JP2002160445A - Ink for forming ink jet ink accepting layer and recording sheet using the ink - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a low cost ink, with which an ink jet ink accepting layer can be formed at necessary points of a base material, due to its excellent in the water resistance of the ink printed on the base material, its development of no blurring in a printed image, its high printing quality obtained in printing and its excellence in fitness of printing ink. SOLUTION: For 100 mass parts of a vehicle including an acrylic photo- setting component having a hydrophilic nature, 10 to 70 mass parts of the mixture of hydrophobic porous fine particles and hydrophilic porous fine particles having the mass ratio of the hydrophobic fine particles and the hydrophilic porous fine particles ranging from 5:95 to 95:5, is added in order to prepare the ink. An ink jet ink accepting layer is formed with this ink at the predetermined part of at least one surface of the base material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an 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. , When printing on high-quality paper, ink-jet printing is blurred, the ink absorbency is poor, and the printed ink remains on the paper surface. There was a problem of poor water resistance. 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.

[0003] Paper (ink-jet paper) or film (OHP film) having an ink-jet ink receiving layer formed thereon has been devised (JP-A-6-183135, JP-A-6-297830, JP-B-8-22).
608, JP-A-8-72390 and JP-A-8-72390
No. 291496). 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.

[0004] On the other hand, water-resistant pigment-type inks have been marketed as ink-jet inks, but they have an effect on the printer head, such as clogging of the printer head and a decrease in the durability of the printer head. There is a problem that it is difficult to make the color thin.

[0005]

SUMMARY OF THE INVENTION A first object of the present invention is to solve the conventional problems, improve the water resistance of ink-jet inks, and reduce the print quality of ink-jet printing by preventing bleeding of printed images. An ink for forming an ink-jet ink receiving layer, which is capable of easily forming an ink-jet ink receiving layer at a required portion of a base material in a printing machine because of excellent printing ink suitability. It is a second object of the present invention to provide a recording sheet having an ink-jet ink receiving layer formed on a predetermined portion of a substrate using such an ink.

[0006]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above-mentioned problems, and as a result, have found that a vehicle containing an acrylic photocurable component having hydrophilicity as a main component has a specific pore size. It has been found that the problem can be solved by using an ink for forming an ink-jet ink receiving layer in which a specific amount of a mixture of fine particles is blended, and the present invention has been completed.

That is, the ink for forming an ink-jet ink receiving layer according to the first aspect of the present invention is a vehicle 1 containing a hydrophilic acrylic photocurable component as a main component.
The hydrophobic porous fine particles and the hydrophilic porous fine particles in which the mass ratio of the hydrophobic porous fine particles to the hydrophilic porous fine particles is in the range of 5:95 to 95: 5 with respect to 00 parts by mass are 10 to 70 parts by mass.
It is characterized by being blended by mass.

In the present invention, an ink for forming an ink-jet ink receiving layer is prepared by blending a specific amount of a mixture of specific porous fine particles with a vehicle containing a hydrophilic acrylic photocurable component as a main component. ,
The ink-jet ink receiving layer formed on the base material has excellent ink-jet ink absorbability, can prevent bleeding of a printed image, and can improve the water resistance of the printed ink-jet ink. In addition, since the ink for forming an ink-jet ink receiving layer is excellent in printing ink suitability, an ink-jet ink receiving layer can be easily formed at a predetermined required portion of a substrate, so that cost can be reduced and offset printing can be performed. Has no effect.

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

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The acrylic photocurable component having hydrophilicity used in the present invention is an acrylic photocurable component that dissolves well in normal-temperature water and does not separate or precipitate even when left standing, and has a known hydrophilicity. Acrylic photopolymerizable monomer having
Alternatively, an acrylic photopolymerizable oligomer having hydrophilicity can be arbitrarily selected and used. As the acrylic photopolymerizable monomer, specifically, for example, polyethylene glycol (n
Is 3 or more and about 14 or less) modified diacrylate, trimethylolpropane EO (n is 3 or more and about 14 or less) triacrylate, phenol EO modified (n is 3 or more and about 14 or less) And 2-hydroxyethyl acrylate (HEA) having a hydroxyl group in the molecule, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, pentaerythritol triacrylate, monohydroxyethyl phthalate, and the like. These photopolymerizable monomers may be used alone or in combination of two or more.

