JPH11192776A - Ink jet recording medium and manufacture thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To raise the ink wettability, a dyeing property, and water resistivity of ink of an ink jet recording medium by laminating an ink receptor layer consisting of a cation-modified acryl copolymer containing a monomer component of methacrylic acid amide or acrylamide on at least one surface of a carrier. SOLUTION: Herein, prepared is a coating liquid component basically having a cation-modified acrylic copolymer containing a monomer component of methacrylic acid amide or acrylamide and multifunctional epoxide. The coating liquid component is applied on at least one surface of a carrier, and thereafter it is heated to be hardened for forming a resin layer as an ink receptor layer, and thereby forming an ink jet recording medium having both of superior ink absorptiveness and water resistance. Both of the cation-modified acrylic copolymer and multifunctional epoxide are used as the coating liquid of an about 10-50 wt.% solution such as water, ethanol, methanol, isopropylalcohol, and acetone.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a recording medium for an ink-jet printer and a method for producing the same, and more particularly to an ink-jet recording medium having satisfactory properties with respect to wettability, absorption and water resistance, and its production. Provide a way.

[0002]

2. Description of the Related Art In recent years, various types of printers for computer output have become widespread. Above all, an ink jet printer is excellent in quietness, cost, and image quality, can reproduce a full-color image with high quality, has excellent performance not found in other systems, and can be expected to spread further. On the other hand, paper is often used for printer paper, and plastic films and synthetic papers are also used for applications requiring smooth images utilizing their smooth surface and transparency.

[0003] Ink-jet inks include:
In order to prevent clogging of the ink nozzle, a slow-drying ink in which a water-soluble dye or the like is dissolved in an aqueous solvent is used. Therefore,
Good if the recording paper is water-absorbent, such as paper, but if it is non-water-absorbing such as a plastic film, the ink will have poor drying properties after printing. A receiving layer is provided.

However, a structure in which an ink receiving layer is provided on a support such as a plastic film has not been obtained with sufficient performance. That is, in order to improve the wettability and dyeability of the slow-drying ink, or to improve the absorbability, a method of forming the ink receiving layer from a water-soluble resin, a hydrophilic resin, or the like has been proposed. By the aqueous solvent,
Alternatively, the ink receiving layer becomes wet and tacky in a high-humidity environment, and blocking occurs when recording media are stacked,
In addition, there is a problem that drying is poor and soiling is easy if touched by hand after printing. The properties of wettability, dyeing properties and absorbency and the properties of water resistance, drying property and blocking resistance are contradictory properties, and a property satisfying these properties has not been obtained at the same time.

[0005]

According to the above prior art, a recording medium using a non-water-absorbing support can provide satisfactory performance even if the ink receiving layer and the like are devised. I didn't. The present invention has been made in view of the problems of the related art, and an object of the present invention is to provide an ink jet recording medium that simultaneously satisfies ink wettability, dyeing properties, and water resistance, and a method for manufacturing the same. is there. Another object of the present invention is to provide an ink jet recording medium having excellent transparency and a method for manufacturing the same.

[0006]

Means for Solving the Problems The means provided by the present invention for solving the above-mentioned problems is that, as set forth in claim 1, at least one surface of a support is provided with either methacrylamide or acrylamide. An ink jet recording medium having an ink receiving layer made of a cation-modified acrylic copolymer containing as a monomer component.

[0007] In the cation-modified acrylic copolymer, mainly the cation-modified portion has ink absorbency. According to the first aspect of the present invention, it is possible to provide the ink jet recording medium with characteristics that simultaneously satisfy the dyeing and wettability of the ink in receiving the ink and the water resistance.

More preferably, as set forth in claim 2,
Based on the constitution of claim 1, in particular, the monomer component of the cation-modified acrylic copolymer is at least one of methacrylamide or acrylamide, methyl methacrylate, and quaternary ammonium salt of dialkylaminoethyl methacrylate. This is an inkjet recording medium composed of three components. Thereby, the above effect can be further enhanced.

