JP2002127595A - Nonaqueous ink for forming ink jet ink acceptive layer and recording sheet using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ink capable of easily forming an ink jet ink acceptive layer at a necessary position of a base having excellent water resistance of printed ink, high print quality of printing without bleeding of a print image, and excellent printing ink suitability. SOLUTION: A nonaqueous ink for forming the ink jet ink acceptive layer comprises a cationic resin of powdery or liquid form by itself of 5 to 120 mass pts. and porous fine particles of 5 to 60 mass pts. blended to 100 mass pts. of a vehicle containing a glycol solvent having a boiling point of 100 deg.C or higher as a main component. The nonaqueous ink preferably further comprises a binder resin to be blended.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-aqueous ink for forming an ink-jet ink receiving layer and a recording sheet using the same.

[0002]

2. Description of the Related Art Conventionally, an ink-jet printer using an ink-jet ink has many advantages such as easy colorization, low cost, high resolution, and excellent storability. However, when printing on high-quality paper, the fixability of the ink is inferior, and the printed ink remains on the surface of the base material.Therefore, there is a problem that the guide roll becomes dirty or the printed image becomes dirty when printing is continuously performed. In addition, there were problems that ink jet printing blurred and water resistance was poor. In particular, when used in the information industry field, barcodes printed with ink-jet printing are blurred and difficult to read, mail items printed with ink-jet are exposed to rain outdoors, or accidentally splashed with water. In some cases, there is a problem that the printed content is melted and the printed content becomes invisible.

An ink jet recording sheet used in an ink jet recording system has a high density of print dots,
It is required that the color tone be bright and vivid, that the ink be absorbed quickly and that the diffusion of print dots in the horizontal direction be not unnecessarily large and that the periphery be smooth and not blurred. .

On the other hand, paper (ink-jet paper) or film (OHP film) having an ink-jet ink receiving layer formed thereon has been devised (JP-A-6-18313).
No. 5, JP-A-6-297830, Japanese Patent Publication No. Hei 8-297.
22608, JP-A-8-72390, JP-A-8-291496, etc.). However, these inks have improved ink absorbency, but have a problem that the cost is high because the ink jet ink receiving layer is provided on the entire surface of the base material, and that they are not suitable for offset printing because they affect the H liquid. Was.

[0005]

SUMMARY OF THE INVENTION It is a first object of the present invention to solve the conventional problems, to have excellent ink-jet ink absorbability in an ink-jet ink receiving layer formed on a substrate, and to provide a printed ink-jet ink having a high water resistance. An ink for forming an ink-jet ink receiving layer, which can improve the printability and improve the print quality of the ink-jet printing by preventing bleeding of the printed image. A second object of the present invention is to provide an ink for forming an ink-jet ink-receiving layer that can easily form an ink-jet ink-receiving layer at a predetermined location. It is another object of the present invention to provide a recording sheet having an ink-jet ink receiving layer formed in the above-described manner.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have used a vehicle mainly containing a specific solvent, and a specific cationic resin and a porous resin for the vehicle. The present inventors have found that the problem can be solved by using a non-aqueous ink for forming an ink-jet ink receiving layer containing a specific amount of fine particles, and have completed the present invention.

That is, the non-aqueous ink for forming an ink-jet ink receiving layer according to claim 1 of the present invention has a boiling point of 10%.
5 to 120 parts by mass of a powdery or liquid cationic resin and 5 to 60 parts by mass of porous fine particles were added to 100 parts by weight of a vehicle containing a glycol solvent at 0 ° C. or higher as a main component. It is characterized by.

A non-aqueous ink for forming an ink-jet ink receiving layer of the present invention is used in which a specific amount of a cationic resin, which is itself in powder form or liquid, and porous fine particles are blended with a vehicle containing a specific solvent as a main component. This eliminates the need for a special drying device, and has excellent inkjet ink absorption to the inkjet ink receiving layer formed on the base material, preventing bleeding of the printed image and improving the water resistance of the printed inkjet ink. The printing quality of inkjet printing can be improved. Further, since the ink jet ink receiving layer can be easily formed at a required portion of the base material due to the excellent printing ink suitability, the cost can be reduced and the offset printing is not affected.

