JP5305217B2 - Inkjet recording method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ideal ink jet recording method which is usable for a wide range of paper, full-color printable especially on commercial printing paper, inexpensive, and good in printing quality, allows easy printing at high speed on a textured material similar to commercial printing, and provides an excellent abrasion resistance with printed materials. <P>SOLUTION: The ink jet recording method includes the following processes: printing on a medium in use of ink including particulate color materials at ink adhesion of 15 g/m<SP>2</SP>or less; finger touch drying the image; thereafter fixing by contacting the medium directly with a heat source. The medium is comprised of: at least one or more pigment layers applied on at least one side of a substrate comprised primarily of cellulose pulp with a transferred amount of pure water to the medium at 1 to 30 ml/m<SP>2</SP>during contact time of 100 ms; and a transferred amount of pure water to the medium at 2 to 35 ml/m<SP>2</SP>during contact time of 400 ms, respectively measured by a dynamic scanning absorptometer. <P>COPYRIGHT: (C)2008,JPO&amp;INPIT

Description

  The present invention relates to a recording medium capable of recording a high-quality image close to commercial printing such as offset printing by an ink jet method, an ink media set, an ink jet recording method using the same, and an ink recorded matter.

Inkjet recording is known as an excellent recording method in which a recording material (medium) is not relatively selected, and research and development are actively conducted on a recording apparatus, a recording method, a recording material, and the like. In recent years, with the improvement in performance of printers, inks, and media, it has become possible to easily obtain image quality equivalent to silver halide photography. The evolution of media is particularly remarkable, and the current media developed to increase gloss while increasing the ink absorption speed and amount is at a level that surpasses conventional commercial printing in terms of gloss and quality. These ink-jet media can be roughly classified into a swelling type and a void type, but recently, a void type that is excellent in the drying speed of ink has been mainstream.
As disclosed in Patent Document 1 (Japanese Patent Application Laid-Open No. 2005-212327) and Patent Document 2 (Japanese Patent Application Laid-Open No. 11-078225), this void-type medium is formed on a substrate using silica or alumina hydrate. The mainstream is an ink absorption layer having a gap for taking in ink, and further provided with a porous gloss layer using colloidal silica as required. Due to this characteristic configuration, the ink absorbability is very excellent and a high-definition output can be obtained. Therefore, it is preferably used for a photographic output application for consumers. On the other hand, this type of media is very expensive compared to coated paper for general commercial and publishing printing because the raw materials are very expensive and the manufacturing process is complicated. Therefore, although the image is high quality, it is not so often used in commercial printing fields such as leaflets, catalogs, pamphlets, etc. that require a large amount of output at low cost. Various efforts have been made to reduce paper costs so far, but fillers that make up the ink absorbing layer (receiving layer) of inkjet media are usually capable of keeping the layer highly transparent and the amount of oil absorbed. Because it is necessary to use a material with a large (specific surface area), it is necessary to use a large amount of specific expensive fillers such as silica, alumina hydrate, colloidal silica, etc. is there.

  On the other hand, coats made at low cost by using a large amount of inexpensive, high concealing and relatively small oil absorption fillers such as calcium carbonate and kaolin for coated layer materials such as coated paper for commercial printing and publication printing. If you try to use paper as inkjet media, the image will bleed vigorously or the density will no longer appear. This is because coated paper for commercial printing is not designed to absorb a large amount of ink in a short time like inkjet paper. Even if soaked, the ink coloring material is concealed by a highly concealing filler such as kaolin in the coat layer. In addition, in coated paper for commercial printing and publishing printing using such a highly concealing filler, when printing with an ink jet printer using a dye ink, it exists near the surface layer, no matter how much ink is applied. Since only the density of the color material is produced, the density is low as a whole and the image has no contrast. For this reason, this type of paper has been considered to be completely unsuitable for ink jet printing.