More preferably, as set forth in claim 3,
On the basis of any one of claims 1 and 2,
The monomer component of the cation-modified acrylic copolymer,
An inkjet recording medium comprising at least four components of either methacrylamide or acrylamide, methyl methacrylate, quaternary ammonium salt of dialkylaminoethyl methacrylate, and 1-vinyl-2-pyrrolidone. This makes it possible to achieve a good balance between wettability and water resistance.

[0010] More preferably, as set forth in claim 4,
On the basis of any one of claims 1 to 3,
An ink jet recording medium in which either methacrylamide or acrylamide is 2 to 30% by weight of all monomer components of the cation-modified acrylic copolymer. Here, if either methacrylamide or acrylamide is less than 2% by weight with respect to the total monomer components, the dyeing property with the ink is reduced, and if the ratio exceeds 30% by weight, However, it is not preferable because hydrophilicity is reduced.

More preferably, as set forth in claim 5,
In particular, based on any one of claims 1 to 4,
The ink receiving layer is an ink jet recording medium obtained by heating and curing a cation-modified acrylic copolymer and a polyfunctional epoxide. Here, by mixing the cation-modified acrylic polymer and the polyfunctional epoxide and using a resin obtained by applying heat, thermosetting occurs, and the water resistance of the resin is significantly improved. Even if the ink is absorbed, no dissolution or stickiness of the ink receiving layer occurs.

Preferably, as set forth in claim 6,
In particular, based on any one of claims 1 to 4,
The cation-modified acrylic copolymer is an ink jet recording medium having the property of dissolving in a mixed solvent of water and alcohol. Here, by dissolving in a mixed solvent of water and alcohol, the coating is facilitated when coating on the support, and the time required for drying is short, which is preferable.

Preferably, as set forth in claim 7,
On the basis of any one of claims 1 to 6,
The ink receiving layer contains a filler having an average particle size of 50 μm or less, either organic or inorganic, in a ratio of 0.1 to 50% by weight based on the cation-modified acrylic copolymer. Item 7. An ink jet recording medium according to any one of Items 1 to 6.

Alternatively, as described in claim 8, based on the constitution of claim 5, an ink jet recording medium in which the polyfunctional epoxide is aliphatic and water-soluble.

According to a ninth aspect of the present invention, there is provided an ink jet printer comprising the support according to any one of the first to eighth aspects, wherein the support is made of paper or a plastic film. It is a recording medium.
Here, any plastic film may be used as long as it has appropriate mechanical rigidity. Most preferably the so-called P
It is an ET film, and more specifically, any one of a white PET film, a transparent PET film, and an aluminum-deposited PET film. If transparency is particularly required as in applications such as OHP films, transparent PET films are preferred.

According to a tenth aspect of the present invention, an ink receiving layer is formed by curing a cation-modified acrylic copolymer containing either methacrylamide or acrylamide as a monomer component on at least one surface of the support. A method for manufacturing an ink jet recording medium characterized by the following.

More preferably, as set forth in claim 11, based on the constitution of claim 10, an ink jet recording medium in which a polyfunctional epoxide is mixed with the cation-modified acrylic copolymer and then cured by heating. It is a manufacturing method of. According to this, by heating and curing, the water resistance of the ink receiving layer is improved.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION The present inventors have conducted intensive studies in order to solve the above-mentioned problems and achieve the object, and as a result, have come to invent an ink jet recording medium according to the present invention. That is, the present invention includes, on a support, an ink receiving layer having a composition based on a cation-modified acrylic copolymer containing either methacrylamide or acrylamide as a monomer component and a polyfunctional epoxide. As a method for forming such an ink receiving layer, for example, a liquid having the above composition and liquefied is coated on at least one surface of a support. Thereafter, a resin layer obtained by curing by heating is used as an ink receiving layer. According to the present invention, there is provided an ink jet recording medium having both excellent ink absorbency and water resistance.

The ink receiving layer in the present invention is a layer for receiving ink of an ink jet printer. In the present invention, the ink jet recording medium simultaneously satisfies the ink dyeing property, wettability and water resistance in receiving ink. It is to try to make it. In the present invention, a cation-modified acrylic copolymer resin containing either methacrylamide or acrylamide as a monomer is basically used for such an ink receiving layer.

