JP2003072226A - Material to be ink-jet-recorded - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a material to be ink-jet-recorded, which is excellent in the drying properties, lustrous properties and image reproducibility of a printed matter after printing in response to a non-water-base pigment type ink jet ink. SOLUTION: In the material to be ink-jet-recorded, which is produced by forming an ink accepting layer on at least one side of a base material, the ink accepting layer is made of a copolymer of vinyl chloride, vinyl acetate and hydroxyalkyl(meth)acrylate having an average degree of polymerization of 200 to 1,100 and a hydroxyl group value of 15 KOH mg/g or more.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a recording material which can be printed using a pigment-dispersed ink jet ink composed of a non-aqueous solvent containing a glycol ether as a main solvent, and has a printing gloss and dryness. The present invention relates to an inkjet recording material having excellent properties, printed image reproducibility, and durability in outdoor use.

[0002]

2. Description of the Related Art Generally, in a printing system using an inkjet ink, ink droplets are jetted from a print head or a spray nozzle at high speed onto a recording material according to an electric signal from a computer or the like, and the recording material is recorded. Printed on the ink receiving layer of the material. These ink receiving layers are mainly composed of a hydrophilic polymer material such as polyvinyl alcohol, polyvinylpyrrolidone, a water-soluble cellulose derivative, gelatin, and starch in order to have absorbability for an aqueous inkjet ink.

The above-mentioned conventional ink receiving layer of the recording material has been used as a coloring agent corresponding to an aqueous ink in which a dye or a pigment is dispersed in an aqueous vehicle. The ink receiving layer of these recording materials is used. The layer is easily wetted by outside air (humidity) during storage and the aqueous solvent in the ink. Therefore, these recording materials are mainly sufficient to withstand the use indoors such as offices and homes, and are sufficient for outdoor applications where water resistance and weather resistance are required. Can not exert such performance.

Further, when printing is performed using the above-mentioned conventional recording material, it is said that the print becomes thicker, the ink bleeds, the ink flows, or the drying property of the ink is slow, or the ink adheres when the print surface is rubbed. There is a problem, moreover, the type of inkjet ink used, the type of printer,
There is a problem that the constituent material of the ink receiving layer must be selected depending on printing conditions, required printing suitability and the like.

Therefore, in order to obtain printed materials that can be used outdoors, such as posters, displays, bulletin boards, etc.,
It is desired to provide a recording material that is compatible with a pigment type inkjet ink in which a pigment is dispersed in a non-aqueous vehicle and has printability such as weather resistance, water resistance, glossiness and image reproducibility.

For this reason, a recording material for the above-mentioned pigment type ink has been proposed. However, the pigment type ink in which the pigment is dispersed in the non-aqueous vehicle is more dried than the conventional aqueous dye ink. Set the drying to slow, to be fast,
Further, the ink receiving layer of the recording material corresponding to the pigment type ink has a porous layer as a matte surface in order to improve absorption and drying properties and fixing property of the ink. Therefore, the gloss required for the printed matter cannot be obtained.
In addition, since the ink receiving layer is the absorption surface of the porous layer, when used outdoors, there is a problem in performance due to the absorption surface becoming dirty or scratched due to the adhesion of foreign matter or moisture. It is necessary to protect the printed surface by laminating a plastic film such as a polyester film or a polypropylene film, if necessary.

As described above, a printed matter using a conventional ink jet recording material and a non-aqueous pigment type ink jet ink suitable for outdoor use has sufficient printability and durability required for outdoor use. Satisfactory results have not been obtained, especially for outdoor use with printing suitability such as printing glossiness, drying property and print image reproducibility, corresponding to the above non-aqueous pigment type inkjet ink. Recording material is not provided.

[0008]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to deal with non-aqueous pigment type ink jet inks, which are excellent in drying property, glossiness and image reproducibility of printed matter after printing. It is to provide a recording material.

[0009]

The above object can be achieved by the present invention described below. That is, the present invention is an inkjet recording material comprising an ink receiving layer formed on at least one surface of a substrate, wherein the ink receiving layer is
Vinyl chloride, vinyl acetate and hydroxyalkyl (meth)
Average degree of polymerization of acrylate is 200 to 1100
And an inkjet recording material comprising a copolymer (a) having a hydroxyl value of 15 KOHmg / g or more.

