JP2010115920A - Image recording method, and recorded matter obtained by the method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an image recording method converting entirely or partially image quality of a medium to be recorded, using an ink composition, in particular, an image recording method reducing partially glossiness of the medium to be recorded, and enhancing an expression effect of a recording medium, and recorded matter obtained by the image recording method. <P>SOLUTION: The glossiness of an area recorded with the ink composition is reduced by recording an image by the ink composition containing a metal compound or a hollow resin particle, in at least one area of the medium to be recorded having the glossiness. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an image recording method capable of changing the surface quality of a recording medium entirely or partially by a simple method.

  Conventionally, an image recording method using white ink is well known. That is, in Patent Document 1, an ink set for a color image including white ink used for a background process of a recording medium on which an image is formed or a complementary color process corresponding to a ground color of the recording medium is used, and the ink is used according to the ground color of the recording medium. An invention for controlling how white ink is applied is described. Thereby, a color image can be reproduced without being influenced by the ground color of the recording medium.

  Patent Document 2 describes an invention in which a translucent white ink composition containing an inorganic oxide pigment as a main component is fixed in advance to a portion on a recording material on which an image of a water-soluble dye ink is recorded. Thereby, when recording on non-coated paper such as plain paper or postcards using water-soluble dye ink, it is possible to record a high-quality image without blurring or showing back of the image.

  Patent Document 3 describes an invention in which a surface treatment of a recording medium is performed with a white ink containing a white pigment, a polymerizable compound, and a photopolymerization initiator. Accordingly, excellent printability can be exhibited even with plain paper and recycled paper having non-uniform ink absorbability, a transparent recording medium without ink absorbability, a recording medium with low brightness, and a recording medium with low whiteness.

  Further, Patent Document 4 discloses an inkjet image forming method in which an image is formed with a first ink containing a coloring material, and then the image is corrected with a second ink containing a white pigment. An invention characterized in that the two inks are not mixed is described.

JP 2002-38063 A JP 2001-171095 A JP 2004-18546 A JP 2005-125690 A

  By the way, a so-called special printing is known, which is a printing technique that gives a texture and feel that cannot be obtained by normal printing. Special printing is a technology that has been attracting attention in recent years, because it can increase the effect of expression by adding elements that appeal to the human senses to the printed matter, so that its use in the fields of magazines and posters is gradually increasing. It is characterized in that it can be printed not only on plain paper but also on almost any recording medium such as glass, synthetic resin, metal, etc., regardless of shape. For example, there is special printing that finishes the texture of “glazing” that gives gloss to the recording surface and “matte” that suppresses gloss.

  The inventions described in Patent Documents 1 to 4 are common in that white ink is used as the background, but as a special printing technique for adjusting the gloss of the recording medium as described above. It is not what has been done. Therefore, there is a need for a new recording method that uses a white ink composition and enhances the recording surface expression effect. Moreover, it is not restricted to the white ink composition of patent documents 1-4, The above expression effects can be heightened, employing the ink composition containing the coloring material which exhibits colors other than white. A recording method is also required.

Further, in recent years, there is an increasing demand for spot varnish techniques that partially change the surface quality of the recording medium. “Surface quality” includes, for example, glossiness, three-dimensionality, surface uniformity, and the like. In particular, if the surface quality of a recorded matter in which an arbitrary image such as a printed matter is formed in advance can be changed, the expression effect and method can be further enhanced.
Therefore, in recent years, in response to the increasing demand for the above technique, a method for easily converting the surface quality of the recording medium partially, and changing the recording medium having gloss to a matte tone is possible. Possible new methods are sought after.

  The present invention has been made in order to solve the above-described problems, and a method for completely or partially converting the surface quality of a recording medium using an ink composition, particularly for improving the gloss of the recording medium. An object of the present invention is to provide an image recording method that can be partially reduced and enhance the expression effect of the recording medium, and a recorded matter obtained by the image recording method.