  On the other hand, in recent years, ink-jet inks that use pigments instead of dyes as coloring materials have attracted attention. Colorant pigments are insoluble in water, so it is common to use fine particles dispersed in a solvent. However, pigment inks for inkjet use disperse colorant pigments in water from the standpoint of safety. It is the mainstream. In general, water-based pigment inks tend to cause aggregation and precipitation of pigment particles compared to dye inks, and various dispersion conditions and additives are necessary to achieve long-term storage stability comparable to dye inks. Since it causes kogation, it is difficult to use with a thermal head, and the colorant color range is inferior to that of dyes. However, from the viewpoint of high density, storage stability and water resistance after recording. , Has come to attract a lot of attention. Ink jet printers using this pigment ink may have the color material of ink close to that of general commercial printing ink, and the texture of the printed matter can be brought close to that of commercial printing. When printing on coated paper for commercial printing and publishing printing with the conventional inkjet printer used, the ink will not be absorbed in time and the image will blur, the pigment will not fix at all after drying, and the gloss will not appear As in the past, the reality is that only printing on media having high ink absorbability such as plain paper and ink jet dedicated paper can be handled. This is because the design philosophy relating to the formation of inkjet images is not different from the philosophy of using dye inks, and color material pigments are only taken from the viewpoint of dyes with high light resistance. It was because it did not consider at all. Research and development has also been conducted on pigment-ink compatible media, but as seen in Patent Document 3 (Japanese Patent Application Laid-Open No. 2001-347749), it is important to develop image gloss while speeding up ink absorption. On the other hand, a method of developing gloss while increasing the porosity of the media surface has been sought on the extension of the prior art using an expensive filler material.

On the other hand, as a method for solving these problems, a highly penetrating pigment ink as disclosed in Patent Document 4 (Japanese Patent Application No. 2006-43240), and a medium having a low ink absorbency, which is opposite to the conventional one, There is an example of realizing a low-cost image forming method on commercial printing paper or the like. That is, printing is performed using a small amount of ultra-high-penetration pigment ink on a recording medium provided with a coating layer for suppressing ink absorption (penetration) so that the colorant pigment in the ink does not penetrate as much as possible. As a result, only the solvent (water or organic solvent) that forms the ink is selectively soaked into the support, and only the color material (pigment) in the ink is efficiently used without using a special material such as a cationic fixing agent. Can stay on the media surface well. For this reason, not only can a sufficient amount of ink and dryness be achieved with a small amount of ink, but also the transparency of the layer, which was a necessary function of conventional inkjet media, by keeping the coloring material in the ink as much as possible on the surface of the media. Therefore, the degree of freedom regarding the material composition of the coating layer can be greatly expanded. By applying this method, it has become possible to perform ink jet printing even on paper having low ink absorption such as commercial printing paper and publication printing paper, which has been considered difficult until now.

On the other hand, when performing commercial printing or publishing printing, it is often necessary to output hundreds to thousands of copies at a time, even if it is a small number of copies, and stable images without image defects are continuously displayed on the printing press. It is required to be obtained. When an inkjet printer is used for such an application, problems that are particularly likely to be caused by problems such as nozzle clogging due to drying of the ink or bending of the ejection angle when the dried ink adheres to the periphery of the nozzle. This is the generation of image streaks. Various attempts have been made in the past to prevent this phenomenon. Regardless of dye ink or pigment ink, the most effective is to add a high-boiling-point wetting agent to the ink to make the ink dry. It is.
By the way, although the method of patent document 4 (Japanese Patent Application No. 2006-43240 specification) is recognized as being very effective for printing on paper with poor ink absorption, it can be used for media with extremely poor ink absorption, such as commercial printing paper. When ink combined with a high boiling point wetting agent is used to prevent printer head drying (nozzle clogging), the dryness of the image does not change much, but it does not bleed even when rubbed after drying. In addition, there is a drawback that it takes a very long time to “fix”. This is because the color material remaining on the surface layer is moistened for a long time while containing a small amount of wetting agent, and it takes just a long time for the offset printing ink using soybean oil to be fixed after printing. This is a similar phenomenon. With respect to the slowness of fixing, the pigment ink is particularly disadvantageous over the dye ink. In the case of ink-jet inks that are currently mainstream dye types, the colorant itself is likely to diffuse into the media, so wetting agents (which are often high-boiling solvents) also diffuse in a relatively short time. . Therefore, based on the method of Patent Document 4 (Japanese Patent Application No. 2006-43240) premised on the use of pigment ink, a printer using ink containing a high-boiling-point wetting agent in order to increase the reliability against image streaks. On the other hand, when printing was performed using commercial printing paper, fixing was time consuming, and in many cases it was inferior in convenience, such as being unable to deal with the case where it was desired to distribute it as a flyer or catalog immediately after printing.

