JPH09254529A - Ink jet recording medium - Google Patents

Abstract

(57) [PROBLEMS] To provide an inkjet recording medium which is excellent in water resistance and light resistance of recording and has good productivity. An ink jet recording medium containing a guanidine derivative condensate containing no quaternary ammonium salt structure in a recording medium containing at least a cationic resin on its surface.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ink jet recording system for recording on a recording medium by using an aqueous ink, and provides an ink jet recording medium having excellent ink absorbency and printing water resistance.

[0002]

2. Description of the Related Art Ink jet recording systems using water-based inks have low noise during recording, are easy to colorize, and are capable of high-speed recording. It is being applied to form printing. Since fine paper and coated paper used for general printing have poor ink absorption,
The printed ink does not dry on the paper surface
It is not practical because it contaminates the device and continuously printed sheets and stains the image. In order to solve such a problem, a recording paper having a low degree of size is used (Japanese Patent Laid-Open No. Sho 52/1987)
No. 53012) or a base paper internally containing a urea-formalin resin is impregnated with a water-soluble polymer (JP-A-53-53).
Japanese Patent No. 49113) is disclosed. Furthermore, a recording paper coated with amorphous silica on the surface for the purpose of enhancing the color developability and reproducibility of the ink (JP-A-55-51583).
Gazette). However, since the recording medium in the above proposal is recorded with a water-based ink, when water or the like adheres to the recording formed on the medium,
It has a drawback that the record is damaged by re-elution.

Therefore, a waterproofing agent that forms a lake with a cationic polymer or a water-soluble metal salt is added after recording (JP-A-55-150396), or a polycationic polyelectrolyte is contained on the surface. Ink jet recording method (JP-A-56-84992) for printing with a water-based ink containing a water-soluble direct dye or an acid dye on a recording medium, or a resin type dye fixing agent or a dye having a quaternary ammonium salt as a basic compound. Applying a fixing agent (JP-A-60-
No. 161188) has been proposed, but the dye mordant composed of various cation resins such as dicyandiamide formaldehyde condensate and polyamine and polyethyleneimine, which are shown in these proposals, can provide sufficient water resistance. When used in a large amount, it has a drawback that it causes yellowing of white paper and fading of dye.

In order to solve these drawbacks, a quaternary ammonium salt having a specific structure (JP-A-61-2938).
No. 86) or a polyalkylene polyamine dicyandiamide ammonium salt condensate (Japanese Patent Publication No. 2-356).
No. 75 gazette) has been proposed, and a tentative effect is recognized, but when these quaternary ammonium salts are applied to an inkjet recording medium, aggregation and precipitation are likely to occur depending on the conditions of the treatment liquid, and therefore uniform. However, it is not always satisfactory in terms of productivity.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide an ink jet recording medium which is improved not only in water resistance and light resistance of recording but also in productivity, by improving the above-mentioned drawbacks. As a result of intensive studies on the waterproofing agent and the production method, the present inventors have found that in the inkjet recording method for recording on a medium using a water-based ink, recording water resistance,
The inventors have found that an ink jet recording medium that is excellent not only in light resistance but also in productivity is obtained, and completed the present invention.

[0006]

The present invention includes the following aspects. [1] An inkjet recording medium comprising a support impregnated or coated with a liquid containing a cationic resin, wherein the cationic resin is a guanidine derivative condensate containing no quaternary ammonium salt structure.

[2] The ink jet recording medium according to [1], wherein the guanidine derivative condensate containing no quaternary ammonium salt structure is a polyalkylene polyamine dicyandiamide condensate.

[3] The ink jet recording medium according to [1] or [2], wherein the nitrogen content is in the range of 30 mg / m ^{2 to} 3000 mg / m ² . [4] The inkjet recording medium as described in [1], [2] or [3], wherein the guanidine derivative condensate containing no quaternary ammonium salt structure is not a formaldehyde condensate.

[5] A high-quality paper type obtained by coating or impregnating a base paper obtained by acidic papermaking or neutral papermaking with a coating solution containing a guanidine derivative condensate containing no quaternary ammonium salt structure [1], 2. The inkjet recording medium according to [3] or [4].

[6] An ink jet recording medium comprising a support impregnated or coated with a liquid containing a cation resin, at least the outermost surface of the recording surface containing the cation resin is the cation resin. The inkjet recording medium according to [1], [2], [3], [4] or [5], which is a guanidine derivative condensate containing no quaternary ammonium salt structure.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION As described above, a guanidine derivative condensate containing no quaternary ammonium salt structure is unlikely to cause aggregation / precipitation in the treatment liquid, and can be easily applied to an inkjet recording medium to obtain uniform water resistance. A chemical treatment can be applied. Such a guanidine derivative condensate containing no quaternary ammonium salt structure needs to be contained at least on the surface of an inkjet recording medium, and in a high-quality paper type (non-coated type) recording medium, it is used as a support.
The aqueous solution can be applied by a method such as impregnation with a size press or coating with a coating device. It is also possible to make a so-called coating type ink jet recording medium by coating the ink receiving layer coating material containing a pigment.

