diallyldimethylammonium chloride polymer, diallylamine / acid salt And a water-soluble cationic resin such as a polymer of vinylpyridine / acid salt, an ethyleneimine polymer, and an epichlorohydrin / dimethylamine addition polymer.

[0004] Of these polymers, dicyandiamide / formaldehyde resin, diethylenetriamine / dicyandiamide / ammonium chloride condensate, ethyleneimine polymer, diallylamine polymer, and the like, when used in an amount that satisfies the water resistance, require light (mainly sunlight and There is a drawback that the recording paper is yellowed by the fluorescent light), and furthermore, the dullness of characters and images is caused, thereby impairing the sharpness. On the other hand, polymers of dialkylaminoalkyl (meth) acrylate, polymers of (meth) acryloyloxyalkyltrialkylammonium chloride, polymers of diallyldimethylammonium chloride, polymers of vinylpyridine acid salts, etc. Although it is a very low polymer, its water resistance is insufficient.

[0005]

SUMMARY OF THE INVENTION The present invention provides a waterproofing agent for obtaining an ink jet recording paper which does not bleed even when water comes into contact with characters and images recorded on the recording paper and which is not accompanied by yellowing. For the purpose.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned drawbacks. As a result, an addition polymer and / or salt of bisphenol A diglycidyl ether and dialkylamine was converted to a waterproofing agent for ink jet recording paper. The present invention was found to show excellent water resistance without yellowing when used in the present invention, and led to the present invention.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. An addition polymer and / or salt of bisphenol A diglycidyl ether and dialkylamine, which is a water-proofing agent of the present invention, is obtained by subjecting bisphenol A diglycidyl ether and dialkylamine to an addition reaction in the presence of a solvent, and then adding various acids. And heated easily. Here, bisphenol A diglycidyl ether is obtained by a reaction between bisphenol A and epichlorohydrin by a usual method, and has already been industrialized for epoxy resins.

The molar ratio of bisphenol A diglycidyl ether to dialkylamine is 1: 1.0 to 1.7.
And particularly preferably 1: 1.05 to 1.5.
Even if the amount of dialkylamine is further increased, the water resistance is deteriorated, and if the amount is decreased below this, there is a disadvantage that gelation is easily caused. The epoxy equivalent of the bisphenol A diglycidyl ether used is 140 to 1,000, preferably 170 to 250. If the epoxy equivalent is more than this, the reactivity is poor and the solubility in water is poor. Dialkylamine is preferably dimethylamine and diethylamine. When the alkyl group is larger than this, the reactivity becomes poor and the solubility in water becomes small, so that it cannot be put to practical use.

The water-proofing agent used in the present invention is prepared by dissolving bisphenol A diglycidyl ether in a water-soluble solvent such as ethylene glycol, propylene glycol, ethyl diglycol, butyl diglycol, methyl ethyl ketone, acetone, and then dialkylamine. After the dropwise addition, the mixture is further heated at 30 to 100 ° C., and finally, the acid is added dropwise and neutralized, or after the dialkylamine is added dropwise, the acid is reacted first and then heated at 30 to 100 ° C. , Can be easily reacted. As the acid, an inorganic acid such as hydrochloric acid, sulfuric acid, nitric acid, and bromic acid, particularly hydrochloric acid is preferable.

As a substrate of the ink jet recording paper used in the water-proofing agent of the present invention, paper is representative, but cloth, resin, film, synthetic paper and the like can also be used, and there is no particular limitation as long as they can be printed.

As a method for producing an ink jet recording paper containing the water-proofing agent of the present invention, there are a method for producing the ink-jet recording paper by an internal addition method using an aqueous solution of the water-proofing agent of the present invention in a papermaking process.
A method of immersing the substrate in the impregnating liquid containing the water-proofing agent of the present invention (post-treatment method), after including the water-proofing agent of the present invention in the coating liquid, and applying the coating liquid to the substrate, Drying method and the like can be mentioned.