The non-aqueous ink for forming an ink-jet ink receiving layer according to claim 2 of the present invention is the non-aqueous ink for forming an ink-jet ink receiving layer according to claim 1, wherein
Further, a vehicle containing a binder resin is used. Further, by blending a binder resin, the ink-jet ink receiving layer formed on the base material becomes more resistant to rubbing, so that the porous fine particles do not separate or the ink-jet ink receiving layer does not peel even when rubbed with an OCR reader or the like.

According to a third aspect of the present invention, there is provided a recording sheet formed on at least a predetermined portion of at least one surface of a substrate by using the non-aqueous ink for forming an ink jet ink receiving layer according to the first or second aspect. It has an ink-jet ink receiving layer.

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS It is essential for the non-aqueous ink for forming an ink-jet ink receiving layer of the present invention to use a vehicle mainly containing a glycol-based solvent having a boiling point of 100 ° C. or higher. It is prepared by blending a specific amount of a cationic resin and a porous fine particle in a liquid state or in a liquid state. The use of such a glycol solvent eliminates the need for a special drying device.

The glycol-based solvent used in the present invention is a medium- and high-boiling solvent (having a boiling point of 100 ° C. or higher) that can be mixed with water. Specifically, for example, glycol (glycerin, ethylene glycol, diethylene glycol, Triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol)
And glycol derivatives (ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monoethyl acetate Butyl ether acetate), and mixtures of two or more thereof.

The cationic resin used in the present invention is an oligomer or polymer of a primary to tertiary amine or quaternary ammonium salt which is itself in a powdery or liquid form. Specific examples of particularly preferred cationic resins include, specifically, for example, dimethylamine / epichlorohydrin polycondensate, acrylamide / diallylamine copolymer, polyvinylamine copolymer, and the like, or a mixture of two or more of these. it can. As the cationic resin in the present invention, a commercially available resin can be suitably used.

Specific examples of commercially available cationic resins include:
For example, in the case of a powdery product, Sanyo Kasei Kogyo Co., Ltd.'s polyamine-based sunfix 555 and sunfix 555 are used.
C, Sunfix 555NK, Sunfix 555U
S, Rheox AS (special cation resin) manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Charol DM-254P (methacrylic acid ester quaternary salt polymer), Charol DM
-283P (methacrylic acid chloride quaternary salt polymer), PAA-HCI-3S manufactured by Nitto Boseki Co., Ltd.
(Polyallylamine hydrochloride), PAA-HCI-10S
(Polyallylamine hydrochloride) and the like,
In the case of liquid, Epomin SP-0 manufactured by Nippon Shokubai Co., Ltd.
12 (polyethyleneimine), Epomin SP-110
(Polyethyleneimine), Epomin SP-200 (polyethyleneimine) and the like.

The mixing ratio of the cationic resin used in the present invention is as follows.
5 to 120 parts by mass, preferably 10 to 11 parts by mass with respect to 0 parts by mass
It is necessary to add 0 parts by mass. If the amount is less than 5 parts by mass, the water resistance may not be improved. If the amount is more than 120 parts by mass, the water resistance is improved, but the printability is deteriorated.

The porous fine particles used in the present invention are not particularly limited, and hydrophilic porous fine particles, hydrophobic porous fine particles and a mixture thereof can be used. The amount of the porous fine particles used in the present invention is 5 to 60 parts by mass, preferably 10 to 10 parts by mass, based on 100 parts by mass of the vehicle.
It is desirable to add 50 parts by mass. If the amount is less than 5 parts by mass, water resistance and bleeding of a printed image may not be improved.
If it exceeds 0 parts by mass, there is a possibility that the suitability for printing ink may be deteriorated, and thus both are not preferred.

Specific examples of the porous fine particles used in the present invention include, for example, silica fine particles and hydrophobic fine particles.
(Nipsil SS-10F, S
S-15, SS-10A, SS-20, SS-30P,
SS-30S, SS-40, SS-50, SS-50
A, SS-60, SS-70, SS-100, SS-1
0F, SS-50F, SS-50B, SS-50C, S
S-72F, SS-170X, SS-178B etc.),
In the case of hydrophilic ones, Tokuyama Fine Seal A,
B, USF, E50, E70, T32, X12, X3
0, X37, X37B, X40, X45, X60, X7
0, X80, RX70, K41, F80, F80B, P
8, CMF, etc.), and further, porous fine particles such as titanium dioxide (Nippon Aerosil T805), alumina fine particles, natural zeolite, synthetic zeolite, calcium carbonate, activated clay, glass, and shirasu balloon.
These may be used alone or in combination of two or more.