The ink jet recording medium thus prepared is subjected to ink jet recording with an aqueous ink containing a direct dye or an acid dye having an anionic dissociative group, whereby the dye in the aqueous ink and the specific guanidine derivative in the recording medium are used. It can be presumed that the condensate is bonded to prevent the dye from being eluted and the light resistance of recording is improved.

Among the guanidine derivative condensates, those having a quaternary ammonium salt structure in the molecule have too strong an adhesiveness to various materials, and therefore aggregate / precipitate due to coexistence of materials used in combination and water-soluble metal salts. Is easily generated, and it is difficult to evenly distribute it on the surface of the recording medium, and as a result, the water resistance of recording is not satisfactory. On the other hand, the guanidine derivative condensate of the present invention has not only a great effect of improving water resistance and light resistance, but also various additives can be selected from a wide range as necessary, and in terms of productivity. It has great advantages.

The guanidine derivative condensate containing no quaternary ammonium salt structure preferably does not use formaldehyde in the production process. The guanidine derivative condensate containing no formaldehyde condensate is preferably used also from the viewpoint of the influence on the production environment of the recording medium. Examples of the guanidine derivative condensate used in the present invention include cationic resins obtained by copolymerizing polyalkylene polyamines and dicyandiamide. For example, a linear polyamine such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, or iminobispropylamine and dicyandiamide may be copolycondensed by heating (referred to as polyalkylenepolyamine dicyandiamide condensate).

The guanidine derivative condensate as described above is usually used in the range of 0.1 to 5.0 g / m ^{2 on} the surface of a recording medium, and contributes to the improvement of recording water resistance and light resistance. The effect of improving water resistance is realized by the cationic property of the guanidine derivative condensate, which is due to the presence of an amine residue in the molecule. By adjusting the amount in the range of 30 mg / m ^{2 to} 3000 mg / m ² , a recording medium having particularly excellent water resistance and light resistance can be obtained, which is a more preferable embodiment. By the way, if the nitrogen content is low, it may not be possible to obtain sufficient recording water resistance. On the other hand, even if the nitrogen content is excessively high, the further improvement of the recording water resistance is slight, but
The light resistance is rather deteriorated, which is not preferable.

The support (base material) of the recording medium is not necessarily limited, but a base paper containing cellulose as a main component can be exemplified. If necessary, fillers such as talc, kaolin, calcined kaolin and calcium carbonate may be added to the pulp for papermaking, and a base paper prepared by a method commonly used for acidic papermaking or neutral papermaking can be appropriately used. Also,
As the support (base material), a dry or wet non-woven fabric can be used.

The application of the specific guanidine derivative of the present invention to a recording medium is carried out by using a condensate prepared as an aqueous solution alone or, if necessary, in combination with a binder or the like which is usually used, in combination with a size press, a gate roll, a roll coater, Bar coater, air knife coater, rod blade coater,
It can be carried out by coating on the above-mentioned substrate by a commonly used coating means such as a blade coater.

The binder is not necessarily limited, but is appropriately selected from polyvinyl alcohol, oxidized starch, cationized starch, other water-soluble polymers and the like. If necessary, additives such as AKD, ASA, other surface sizing agents, and various pigments having an ink absorbing ability can be used together. Examples of such pigments include inorganic pigments such as amorphous silica, alumina, hydrated alumina, calcined kaolin and calcium carbonate, or urea-formaldehyde resin fine particles, melamine-
Examples include organic pigments such as formaldehyde resin fine particles and benzoguanamine resin fine particles, but are not limited thereto.

On the other hand, the water-based ink used in the present invention contains at least one of a water-soluble direct dye and a water-soluble acid dye as a dye, and in addition thereto, a wetting agent, a dye dissolving agent, an antiseptic agent are appropriately added. , Containing antifungal agents. Examples of water-soluble direct dyes include CI. Direct black, CI. Direct Yellow, CI. Direct blue, CI. Direct Red and the like can be mentioned. As the water-soluble acid dye, CI. Acid Black, CI. Acid Yellow, CI. Acid Blue, CI. Acid red and the like can be mentioned, but the invention is not limited thereto. Such a dye is water-soluble due to sulfonic acid or a salt thereof, an amino group, or the like in the dye molecule, and when recording printing is performed on the surface of the recording medium of the present invention using such an ink, the ink The anionic residue therein is ionically captured by the cationic guanidine derivative condensate contained in the recording medium and becomes insoluble in water, thereby improving the water resistance of the image.

[0020]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. The parts and percentages shown in the examples mean parts by weight and percentages by weight.