The cation-modified acrylic copolymer described in the present invention particularly includes an acrylic monomer having a quaternary ammonium base in a side chain as a monomer component constituting the copolymer. In addition, any of methacrylamide, acrylamide, ethyl methacrylate, and ethyl acrylate is used as a monomer for adjusting the flexibility of the cation-modified acrylic copolymer. In order to adjust the glass transition point, it is preferable to carry out polymerization by changing the ratio.

Examples of the acryl monomer having a quaternary ammonium base include dimethylaminoethyl (meth) acrylate, diethylamino (meth) acrylate, diethanolamino (meth) acrylate, dipropylamino (meth) acrylate, and dibutylamino. Examples include monomers obtained by converting any of (meth) acrylate and the like into a quaternized salt with an alkyl halide (for example, any of methyl chloride and ethyl chloride).

Further, by mixing the above-mentioned cation-modified acrylic copolymer and polyfunctional epoxide and applying a resin obtained by heating to the receiving layer, the water resistance is remarkably improved. As the polyfunctional epoxide, two epoxy groups
A bifunctional or more epoxy compound having the above is used.
Examples of such an epoxy compound include polyglycerol polyglycidyl ether, pentaethylitol polyglycidyl ether, diglycerol polyglycidyl ether, glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, resorcinol diglycidyl ether, and polypropylene glycol diglycol. It is an aliphatic and water-soluble epoxy compound such as glycidyl ether.

The above-mentioned cation-modified acrylic copolymer and polyfunctional epoxide are all water, methanol, ethanol, isopropyl alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate,
It is used as a coating liquid of a 10 to 50% by weight solution using one or a mixture of two or more solvents such as toluene and xylene. To improve the water resistance, the polyfunctional epoxide is used in an amount of 0.1% to 50% based on the weight of the cation-modified acrylic copolymer.
May be added, and in that case, it may be diluted as necessary.

In order to improve the transportability and the blocking resistance, a filler may be added to the ink receiving layer as required. The amount of addition should be within a range that does not impair the transparency for use in transparent images such as OHP.

As the organic or inorganic filler described in the present invention, for example, as inorganic particles, silica, clay, calcium carbonate, barium sulfate, alumina white, aluminum hydroxide, talc, bentonite, titanium oxide, etc. As organic fine particles, polymethyl methacrylate, polystyrene, fluororesin vinyl resin, polyethylene, polyolefin resin such as polypropylene,
Thermoplastic resin such as polyamide, polybenzoguanamine resin, thermosetting resin such as urea resin, and fine particles made of any of the above, the particle size is 0.1-30 μm, preferably 0.1
２０20 μm.

Further, for example, silicic anhydride, hydrous silicic acid, hydrous calcium silicate known as colloidal silica, etc.
If inorganic particles having a particle size of usually about 10 to 300 nm such as white carbon such as hydrous aluminum silicate and alumina sol are used, the ink printed on the ink receiving layer is appropriately diffused, which is effective in forming high quality images. .

0.1 to 50% by weight in the ink receiving layer
Used in a range of about 0.1 to 20% by weight.
Use within the range. If the amount is too small, sufficient transportability and blocking resistance cannot be obtained. In the case of a transparent image such as OHP, if the amount is too large, the transparency is impaired.
Less is better. In the case of an opaque image, it also has the meaning of providing whiteness, so that a large amount is contained. If it exceeds 50% by weight, the proportion of the cation-modified acrylic polymer that accepts ink decreases, so if it is desired to exhibit sufficient ink absorption capacity, the thickness of the ink receiving layer must be reduced. It is necessary to make the ink jet recording medium thicker, which leads to an increase in cost and is also not preferable because a large curl easily occurs in the ink jet recording medium.

In addition, the ink receiving layer may have, depending on the purpose,
In addition to the above fillers, other resins other than those mentioned above, or surfactants, ultraviolet absorbers, antioxidants, PH adjusters, defoamers and other additives are appropriately mixed within a range not departing from the performance. Is also good.

