JP4022834B2 - INK JET RECORDING BODY AND METHOD FOR PRODUCING INK JET RECORDING BODY - Google Patents

Description

  The present invention is suitable for high-quality image printing close to a photographic image because the dot diameter per ink droplet is small, and has excellent image storage stability because of excellent water resistance of the printed image, and absorbs ink quickly. The present invention relates to providing a recording sheet suitable for an inkjet printer.

  In recent years, with the widespread use of electronic still cameras, computers, and the like, hard copy technology for recording these images on paper has rapidly developed. The ultimate goal of these hard copies is silver salt photography, and in particular, how to bring color reproducibility, image density, gloss, weather resistance, etc. closer to silver salt photography has become a development issue. As a hard copy recording method, various methods such as a sublimation type thermal transfer method, an ink jet method, and an electrostatic transfer type method are known in addition to directly photographing a display displaying an image by a silver salt photograph.

  Inkjet printers have been rapidly spreading in recent years because they are easy to make full color and have low printing noise. The ink jet system ejects ink droplets from a nozzle toward a recording material at high speed, and includes a large amount of solvent in the ink. For this reason, a recording sheet for an ink jet printer is required to absorb ink quickly and to have excellent color developability.

  In addition, even when water is accidentally spilled on a printed image, the image is not erased or stained, and ink retention and water resistance of the ink receiving layer are required. In addition, in order to bring the image quality close to the silver halide photograph, which is the ultimate purpose of hard copy, it is required to reduce the dot diameter per droplet of ink. For this, the ink 1 ejected from the nozzle of the printer is used. In addition to reducing the amount per droplet, it is necessary that the ink does not spread on the surface of the receiving layer and maintains a perfect circle shape. However, the present situation is that an ink jet recording body satisfying all the above required characteristics has not been obtained.

  The present invention has a small dot diameter per ink droplet, and therefore is suitable for high-quality image printing close to a photographic image, and further excellent in water resistance of the printed image. An object of the present invention is to provide a recording sheet suitable for an ink jet printer capable of absorbing.

The present invention provides an ink jet coating in which an ink receiving layer is provided by applying and drying a coating liquid containing water, a hydrophilic resin, a crosslinking agent and a fluorosurfactant on at least one surface of a support via an anchor coat layer. The fluorosurfactant is localized on the surface of the ink receiving layer, and is recorded in the receiving layer by ESCA (light source: Mg—Kα ray (1254 eV), output: 9 kV × 30 mA). The area of the peak derived from fluorine, carbon, oxygen, and hydrogen present on the surface of the ink-receiving layer is observed on the surface of the ink-receiving layer, which is obtained by multiplying the area by the coefficient of detection sensitivity of each element and converting it to the number of atoms. Ri ratio of 10% to 30% der of the number of fluorine atoms to the number of all atoms, polyester resin between the support and the ink receiving layer, a polyurethane resin, or polyester urethane resin, It is an inkjet recording element, characterized that you have provided an anchor coat layer containing an acrylic resin.

  In a more preferred embodiment of the present invention, the ink receiving layer consists essentially of a crosslinking agent capable of crosslinking polyvinyl alcohol (PVA) and PVA, and in a more preferred embodiment, the crosslinking agent capable of crosslinking PVA is more than a melamine compound. It is to become.

  In a preferred embodiment of the present invention, the ink receiving layer includes a compound having a cationic group, and in a more preferred embodiment, the compound having a cationic group is a cation-modified PVA. It is a characteristic recording body.

In addition, the ink jet recording material is coated with a coating liquid containing water, a hydrophilic resin, a crosslinking agent and a fluorosurfactant on at least one surface of a support via an anchor coat layer , and dried to receive ink. A method for producing an ink jet recording body provided with a layer, wherein an anchor coat layer containing a polyester resin, a polyurethane resin, a polyester urethane resin, or an acrylic resin is provided between a support and an ink receiving layer, and the fluorine interface The addition amount of the activator is 0.05 to 20 parts by weight with respect to 100 parts by weight of the dry weight of the ink receiving layer, the initial stage drying temperature is not less than the boiling point of the solvent of the coating liquid and the boiling point is not more than + 30 ° C. The surface active agent is localized on the surface of the ink receiving layer, and the receiving layer is obtained by ESCA (light source: Mg-Kα ray (1254 eV), output: 9 kV × 30 mA). Obtain the area of the peak derived from fluorine, carbon, oxygen, and hydrogen present in the surface, multiply the area by the coefficient of detection sensitivity of each element, and convert it to the number of atoms, and observe it on the surface of the ink receiving layer It can manufacture by making the ratio of the number of fluorine atoms with respect to the number of all the atoms made into 10%-30%.