The coating liquid includes synthetic silica, clay, talc,
Inorganic pigments such as diatomaceous earth, calcium carbonate, calcium sulfate, barium sulfate, zinc oxide, titanium oxide, titanium white, aluminum silicate, etc., oxidized starch, cationic starch, esterified starch, pregelatinized starch, etherified starch, gelatin , Casein, carboxymethylcellulose, hydroxyethylcellulose, methylcellulose,
Polyvinyl alcohol, polyacrylamide, polyethylene oxide, water-soluble polymers such as polyvinylpyrrolidone, styrene-butadiene copolymer 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, water retention agent,
Waterproofing agent, optical brightener, pH adjuster, defoamer, lubricant,
It may contain commonly used chemicals such as preservatives, surfactants, and conductive agents, and is not particularly limited.

The concentration of the waterproofing agent of the present invention in the coating solution varies depending on the treatment conditions and the like, but is usually 0.01 to 10% by weight, preferably 0.05 to 5% by weight. Aperture ratio is usually 30
To 150%, preferably 50 to 100%.

The concentration of the water-proofing agent of the present invention in the coating solution can be variously changed, but is usually 0.01 to 10% by weight, preferably 0.05 to 5% by weight. The coating amount of the waterproofing agent is usually 0.01 to 10 g / m ² (dry coating amount), and preferably 0.05 to 5 g / m ² . As a coating method, a known method such as a roll coater method, an air knife coater method, a blade coater method, and a size press method can be used.

As a drying method, for example, a usual 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 inkjet, 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 for 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. Other additives, for example, fungicides,
Examples include a bactericide, an antioxidant, a pH adjuster, a dispersant, a rust inhibitor, a chelating agent, a surfactant, and a viscosity adjuster.

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

Heretofore, there has been no inkjet recording paper which satisfies both at once, such as no bleeding even when water comes in contact with characters or images recorded on the recording paper, and very little yellowing. This has been made possible by using the product of the present invention.

[0019]

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. The percentages in the examples are by weight unless otherwise specified.

Synthesis of addition polymer and / or salt with bisphenol A diglycidyl ether (epoxy equivalent 190) -dimethylamine

Synthesis Example 1 (1: 1.05 mole ratio, reaction temperature 90 ° C.) In a reaction vessel equipped with a stirrer, a dropping funnel and a thermometer, 149.6 g of bisphenol A diglycidyl ether (epoxy equivalent 190) and propylene were added. Glycol 200.
After adding 0 g and stirring to dissolve uniformly, 38.0 g of dimethylamine was dropped into this mixture from a dropping funnel over about 1 hour. After the completion of the dropwise addition, the reaction was continued at 90 ° C. for 3 hours.
The solution was added dropwise over a period of minutes to obtain a brown water-resistant agent solution of the present invention having a concentration of 38%.

Synthesis Example 2 (1: 1.25 molar ratio, reaction temperature 90 ° C.) In a reaction vessel equipped with a stirrer, a dropping funnel and a thermometer, 149.6 g of bisphenol A diglycidyl ether (epoxy equivalent 190) and ethylene were added. Glycol 200.0
g was stirred and uniformly dissolved, and then 45.0 g of dimethylamine was added dropwise to the mixture from a dropping funnel over about 4 hours. After the completion of the dropwise addition, the reaction was continued at 90 ° C. for 10 hours.
The mixture was added dropwise over a period of minutes to obtain a brown water-resistant agent solution of the present invention having a concentration of 37%.

Synthesis Example 3 (1: 1.25 mol ratio, dropwise addition of concentrated hydrochloric acid during the reaction) In a reaction vessel equipped with a stirrer, a dropping funnel and a thermometer, 149.6 g of bisphenol A diglycidyl ether (epoxy equivalent: 190) was added. Ethylene glycol 200.0
g was stirred and uniformly dissolved, and then 45.0 g of dimethylamine was added dropwise to the mixture from a dropping funnel over about 4 hours. After completion of the dropwise addition, the reaction was continued at 90 ° C. for 1 hour. Then, 57.2 g of concentrated hydrochloric acid was added dropwise from the dropping funnel over about 30 minutes, and the reaction was further continued at 90 ° C. for 10 hours to obtain a brown book of 37% concentration. An inventive waterproofing agent solution was obtained.

