JP2002019272A - Sealing material having ink receiving layer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a sealing material having an ink receiving layer having a high printing quality, excellent light resistance and moisture resistance for an aqueous pigment ink. SOLUTION: The sealing material having the flexible ink receiving layer comprises a composition containing at least (A) a polymer of a water soluble crosslinkable substance having a radical polymerizable water soluble monomer and two or more radical polymerizable groups in a molecule of a special structure, (B) a water soluble crosslinkable substance having two or more radical polymerizable groups in a molecule and a water soluble UV curing polymer, and (C) a photopolymerization initiator in such a manner that a photopolymerizable site is cured by emitting a light after printing and an adhesive layer provided on a surface opposed to a printing 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 printed material, and more particularly to a sealing material having an ink receiving layer which can be printed at a required place. Further, the present invention is suitable for aqueous pigment-based ink, high print quality,
The present invention relates to a sealing material having an ink receiving layer having excellent light resistance and moisture resistance.

[0002]

2. Description of the Related Art Ink jet recording is a recording method capable of high-speed printing with low noise, and is a recording method that has been rapidly spreading recently. In such ink jet recording, recording is performed by discharging a recording liquid as small droplets by a method such as heating or pressurization and attaching the recording liquid to a recording material such as paper.

[0003] Dyes have been used as coloring materials for recording liquids. However, there are many cases where printed matter is exposed to the outdoors with diversification of recorded matter. Therefore, it is more advantageous to use a pigment than a dye in terms of water resistance and weather resistance of the ink. From the viewpoint of environment, it is more advantageous to use an aqueous liquid medium than a non-aqueous liquid medium.

[0004] Therefore, an aqueous pigment-based ink in which a pigment is used as a coloring material of a recording liquid and the pigment is dispersed in an aqueous liquid medium has been actively developed, and printing on various types of recorded materials has been spreading.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a sealing material having an ink receiving layer which is suitable for aqueous pigment-based inks, has high printing quality, and is excellent in light resistance and moisture resistance.

[0006]

According to the present invention, there is provided a sealing material having an ink receiving layer, which can be stuck to a flexible base material such as urethane rubber, contains at least the following composition, and is irradiated with light after printing. A flexible ink-receiving layer for curing the photopolymerizable portion, and an adhesive layer provided on a surface facing the printing surface. (A) Polymer of a water-soluble radically polymerizable water-soluble monomer and a water-soluble cross-linkable substance having two or more radically polymerizable groups in the molecule (B) Water-soluble cross-linking having two or more radically polymerizable groups in the molecule Substance and water-soluble UV curable polymer (C) Photopolymerization initiator

The radically polymerizable water-soluble monomer of the composition (A) of the ink receiving layer of the sealing material of the present invention is N, N
-Dimethylacrylamide.

The water-soluble crosslinkable substance having two or more radical polymerizable groups in one or both of the compositions (A) and (B) of the ink receiving layer of the sealing material of the present invention is It has a polyethylene glycol chain which may have an aromatic ring in the molecule, and the total of ethylene oxide units of the polyethylene glycol chain is 20 to 30.

A water-soluble crosslinkable substance having two or more radically polymerizable groups in one or both of the compositions (A) and (B) of the ink-receiving layer of the sealing material of the present invention. Is a urethane acrylate.

The ink-receiving layer composition (A) and the water-soluble UV-curable polymer (B) of the sealing material of the present invention each have a film-forming ability alone.

Further, the printing method for the ink receiving layer of the sealing material of the present invention is an ink jet method, and the ink used is an aqueous pigment based ink comprising at least a dispersant, an aqueous liquid medium, a humectant, a pigment and water. It is characterized by being ink.

The sealing material having an ink receiving layer according to the present invention, the sealing material which can be stuck to a non-flexible substrate contains at least the following composition, and is an ink which cures a photopolymerizable portion by light irradiation after printing. It has a receiving layer and is provided with an adhesive layer on the surface facing the printing surface. (D) a polymer of a water-soluble cross-linkable substance having two or more radically polymerizable groups in a molecule and a water-soluble cross-linkable substance (E) a water-soluble UV-curable polymer (F) Polymerization initiator

The radical polymerizable water-soluble monomer of the ink receiving layer composition (D) of the sealing material of the present invention is N, N
-Dimethylacrylamide.

The water-soluble crosslinkable substance having two or more radically polymerizable groups in the molecule of the composition (D) of the ink receiving layer of the sealing material of the present invention may have an aromatic ring in the molecule. Has a good polyethylene glycol chain, the total of the ethylene oxide units of the polyethylene glycol chain is 10
20.