In the case of an acrylic photocurable component having an ethylene glycol unit in the molecule, the polyethylene glycol unit is such that n is 3 or more, and if n is less than 3, the hydrophilicity is inferior. The upper limit of n is not particularly limited, but is about 14 or less for commercially available products.

The photopolymerization initiator used in the present invention may be a conventionally known photopolymerization initiator, for example, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-ketone.
1-phenyl-propan-1-one, 1- [4- (2-
Hydroxyethoxy) -phenyl] -2-hydroxy-
Methyl-1-propan-1-one, 2-methyl-1-
[4- (Methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1-
Bis (2,6-dimethoxybenzoyl) -2,4,4-
And trimethyl-pentylphosphine oxide-bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide. These photopolymerization initiators may be used alone or in combination of two or more. The content is usually preferably selected in the range of 5 to 15 parts by mass per 100 parts by mass of the acrylic photocurable component.

The hydrophobic porous fine particles used in the present invention are difficult to disperse in water, and even when dispersed in water, they precipitate and separate into two layers when left standing and allowed to stand. It is. On the other hand, the hydrophilic porous fine particles used in the present invention can be easily dispersed in water, and after the dispersion, precipitation does not occur even when the dispersion is allowed to stand, thereby maintaining a uniform suspension state. It is a porous fine particle as follows.

Examples of the hydrophobic porous fine particles include hydrophobic inorganic oxide porous fine particles and hydrophobic resin porous fine particles. Specific examples of the hydrophobic inorganic oxide porous fine particles include, for example, silica fine particles (Nippon Silica Industry Co., Ltd. SS-
10, SS-15, SS-10A, SS-20, SS-
30P, SS-30S, SS-40, SS-50, SS
-50A, SS-60, SS-70, SS-100, S
S-10F, SS-50F, SS-50B, SS-50
C, SS-72F, SS-170X, SS-178B)
And titanium dioxide (Nippon Aerosil T805).

Specific examples of the hydrophobic fine resin particles include, for example, ethylene tetrafluoride resin (Teflon 30J, manufactured by DuPont-Mitsui Fluorochemicals), vinylidene hexafluoride resin (Daikin Industries NEOFLON CTFE), and trifluorinated chloride. Ethylene resin (Daikin Neoflon V)
DF), propylene hexafluoride resin (Daikin Industries NEOFRON FEP), fluorinated ethylene-propylene copolymer resin (Teflon 12 by Mitsui Dupont Fluorochemical Co., Ltd.)
0J). These may be used alone or in combination of two or more.

On the other hand, examples of the hydrophilic porous fine particles include hydrophilic inorganic oxide porous fine particles and hydrophilic resin porous fine particles. Specific examples of the hydrophilic porous fine particles include, for example, alumina fine particles, various starch-based fine particles, fine acrylic resin, fine methacrylic resin, natural zeolite, synthetic zeolite, calcium carbonate, activated clay, and the like. These may be used alone or in combination of two or more.

In the present invention, the non-aqueous vehicle 100
It is possible to mix 10 to 70 parts by mass, preferably 20 to 60 parts by mass, more preferably 25 to 55 parts by mass of the hydrophobic porous fine particles and the hydrophilic porous fine particles having a specific mass ratio with respect to parts by mass. desirable. If the amount is less than 10 parts by mass, the water resistance and bleeding of the printed image may not be improved, and the ink absorbability is poor, and the printed ink remains on the paper surface. The image may be stained, and if it exceeds 70 parts by mass, the suitability for printing ink may be undesirably reduced.

The mass ratio of the hydrophobic porous fine particles to the hydrophilic porous fine particles is from 5:95 to 95: 5, preferably 30:70.
７０70: 30, more preferably 40:60 to 60:40
It is. When the mass ratio of the hydrophobic porous fine particles to the hydrophilic porous fine particles is out of the range of 5:95 to 95: 5, there is a possibility that the water resistance of the inkjet ink printed on the base material and the bleeding of the printed image may not be improved.

The ink for forming an ink-jet ink receiving layer of the present invention may further contain, if desired, commonly used additives such as a reactive diluent, a tackifier, a viscosity modifier, an antioxidant, and an ultraviolet absorber. Agents, pH adjusters, defoamers,
Various stabilizers, coloring agents, lubricants, sensitizers, and the like can be contained.

The ink for forming an ink-jet ink receiving layer of the present invention is applied to at least a predetermined portion of at least one surface of a substrate by a coating means such as a gravure coater, flexo, air knife coater, bar coater and the like. After drying, a recording sheet having an inkjet ink receiving layer can be formed.