The present invention is as follows.
(1) To reduce the gloss of the area where the ink composition is recorded by recording an image with an ink composition containing a metal compound or hollow resin particles in at least one area of the glossy recording medium. An image recording method characterized by the above.
(2) The image recording method as described in (1) above, wherein a ground image is recorded in advance in one area of the recording medium with a color ink composition.
(3) The image recording method according to (1), wherein an image of the ink composition in one area of the recording medium and an image in an area other than the one area are simultaneously recorded.
(4) The image recording method as described in any one of (1) to (3) above, wherein the color ink composition is overlaid and recorded in one area where the ink composition is recorded.
(5) A recorded matter obtained by the image recording method according to any one of (1) to (4) above.

  Note that the glossy recording medium includes a medium on which an image is recorded in advance and a medium on which nothing is recorded. Further, the background image is not limited to an image recorded by an ink jet printer, and may be another recording device such as a laser printer. The “glossy recording medium” in the present invention refers to, for example, 10 or more recording media in 60 degree glossiness measurement in Examples described later.

Even when a normal color image is recorded on a glossy recording medium such as photographic paper, coated paper, or a plastic substrate, the gloss of the recording medium is not absorbed by the color image. For this reason, the recorded matter is also a printed matter with high gloss. According to the image recording method of the present invention, an ink composition containing a general-purpose metal compound or hollow resin particles is recorded on a recording medium having a high glossiness, so that a matte-like recording can be performed easily or entirely. Can be done partially. In addition, matte color printing can be performed by recording the color ink composition on a matte surface quality portion formed of the ink composition as necessary.
Furthermore, the image recording method of the present invention can change the surface quality easily and partly even when the recording medium is a recorded material in which an arbitrary image such as a printed material is formed in advance. It is possible to partially convert a desired glossy area into a matte tone.

An embodiment of the image recording method of the present invention will be described. First, the ink composition used in the image recording method of the present invention will be described in detail.
[Ink composition]
Hereinafter, the ink composition in the present invention will be described in detail.

1. Metal Compound, Hollow Resin Particle The ink composition in the present invention contains a metal compound or hollow resin particles as a coloring material. In addition, although it is preferable that the metal compound and hollow resin particle which are the color materials of this invention are applied to a white ink composition as a white color material, you may exhibit other than white.

The metal compound in the present invention is not particularly limited as long as it is a metal atom-containing compound that can be used as a pigment, and is preferably a metal oxide, barium sulfate or calcium carbonate conventionally used as a white pigment. is there. Although it does not restrict | limit especially as a metal oxide, For example, titanium dioxide, a zinc oxide, a silica, an alumina, magnesium oxide etc. are mentioned. Of these, titanium dioxide and alumina are preferable.
The content of the metal compound is preferably 1.0 to 20.0% by mass and more preferably 5.0 to 10.0% by mass with respect to the total mass of the ink composition. When the content of the metal compound exceeds 20.0% by mass, reliability such as clogging of the ink jet recording head may be impaired. On the other hand, if it is less than 1.0% by mass, the color density such as whiteness tends to be insufficient.

  The average particle diameter (outer diameter) of the metal compound is preferably 30 to 600 nm, more preferably 200 to 400 nm. When the outer diameter exceeds 600 nm, the particles may settle and the dispersion stability may be impaired, and the reliability such as clogging of the ink jet recording head may be impaired. On the other hand, when the outer diameter is less than 30 nm, the whiteness tends to be insufficient.

  The average particle diameter of the metal compound can be measured by a particle size distribution measuring apparatus using a laser diffraction scattering method as a measurement principle. As the laser diffraction type particle size distribution measuring device, for example, a particle size distribution meter (for example, “Microtrack UPA” manufactured by Nikkiso Co., Ltd.) having a dynamic light scattering method as a measurement principle can be used.

  The hollow resin particles in the present invention preferably have a cavity in the inside thereof and the outer shell is formed of a resin having liquid permeability. With such a configuration, when hollow resin particles are present in the aqueous ink composition, the internal cavity is filled with the aqueous medium. Since the particles filled with the aqueous medium have a specific gravity almost equal to that of the external aqueous medium, the dispersion stability can be maintained without settling in the aqueous ink composition. Thereby, the storage stability and ejection stability of the ink composition can be enhanced.