In the present invention, a vehicle further containing a binder resin can be used if necessary. By further blending the binder resin, the formed inkjet ink receiving layer becomes stronger against abrasion,
Even if rubbed with an OCR reader or the like, it is preferable because the porous fine particles do not separate or the ink jet ink receiving layer does not peel off.

The binder resin used in the present invention is not particularly limited as long as it can be used together with the glycol solvent. Specifically, for example, albumin, gelatin, casein, starch, gum arabic, natural resins such as sodium alginate, carboxymethyl cellulose, cellulose derivatives such as hydroxyethyl cellulose, polyamide, polyacrylamide, polyhydroxyethyl methacrylate, polyphenylacetoacetal, Polyethylene imine, polyvinyl pyrrolidone, polyvinyl pyridium halide, melamine resin, polyurethane, polyvinyl alcohol and its derivatives, polyester, polyacrylic acid soda, synthetic resin such as acrylate copolymer, dimethylamine / epichlorohydrin polycondensate, acrylamide Diallylamine copolymer, polyvinylamine copolymer, dicyandiamide, dimethyl
Cationic resin such as a compound containing diallyl ammonium chloride as a main component or a mixture of two or more of these, electron beam curable ink, ultraviolet curable ink, sulfonic acid group, carboxyl group, sulfate group,
Anionic resins such as rosin-modified maleic acid having an anionic group such as a phosphate group can be exemplified.

Known additives can be added to the non-aqueous ink for forming an ink-jet ink receiving layer of the present invention, if necessary. Examples of the additive include a viscosity adjuster, an antioxidant, a pH adjuster, an antifoaming agent, various stabilizers, a colorant, and a roll transferability improver such as glycerin.

The non-aqueous ink for forming an ink-jet ink receiving layer of the present invention is applied to a predetermined portion of at least one surface of a substrate by a coating means such as a gravure coater, flexo, air knife coater or bar coater. A recording sheet having a receiving layer can be formed. Therefore, a special drying device is not required in the present invention.

As the substrate used in the present invention, in addition to ordinary paper, synthetic paper or a synthetic film of polyethylene, transparent polyethylene terephthalate, polypropylene, vinyl chloride or the like can be used. When using these synthetic films, the surface of the substrate is preferably subjected to a surface treatment such as a mat treatment or a corona treatment. The coating amount of the ink on the substrate surface is not particularly limited, but is, for example, 0.5 to 30 g / m ² , preferably 3 to 20 g / m ² .
g / m ^2, further preferably 5 to 15 g / m ^2.

As the ink-jet ink used in the present invention, for example, JP-A-7-228808,
No. 7,228,809 can be used. In particular, at least one anionic selected from the group consisting of anthraquinone, benzoquinone, naphthoxyquinone, xanthene, triphenylmethane, quinoline, indigoid, azine, oxazine, thiazine and methine dyes Ink is preferably used. These specific examples are described in JP-A-7-2288.
No. 09, paragraph No. 0015. As a medium used for this ink, a mixed solvent of water and a water-soluble organic solvent can be used. In addition, a pH adjuster, a viscosity adjuster, a surface tension adjuster and the like can be contained.

FIG. 1 is an explanatory diagram illustrating an embodiment of the recording sheet of the present invention. In FIG. 1, a recording sheet 1 of the present invention has an ink-jet ink receiving layer 3 formed at a predetermined position on the upper surface of a substrate 2 using the ink for forming an ink-jet ink receiving layer of the present invention. Reference numeral 4 denotes printing printed on the inkjet ink receiving layer 3 by an inkjet printer (not shown).