  By the way, conventionally, various attempts have been made to improve the drying property and the fixing property of the ink jet printed material immediately after printing. In particular, when ink-jet technology began to be adopted for consumer products, heat drying was considered effective for improving the drying properties of ink and media. For example, Patent Document 5 (Japanese Patent Laid-Open No. 8-92513) proposes to heat and fix an image after printing using colored resin particles dispersed in fine particles. However, the main purpose of this example is to reduce the bleeding of paper with much bleeding such as recycled paper and copy paper, and the fixing also applies to paper with relatively fast ink absorption such as recycled paper and copy paper. . Patent Document 6 (Patent No. 2860123) describes that a heating roller is useful as a drying assisting means for ink-jet printed matter, but it has been proposed mainly for dye-based oil-based inks. There is no mention of pigment ink and commercial printing paper. In Patent Document 7 (Japanese Patent No. 2590822), a device is devised to improve the fixing property by heating the media after ink jet printing from the back side and promoting drying. According to this, it is stated that dry fixing is possible by heating from the back side. However, this method often has very poor thermal efficiency because the image cannot be directly heated, and is effective when drying a large amount of water contained in the entire media after printing, but a wetting agent (high boiling point solvent) in the image. In many cases, there is almost no effect. When trying to dry a high-boiling solvent, although it depends on the solvent, it must generally be heated at a high temperature such as hundreds of degrees, resulting in paper damage such as yellowing and deformation of the paper, and in the worst case ignition. It cannot be ignored and is not realistic at all.

  In the past, products that promote the drying of plain paper in inkjet printers using water-based ink by applying these technologies have been put on the market. However, unlike electrophotography, in the case of inkjet recording, a large amount of water contained in the ink is vaporized and fills the machine, causing problems such as condensation, corrosion, etc. Currently, except for printers for industrial use, which require very high-speed printing on a small amount of plain paper, for example, because drying assistance is no longer necessary for printing on paper or plain paper. The situation is almost disappearing. In addition, when an ink-jet printed matter is actually dried by using a drying process represented by the method of Patent Document 7 (Patent No. 2590822), the surface melts on part of the ink-jet dedicated paper and an image is deposited. It is known that there are things that can be trapped.

In recent years, as a part of movement, as shown in Patent Document 8 (Japanese Patent Laid-Open No. 2004-209799), an image receiving paper containing a thermoplastic resin on the outermost layer is subjected to a transparent / smoothing process by heating to give gloss to printed matter. There are examples and attempts to improve the image storability by adding a chemical substance that reacts with heat in the ink and media, and reacting by heating after printing, but all of them are subjected to heat treatment after printing. This is for the pre-supplied inkjet dedicated supply, and it does not enable application to general commercial printing paper.
As described above, the ink jet recording technology that can be used immediately by performing ink jet printing and fixing processing on commercial printing paper using water-based pigment ink has not been realized so far.

JP 2005-212327 A Japanese Patent Application Laid-Open No. 11-078225 JP 2001-347749 A Japanese Patent Application No. 2006-43240 JP-A-8-92513 Japanese Patent No. 2860123 Japanese Patent No. 2590822 JP 2004-209799 A

  The present invention has been made in order to solve the following problems in view of the above results. In other words, the ink jet recording method shown in the present invention has a wide paper adaptability, especially full-color printing is possible on commercial printing paper, is inexpensive, has good print quality, and has a texture close to that of commercial printed matter. An object of the present invention is to provide an ideal ink jet recording method in which an object can be printed easily and at high speed and the printed material is excellent in abrasion resistance.