  Further, when the ink composition of the present invention is ejected onto a paper or other recording medium, the aqueous medium inside the particles escapes during drying to form a cavity. When the particles contain air inside, the particles form a resin layer and an air layer having different refractive indexes, and effectively scatter incident light, so that white can be exhibited.

  The hollow resin particles used in the present invention are not particularly limited, and known ones can be used. For example, hollow resin particles described in specifications such as US Pat. No. 4,880,465 and Japanese Patent No. 3,562,754 can be preferably used.

  The average particle diameter (outer diameter) of the hollow resin particles is preferably 0.2 to 1.0 μm, and more preferably 0.4 to 0.8 μm. When the outer diameter exceeds 1.0 μm, the particles may settle and the dispersion stability may be impaired, and the reliability such as clogging of the ink jet recording head may be impaired. On the other hand, when the outer diameter is less than 0.2 μm, the whiteness tends to be insufficient. The inner diameter is suitably about 0.1 to 0.8 μm.

  The average particle diameter of the hollow resin particles can be measured by a particle size distribution measuring apparatus using a laser diffraction scattering method as a measurement principle. As the laser diffraction type particle size distribution measuring device, for example, a particle size distribution meter (for example, “Microtrack UPA” manufactured by Nikkiso Co., Ltd.) having a dynamic light scattering method as a measurement principle can be used.

  The content (solid content) of the hollow resin particles is preferably 5 to 20% by mass and more preferably 8 to 15% by mass with respect to the total mass of the ink composition. When the content (solid content) of the hollow resin particles exceeds 20% by mass, reliability such as clogging of the ink jet recording head may be impaired. On the other hand, when it is less than 5% by mass, the whiteness tends to be insufficient.

  The method for preparing the hollow resin particles is not particularly limited, and a known method can be applied. As a method for preparing the hollow resin particles, for example, a so-called emulsion polymerization method in which a hollow resin particle emulsion is formed by stirring a vinyl monomer, a surfactant, a polymerization initiator, and an aqueous dispersion medium while heating in a nitrogen atmosphere. Can be applied.

  Examples of vinyl monomers include nonionic monoethylenically unsaturated monomers such as styrene, vinyl toluene, ethylene, vinyl acetate, vinyl chloride, vinylidene chloride, acrylonitrile, (meth) acrylamide, (meth) acrylic acid esters, and the like. Can be mentioned. As (meth) acrylic acid ester, methyl acrylate, methyl methacrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl methacrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, lauryl (Meth) acrylate, oleyl (meth) acrylate, palmityl (meth) acrylate, stearyl (meth) acrylate and the like can be mentioned.

  Moreover, a bifunctional vinyl monomer can also be used as a vinyl monomer. Examples of the bifunctional vinyl monomer include divinylbenzene, allyl methacrylate, ethylene glycol dimethacrylate, 1,3-butane-diol dimethacrylate, diethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, and the like. By hollowly copolymerizing the above monofunctional vinyl monomer and the above bifunctional vinyl monomer and highly crosslinked, not only light scattering properties but also hollow properties with heat resistance, solvent resistance, solvent dispersibility, etc. Resin particles can be obtained.

  The surfactant is not particularly limited as long as it forms a molecular aggregate such as micelles in water, and examples thereof include anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants. Can be mentioned.

  As the polymerization initiator, a known compound soluble in water can be used, and examples thereof include hydrogen peroxide and potassium persulfate.

  Examples of the aqueous dispersion medium include water and water containing a hydrophilic organic solvent.

2. Fixing Resin The ink composition in the present invention preferably contains a resin for fixing the color material. Examples of such resins include acrylic resins (for example, Almatex (manufactured by Mitsui Chemicals)) and urethane resins (for example, WBR-022U (manufactured by Taisei Fine Chemical Co., Ltd.)).
The content of these fixing resins is preferably 0.5 to 10% by mass and more preferably 0.5 to 3.0% by mass with respect to the total mass of the ink composition.

3. Penetration Organic Solvent The ink composition in the invention preferably contains at least one selected from alkanediols and glycol ethers. Alkanediols and glycol ethers can enhance the wettability of a recording surface such as a recording medium and improve the ink permeability.