Synthesis of addition polymer and / or salt with bisphenol A diglycidyl ether (epoxy equivalent 190) -diethylamine

Synthesis Example 4 (1: 1.05 mole ratio, reaction temperature 90 ° C.) In a reaction vessel equipped with a stirrer, a dropping funnel and a thermometer, 149.6 g of bisphenol A diglycidyl ether (epoxy equivalent 190) and ethylene were added. Glycol 200.0
g was stirred and uniformly dissolved, and then 30.7 g of diethylamine was added dropwise to this mixture from a dropping funnel over about 4 hours. After the completion of the dropwise addition, the reaction was continued at 90 ° C. for 10 hours.
The solution was added dropwise over a period of minutes to obtain a brown water-resistant agent solution of the present invention having a concentration of 38%.

Synthesis of addition polymer and / or salt with bisphenol A diglycidyl ether (epoxy equivalent 240) -dimethylamine

Synthesis Example 5 (1: 1.25 mole ratio, reaction temperature 90 ° C.) In a reaction vessel equipped with a stirrer, a dropping funnel and a thermometer, 193.6 g of bisphenol A diglycidyl ether (epoxy equivalent 240) and propylene Glycol 200.
After adding 0 g and stirring to dissolve uniformly, 45.0 g of dimethylamine was added dropwise to the mixture from the dropping funnel over about 4 hours. After the completion of the dropwise addition, the reaction was continued at 90 ° C. for 10 hours.
The solution was added dropwise over 0 minutes to obtain a brown water-resistant agent solution of the present invention having a concentration of 37%.

Synthesis of addition polymer and / or salt with bisphenol A diglycidyl ether (epoxy equivalent: 660) -dimethylamine

Synthesis Example 6 (1: 1.25 mol ratio, reaction temperature 90 ° C.) In a reaction vessel equipped with a stirrer, a dropping funnel and a thermometer, 158.9 g of bisphenol A diglycidyl ether (epoxy equivalent 660) and propylene were added. Glycol 250.
After 0 g was added and stirred to dissolve uniformly, 13.5 g of dimethylamine was dropped into this mixture from a dropping funnel over about 4 hours. After the completion of the dropwise addition, the reaction was continued at 90 ° C. for 10 hours.
The solution was added dropwise over 0 minutes to obtain a brown water-resistant agent solution of the present invention having a concentration of 37%.

Synthesis of addition polymer and / or salt with bisphenol A diglycidyl ether (epoxy equivalent: 950) -dimethylamine

Synthesis Example 7 (1: 1.25 molar ratio, reaction temperature 90 ° C.) In a reaction vessel equipped with a stirrer, a dropping funnel and a thermometer, 190.4 g of bisphenol A diglycidyl ether (epoxy equivalent 950) and propylene were added. Glycol 300.
After adding 0 g and stirring to dissolve uniformly, 11.3 g of dimethylamine was dropped into this mixture from a dropping funnel over about 4 hours. After completion of the dropwise addition, the reaction was continued at 90 ° C. for 10 hours.
The solution was added dropwise over 0 minutes to obtain a brown water-resistant agent solution of the present invention having a concentration of 37%.

Example 1 The water-resistant agent of the above-mentioned Synthesis Example 1 was reduced to 2% in terms of resin solid content.
2% of oxidized starch was added and mixed with stirring to obtain a coating solution having a solid content of 4%. This coating liquid is applied to commercially available ordinary paper (basis weight 60 g /
m ² ) with a coating amount of 2 g /
After coating so as to obtain m ² and 4 g / m ² , it was dried at 110 ° C. to obtain a test recording paper. Hereinafter, all the waterproofing agents used are in terms of solid content of the resin. The results of the water resistance test are shown in Tables 1 to 7. The water resistance test and the white paper yellowing test were performed by the following methods.

The water resistance test was carried out using an ink jet printer (BJC-600J) manufactured by Canon Inc., and printing of English characters with cyan (C), magenta (M), yellow (Y) and black (BK) inks, followed by a dipping method. Tested by the transcription method. Further, with regard to Cytex 1007 ink (BK), a fine line pattern was similarly printed, and then tested by an immersion method, a transfer method, and a dropping method.

Hereinafter, each test method (immersion method, transfer method, and dropping method) will be described. The immersion method was performed by immersing the printed paper in water for 30 seconds, drying at room temperature, and visually observing the degree of bleeding of the printed portion. In the transfer method, unprinted commercial plain paper is wetted with water, and Pick Up 10
Squeeze to 0%, superimpose 3k on wet printed paper
After pressurizing g / cm ² × 5 minutes, the degree of ink contamination on unprinted commercial plain paper was visually observed. In the dropping method, one drop of water is dropped on the printed part of the printed paper,
After standing at room temperature for 12 hours, the degree of bleeding of the printed portion was visually observed.