The above object is achieved by the following means.
That is, (1) “pure water at a contact time of 100 ms measured with a dynamic scanning absorptiometer, having a single or multi-layer pigment layer coated on at least one surface on a support mainly composed of cellulose pulp. the transfer amount of the media is at 1 ml / ^{m 2} or more 1 0 ml / ^{m 2} or less, and the contact time in the recording medium transfer amount to the pure water medium is 2 ml / ^{m 2} or more 35 ml / ^{m 2} or less in 400ms against, printed below the ink adhesion amount 15 g / m ² by using an ink containing a particulate colorant, after the image was finger touch drying, those having the step of fixing by contacting the media with the heat source directly Ink jet recording method , wherein the ink contains at least water and a wetting agent, and the content of the wetting agent is 20 to 50% by mass ",
(2) “Inkjet recording method according to item (1), wherein the heat source uses a fixing roller that is a heat roller”;
(3) “Pure water medium with a contact time of 100 ms measured with a dynamic scanning absorptiometer is preferably 1 ml / m ² or more and 10 ml / m ² or less and the pure water medium at a contact time of 400 ms. to transfer the amount of 2 ml / m ² or more 11 ml / m ² or less is a recording medium to the first, characterized in that printing with solid content of 3% or more of the ink containing a particulate colorant (1 ) Or inkjet recording method according to item (2) ",
(4) “The inkjet recording method according to any one of (1) to (3) above, wherein the fixing temperature is 100 ° C. or higher, desirably 140 ° C. or higher and 150 ° C. or lower”;
(5) Any of the above items (1) to (4), wherein the nip time of the fixing roller is 0.3 seconds or more, preferably 0.5 seconds or more and 1 second or less. Or inkjet recording method according to
(6) “The inkjet recording method according to any one of Items (1) to (5), wherein a non-contact drying unit is used for drying the touch”,
(7) “In an ink jet recording apparatus in which a head unit provided with a nozzle for ejecting each color ink necessary for color printing on the surface of the recording medium is mounted and recording is performed by ejecting ink droplets on the surface of the recording medium. Items (1) to (6) are characterized in that an image is formed on a recording medium in which the spread of ink dots is small and agglomerates, and the ink adhesion amount is suppressed within a regulation value by a total quantity regulation process. ) Inkjet recording method according to any one of items
(8) The above-mentioned recording medium is composed of at least a base material and a coating layer, and the solid content of the coating layer is 0.5 to 20.0 g / m ^2. The inkjet recording method according to any one of Items (1) to (7),
(9) “The inkjet recording method according to any one of (1) to (8), wherein the recording medium has a basis weight of 50 to 250 g / m ² ”,
(10) "The inkjet recording method according to any one of (1) to (9) above, wherein the recording medium contains a pigment, and the pigment is kaolin",
(11) “The inkjet recording method according to any one of (1) to (9) above, wherein the recording medium contains a pigment, and the pigment is heavy calcium carbonate” ,
(12) "The inkjet recording method according to any one of (1) to (11) above, wherein the recording medium contains an aqueous resin";
(13) “The inkjet recording method according to item (12), wherein the aqueous resin is a water-soluble resin or a water-dispersible resin”;
(14) “The inkjet recording method according to any one of (1) to (13), wherein the ink is at least one selected from cyan ink, magenta ink, yellow ink, and black ink” ,
(15) In the above items (1) to (14), the method includes at least an ink flying step of applying a stimulus to the ink and flying the ink to form an image on the recording medium. Any inkjet recording method "
(16) “The inkjet recording method according to (15), wherein the stimulus is at least one selected from heat, pressure, vibration, and light”;
(17) “Inkjet recording method according to item (1), wherein an ink repellent layer is formed on a surface of an inkjet head used for inkjet recording on which an ink discharge opening is formed”. ,
(18) “The ink jet recording method according to item (17), wherein the ink repellent layer is made of a fluorine-based material or a silicone-based material”;
(19) "The inkjet recording method according to (17) or (18) above, wherein the surface roughness Ra of the ink repellent layer is 0.2 µm or less",
(20) “The cross-sectional area in a plane perpendicular to the center line of the opening in the vicinity of the opening of the ink-repellent layer is formed so as to gradually increase as the distance from the substrate surface increases. The inkjet recording method according to any one of (17) to (19),
(21) "The ink jet recording method according to any one of claims 17 to 20, wherein the ink repellent layer has a thickness of 1 mm or more",
(22) “The inkjet recording method according to any one of items (17) to (21), wherein the critical surface tension γc of the ink repellent layer is 5 to 40 mN / m”;
( 23 ) “The ink according to any one of (1) to (22), wherein the volume average particle diameter of the pigment or colored fine particles is 0.01 to 0.16 μm . Inkjet recording method ",
( 24 ) " The inkjet recording method according to any one of items (1) to (23) , wherein the ink has a viscosity at 25 ° C of 1 cps to 30 cps",
( 25 ) " The inkjet recording method according to any one of (1) to (24) above, wherein the ink has a surface tension at 25 ° C of 30 mN / m or less",
(26) "the ink comprises a water-soluble organic solvent in the ink, the water-soluble organic solvent, wherein the first (1, characterized in that any of 8 or more polyol compounds having a carbon number and glycol ether compounds ) To thirty-fifth (25) inkjet recording method ”,
( 27 ) "In the ink, the polyol compound having 8 or more carbon atoms is at least one of 2-ethyl-1,3-hexanediol and 2,2,4-trimethyl-1,3-pentanediol. The inkjet recording method according to item (26), wherein:
( 28 ) "The ink contains a surfactant, and the surfactant is selected from the following general formulas (I), (II), (III), (IV), (V), and (VI) The inkjet recording method according to any one of (1) to (27), wherein the inkjet recording method is characterized in that :