The thickness of the ink receiving layer is usually from 1 to 50 μm.
m, preferably about 3 to 20 μm. If the thickness is too small, the dyeing properties will be insufficient, and the drying property and the anti-blocking property will be reduced. Conversely, if the thickness is too large, the cost will increase and the curl will increase.

The ink receiving layer is formed by applying a coating liquid obtained by mixing the above-mentioned cation-modified acrylic copolymer and polyfunctional epoxide at an appropriate equivalent ratio on at least one surface of the support, by gravure coating, roll coating, wire bar coating. What is necessary is just to apply by well-known coating means, such as.

Examples of the support for the ink jet recording medium include polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyolefins such as polyethylene and polypropylene, polyvinyl chloride, polystyrene, polymethyl methacrylate, polycarbonate, cellophane, cellulose acetate, and polyarylate. A film or plate made of a resin such as polyether sulfone can be used. OHP for inkjet recording media
If it is intended for use, it is transparent, especially polyethylene terephthalate film, rigid polyvinyl chloride film,
Use a polypropylene film, a triacetate film, or the like. Also, a glass plate or the like can be used. On the other hand, OHP
If it is not a transparent image application such as a transparent image, an opaque support such as white may be used, and various papers such as synthetic paper, high-quality paper, art paper, coated paper, cast coated paper, and paperboard can also be used.

The thickness of the support is appropriately selected in consideration of the strength depending on the application, and is not particularly limited.
About 200 μm. Further, the surface of the support may be subjected to a known easy adhesion treatment such as a corona discharge treatment or an anchor layer made of polyurethane resin or the like for the purpose of improving the adhesion of the ink receiving layer provided on the surface.

The aqueous ink that can be used in the ink jet recording medium of the present invention is a known ink jet ink, and is usually a water-soluble dye, a wetting agent, a dye solubilizing agent, a preservative, water, and water affinity. It consists of an organic solvent and the like.

As described above, in the ink jet recording medium of the present invention, by using a resin obtained by adding a polyfunctional epoxide to a specific cation-modified acrylic copolymer, coating and heating the ink-receiving layer, Both wettability and dyeability and water resistance are compatible. The cation-modified portion in the cation-modified acrylic copolymer mainly has ink absorbency, and on the other hand, is heat-cured by adding a polyfunctional epoxide and applying heat to obtain water resistance.

[0035]

The present invention will be described below in more detail with reference to specific examples. The following synthesis examples (<Synthesis Example 1> to <Synthesis Example 8>) use methacrylamide or acrylamide, while comparative synthesis examples (<Comparative Synthesis Example 1> to <Comparative Synthesis Example 1> to <
Comparative Synthesis Example 3>) does not use them. still,
“Parts” described in the text are weight standards and solid content standards unless otherwise specified. And this invention is not limited to this.

<Synthesis Example 1> In a four-necked flask equipped with a stirrer, a nitrogen inlet tube and a reflux condenser, 7 g of methacrylamide, 45 g of methyl methacrylate, and quaternized dimethylaminoethyl methacrylate were placed. 25 g, further 21 g of 1-vinyl-2-pyrrolidone were introduced, 240 g of distilled water and 1 g of 2-propanol were introduced.
60 g was added and dissolved, and the mixture was stirred under a nitrogen atmosphere on an oil bath. The polymerization was started by adding 0.48 g of α, α'-azobisisobutyronitrile thereto, and the mixture was heated and stirred on a 60 ° C. oil bath for 7 hours. A colorless, viscous polymer solution was obtained.

<Synthesis Example 2> As monomers to be added to a four-necked flask, 7 g of acrylamide, 45 g of methyl methacrylate, 25 g of trimethylaminoethyl methacrylate chloride, and 21 g of 1-vinyl-2-pyrrolidone were used. Except for the introduction, a colorless and viscous polymer solution was obtained in the same manner as in Synthesis Example 1.

Synthesis Example 3 As monomers to be added to a four-necked flask, 7 g of methacrylamide, 45 g of methyl methacrylate, 21 g of ethyl acrylate, and 25 g of trimethylaminoethyl methacrylate were introduced. A colorless and viscous polymer solution was obtained in the same manner as in Synthesis Example 1 except for the above.