As a result of earnest studies to solve the above problems, the inventor of the present invention formed a non-aqueous pigment type ink jet ink by forming an ink receiving layer using the above-mentioned copolymer (a). It is possible to obtain a recording material that gives a printed image with excellent glossiness, dryness and image reproducibility of printed matter, and with a performance that can withstand outdoor use sufficiently even without laminating a plastic film. I found it.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail with reference to the following preferred embodiments. The copolymer (a), which is the main feature of the present invention, has an average degree of polymerization of vinyl chloride, vinyl acetate and hydroxyalkyl (meth) acrylate (“(meth) acrylate” means both acrylate and methacrylate). 200-110
The copolymer is 0 and has a hydroxyl value of 15 KOHmg / g or more.

Generally, an ink receiving layer formed by using a vinyl chloride-vinyl acetate copolymer is repelled by a non-aqueous pigment type ink jet ink using glycol ethers as a solvent. The printability is not good. When the recording material of the present invention having an ink receiving layer formed using the above copolymer (a) is printed with the above ink, the printed matter after printing is excellent in glossiness, drying property and image reproducibility, Moreover, a printed image having sufficient performance to withstand outdoor use can be obtained without laminating the plastic film.

The above-mentioned hydroxyalkyl (meth) acrylate is used for the purpose of improving the ink absorption and the drying property of the resulting copolymer (a), and examples thereof include hydroxyethyl (meth) acrylate and hydroxypropyl (meth). Acrylate, hydroxybutyl (meth) acrylate, hydroxypentyl (meth) acrylate, etc.
Specifically, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3
-Hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate and the like, and mixtures thereof are preferable, and 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl are preferable. (Meth) acrylate and 4-hydroxybutyl (meth) acrylate are mentioned.

The copolymer (a) which characterizes the present invention is produced by a known solution polymerization method or suspension polymerization method,
Average degree of polymerization is 200-1100, hydroxyl value is 15KOH
mg / g or more, preferably an average degree of polymerization of 400 to 110
0, the hydroxyl value is 35 KOHmg / g or more. The blending ratio of vinyl chloride, vinyl acetate and hydroxyalkyl (meth) acrylate used for the copolymerization is not particularly limited, but the repelling phenomenon of the above-mentioned pigment type inkjet ink with respect to the obtained inkjet recording material does not appear. The ink absorption and drying properties and the ink transferability (printability) may be in a balanced range. The blending ratio (weight ratio) of vinyl chloride and vinyl acetate in the copolymer (a) is preferably vinyl chloride weight%> vinyl acetate weight%. Particularly preferably, when the total amount of vinyl chloride, vinyl acetate and hydroxyalkyl (meth) acrylate is 100 parts by weight, 70 to 90 parts by weight of vinyl chloride, 3 to 20 parts by weight of vinyl acetate and 2 to 2 parts of hydroxyalkyl (meth) acrylate are used. It is a copolymerization ratio of 20 parts by weight.

When the average degree of polymerization of the copolymer (a) exceeds the above upper limit, the viscosity of the coating solution used for forming the ink receiving layer increases and the suitability for coating on the substrate decreases. On the other hand, when the average degree of polymerization is less than the lower limit, there is a problem that the drying property of the coating film is lowered and the coating film becomes brittle. Also, the hydroxyl value is 15
If it is less than KOHmg / g, there is a problem that the ink absorbency of the ink receiving layer is lowered and the image reproducibility is lowered. These copolymers (a) can be obtained from Electrochemical Co., Ltd. [DVO46] and from Nissin Chemical Co., Ltd. [Solvane TA
2K] and the like and can be used in the present invention.

The above-mentioned polymer (a) can be used alone, but if necessary, a plasticizer such as phthalic acid, isophthalic acid, tetrahydrophthalic acid, maleic acid or fumaric acid is added to the substrate used. Low molecular weight ester plasticizers of carboxylic acid compounds such as acids and alcohol compounds,
In order to prevent polyester-based plasticizers, alkyd-based plasticizers and the like from bleeding out from the base material to cause stickiness, or to improve printability at low temperatures, it is possible to improve the printability of the polymer (a) other than the polymer (a). ) A polymer or copolymer (b) and / or cellulose acetate butyrate (c) made of acrylate can be added and used. The addition amount thereof is preferably 10 to 60 parts by weight of (b) and / or (c) with respect to 40 to 90 parts by weight of the copolymer (a). When (b) and (c) are used in combination, the mixing ratio thereof is preferably 1.0 / 1 to 5.0 / 1 in terms of the weight ratio of (b) / (c).