ただし、前記一般式（Ｉ）中、Ｒ^１は、アルキル基を表す。ｈは、３〜１２の整数を表す。Ｍは、アルカリ金属イオン、第４級アンモニウム、第４級ホスホニウム、及びアルカノールアミンから選択されるいずれか１つ以上の塩基を表す。

In the general formula (I), ^{R 1} represents an alkyl group. h represents an integer of 3 to 12. M represents one or more bases selected from alkali metal ions, quaternary ammonium, quaternary phosphonium, and alkanolamine.

ただし、前記一般式（II）中、Ｒ^２は、アルキル基を表す。Ｍは、アルカリ金属イオン、第４級アンモニウム、第４級ホスホニウム、及びアルカノールアミンから選択されるいずれか１つ以上の塩基を表す。

In the general formula (II), ^{R 2} represents an alkyl group. M represents one or more bases selected from alkali metal ions, quaternary ammonium, quaternary phosphonium, and alkanolamine.

ただし、前記一般式（III）中、Ｒ^３は、炭化水素基を表す。ｋは５〜２０の整数を表す。

In the general formula (III), R ³ is represents a hydrocarbon group. k represents an integer of 5 to 20.

ただし、前記一般式（IＶ）中、Ｒ^４は、炭化水素基を表す。ｊは、５〜２０の整数を表す。

In the general formula (IV), ^{R 4} represents a hydrocarbon group. j represents an integer of 5 to 20.

ただし、前記一般式（Ｖ）中、Ｒ^６は、炭化水素基を表す。Ｌ及びｐは、１〜２０の整

In the general formula (V), ^{R 6} represents a hydrocarbon group. L and p are an integer of 1 to 20

ただし、前記一般式（ＶI）中、ｑ及びｒは０〜４０の整数を表す。」、
（２９）「前記湿潤剤がポリオール化合物、ラクタム化合物、尿素化合物及び糖類から選択される少なくとも１種であることを特徴とする前記第（１）項乃至第（２８）項のいずれかに記載のインクジェット記録方法」、
（３０）「前記ポリオール化合物が、グリセリン、エチレングリコール、ジエチレングリコール、トリエチレングリコール、テトラエチレングリコール、ポリエチレングリコール、プロピレングリコール、ジプロピレングリコール、トリプロピレングリコール、１，３−ブタンジオール、２，３−ブタンジオール、１，４−ブタンジオール、３−メチル−１，３−ブタンジオール１，３−プロパンジオール、１，４−ブタンジオール、１，５−ペンタンジオール、１，６−ヘキサンジオール、２−メチル−２，４−ペンタンジオール、１，２，４−ブタントリオール、１，２，６−ヘキサントリオール、チオジグリコール、ペンタエリスリトール、トリメチロールエタン及びトリメチロールプロパンから選択される少なくとも１種である前記第（２９）項のいずれかに記載のインクジェット記録方法」、
（３１）「前記ラクタム化合物が、２−ピロリドン、Ｎ−メチル−２−ピロリドン、Ｎ−ヒドロキシエチル−２−ピロリドン及びε−カプローラクタムから選択される少なくとも１種である前記第（２９）項または第（３０）項のいずれかに記載のインクジェット記録方法」、
（３２）「前記尿素化合物が、尿素、チオ尿素、エチレン尿素及び１，３−ジメチル−２−イミダゾリジノンから選択される少なくとも１種である前記第（２９）項乃至第（３１）項のいずれかに記載のインクジェット記録方法」、
（３３）「前記糖類が、マルチトース、ソルビトース、グルコノラクトン及びマルトースから選択される少なくとも１種である前記第（２９）項乃至第（３２）項のいずれかに記載のインクジェット記録方法」、
また、（３４）「前記インクは、インクカートリッジに充填されたものであることを特徴とする第（１）項乃至第（３３）項のいずれかに記載のインクジェット記録方法」。