<Synthesis Example 4> As monomers to be added to the four-necked flask, 7 g of acrylamide, 45 g of methyl methacrylate, 21 g of ethyl acrylate,
And trimethylaminoethyl methacrylate
A colorless, viscous polymer solution was obtained in the same manner as in Synthesis Example 1 except that 5 g of the polymer solution was introduced.

<Synthesis Example 5> As monomers to be added to a four-necked flask, 7 g of methacrylamide, 34 g of methyl methacrylate, 17 g of ethyl acrylate, and 40 g of trimethylaminoethyl methacrylate were introduced. A colorless and viscous polymer solution was obtained in the same manner as in Synthesis Example 1 except for the above.

<Synthesis Example 6> As monomers to be added to the four-necked flask, 7 g of methacrylamide, 20 g of methyl methacrylate, 10 g of ethyl acrylate, and 40 g of trimethylaminoethyl methacrylate were used.
g, and 21 grams of 1-vinyl-2-pyrrolidone;
Was carried out in the same manner as in Synthesis Example 1 except that a polymer solution was introduced to obtain a colorless and viscous polymer solution.

<Synthesis Example 7> As monomers to be added to the four-necked flask, 15 g of methacrylamide, 45 g of methyl methacrylate, 25 g of trimethylaminoethyl methacrylate, and 13 g of 1-vinyl-2-pyrrolidone were used. Synthesis Example 1 except that
In the same manner as in the above, a colorless and viscous polymer solution was obtained.

<Synthesis Example 8> As monomers to be added to a four-necked flask, 15 g of methacrylamide, 45 g of methyl methacrylate, 25 g of trimethylaminoethyl methacrylate, and 13 g of 1-vinyl-2-pyrrolidone were used. Was carried out in the same manner as in Synthesis Example 1 except that a polymer solution was introduced to obtain a colorless and viscous polymer solution.

<Comparative Synthesis Example 1> As monomers to be added to a four-necked flask, 45 g of methyl methacrylate, 7 g of 2-hydroxyethyl methacrylate, 25 g of trimethylaminoethyl methacrylate, and 1-
A colorless and viscous polymer solution was obtained in the same manner as in Synthesis Example 1 except that 21 g of vinyl-2-pyrrolidone was introduced.

<Comparative Synthesis Example 2> As monomers to be added to the four-necked flask, 45 g of methyl methacrylate, 7 g of 2-hydroxyethyl methacrylate, 21 g of ethyl acrylate, and 25 g of trimethylaminoethyl methacrylate were introduced. Synthesis example 1 except that
In the same manner as in the above, a colorless and viscous polymer solution was obtained.

<Comparative Synthesis Example 3> As the monomers to be added to the four-necked flask, 45 g of methyl methacrylate, 15 g of 2-hydroxyethyl methacrylate, 25 g of trimethylaminoethyl methacrylate, and 1 g of
A colorless, viscous polymer solution was obtained in the same manner as in Synthesis Example 1 except that 13 g of -vinyl-2-pyrrolidone was introduced.

<Example 1> As a support, 100 μm
A polyethylene terephthalate film (trade name: Lumirror E63S, manufactured by Toray Industries, Inc.) having an m-thick surface whose adhesion was easily treated was used. On top of this, glycerol polyglycidyl ether (trade name) as a polyfunctional epoxide was added to the polymer solutions obtained in <Synthesis Example 1> to <Synthesis Example 8>.
Denacol EX-314 (manufactured by Nagase Kasei Kogyo Co., Ltd.) was added to the polymer solution in an amount of 2% by weight, and this was applied by bar coating so that the film thickness after drying was 15 μm. After drying for an minute, an ink jet recording medium was obtained. The obtained ink jet recording medium was printed with four color inks of yellow (Y), magenta (M), cyan (C) and black (K) using a Canon ink jet printer (product name: BJC-420J). An image was formed. The results of these evaluations are shown in (Table 1).

<Example 2> An ink jet recording medium was prepared and evaluated in the same manner as in Example 1 except that the polyfunctional epoxide was not added. Example 1
And showed almost the same good results.