  The present invention quickly absorbs ink, is excellent in ink stickiness and water resistance when an image touches water, and is a recording material suitable for an ink jet printer having a small ink dot diameter.

In the present invention, the ratio of the number of fluorine atoms to the number of all atoms on the surface of the ink receiving layer (measured by ESCA) is 10% to 30%. As such an ink receiving layer, for example, a coating liquid containing a resin component and a fluorine compound is applied to a support and dried to localize the fluorine compound on the surface of the ink receiving layer .

  As the resin component, those conventionally known in this field may be used. For example, polyvinyl alcohol (PVA), acrylic resin, styrene-acrylic polymer, ethylene-vinyl acetate polymer, starch, polyvinyl butyral, gelatin, casein, Examples include gum arabic, carboxymethyl cellulose, polyvinyl pyrrolidone, polyacrylamide, polyester resin, phenol, melamine, epoxy, styrene-butadiene rubber and the like, and hydrophilic resins, especially PVA are most preferably used. Those having 1400 to 2500 and a saponification degree of 85 to 90 are most preferably used.

  In addition, the receptor layer is added with a compound having a crosslinkable functional group such as a melamine compound, an epoxy compound, an isocyanate compound, or a maleic anhydride copolymer, that is, a curing agent of the receptor layer. The water resistance is improved. Two or more kinds of such crosslinking agents can be used in combination. In the present invention, a water-soluble melamine compound is most preferably used. Moreover, it is also possible to use a catalyst for promoting the reaction as necessary.

  In the present invention, the ratio of the number of fluorine atoms to the total number of atoms observed on the surface of the ink receiving layer is observed by ESCA. Specifically, using an ESCA-850 manufactured by Shimadzu Corporation, Mg-Kα ray (1254 eV) is used as a light source, and the output is 9 kV × 30 mA. The atomic ratio of the surface layer is determined by weighting the detection sensitivity of each element to the electron energy spectrum intensity of the atoms present in the receiving layer.

  Although the reason why an excellent ink receiving layer is formed by limiting the abundance ratio of fluorine atoms on the receiving layer surface as described above is not clear, the receiving layer surface (especially the hydrophilic receiving layer surface) has a certain ratio. It is presumed that the spread of the ink can be suppressed and the absorptivity can be maintained by covering with a hydrophobic substance in a mosaic shape. If the atomic ratio is 10% or less, the effect of reducing the dot diameter of the ink is insufficient, and if it is 30% or more, the ink absorbability is lowered.

In the present invention, the existence ratio of the fluorine atoms of the receiving layer surface to the specified range, adding a full Tsu-containing surfactant in the receiving layer, the surface layer of fluorine-based compound in the ink receiving layer A method of selecting a condition that localizes to the above is used .

As a method for providing the coating layer, a conventionally used method such as a gravure coating method, a kiss coating method, a dip method, a spray coating method, a curtain coating method, an air knife coating method, a blade coating method, a reverse roll coating method, etc. can be applied. . Further, the temperature of the fluorinated particular drying early stage a surfactant as coating methods to localize near the surface layer is important, the drying temperature of the initial stage the coating liquid solvent boiling point above, boiling point + It is suitable to set at 30 ° C. or lower, preferably above the boiling point and boiling point + 20 ° C. If the initial drying is performed at a temperature higher than that, the surface layer of the coat layer is dried first, so that the surfactant is difficult to move to the surface layer.

  Examples of the fluorine-containing polymer compound include polytetrafluoroethylene and polyvinylidene fluoride. Examples of the fluorine-containing surfactant include perfluoroalkyl sulfonate, perfluoroalkyl carboxylate, and perfluoroalkylethylene oxide adduct. Perfluoroalkyltrimethylammonium salt, perfluoroalkylaminosulfonate, perfluoroalkylbetaine and the like. The addition amount is not particularly limited, but is 0.05 to 20 parts by weight, preferably 0.1 to 10 parts by weight, with respect to 100 parts by weight of the dry weight of the ink receiving layer.

  The amount of the crosslinking agent added in the present invention is not particularly limited, but is usually 0.5 to 10 parts by weight, preferably 1. 0 to 7.0 parts by weight. If it is less than 0.5 part by weight, the water resistance of the ink receiving layer tends to be insufficient, and if it exceeds 10 parts by weight, the ink absorption ability tends to be lowered.