The composition (D) and the water-soluble UV-curable polymer (E) of the ink-receiving layer of the sealing material of the present invention each have a film-forming ability alone.

Further, the printing method on the ink receiving layer of the seal material of the present invention is an ink jet method, and the ink used is an aqueous pigment system comprising at least a dispersant, an aqueous liquid medium, a humectant, a pigment, and water. It is characterized by being ink.

[0017]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In the practice of the present invention, the material to be sealed is a non-flexible plastic material such as polyester resin, polyolefin resin, acrylic resin, and the like.
Alternatively, a glass material, a metal material, or a material whose surface is coated can be used. Further, as the flexible base material, for example, urethane rubber, natural or synthetic leather, soft vinyl, or a product obtained by coating them can be used.

As the pressure-sensitive adhesive for the pressure-sensitive adhesive layer used in the practice of the present invention, a pressure-sensitive adhesive material that can be adhered to a substrate to be sealed by pressure, heat, or light can be used. You can do it.

The adhesive layer to be used may be one having a base material such as paper or PET film provided in the middle, for example, a common double-sided tape. It is preferable to use an adhesive layer.

Further, when the material to be sealed is transparent, it is preferable that the adhesive layer has as high transparency as possible. For example, when the adhesive layer is attached to glass or the like, the pattern is also applied from the opposite surface opposite to the attached surface. Can be confirmed.

As necessary, other additives such as an ultraviolet absorber, an antioxidant and an antifoaming agent may be added to the ink receiving layer.

The thickness of the ink receiving layer is not particularly limited, and can be changed in a wide range according to the amount of ink to be received. Usually, it is in the range of several μm to 50 μm, but preferably in the range of 20 μm to 50 μm in consideration of the ease of handling as a sealing material.

The surface of the ink receiving layer may additionally have other conventional layers such as an overcoat layer, depending on the environment in which the ink is used. It is particularly useful when water resistance and abrasion resistance are required, such as wristwatch bands and sports bags.

In the practice of the present invention, the radically polymerizable water-soluble monomer of the composition (A) or (D) of the ink receiving layer and the water-soluble crosslinkable substance having two or more radically polymerizable groups in the molecule are used. The step of forming a polymer can be basically performed using a conventional polymerization method. For example, in the presence of a polymerization initiator, 50-7
The polymerization can be carried out by reacting at an elevated temperature of 0 ° C.

The polymerization initiator used here is preferably a water-soluble polymerization initiator. As a suitable polymerization initiator, for example, 2,2′-azobis (2-amidinopropane) dihydrochloride, 4,4′-azobis ′ (4,4-cyanovaleric acid), 2,2′-azobis [2 -(2-Imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis [2- (2-imidazolin-2-yl) propane]
Disulfate dihydrate, 2,2′-azobisisobutyramide dihydrate, persulfate and the like can be mentioned. Furthermore,
If necessary, a polymerization accelerator and other additives may be added.

In the practice of the present invention, the ink receiving layer coating solution is basically composed of a solution containing the composition (A) and a solution containing the composition (B).
And a solution containing the composition (C) and a solution containing the composition (D) and a solution containing the composition (D), and then diluting with water or a water-soluble organic solvent depending on the coating method. Use what was done. Examples of the water-soluble organic solvent include, but are not limited to, alcohols such as methanol, ethanol, isopropyl alcohol, and 1,3-propanediol, and glycols such as ethylene glycol and propylene glycol.

In the practice of the present invention, the water-soluble UV-curable polymers of the composition (A) and the composition (D) and the composition (B) and the composition (E) of the ink-receiving layer each form a single film. By having the function, even when the ink receiving layer before printing is touched with a finger, it is not sticky and handling is easy.

In the practice of the present invention, after a target picture is printed on the ink receiving layer by an ink jet method using an aqueous pigment-based ink, the printed matter is dried for the purpose of removing moisture and a humectant in the ink, and then subjected to ultraviolet light. The composition (B) in the ink receiving layer is cured by irradiating ultraviolet rays using an irradiation device. The curing conditions depend on the absorption wavelength of the photopolymerization initiator used, but a general ultraviolet curing light source (wavelength 300 to 450 n)
m) can be used. By curing the composition (B) uniformly dispersed in the ink receiving layer, the printed ink is taken into the polymer and fixed. Further, the ink receiving layer itself becomes a tough and flexible film, and the moisture resistance is dramatically improved.

An embodiment of the present invention will be described below. The present invention is not limited by the following examples.