  Examples of the alkanediol include 1,2-butanediol, 1,2-pentanediol, 1,2-hexanediol, 1,2-heptanediol, 1,2-octanediol, 2-Alkanediol is preferred. Of these, 1,2-hexanediol, 1,2-heptanediol, and 1,2-octanediol having 6 to 8 carbon atoms are more preferred because of their particularly high permeability to recording media.

  The glycol ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol. Mention may be made of lower alkyl ethers of polyhydric alcohols such as monomethyl ether, triethylene glycol monobutyl ether and tripropylene glycol monomethyl ether. Among these, when triethylene glycol monobutyl ether is used, good recording quality can be obtained.

  The content of at least one selected from these alkanediols and glycol ethers is preferably 1 to 20% by mass, more preferably 1 to 10% by mass, based on the total mass of the ink composition.

4). Surfactant The ink composition according to the invention preferably contains an acetylene glycol surfactant or a polysiloxane surfactant. Acetylene glycol surfactants or polysiloxane surfactants can increase the wettability of a recording surface such as a recording medium to increase the ink permeability.

  Examples of the acetylene glycol surfactant include 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, 3, 5-dimethyl-1-hexyn-3-ol, 2,4-dimethyl-5-hexyn-3-ol and the like can be mentioned. Moreover, a commercial item can also be utilized for acetylene glycol type-surfactant, for example, Orphine E1010, STG, Y (above, Nissin Chemical Co., Ltd.), Surfinol 104, 82, 465, 485, TG (above , Air Products and Chemicals Inc.).

  Commercially available products can be used as the polysiloxane surfactant, and examples thereof include BYK-347, BYK-348 (manufactured by BYK Japan).

  Furthermore, the ink composition in the present invention can also contain other surfactants such as an anionic surfactant, a nonionic surfactant, and an amphoteric surfactant.

  The content of the surfactant is preferably 0.01 to 5% by mass and more preferably 0.1 to 0.5% by mass with respect to the total mass of the ink composition.

5). Polyhydric alcohol The ink composition in the invention preferably contains a polyhydric alcohol. When the ink composition of the present invention is applied to an ink jet recording apparatus, the polyhydric alcohol can suppress ink drying and prevent ink clogging in the ink jet recording head portion.

  Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, propylene glycol, butylene glycol, 1,2,6-hexanetriol, thioglycol, hexylene glycol, glycerin, and trimethylolethane. And trimethylolpropane.

  The content of the polyhydric alcohol is preferably 0.1 to 30% by mass and more preferably 0.5 to 20% by mass with respect to the total mass of the ink composition.

6). Tertiary amine The ink composition in the invention preferably contains a tertiary amine. The tertiary amine has a function as a pH adjusting agent and can easily adjust the pH of the ink composition.

  Examples of the tertiary amine include triethanolamine.

  The content of the tertiary amine is preferably 0.01 to 10% by mass and more preferably 0.1 to 2% by mass with respect to the total mass of the ink composition.

7). Solvent and Additive The ink composition in the invention usually contains water as a solvent. It is preferable to use pure water or ultrapure water such as ion exchange water, ultrafiltered water, reverse osmosis water, or distilled water. In particular, water obtained by sterilizing these waters by ultraviolet irradiation or addition of hydrogen peroxide is preferable because generation of mold and bacteria can be suppressed over a long period of time.

  The ink composition according to the present invention includes a fixing agent such as a water-soluble rosin, an antifungal / preservative such as sodium benzoate, an antioxidant / ultraviolet absorber such as an allophanate, a chelating agent, and an oxygen absorbing agent as necessary. Additives such as agents can be included. These additives can be used alone or in combination of two or more.

8). Adjustment Method The ink composition in the present invention can be prepared in the same manner as the conventional pigment ink using a conventionally known apparatus such as a ball mill, a sand mill, an attritor, a basket mill, a roll mill, or the like. In the preparation, it is preferable to remove coarse particles using a membrane filter or a mesh filter.