  If desired, the ink-receiving layer may contain silica, kaolinite, talc, calcium carbonate, zeolite, alumina, barium sulfate, carbon black, zinc oxide, organic white pigment, benzoguanamine particles, crosslinked polystyrene, crosslinked acrylic particles, aluminum hydroxide. It is also possible to add particles such as, and the ink absorbency and surface gloss can be controlled by appropriately selecting the addition amount.

  In the present invention, the fixing property of the ink can be improved by adding a compound containing a cationic group to the receptor layer. The compound containing a cationic group used at this time is not particularly limited, and known compounds such as a cation-modified acrylic resin, a diallylamine derivative, and a diallyldialkylammonium chloride derivative can be used.

  The addition amount of the cationic group-containing ink fixing agent is not particularly limited, but is preferably 0.5 to 10 parts by weight, preferably 1 to 7 parts by weight with respect to 100 parts by weight of the dry weight of the ink receiving layer. It is. If the amount is less than 0.5 part by weight, the ink fixing ability is insufficient. Further, from the viewpoint of fixing properties of the ink, instead of adding the above-mentioned compound containing a cationic group, the above-described resin component, particularly a hydrophilic resin may be cation-modified, and cation-modified PVA is particularly preferable. Used.

The receiving layer may be a single layer or may have two or more layers. In the present invention, an anchor coat layer is provided between the support and the receiving layer to improve the adhesion between the support and the receiving layer. The material constituting the anchor coating layer, although polyester resins are preferred, Besides this, polyurethane resins, polyester urethane resins or acrylic resins are applicable.

  Anchor coat layer includes crosslinkers such as melamine resin, isocyanate, epoxy resin, silica, kaolinite, talc, calcium carbonate, zeolite, alumina, barium sulfate, carbon black, zinc oxide, titanium oxide, organic white pigment, benzoguanamine particles, Particles such as crosslinked polystyrene, crosslinked acrylic particles, and aluminum hydroxide may be added.

  The support in the present invention is not particularly limited, and any of transparent and opaque supports can be used. Natural paper, plastic film, synthetic paper, cloth, non-woven fabric, wood, metal, artificial leather, natural leather, In addition, those obtained by bonding two or more of these arbitrarily are mainly used. When a plastic film or synthetic paper is used, smoothness is high and a high gloss surface is obtained, so that it is more suitable for printing a high-quality image.

  Next, examples and comparative examples of the present invention will be shown. First, the measurement / evaluation method used in the present invention is shown below.

1) Ink absorbability Four colors were printed with an inkjet printer (MJ-700V2C manufactured by Seiko Epson Corporation), and the printed surface was rubbed with a finger after 1 minute. At this time, if the printed surface was not rubbed, it was rated as ◯, and if rubbed, it was marked as x.

2) Ink adhesion If four characters of alphabet letters are printed with an inkjet printer (MJ-700V2C manufactured by Seiko Epson Corporation), and after drying, the water drops are dropped on the printed letters, and if the water drops dry, the letters can be discriminated. ○, x if not possible.

3) Water resistance Four colors of alphabet letters were printed with an inkjet printer (MJ-700V2C, manufactured by Seiko Epson Corporation). After drying, water drops were dropped on the printed letters, left for 1 minute, and the printed part was rubbed with tissue paper. . At this time, if the print part was not detached, it was rated as ◯, and if it was detached, it was marked as x.

4) Dot diameter Four colors of single dots are printed with an inkjet printer (MJ-700V2C manufactured by Seiko Epson Corporation), and the printed image is observed under a microscope. The average value of the dot diameters of the four colors is determined as the dot diameter. did.

5) Fluorine atom surface coverage by ESCA Derived from fluorine, carbon, oxygen, nitrogen and hydrogen at an output of 9 kV × 30 mA using Mg-Kα ray (1254 eV) as a light source by ESCA (850) manufactured by Shimadzu Corporation The area of the peak was determined, and this area was multiplied by a coefficient depending on the detection sensitivity of each element, and converted into the number of atoms to determine the ratio.