(Example 1) 80 parts by weight of pure water was charged into a reaction vessel, and was replaced with nitrogen. Then, 10 parts by weight of N, N-
Dimethylacrylamide, 0.1 part by weight of N, N, N ', N'-tetramethylenediamine as a polymerization accelerator and 0.01 part by weight of ammonium persulfate as a polymerization initiator are added, and the mixture is stirred at 70 ° C. for 45 minutes. Was. Then, water-soluble urethane acrylate (trade name "UA-7000")
1.0 parts by weight and 0.01 parts by weight of ammonium persulfate were added and stirred at 70 ° C. for 1 hour to obtain an aqueous solution of the polymer (A).

Thereafter, the heating was stopped, and 2.5 parts by weight of water-soluble U as a solid content was added to the aqueous solution of the polymer (A) which had dropped to room temperature.
V-curable polymer (trade name "NK Polymer B-1516"
S-11 "), 1.0 parts by weight of UA-7000 and 0.15 parts by weight of a photopolymerizable initiator (trade name" Irgacure 1173 "), and a flexible ink receiving layer comprising the following composition: Was obtained. Composition (A): Polymer of N, N-dimethylacrylamide and UA-7000 Composition (B): NK Polymer B-1516S-11
And UA-7000 Composition (C): Irgacure 1173

The resin solution of the ink receiving layer was applied on a smooth polypropylene plate using a bar coater so that the dry film thickness became 30 μm, and then dried at 60 ° C. for 3 hours.

Next, the adhesive part on one side of the double-sided adhesive sheet having high transparency and using no base material is adhered to the surface of the ink receiving layer, and the ink receiving layer is peeled off from the polypropylene plate to form a sealing material having the ink receiving layer. Produced.

(Example 2) In place of the water-soluble urethane acrylate used in the composition (A) and the composition (B) of Example 1, 1. A sealing material having an ink-receiving layer was prepared in the same manner as in Example 1 except that the diacrylate compounds represented by Chemical Formula 1 were used by weight.

Embedded image

A water-soluble urethane acrylate used in the composition (A) and the composition (B) in Example 1 was replaced with the same amount (weight) of a diacrylate compound represented by the following formula (2). A sealing material having an ink receiving layer was produced in the same manner as in Example 1.

Embedded image

In place of the water-soluble urethane acrylate used in the composition (A) of Example 1, 0.64 times by weight of
Example 1 except that the water-soluble urethane acrylate used in the composition (B) was used, except that the diacrylate compound shown in
A sealing material having an ink receiving layer was produced in the same manner as in the above.

Embedded image

Composition (D): Polymer of N, N-dimethylacrylamide and Chemical Formula 3 Composition (E): NK Polymer B-1516S-11 Composition (F): Irgacure 1173

Comparative Example 1 A resin solution for a flexible ink receiving layer was prepared using the composition (A) and the composition (C) of Example 1.

Comparative Example 2 The composition (E) and the composition (F) of Example 4 were used as a resin solution for a flexible ink receiving layer.

Example 5 Examples 1-4 and Comparative Example 1
The pattern was printed in full color by an inkjet printer equipped with an aqueous pigment-based ink on the ink-receiving layer of the sealing material prepared in Nos. 1 to 2.

After printing, drying was performed at 60 ° C. for 3 hours, and curing was performed with ultraviolet rays of 3000 mJ / cm 2 using an ultraviolet curing lamp. After curing, the periphery of the pattern was cut, and the material to be sealed and the adhesive layer were stuck.

The sealing materials having an ink receiving layer of Examples 1 to 3 and Comparative Example 1 were 1.5 cm long, 6.0 cm wide, and 2 cm thick.
mm urethane resin substrate.

The sealing material having an ink receiving layer of Example 2 and Comparative Example 2 was 2.5 cm long, 7.0 cm wide, and 1 mm thick.
On a glass substrate.

Various tests were conducted using the samples prepared as described above. The bending test of the following (4) was not performed on the samples of Example 2 and Comparative Example 2. In addition, those that failed in the initial test will not conduct subsequent tests,
"-(Not tested)".

(1) Print Quality The print quality was observed with a magnifying glass of 24 times magnification, and those with good print quality were evaluated as “） (pass)”, and those with bleeding or color mixing were evaluated as “x (fail)”. "

(2) Light Resistance Test Printed samples were prepared using a sunshine weather meter (light source:
Light irradiation was performed for 100 hours using a carbon arc lamp. If there is no fading in the design after the test, "○ (pass)"
Those which showed fading were evaluated as "x (fail)".