  The recording medium that can be applied to the image recording method of the present invention is not particularly limited as long as it is a recording medium having gloss. For example, a plastic substrate such as photographic paper, coated paper, sheet or film, glass, Examples include ceramics. Even if the material is not glossy, such as paper, cardboard, and textiles, the recording surface may be coated with a glossy ink composition. “Glossy recording medium” in the present invention refers to, for example, 10 or more recording media in 60 degree glossiness measurement in Examples described later.

  The use of the ink composition in the present invention is not particularly limited, but can be applied to various ink jet recording systems. Examples of the ink jet recording method include thermal jet ink jet, piezo ink jet, continuous ink jet, roller application, and spray application.

[Recordings]
The present invention can also provide a recorded matter in which the surface quality is changed entirely or partially by using the ink composition described above, in particular, the gloss is partially reduced and the expression effect is enhanced. .

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited at all by these. As an example of the ink composition in the present invention, a white ink composition containing a white metal oxide or white hollow resin particles as a color material was used in this example.

1. Preparation of white ink composition In the blending amounts shown in Table 1, hollow resin particles or metal oxides, resins, organic solvents, polyhydric alcohols, tertiary amines, surfactants, and ion-exchanged water were mixed and stirred to obtain pore sizes. Ink compositions 1 and 2 were obtained by filtration with a 5 μm metal filter and deaeration using a vacuum pump. In addition, the unit of the numerical value described in Table 1 is mass%, and all are converted into solid content about a metal oxide, a hollow resin fine particle, and a urethane resin particle.

  As the metal oxide, a commercially available product “NanoTek® Slurry” described in Table 1 (manufactured by CI Kasei Co., Ltd.) was used. NanoTek (R) Slurry is a slurry containing titanium dioxide having an average particle size of 36 nm as a solid content at a rate of 15%.

  As the hollow resin particles, commercially available products “SX8782 (D)” (manufactured by JSR Corporation) shown in Table 1 were used. SX8782 (D) is an aqueous dispersion type having an outer diameter of 1.0 μm and an inner diameter of 0.8 μm, and has a solid content concentration of 20.5%.

  As the urethane resin, “WBR-022U” (manufactured by Taisei Fine Chemical Co., Ltd.) polyester anionic polyurethane resin, Tg = −30 ° C.) was used.

2. Evaluation Method Each white ink composition shown in Table 1 was filled in a black ink chamber of a dedicated cartridge of an inkjet printer (“PX-G930” manufactured by Seiko Epson Corporation). The ink cartridge thus produced was mounted on a printer and a printing test was performed. Commercially available ink cartridges other than black (ICC33 cyan, ICM33 magenta, ICY33 yellow, ICR33 red, ICBL33 blue, ICGL33 gloss optimizer) were mounted.

  Next, output was performed at a resolution of 720 × 720 dpi on an inkjet recording sheet (“photographic paper <glossy”, “OHP sheet” manufactured by Seiko Epson Corporation, “PET film” manufactured by Toray Industries, Inc.). The printing pattern was 100% duty solid pattern for white printing and 100% duty solid pattern for color printing.

In this specification, “duty” is a value calculated by the following equation.
duty (%) = actual print dot number / (vertical resolution × horizontal resolution) × 100 (where “actual print dot number” is the actual print dot number per unit area, “vertical resolution” and “horizontal resolution”. (The resolution is per unit area. 100% duty means the maximum ink mass of a single color for a pixel.)

3. Glossiness Measurement Method The glossiness of one area recorded by each example was measured using MINOLTA MULTI GLOSS 268 (Minolta Co., Ltd.). As measurement conditions, the measurement angle was set to 60 degrees. Since the OHP sheet and the PET film are affected by the base during measurement, the measurement was performed using plain paper as the base. When the glossiness of plain paper was measured at a measurement angle of 60 degrees, it was 4.0.

  In Example 1, with respect to a recording paper (recording medium) on which a base image has been recorded in advance, a white ink composition is recorded on only one region of the recording paper so as to overlap the base image, and the white ink composition is recorded. The glossiness of one area was measured.