The evaluations shown in Table 1 were carried out on the printed recorded material according to the following operations and in accordance with the respective evaluation criteria.

[Ink Absorption] Immediately after printing, the degree of outflow of ink when the recording portion of the recorded matter was rubbed with a finger was evaluated. ◎: Completely dried and did not flow out at all. ○: The recording section is slightly wet, though it does not flow out. Δ: A small amount of outflow is observed. ×: A large amount of outflow is observed.

[Water resistance (recording part)] Water was dropped on the recording part with a dropper and immediately wiped lightly with gauze. A: Ink hardly flows out. ；: Ink slightly leaked, but no significant change in color tone. Δ: Ink spilled, and change in color tone was observed. ×: The coating film is dissolved, and the ink is also peeled off.

[Water resistance (unrecorded portion)] Water was dropped on the unrecorded portion with a dropper and immediately wiped lightly with gauze. A: There is almost no damage to the coating film. ；: The coating film is slightly damaged, but there is no practical problem. Δ: Part of the coating film is dissolved. ×: Most of the coating film is dissolved.

[0053]

[Table 1]

[0054]

As described above, according to the present invention, all of the ink jet recording media were excellent in ink wettability and dyeing property, excellent in ink absorption, and excellent in water resistance. Furthermore, because of its excellent transparency, OHP
It also has excellent suitability for applications such as film. That is, according to the present invention, it was possible to provide an ink jet recording medium which simultaneously satisfies the wettability, the dyeing property, and the water resistance of the ink, and also has excellent transparency, and a method for producing the same.

[Brief description of the drawings]

FIG. 1 is a longitudinal sectional view showing one embodiment of an ink jet recording medium of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Ink jet recording medium 2 ... Support body 3 ... Ink receiving layer

Claims (11)

[Claims] 1. An ink jet recording medium comprising at least one surface of a support having an ink receiving layer made of a cation-modified acrylic copolymer containing either methacrylamide or acrylamide as a monomer component. 2. The method according to claim 1, wherein the monomer component of the cation-modified acrylic copolymer comprises at least three components of either methacrylamide or acrylamide, methyl methacrylate, and a quaternary ammonium salt of dialkylaminoethyl methacrylate. The ink jet recording medium according to claim 1, wherein: 3. The cation-modified acrylic copolymer as claimed in claim 1, wherein the monomer component is either methacrylamide or acrylamide, methyl methacrylate, quaternary ammonium salt of dialkylaminoethyl methacrylate, and 1-vinyl-2-pyrrolidone. 3. The ink jet recording medium according to claim 1, comprising at least four components. 4. A method according to claim 1, wherein, of all the monomer components of the cation-modified acrylic copolymer, either methacrylamide or acrylamide is used in an amount of 2 to 30 with respect to the total monomer components.
The ink jet recording medium according to any one of claims 1 to 3, wherein the content is% by weight. 5. The ink jet recording medium according to claim 1, wherein said ink receiving layer is formed by heat-curing a cation-modified acrylic copolymer and a polyfunctional epoxide. 6. An ink jet recording medium according to claim 1, wherein said cation-modified acrylic copolymer has a property of being dissolved in a mixed solvent of water and alcohol. 7. The ink receiving layer contains a filler having an average particle size of 50 μm or less, either organic or inorganic, in a ratio of 0.1 to 50% by weight based on the cation-modified acrylic copolymer. The inkjet recording medium according to any one of claims 1 to 6, wherein: 8. The ink jet recording medium according to claim 5, wherein said polyfunctional epoxide is aliphatic and water-soluble. 9. The ink jet recording medium according to claim 1, wherein the support is one of paper and a plastic film. 10. An ink jet recording medium comprising an ink receiving layer formed by curing a cation-modified acrylic copolymer containing either methacrylamide or acrylamide as a monomer component on at least one surface of a support. Production method. 11. The method for producing an ink jet recording medium according to claim 10, wherein a polyfunctional epoxide is mixed with the cation-modified acrylic copolymer, and then the mixture is cured by heating.