(3) Moisture Resistance Test The printed sample was placed horizontally and vertically on an environmental tester (constant humidity chamber) and left at 40 ° C./90% RH (relative humidity) for 100 hours. A symbol having no change in the design after standing was rated as “○ (pass)”, and a symbol with a change in picture flow or the like was rated “x (fail)”.

(4) Bending test (Examples 1-3, Comparative Example 1)
For the print sample, the bending test was repeated 10,000 times by the method shown in FIG. After the test, those having no change in the pattern and the ink-receiving layer in the non-printed part were evaluated as “○ (pass)”, and those having cracks or peeling were evaluated as “x (fail)”.

Table 1 summarizes the results of each of the tests (1) to (4) described above.

[Table 1]

As described above, from the results of Examples and Comparative Examples, the sealing material having the ink receiving layer of the present invention has high printing quality, light resistance,
It can be seen that the sealing materials shown in Examples 1 to 3 have moisture resistance and are useful as a sealing material having an ink receiving layer for a flexible base material.

[0051]

As described above, the sealing material having the ink receiving layer of the present invention can be used for partial printing on a non-flexible substrate or a flexible substrate. Partial printing using a sealing material is very advantageous in terms of cost because printing can be performed by attaching a seal to a desired portion after assembling a product.

That is, the sealing material having the ink-receiving layer of the present invention can be applied to, for example, timepiece dials, watchbands, carrying straps, one-point printing, or timepiece printing of clockfaces. . Watch band,
When used for flexible substrates such as mobile phone straps,
Further, although water resistance and scratch resistance are required, these properties can be sufficiently satisfied by providing an overcoat layer on the ink receiving layer.

[Brief description of the drawings]

FIG. 1 shows a form of a bending test in Example 5 of the present invention.

Claims (11)

[Claims] 1. A sealing material having an ink receiving layer for curing a photopolymerizable portion by light irradiation after printing, and an ink receiving layer having an adhesive layer on a surface facing a printing surface. 2. A flexible ink receiving layer comprising at least the following composition, wherein a photopolymerizable site is cured by light irradiation after printing, and a pressure-sensitive adhesive layer on a surface facing the printing surface. A sealing material having a flexible ink receiving layer provided with: (A) Polymer of a water-soluble radically polymerizable water-soluble monomer and a water-soluble cross-linkable substance having two or more radically polymerizable groups in the molecule (B) Water-soluble cross-linking having two or more radically polymerizable groups in the molecule Substance and water-soluble UV curable polymer (C) Photopolymerization initiator 3. The flexible ink-receiving layer according to claim 2, wherein the radically polymerizable water-soluble monomer (A) is N, N-dimethylacrylamide. 4. The water-soluble crosslinkable substance having two or more radically polymerizable groups in one or both of (A) and (B) may have an aromatic ring in the molecule. 3. The flexible ink receiving layer according to claim 2, wherein the flexible ink receiving layer has a polyethylene glycol chain, and the total of the ethylene oxide units of the polyethylene glycol chain is 20 to 30. 5. The water-soluble crosslinkable substance having at least two radically polymerizable groups in one or both of (A) and (B) is urethane acrylate. 2. The flexible ink receiving layer according to item 2. 6. The polymer according to claim 2, 3, 4 or 5, wherein the polymer (A) and the water-soluble UV-curable polymer (B) each have a film-forming ability alone. Flexible ink receiving layer 7. An ink containing at least the following composition, wherein the photopolymerizable site is cured by light irradiation after printing, and an ink receiving layer provided with an adhesive layer on the surface facing the printing surface. Sealing material having receiving layer (D) Polymer of water-soluble radically polymerizable water-soluble monomer and water-soluble crosslinkable substance having two or more radically polymerizable groups in the molecule (E) Water-soluble UV-curable polymer (F) Light Polymerization initiator 8. The flexible ink receiving layer according to claim 7, wherein the radically polymerizable water-soluble monomer (D) is N, N-dimethylacrylamide. 9. The water-soluble crosslinkable substance having two or more radically polymerizable groups in the molecule of (D) has a polyethylene glycol chain, and the total of ethylene oxide units of the polyethylene glycol chain is 10 to 20. The ink receiving layer according to claim 7, wherein 10. The ink-receiving layer according to claim 7, wherein the polymer (D) and the water-soluble UV-curable polymer (E) each have a film forming ability alone. 11. The ink receiving layer according to claim 2, wherein the printing method is an ink jet method, and the ink used is an aqueous pigment-based ink.