[0025]

The present invention will be described in more detail with reference to the following Examples and Comparative Examples, but the present invention is not limited to these Examples. Example 1 10 parts by mass of rosin-modified maleic acid (trade name: Tespol 1152 (manufactured by Hitachi Chemical Co., Ltd.)) is dissolved in 90 parts by mass of propylene glycol. To 100 parts by mass of the obtained vehicle liquid, 22 parts by mass of synthetic hydrophilic silica fine particles (trade name: NIPGEL AZ-200 (manufactured by Nippon Silica Industry Co., Ltd.)) are kneaded. Subsequently, 22 parts by mass of synthetic hydrophobic silica fine particles (trade name: Nipsil SS-10F (manufactured by Nippon Silica Industry Co., Ltd.)) are kneaded. Furthermore, a polyamine-based cationic resin <trade name:
Sunfix 555 (manufactured by Sanyo Chemical Industries)> 22
Dissolve parts by mass. To this, 15 parts by mass of diethylene glycol and 5 parts by mass of glycerin were added as a roll transferability improver, and a three-roll mill was used to prepare a non-aqueous ink for forming an inkjet ink receiving layer of the present invention. Next, the obtained non-aqueous ink for forming an ink jet ink receiving layer of the present invention is subjected to offset printing on high quality paper using a resin relief plate under the following conditions to evaluate printability, and has an ink jet ink receiving layer. A recording sheet of the present invention was made. After printing (black, red, blue, and green dye inks) on the inkjet ink receiving layer of the obtained recording sheet of the present invention with a Cytex inkjet printer, the water resistance and STI grade (% ) (Print quality) was evaluated. Table 1 shows the results of these evaluations.

(Evaluation method) <Evaluation of printability> Offset printing machine Hamadaster 800
Letterpress offset printing using DX (manufactured by Hamada Press) (resin letterpress is WF45BH (manufactured by Fuji Film))
Then, printing is performed on high-quality paper (70 kg continuous mass) so as to be 2 g / m ² . At this time, the behavior of the ink (stagnation of the ink) on the ink roller, on the resin relief printing plate and on the blanket was observed.

<Water resistance> A printing location is washed away with running water for a predetermined time, or a water drop is dropped on the printing location for a predetermined time, and then wiped off to visually determine the state of the ink. When the print completely remained, it was judged as ◎, when the print almost completely remained, as ○, when the print became slightly thinner, as Δ, and when the print became thinner, as ×.

<STI Grade (%) (Print Quality)> A bar code is printed with an ink jet printer, and the read quality is checked with a bar code tester (LASER CHEK).
In II), evaluation was made by measuring the STI grade (%). In general, STI grade 50
% Or more can be evaluated as standard good quality.

(Example 2) An ink-jet ink of the present invention was prepared in the same manner as in Example 1 except that the cationic resin used in Example 1 was changed to Charol DM-283P (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.). After preparing a non-aqueous ink for forming an ink receiving layer, a recording sheet of the present invention having an ink jet ink receiving layer is similarly prepared, and printability, water resistance, and STI grade (%) (print quality) are evaluated. Was. Table 1 shows the evaluation results.

Example 3 An ink jet ink of the present invention was prepared in the same manner as in Example 1 except that the cationic resin used in Example 1 was changed to Charol DM-254P (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.). After preparing a non-aqueous ink for forming an ink receiving layer, a recording sheet of the present invention having an ink jet ink receiving layer is similarly prepared, and printability, water resistance, and STI grade (%) (print quality) are evaluated. Was. Table 1 shows the evaluation results.

Example 4 A non-aqueous ink for forming an ink jet ink receiving layer of the present invention was prepared in the same manner as in Example 1 except that the amount of the cationic resin used in Example 1 was changed to 44 parts by mass. In the same manner, a recording sheet of the present invention having an ink-jet ink receiving layer was prepared, and printability, water resistance, and STI grade (%) (print quality) were evaluated. Table 1 shows the evaluation results.

Example 5 A non-aqueous ink for forming an ink jet ink receiving layer of the present invention was prepared in the same manner as in Example 1 except that the amount of the cationic resin used in Example 1 was changed to 66 parts by mass. In the same manner, a recording sheet of the present invention having an ink-jet ink receiving layer was prepared, and printability, water resistance, and STI grade (%) (print quality) were evaluated. Table 1 shows the evaluation results.