However, q and r represent the integer of 0-40 in the said general formula (VI). "
(29) "the wetting agent is a polyol compound, a lactam compound, according to any one of paragraph (1), second (28) section, wherein the at least one selected from urea compounds and saccharides Inkjet recording method ",
( 30 ) "The polyol compound is glycerin, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-butanediol, 2,3-butane. Diol, 1,4-butanediol, 3-methyl-1,3-butanediol 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl Before being at least one selected from -2,4-pentanediol, 1,2,4-butanetriol, 1,2,6-hexanetriol, thiodiglycol, pentaerythritol, trimethylolethane and trimethylolpropane The (29) The ink jet recording method according to any one of Items "
( 31 ) [ Item (29) wherein the lactam compound is at least one selected from 2-pyrrolidone, N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone and ε-caprolactam. Or the inkjet recording method according to any one of (30), "
( 32 ) “In the above items (29) to (31) , the urea compound is at least one selected from urea, thiourea, ethylene urea, and 1,3-dimethyl-2-imidazolidinone . Inkjet recording method according to any one of "
( 33 ) " The inkjet recording method according to any one of items (29) to (32) , wherein the saccharide is at least one selected from maltose, sorbitol, gluconolactone, and maltose".
( 34 ) “The ink jet recording method according to any one of items (1) to (33), wherein the ink is filled in an ink cartridge ”.

  As is clear from the following detailed and specific description, according to the present invention, when performing ink jet recording, it is possible to provide a recording method with good print quality, high speed, low cost, and high reliability. It has an extremely excellent effect that it has become possible.

Hereinafter, the ink jet recording method of the present invention will be described in detail.
As a result of intensive research on low-cost, high-speed inkjet recording methods, we have developed highly penetrating pigment inks and media with poor ink penetrability, especially commercial printing media and publication printing media coated with white pigments. By using the combination and post-processing technique, the inventors have invented a low-cost and on-demand image forming method based on a new design concept.

  That is, in the ultra-high penetration ink of the configuration of the present invention, a small amount of the solvent in the ink penetrates in a certain speed range, but does not permeate the color material particles while regulating the amount of ink used. After creating a combination of methods that can produce high-quality images even with ink, ensure the carrier absorption time in a non-contact state (preliminary drying), and then contact the heat source directly to damage the substrate. The present inventors have found that sufficient handling can be realized even immediately after ink jet printing by subjecting only the color material that forms an image to dry fixing processing.

  Conventionally, when it is desired to perform high-speed drawing without incurring costs in ink jet recording, it is most effective to increase the size of ink droplets to be used and draw with a reduced resolution. That is, the image created at 1200 dpi is reduced to 600 dpi. At this time, the ink droplet amount set for 600 dpi is usually determined on the premise that printing is performed on a medium that absorbs ink. That is, when it is desired to reproduce a dot diameter that is twice as large as when a dot is formed with a small droplet, a droplet having a droplet diameter nearly twice as large is ejected. At this time, in order to improve the filling, the drawing is performed so as to overlap with the adjacent dots little by little. Assuming that the ink droplet is spherical, if the droplet diameter is doubled, the amount of the droplet increases by about 2.8 times. Therefore, reducing the resolution to ½ is very disadvantageous for ink absorption. Adopting this method for media with slow ink absorption such as offset printing paper coated with conventional low viscosity, low penetrability and easy to mix with other colors will make adjacent dots easily Fusion will cause bleeding in beading and color boundaries. On the other hand, if the interval is set so as not to be fused with the adjacent dots, the dots are not filled, and the image quality is greatly lowered, for example, the image density is lowered or the graininess is conspicuous. Also, when creating secondary and tertiary colors, control is performed to avoid placing dots at the same address as much as possible in image formation. However, due to the problem of dot position accuracy, dots appear to land at the same address. If you want an image with a high density, it is necessary to place a drop at the same address, which causes more severe bleeding and beading.