Examples of the (meth) acrylate constituting the above-mentioned polymer or copolymer (b) include methyl (meth) acrylate, ethyl (meth) acrylate,
Examples include (meth) acrylates such as butyl (meth) acrylate and propyl (meth) acrylate. Examples of the copolymers include styrene- (meth) acrylate copolymers, styrene- (meth) acrylic acid ester- (meth) acrylic acid copolymers and the like, and mixtures thereof. These polymers or copolymers (b) are commercially available from Mitsubishi Rayon Co., Ltd.
R-90 "and the like can be obtained and used in the present invention.

The above-mentioned cellulose acetate butyrate (c) is used for suppressing stickiness due to the plasticizer bleeding out from the substrate as described above and improving printability, and preferably has an acetyl group of 3 to 29. 0.5 wt%, butanoyl group 17-50 wt% and hydroxyl group 1-
Cellulose acetate butyrate containing 3% by weight. These cellulose acetate butyrate are commercially available from Eastman Chemical Company as "CAB-381-0.1".
, Etc., and can be used in the present invention.

The ink receiving layer of the recording material of the present invention comprises:
In addition to the above-mentioned polymers, known additives such as slip agents and leveling agents may be added and used within a range not hindering the achievement of the object of the present invention. As a slip agent,
For example, aluminum stearate, calcium stearate, silicone, polyethylene wax and the like, and examples of the leveling agent include fatty acid amide type, metal soap type, acrylic type, vinyl type and silicone type. The amount of the above slip agent and leveling agent added is preferably 0.1 to 3% by weight of the ink receiving layer.

The coating liquid used for forming the ink-receiving layer of the recording material of the present invention contains the above components in a suitable solvent, for example, a ketone system such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, ethyl acetate, acetic acid n. −
Obtained as a 15 to 28 wt% solution by dissolving in an ester system such as butyl and methyl acetate, an aromatic system such as toluene and xylene, a proton system such as tetrahydrofuran and dimethylformamide, and a mixed solvent thereof and homogenizing. Then, at least one surface of the substrate is coated with the coating solution and dried by a known drying method to provide the recording material of the present invention.

As the base material of the recording material of the present invention, a polyester film such as polyethylene terephthalate,
Examples include polyolefin films such as polyethylene and polypropylene, synthetic resin films such as polyvinyl chloride, polycarbonate, polystyrene, polymethylmethacrylate, and cellulose acetate, and synthetic paper. In addition, composites of synthetic resin and woven cloth, non-woven cloth or knitted cloth. Examples include a sheet, for example, a composite sheet such as tarpaulin. The above-mentioned substrate can be used after being subjected to corona treatment or primer treatment by a known method in order to improve the adhesiveness of the ink receiving layer, if necessary.

The method of coating the above-mentioned coating liquid on the above-mentioned substrate is not particularly limited, but for example, a gravure coater (gravure direct coater, gravure reverse roll coater, etc.), a reverse roll coater, a bar coater, a blade coater. A known method such as an air knife coater, a spray coater, or a curtain coater can be used. The drying conditions of the above coating liquid are not particularly limited as long as the above base material and ink receiving layer are not deteriorated. The thickness of the ink receiving layer after coating drying is preferably 5 to
It is 25 μm.

The recording material of the present invention is suitable for printing a printed image with a pigment type ink jet ink in which an inorganic pigment and / or an organic pigment are dispersed in a non-aqueous vehicle, and glycol ethers are preferably used as a solvent for the ink. It is effective for printing with the above-mentioned pigment type ink jet ink using. Examples of the glycol ethers include diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, monopropylene glycol monobutyl ether, monopropylene glycol monoethyl ether, monopropylene glycol monopropyl ether, monopropylene glycol monomethyl ether, dipropylene glycol monobutyl ether. Butyl ether, diethylene glycol monohexyl ether, and the like, and mixtures thereof.