  In Example 2, the background image and the image of the white ink composition were simultaneously recorded on a non-recording recording paper on which the background image was not recorded. In this case, the inkjet printer can print simultaneously by combining the image of the color ink composition and the image of the white ink composition into one image data. In an area where the images overlap each other, only the image of the white ink composition needs to be taken out. Therefore, the white ink composition is directly recorded on one area of the recording paper. Thereafter, the glossiness of one area where the white ink composition was recorded was measured.

  In Example 3, after recording a base image with a color ink composition on a non-recording recording paper on which no base image is recorded, a white ink is applied to an area of the recording paper on which the base image is recorded. Images from the composition were recorded. In this case, in one area of the recording paper, an image of the white ink composition is recorded on the base image. Thereafter, the glossiness of one area where the white ink composition was recorded was measured.

  In Example 4, a non-recording recording paper on which no background image was recorded was recorded simultaneously with a background image and an image of a white ink composition, and then overlaid on the white ink composition. The thing was recorded. Therefore, the color ink composition is further recorded on the white ink composition directly recorded on one area of the recording paper. Thereafter, the glossiness of one region where the color ink composition was recorded on the white ink composition was measured.

  In Example 5, after recording a base image with a color ink composition on a non-recording recording paper on which no base image is recorded, a white ink is applied to one area of the recording paper on which the base image is recorded. An image of the composition was recorded, and a color ink composition was recorded on the white ink composition. In this case, in one area of the recording paper, an image of the white ink composition is overlaid on the base image, and further an image of the color ink composition is recorded. Thereafter, the glossiness of one region where the color ink composition was recorded on the white ink composition was measured.

  Table 2 shows the measurement results when the ink composition 1 was used for recording.

  Table 3 shows the measurement results when the ink composition 2 was used for recording.

Comparative Example 1 is a state in which nothing is recorded on the recording paper, and indicates the glossiness of the recording paper itself.
Comparative Example 2 shows the glossiness when only the base image of the color ink composition is recorded on the recording paper. According to Comparative Example 2, it can be seen that the glossiness of the recording paper is reduced only by recording a ground image with a normal color ink composition.

  As shown in Table 2 and Table 3, the glossiness obtained in Examples 1 to 5 resulted in a reduction in glossiness compared to Comparative Examples 1 and 2. Further, as in Examples 1 and 3 in Table 2, when the ink composition 1 is recorded on the base image, the glossiness of the recording paper can be further reduced. Further, in the case of the ink composition 1 shown in Table 2, as in Examples 1 and 3, the gloss when recorded on photographic paper <gloss> or PET film is 3.0, and the gloss of plain paper ( 4.0).

  In the case of the ink composition 1 shown in Table 2, the glossiness of one area where the ink composition 1 was recorded as in Examples 1 to 3, and the image of the color ink composition on the recording paper as in Comparative Example 2. The difference between the glossiness and the recording degree of only recording is remarkable in any recording paper. That is, the matte tone can be recorded only in one area of the recording paper, and only the matte portion can be expressed more characteristically than the other portions. For this reason, it can employ | adopt as another method of special printing, such as a poster and package printing.

  Further, as shown in Examples 4 and 5 of Table 2 and Table 3, a mat-like color partially reduced in gloss by recording an image of the color ink composition on the white ink composition. An image can be formed. Thereby, the variation of special printing can be increased and the recorded matter with a higher expression effect can be provided.

Claims (6)

  It is characterized in that the gloss of the area where the ink composition is recorded is reduced by recording an image with an ink composition containing a metal compound or hollow resin particles in at least one area of the recording medium having gloss. Image recording method.   2. The image recording method according to claim 1, wherein a base image is recorded in advance in one area of the recording medium with a color ink composition.   The image recording method according to claim 1, wherein an image of the ink composition in one area of the recording medium and an image in an area other than the one area are simultaneously recorded.   The image recording method according to any one of claims 1 to 3, wherein the color ink composition is overlaid and recorded in one area where the ink composition is recorded.   A recorded matter obtained by the image recording method according to claim 1.   A recording apparatus for recording an image by the image recording method according to claim 1.