Example 1 80 parts of LBKP having a freeness of 400 ml and a freeness of 450 ml
25 parts of light calcium carbonate (trade name: PC, manufactured by Shiraishi Kogyo Co., Ltd.) and 1 part of cationized starch (trade name: Cato F, manufactured by Oji National Co., Ltd.) were added to a pulp slurry in which 20 parts of NBKP were mixed and the basis weight was 70 g / m. The base paper of No. ² was made with a Fourdrinier paper machine. 2% of oxidized starch (trade name: Ace A, manufactured by Oji Corn Starch) and polyethylene polyamine dicyandiamide condensate (trade name: PAP-
1. An ink jet recording medium was obtained by adhering a liquid containing 2% of 1, manufactured by Nippon Senka Kogyo Co., Ltd. to a solid content of 3 g / m ² using a size press device and drying.

Example 2 The size press liquid in Example 1 was converted to oxidized starch (trade name:
Ace A, made by Oji Corn Starch) 4%, salt 0.5
% And polyethylene polyamine dicyandiamide condensate (trade name: Neofix E-117, Nichika Chemical Co., Ltd.)
An ink jet recording medium was obtained in the same manner as in Example 1 except that a liquid of 1%) was applied to the base paper so as to have a solid content of 1 g / m ² .

Comparative Example 1 The size press liquid in Example 1 was converted to oxidized starch (trade name:
Ace A, made by Oji Corn Starch) 4%, salt 0.5
% And polyethylene polyamine dicyandiamide ammonium salt condensate (trade name: Neofix PNF-7
No. 0, manufactured by Nichika Kagaku Co., Ltd.), and was mixed as it was prepared as a liquid, and as a result, aggregates were generated and coating could not be performed.

Comparative Example 2 In Example 1, the size press liquid was converted to oxidized starch (trade name:
Ace A, made by Oji Corn Starch) 4%, salt 0.5
% And formaldehyde dicyandiamide condensate (trade name: Neofix FY, manufactured by Nichika Kagaku Co., Ltd.), the mixture was prepared and mixed, but agglomerates were generated, and coating could not be performed.

Comparative Example 3 In Example 1, the size press liquid was mixed with oxidized starch (trade name:
Ace A, made by Oji Corn Starch) 4%, salt 0.5
% And diallylamine derivative (trade name: Unisense C
An ink jet recording medium was obtained in exactly the same manner as in Example 1 except that this was used in a size press as a liquid consisting of P-102, manufactured by Senka Co., Ltd., 1%.

Comparative Example 4 The size press liquid in Example 1 was treated with oxidized starch (trade name:
Ace A, 4% made by Oji Corn Starch Co., Ltd. and diallyldimethylammonium sulfonic acid copolymer (trade name: P
An inkjet recording medium was obtained in exactly the same manner as in Example 1 except that this liquid was used in a size press as a liquid consisting of AS-A-120L and Nitto Boseki Kogyo Co., Ltd. 1%.

Table 1 shows the results of evaluation of the preparation of the size press treatment liquid, water resistance and light resistance of each of the above recording media.

The methods for measuring various physical properties in the examples are shown below. 1) Water resistance A solid image recorded with each ink of cyan (C), magenta (M), yellow (Y), and black (Bk) is printed and dried for 1 hour, and then dried in still water at 30 ° C. for 3 minutes. Immerse the image density before and after immersion in a Macbeth reflection densitometer (RD-
914), and the value obtained by dividing the post-immersion concentration by the pre-immersion concentration was shown as% and used as a measure of water resistance.

2) Lightfastness Solid print recording is performed with each of C, M, Y, and Bk inks, and the obtained image is recorded in an atlas fade imager (ATLAS E).
LECTRIC DEVICES CO. Made, CI35
F type) 60 ° C., 53% RH, 420 nm illuminance 0.7
Irradiation was performed at 5 W / m ² for 50 hours, the color density before and after irradiation was measured with a Macbeth reflection densitometer RD-914, and the value obtained by dividing the density after irradiation by the density before irradiation was shown in%, which was used as a measure of light resistance.

3) White Paper Yellowing The recording paper was left in a room at 20 ° C. and 65% RH for 1 month, and the yellowing degree of the recording surface was visually evaluated. ○ (almost no yellowing), △ (slightly discolored), × (clear yellowing).

[0031]

[Table 1]

As is clear from Table 1, Comparative Examples 1 and 2 could not prepare the size press treatment liquid, and Comparative Examples 3 and 4 were poor in both water resistance and light resistance, whereas in Examples 1 and 2. No. 2 was improved in both water resistance and light resistance.

Claims (3)

[Claims] 1. An ink jet recording medium comprising a support impregnated or coated with a liquid containing a cationic resin, wherein the cationic resin is a guanidine derivative condensate containing no quaternary ammonium salt structure. 2. The ink jet recording medium according to claim 1, wherein the guanidine derivative condensate containing no quaternary ammonium salt structure is a polyalkylene polyamine dicyandiamide condensate. 3. Nitrogen content of 30 mg / m ^{2 to} 300
The inkjet recording medium according to claim 1 or 2, which has a range of 0 mg / m ² .