As the base material used in the present invention, ordinary paper,
In addition to coated papers, art papers, papers and films with overcoat layers (protective layers), brochures, catalogs, and documents with process color printing, synthetic papers,
Alternatively, 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 amount of coating on the substrate surface is not particularly limited, but is, for example, 1 to 30 g / m
² , preferably 3 to 20 g / m ² , more preferably 5 to ²⁰ g / m ² .
１５15 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).

[0024]

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 Polyethylene glycol diacrylate (n = 1) which is an acrylic photopolymerizable monomer having high hydrophilicity
3-14) <trade name: ARONIX M-260 (manufactured by Toa Gosei Chemical Co., Ltd.)> 92 parts by mass and a photopolymerization initiator <trade name: V
8 parts by mass of ICURE55 (manufactured by Akzo Nobel)>. Alumina fine particles (trade name: aluminum oxide C (manufactured by Nippon Aerosil Co., Ltd.)) as hydrophilic porous fine particles in 100 parts by mass of the obtained vehicle liquid and silica fine particles as hydrophobic porous fine particles (trade name: SS-10)
F (manufactured by Nippon Silica Industry Co., Ltd.)> 15 parts by mass. Further, 0.1 parts by mass of methylhydroquinone (stabilizer) is added as an additive and kneaded using a three-roll mill,
An ink for forming an inkjet ink receiving layer of the present invention was prepared. The ink for forming an ink-jet ink receiving layer of the present invention thus obtained is subjected to dry offset printing on a high-quality paper (70 kg continuous weight) using a resin relief printing plate so that the ink becomes 1.0 g / m ^2. A recording sheet of the present invention having an ink receiving layer was prepared. The ink jet ink receiving layer of the obtained recording sheet of the present invention is printed (black,
Red, blue and green dye inks)
Water resistance and print quality were evaluated by the following evaluation methods. Table 1 shows the evaluation results.

(Evaluation method) <Water resistance> The printing location is washed away with running water for a certain time, or a water drop is dropped on the printing location for a certain 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 by 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 The 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 alumina fine particles used in Example 1 were changed to 10 parts by mass and the silica fine particles were changed to 20 parts by mass. Was prepared, a recording sheet of the present invention having an ink-jet ink receiving layer was prepared using this ink, and the water resistance and print quality were evaluated. Table 1 shows the evaluation results.

Example 3 The 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 alumina fine particles used in Example 1 were changed to 20 parts by mass and the silica fine particles were changed to 10 parts by mass. Was prepared, a recording sheet of the present invention having an ink-jet ink receiving layer was prepared using this ink, and the water resistance and print quality were evaluated. Table 1 shows the evaluation results.

Example 4 An ink-jet ink receiving ink of the present invention was prepared in the same manner as in Example 1 except that the alumina fine particles used in Example 1 were changed to 7.5 parts by mass and the silica fine particles were changed to 22.5 parts by mass. After preparing the ink for forming a layer, a recording sheet of the present invention having an ink-jet ink receiving layer was prepared using this ink, and the water resistance and print quality were evaluated. Table 1 shows the evaluation results.

(Example 5) The alumina fine particles used in Example 1 were replaced with hydrophilic synthetic silica fine particles (trade name: SYLOS)
After preparing an ink for forming an ink-jet ink receiving layer of the present invention in the same manner as in Example 1 except that HERE C-1504 (manufactured by Fuji Silysia Chemical Ltd.) was used, the ink was used to have an ink-jet ink receiving layer. The recording sheet of the present invention was prepared, and the water resistance and print quality were evaluated. Table 1 shows the evaluation results.

Example 6 Same as Example 1 except that the hydrophobic silica fine particles used in Example 1 were changed to hydrophobic calcium carbonate fine particles (trade name: Ryton # 2600 (manufactured by Bihoku Powder Chemical Industry Co., Ltd.)). After preparing the ink for forming an ink-jet ink receiving layer of the present invention as described above, a recording sheet of the present invention having an ink-jet ink receiving layer was prepared using this ink, and the water resistance and print quality were evaluated.
Table 1 shows the evaluation results.

Comparative Example 1 The procedure of Example 1 was repeated, except that the polyethylene glycol diacrylate (n = 13 to 14) used in Example 1 was changed to a trimethylolpropane PO-modified (n = 1) triacrylate. After preparing an ink for forming an ink jet ink receiving layer for comparison, a recording sheet having an ink jet ink receiving layer was prepared using this ink, and the water resistance and print quality were evaluated. Table 1 shows the evaluation results.