Examples of pigments used in the above ink jet inks include inorganic pigments such as carbon black, titanium oxide, iron oxide, zinc white, ultramarine blue, dark blue, and yellow lead, insoluble azo pigments such as allylide and pyrazolone, and quinacridone. Examples of the organic pigments include thioindigo-based, thioindigo-based and indathlon-based. Further, the recording material of the present invention can also be applied to dye type inks other than the above-mentioned pigments depending on the application, and examples of the dyes include azo dyes, quinoline dyes, indigo dyes, anthraquinone dyes, and naphthoquinone dyes. Examples include dyes such as nitro dyes and metal complex dyes.

Further, as the above-mentioned non-aqueous vehicle,
Any known vehicle for inkjet ink that can be mixed and dispersed in a solvent containing the glycol ethers can be used. Examples of the resin used for the vehicle of the inkjet ink include acrylic resin, styrene acrylic resin, vinyl chloride-vinyl acetate copolymer resin, rosin-modified phenol resin, polyester resin, fibrin resin, polyamide resin and the like. . These resins, if necessary,
Dispersant, wax, antistatic agent, defoaming agent, antioxidant,
What added well-known additives, such as an ultraviolet absorber, can be used.

Printing on the recording material of the present invention is carried out by a general inkjet printer or plotter using the above-mentioned known non-aqueous pigment type inkjet ink, and the printing conditions are not particularly limited. Instead, it can be printed under normal printing conditions.

[0027]

EXAMPLES Next, the present invention will be described more specifically with reference to Examples and Comparative Examples. In addition, "part" and "%" in the text are based on weight. (Examples 1 to 5 and Comparative Examples 1 and 2) The components below were uniformly mixed by stirring to prepare coating liquids V1 to V7, and the coating liquid was tarpaulin (polyvinyl chloride sheet, 0.2 mm thickness).
The surface was coated with a film thickness (dry film thickness) of 15 μm to prepare recording materials V1 to V7 of the invention and comparative examples.

[0028] (Example 1) Coating liquid V1 ・ Vinyl chloride-vinyl acetate-hydroxyalkyl acrylate copolymer Gaku Co., Ltd., DV046, average degree of polymerization 860, hydroxyl value 46 KOHmg / g)                                                               15.0 copies ・ Methyl ethyl ketone 50.0 parts ・ Toluene 35.0 parts

[0029] (Example 2) Coating liquid V2 ・ Vinyl chloride-vinyl acetate-hydroxyalkyl acrylate copolymer (Nisshin Chemical Gaku Kogyo Co., Ltd., solvine TA2K, average degree of polymerization 780, hydroxyl value 58KOH mg / g) 15.0 parts ・ Methyl ethyl ketone 50.0 parts ・ Toluene 35.0 parts

[0030] (Example 3) Coating liquid V3 ・ Vinyl chloride-vinyl acetate-hydroxyalkyl acrylate copolymer Gaku Co., Ltd., DV046, average degree of polymerization 860, hydroxyl value 46 KOHmg / g)                                                               15.0 copies -Ethyl methacrylate polymer (Mitsubishi Rayon Co., Ltd., Dinal BR- 90) 5.0 copies ・ Methyl ethyl ketone 45.0 parts ・ Toluene 35.0 parts

[0031] (Example 4) Coating liquid V4 ・ Vinyl chloride-vinyl acetate-hydroxyalkyl acrylate copolymer (Nisshin Chemical Gaku Kogyo Co., Ltd., solvine TA2K, average degree of polymerization 780, hydroxyl value 58KOH mg / g) 15.0 parts -Ethyl methacrylate polymer (Mitsubishi Rayon Co., Ltd., Dinal BR- 90) 5.0 copies ・ Methyl ethyl ketone 45.0 parts ・ Toluene 35.0 parts

[0032] (Example 5) Coating liquid V5 ・ Vinyl chloride-vinyl acetate-hydroxyalkyl acrylate copolymer Gaku Co., Ltd., DV046, average degree of polymerization 860, hydroxyl value 46 KOHmg / g)                                                               15.0 copies -Ethyl methacrylate polymer (Mitsubishi Rayon Co., Ltd., Dinal BR- 90) 5.0 copies -Cellulose acetate butyrate (Eastman Chemical Co., CAB-38 1-0.1) 2.0 parts ・ Methyl ethyl ketone 43.0 parts ・ Toluene 35.0 parts