(Comparative Example 1) 222.3 parts by mass of the cationic resin used in Example 1 were added to Sunfix 70 (aqueous solution, resin content: 52%) (trade name, manufactured by Sanyo Chemical Industry Co., Ltd.) 42.3 parts by mass (active ingredient) Example 1 except that the amount was changed to 22 parts by mass).
After preparing a non-aqueous ink for forming an ink-jet ink receiving layer for comparison in the same manner as described above, a recording sheet having an ink-jet ink receiving layer was similarly prepared, and the printability, water resistance and STI grade (%) ( (Print quality) was evaluated. Table 1 shows the evaluation results.

Comparative Example 2 22 parts by weight of the cationic resin used in Example 1 was replaced with Alkofix 169 (trade name,
A non-aqueous ink for forming an inkjet ink receiving layer for comparison was prepared in the same manner as in Example 1 except that the amount was changed to 55 parts by mass (manufactured by Kyowa Sangyo Co., Ltd.) (the amount of the active ingredient was 22 parts by mass). A recording sheet having an inkjet ink receiving layer was prepared and evaluated for printability, water resistance, and STI grade (%) (print quality). Table 1 shows the evaluation results.

[0035]

[Table 1]

From Table 1, it can be seen that the non-aqueous inks for forming the ink-jet ink-receiving layer of Examples 1 to 5 are excellent in printability and water resistance of the prints (black, red, blue and green dye inks) printed by the ink-jet printer. It turns out that it is excellent in STI grade (%) (print quality). On the other hand, the non-aqueous inks for forming an ink-jet ink receiving layer of Comparative Examples 1 and 2 are inferior in printability, water resistance and S
Poor in TI grade (%) (print quality).

[0037]

The non-aqueous ink for forming an ink-jet ink receiving layer according to claim 1 of the present invention solves the problems of the conventional ink for forming an ink-jet ink receiving layer and contains a specific glycol-based solvent as a main component. Because the ink is a specific amount of the cationic resin and the porous fine particles, which are in powder or liquid form, mixed with the vehicle,
Shows high ink absorbency without special drying equipment, excellent water resistance of inkjet ink printed on inkjet ink receiving layer formed on substrate, does not cause bleeding of printed image, and high print quality of print In addition, since the ink jet ink receiving layer can be easily formed only at a necessary predetermined portion of the base material because of its excellent printability, the cost can be reduced and the offset printing is not affected. .

The non-aqueous ink for forming an ink-jet ink receiving layer according to claim 2 of the present invention is the non-aqueous ink for forming an ink-jet ink receiving layer according to claim 1,
Furthermore, since a vehicle containing a binder resin is used, the ink-jet ink receiving layer formed on the base material becomes more resistant to rubbing, and inorganic porous fine particles are detached even when rubbed with an OCR reader or the like. Has a remarkable effect that it does not peel off.

According to a third aspect of the present invention, there is provided a recording sheet formed on at least a predetermined portion of at least one surface of a substrate by using the non-aqueous ink for forming an ink jet ink receiving layer according to the first or second aspect. Since it has an ink-jet ink receiving layer, it exhibits high ink absorbency, has excellent water resistance of the ink-jet ink printed on the ink-jet ink receiving layer, does not cause bleeding of a printed image, and has a remarkable effect of high print quality. Play.

[Brief description of the drawings]

FIG. 1 is an explanatory diagram illustrating an embodiment of a recording sheet of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Recording sheet of this invention 2 Substrate 3 Ink jet ink receiving layer 4 Printing

Claims (3)

[Claims] 1. A powdery or liquid cationic resin is used in an amount of 5 to 12 parts by mass per 100 parts by mass of a vehicle containing a glycol solvent having a boiling point of 100 ° C. or higher as a main component.
A non-aqueous ink for forming an inkjet ink receiving layer, wherein 0 parts by mass and 5 to 60 parts by mass of porous fine particles are blended. 2. The non-aqueous ink for forming an ink-jet ink receiving layer according to claim 1, wherein a vehicle further containing a binder resin is used. 3. A recording comprising an ink-jet ink receiving layer formed by using the non-aqueous ink for forming an ink-jet ink receiving layer according to claim 1 on at least a predetermined portion of at least one surface of a substrate. Sheet.