Comparative Example 2 The procedure of Example 1 was repeated, except that the polyethylene glycol diacrylate (n = 13 to 14) used in Example 2 was changed to a trimethylolpropane PO-modified (n = 1) triacrylate. After preparing an ink for forming an ink jet ink receiving layer for comparison, a recording sheet having an ink jet ink receiving layer was prepared using this ink, and the water resistance and print quality were evaluated. Table 1 shows the evaluation results.

Comparative Example 3 The procedure of Example 1 was repeated, except that the polyethylene glycol diacrylate (n = 13 to 14) used in Example 3 was changed to a trimethylolpropane PO-modified (n = 1) triacrylate. After preparing an ink for forming an ink jet ink receiving layer for comparison, a recording sheet having an ink jet ink receiving layer was prepared using this ink, and the water resistance and print quality were evaluated. Table 1 shows the evaluation results.

Comparative Example 4 76 parts by mass of a rosin-modified phenol resin varnish and 14 parts by mass of linseed oil varnish were mixed.
To a varnish obtained by mixing 7 parts by mass of wood wax (baltimic acid glyceride) and 3 parts by mass of a dryer, 32 parts by mass of alumina fine particles of alumina (trade name: aluminum oxide C (manufactured by Nippon Aerosil Co., Ltd.)) are added, and a three-roll mill is added. To obtain an inkjet ink receiving layer forming ink for comparison. Using the obtained ink, dry offset printing was performed on a high-quality paper (70 kg continuous amount) using a resin relief printing plate so as to obtain a recording sheet of 1.0 g / m ² to prepare a recording sheet for comparison. After printing (black, red, blue, and green dye inks) on the inkjet ink receiving layer of the obtained recording sheet using a Cytex inkjet printer, evaluation of water resistance and print quality was performed in the same manner as in Example 1. Was done. Table 1 shows the evaluation results.

[0036]

[Table 1]

The inks for forming the ink-jet ink receiving layer of Examples 1 to 6 have excellent suitability for printing inks, and Table 1 shows that the inks printed with an ink-jet printer (black, red, blue and green dye inks) have water resistance and water resistance. Print quality (ST
I grade). On the other hand,
From Table 1, the inks for forming the inkjet ink receiving layer of Comparative Examples 1 to 4 are inferior in water resistance and print quality (STI grade).

[0038]

The ink for forming an ink-jet ink receiving layer according to the first aspect of the present invention solves the problems of the conventional ink for forming an ink-jet ink receiving layer and can be used as a base material (normal paper, coated paper, art paper). Excellent water resistance of the ink jet ink printed on the ink jet ink receiving layer formed on paper or film with an overcoat layer (protective layer), brochures, catalogs, and documents on which process color printing has been performed, and bleeding of printed images Does not occur,
Since the printing quality of printing is high and the printing ink suitability is excellent, the ink-jet ink receiving layer can be easily formed only at the required predetermined portion of the base material, so that the cost can be reduced and the offset printing is affected. There is a remarkable effect that there is no.

The recording sheet according to the second aspect of the present invention comprises:
The ink jet ink printed on the ink jet ink receiving layer formed on a predetermined portion of at least one surface of the base material has excellent water resistance, does not cause bleeding of a printed image, and has high printing quality.

[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

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Akira Hirasawa 1-6-6 Kanda Surugadai, Chiyoda-ku, Tokyo Toppan Forms Co., Ltd. F-term (reference) 2C056 EA13 FC06 2H086 BA15 BA33 BA34 4J039 AB01 AD04 AD10 AD21 BA13 BA16 BA20 BA21 BA23 BE01 BE27 EA42 EA47 FA02 GA24

Claims (2)

[Claims] 1. A mass ratio of hydrophobic porous fine particles to hydrophilic porous fine particles of 5: 100 parts by mass of a vehicle containing a hydrophilic acrylic photocurable component as a main component.
An ink for forming an ink-jet ink receiving layer, comprising 10 to 70 parts by mass of hydrophobic porous fine particles and hydrophilic porous fine particles in the range of 95 to 95: 5. 2. A recording sheet having an ink-jet ink receiving layer formed by using the ink for forming an ink-jet ink receiving layer according to claim 1 on a predetermined portion of at least one surface of a substrate.