[0033] (Comparative Example 1) Coating liquid V6 -Vinyl chloride-vinyl acetate copolymer (VAGH manufactured by Union Carbide)                                                               15.0 copies ・ Methyl ethyl ketone 50.0 parts ・ Toluene 35.0 parts

[0034] (Comparative example 2) Coating liquid V7 ・ Vinyl chloride-vinyl acetate copolymer (Nisshin Chemical Industry, Solvain CN)                                                               15.0 copies ・ Methyl ethyl ketone 50.0 parts ・ Toluene 35.0 parts

A commercially available ink jet printer (MJ-8000C, manufactured by Epson Corp.) was used in the ink receiving layer of each recording material obtained as described above, using a non-aqueous pigment type ink jet ink containing glycol ether as a main solvent.
Was used to print at a resolution of 720 dpi, and the ink drying property, glossiness, and image reproducibility of the ink receiving layer were evaluated by the following measuring methods. Table 1 shows the evaluation results
Shown in.

(Drying property) The dryness of the touch of the above-mentioned printed matter immediately after printing was judged according to the following criteria. ⊚: The printed surface layer and the inside of the printed surface are well dried, and no ink stickiness is observed. X: The printing surface layer portion and the inside of the printing surface layer are poorly dried, and the ink is sticky.

(Glossiness) The glossiness of the above-mentioned printed matter was visually judged according to the following criteria. ⊚: The printed surface is glossy without clouding, whitening, or matting. X: The printed surface is clouded, whitened, and matted, and has no gloss.

(Image reproducibility) The image reproducibility of the printed matter was visually evaluated according to the following criteria. ⊚: No phenomena such as cracks and distortions on the printed surface are recognized, and the printing tone is reproducible comparable to the printed original. Poor: The printed surface was found to have cracks, distortions, etc., and there was no print reproducibility comparable to that of the printed document.

[0039]

[0040]

INDUSTRIAL APPLICABILITY The recording material of the present invention is excellent in the drying property, glossiness and image reproducibility of the printed matter after printing with respect to the non-aqueous pigment type ink jet ink. When used outdoors, it is possible to obtain sufficiently durable physical properties without laminating the plastic film that protects the printed surface.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Shuji Akeda             450 Aoto-cho, Midori-ku, Yokohama-shi, Kanagawa The             Inktech Co., Ltd. (72) Inventor Satoshi Tsunoda             450 Aoto-cho, Midori-ku, Yokohama-shi, Kanagawa The             Inktech Co., Ltd. F-term (reference) 2C056 EA13 FC06                 2H086 BA15 BA19 BA22 BA31 BA34                       BA35 BA41

Claims (8)

[Claims] 1. An inkjet recording material comprising an ink receiving layer formed on at least one surface of a substrate,
The ink receiving layer has an average degree of polymerization of vinyl chloride, vinyl acetate and hydroxyalkyl (meth) acrylate of 200 to 1100 and a hydroxyl value of 15 KOHm.
An inkjet recording material comprising a copolymer (a) of g / g or more. 2. The ink jet recording material according to claim 1, wherein the ink receiving layer further contains a polymer (a) other than (a) and / or a copolymer (b) comprising a (meth) acrylate. 3. The ink receiving layer further comprises an acetyl group of 3 to
The ink jet recording material according to claim 1 or 2, containing a cellulose acetate butyrate (c) containing 29.5 wt%, butanoyl group 17 to 50 wt% and hydroxyl group 1 to 3 wt%. 4. The ink-receiving layer contains 40% of the copolymer (a).
% To 90% by weight of the polymer and / or copolymer (b) and / or cellulose acetate butyrate (c) in a proportion of 10 to 60% by weight. Inkjet recording material. 5. The weight ratio of (b) / (c) is 1.0 /
The inkjet recording material according to claim 4, wherein the recording material is 1 to 5.0 / 1. 6. The hydroxyalkyl (meth) acrylate is at least one selected from hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and hydroxybutyl (meth) acrylate. Inkjet recording material according to the item. 7. The ink jet recording material according to claim 1, wherein the ink receiving layer further contains a leveling agent and / or a slip agent. 8. The substrate is a vinyl chloride resin film, synthetic paper, polypropylene, polycarbonate, polyester film, a polyester film treated with a primer, or a composite sheet of synthetic resin and woven cloth, non-woven cloth or knitted cloth. The inkjet recording material according to any one of 1 to 7.