The white paper yellowing test is performed by irradiating a test recording paper provided with various water-proofing agents with a carbon arc lamp (Standard Fade Meter, manufactured by Toyo Rika Kogyo Co., Ltd.) at 63 ° C. for 80 hours, and using a colorimeter (CR-200 Minolta Camera). Was measured for the color difference ΔE from the test recording paper to which no waterproofing agent was added.

Examples 2 to 7 The procedure of Example 1 was repeated, except that the waterproofing agent of Synthesis Example 1 was replaced with the waterproofing agent of Synthesis Examples 2 to 7. Tables 1 to 7 show the results of the water resistance test, and Table 8 shows the results of the white paper yellowing test.

Comparative Example 1 The same treatment as in Example 1 was carried out except that the recording sheet for the test was used without adding the waterproofing agent. Tables 1 to 7 show the results of the water resistance test.

Comparative Example 2 The procedure of Example 1 was repeated except that the water-proofing agent of Synthesis Example 1 was changed to a diallyldimethylammonium chloride polymer (molecular weight: about 20,000: manufactured by Sengka). Tables 1 to 7 show the results of the water resistance test, and Table 8 shows the results of the white paper yellowing test.

Comparative Example 3 The procedure of Example 1 was repeated except that the water-proofing agent of Synthesis Example 1 was replaced by a dimethylaminoethyl methacrylate hydrochloride polymer (molecular weight: about 100,000; manufactured by Sengka). Tables 1 to 7 show the results of the water resistance test, and Table 8 shows the results of the white paper yellowing test.
Shown in

Comparative Example 4 The procedure of Example 1 was repeated except that the water-proofing agent of Synthesis Example 1 was changed to a diethylene triamine / dicyandiamide / ammonium chloride condensate (molecular weight: 55,000; manufactured by Sengka). Tables 1 to 7 show the results of the water resistance test, and Table 8 shows the results of the white paper yellowing test.

Comparative Example 5 The procedure of Example 1 was repeated except that the water-proofing agent of Synthesis Example 1 was replaced by a diallylamine polymer hydrochloride (molecular weight: about 20,000: manufactured by Sengka). Tables 1 to 7 show the results of the water resistance test.
Table 8 shows the results of tests for yellowing of white paper.

Results The results of Examples 1 to 7 and Comparative Examples 1 to 5 are shown in Tables 1 to 8. As can be seen from Tables 1 to 8, Examples 1 to 7 of the present invention.
The addition of an addition polymer of bisphenol A diglycidyl ether and dialkylamine and / or a salt thereof showed good water resistance and little yellowing of white paper. On the other hand, those to which the water-proofing agents of Comparative Examples 2 and 3 were added exhibited little white paper yellowing and were good, but could not obtain sufficient performance in terms of water resistance. The samples to which the water-proofing agents of Comparative Examples 4 and 5 were added had good water resistance, but could not obtain sufficient performance with white paper yellowing.

[0043]

According to the above results, bisphenol A diglycidyl ether (epoxy equivalent: 140 to 1,000)
Use of a water-resistant agent for ink-jet recording paper comprising an addition polymer and / or a salt of a dialkylamine (dimethylamine or diethylamine) with a dialkylamine (dimethylamine or diethylamine) so that even if water comes into contact with characters or images recorded on the recording paper, First, an ink jet recording sheet suitable for multicolor recording without yellowing can be obtained.

[Table 1]

[Table 2]

[Table 3]

[Table 4]

[Table 5]

[Table 6]

[Table 7]

[Table 8]

Claims (3)

[Claims] 1. A waterproofing agent for recording paper comprising an addition polymer and / or a salt of bisphenol A diglycidyl ether and dialkylamine. 2. The waterproofing agent for recording paper according to claim 1, wherein the bisphenol A diglycidyl ether has an epoxy equivalent of 140 to 1,000. 3. The waterproofing agent for recording paper according to claim 1, wherein the dialkylamine is dimethylamine or diethylamine.