Example 1
Coated polyester resin (Toyobo Co., Ltd. Byron MD-16) was coated with a wire bar (# 5) on the corona-treated surface of a polyester-based void-containing white film (Toyobo Co., Ltd., Crisper G2312, 100 microns). Dried.
On this coated surface, 20 parts by weight of polyvinyl alcohol (GH20 manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) was dissolved in 200 parts by weight of water, and a cationic multimer (Adeka thioace PD- 50) and water-soluble melamine (Sumitex Resin M3, manufactured by Sumitomo Chemical Co., Ltd.) were added in an amount of 0.4 and 1 part by weight, respectively, and a fluorosurfactant (Unidyne DS402, manufactured by Daikin Co., Ltd.) The mixed solution obtained by adding parts by weight was coated with a wire bar so as to be 10 g / m ² after drying, dried at 120 ° C. for 1 minute, then dried at 160 ° C. for 3 minutes, and cured for an inkjet recording film. Obtained.

Example 2
Coated polyester resin (Toyobo Co., Ltd. Byron MD-16) is coated with a wire bar (# 5) on the corona-treated surface of a polyester-based void-containing white film (Toyobo Co., Ltd., Crisper G2312, 100 microns). And dried.
On this coated surface, 20 parts by weight of cation-modified PVA (CM-318 manufactured by Kuraray Co., Ltd.) was dissolved in 200 parts by weight of water, and water-soluble melamine (Sumitex Resin M-3 manufactured by Sumitomo Chemical Co., Ltd.) was dissolved in this aqueous solution. 1 part by weight), and 0.8 parts by weight of a fluorosurfactant (Unidyne DS402 manufactured by Daikin Co., Ltd.) was added and dried in the same manner as in Example 1 for inkjet recording. A film was obtained.
The properties of the obtained film are shown in Table 1.

Comparative Example 1
In Example 1, an ink jet recording film was obtained in the same manner as in Example 1 except that the fluorosurfactant was not added.

Comparative Example 2
An ink jet recording film was obtained in the same manner as in Example 1, except that drying and curing were carried out at 160 ° C. for 4 minutes in Example 1. The properties of the obtained film are shown in Table 1.

Claims (6)

An ink jet recording medium in which a coating liquid containing water, a hydrophilic resin, a crosslinking agent and a fluorosurfactant is applied and dried on at least one surface of a support via an anchor coat layer and an ink receiving layer is provided. The fluorine-based surfactant is localized on the surface layer of the ink receiving layer, and fluorine existing in the receiving layer by ESCA (light source: Mg—Kα ray (1254 eV), output: 9 kV × 30 mA). The area of the peak derived from carbon, oxygen, and hydrogen is calculated, and the total number of atoms observed on the surface of the ink receiving layer is obtained by multiplying this area by a coefficient depending on the detection sensitivity of each element and converting to the number of atoms. ratio is 10% to 30% der of the number of fluorine atoms to the number of is, polyester resin between the support and the ink receiving layer, a polyurethane resin, a polyester urethane resin or acrylic tree, Inkjet recording element, characterized that you have provided an anchor coat layer containing fat.   The inkjet recording body according to claim 1, wherein the hydrophilic resin is polyvinyl alcohol (PVA), and the crosslinking agent is a crosslinking agent capable of crosslinking PVA.   3. The recording material according to claim 2, wherein the crosslinking agent capable of crosslinking PVA is a melamine compound.   The recording medium according to claim 1, wherein the ink receiving layer contains a compound having a cationic group.   5. The recording material according to claim 4, wherein the compound having a cationic group is cation-modified PVA. An ink jet recording medium in which an ink receiving layer is provided by applying and drying a coating liquid containing water, a hydrophilic resin, a crosslinking agent, and a fluorosurfactant on at least one surface of a support via an anchor coat layer . In the production method, an anchor coat layer containing a polyester resin, a polyurethane resin, a polyester urethane resin, or an acrylic resin is provided between the support and the ink receiving layer, and the amount of the fluorosurfactant added is determined by the ink receiving layer. 0.05 to 20 parts by weight with respect to 100 parts by weight of the dry weight, and the initial drying temperature is not less than the boiling point of the solvent of the coating solution and not more than the boiling point + 30 ° C. Fluorine, carbon, oxygen, hydrogen existing in the receiving layer by ESCA (light source: Mg—Kα ray (1254 eV), output: 9 kV × 30 mA) localized on the surface layer The number of fluorine atoms relative to the total number of atoms observed on the surface of the ink-receiving layer, obtained by calculating the area of the peak derived from, multiplying this area by the coefficient of detection sensitivity of each element, and converting to the number of atoms The manufacturing method of the recording body for inkjets characterized by making the ratio of 10 to 30%.