The ink of the present invention has been invented in view of these points, and has excellent wettability due to its low surface tension compared to ordinary inkjet ink, and has carrier permeability even for media with few pores. It is strong and exhibits a characteristic that the ink viscosity is greatly increased only by penetration of a small amount of carrier. For this reason, conventionally, it is difficult to fuse with adjacent dots after landing even on media with poorly penetrable properties where adjacent dots can be easily fused, and stable dot formation is possible. Further, since the color material hardly penetrates into the medium and remains on the surface, it is not necessary to place drops on the same address, and sufficient color development and image density can be obtained even with a very small amount of ink in total.
In this way, drawing with a much smaller amount of ink than before can be used to reduce the amount of carrier to penetrate the media, and not only curling and cockling but also the stiffness of the paper after printing can be printed. Since it is almost the same as before, even media that do not take ink absorption into consideration, such as commercial printing paper, can be printed without damaging the substrate.

  After the ink droplet is placed on the surface of the medium, when the absorption of the carrier is completed, the coloring material is set in a state where a trace amount of the wetting agent is contained. It looks just after offset printing with ink using soybean oil. At this time, the image does not bleed even if it is lightly touched, but is in a state where it is transferred when it is rubbed or a strong pressure is applied. In the present invention, by applying a temperature of 100 ° C. or higher to the image (coloring material) in contact with the heat source in this state, only the wetting agent in the coloring material is effectively diffused inside the medium, and there is no offset of the coloring material. We found that fixing was completed in a very short time. Conventionally, when such a method is used for the pigment ink, the transfer of the coloring material to the heating member is intense and practically difficult, but the ink of the present invention has a high cohesive force and a low surface tension. Color material transfer to the contact member hardly occurs, and heat fixing by the contact member is possible. As a heat fixing method, heating by direct contact is the most effective from the viewpoint of heat efficiency and heating only the wetting agent in the coloring material. Further, only the coloring material needs to be heated, and there is no need to dry the entire medium. Therefore, problems of substrate damage and water vapor condensation can be prevented.

<Media conditions>
As an index as to whether or not it is suitable as a medium of the present invention, it can be determined by a transfer amount of pure water of a dynamic scanning absorption meter. That is, the transfer amount of the recording medium of pure water at the contacting time 100ms was measured 1 ml / ^{m 2} or more 30 ml / ^{m 2} or less by a dynamic scanning absorptometer, and the recording medium of pure water at the contacting time 400ms The transfer amount to is 2 ml / m ² or more and 35 ml / m ² or less. The media coat layer that satisfies this condition can be regarded as having the function of the coat layer of the present invention, and when combined with the ink of the present invention, the so-called “cut” is good, the character, the peripheral portion of the image is blurred, A recorded image having high optical density (OD) without feathering and bleeding can be obtained. If the amount of water absorption is larger than this, the coloring material will permeate into the layer or the base material, so that the coloring material is concealed in the coat layer pigment, and a high-density image cannot be obtained.
Such a coating layer of the recording medium of the present invention is composed mainly of a resin binder and a pigment, but by making the resin blending amount rich, the pigment blending amount is made rich so that the transfer amount decreases. It is possible to adjust the direction in which the amount of transfer increases in the direction. Also, the amount of transition can be increased by increasing the specific surface area of the pigment particles constituting the coat layer, for example, by reducing the particle size or using a pigment having a large specific surface area.
The function necessary for the image processing method of the present invention and the coating layer of the present invention is to separate the pigment and the solvent in the ink and allow only the solvent to penetrate into the substrate. For this purpose, the coating layer has pores. It is desirable to take a fine structure. If there is no fine structure in the coating layer, the penetration of the solvent component in the ink is delayed, and the phenomenon that the ink does not dry easily occurs. However, if there are too many fine structures, the function of separating the colorant pigments in the ink will be reduced, resulting in a decrease in image density, or the colorant pigments present on the media surface after printing will migrate inside the media over time. Cause color changes. Any commercial printing paper or publication printing paper can be used as long as these conditions are satisfied.

In the recording medium, the transfer amount of the ink of the present invention to the recording medium at a contact time of 100 ms measured with a dynamic scanning absorption meter is ² to 40 ml / m ² , and 3 to 30 ml / m. ² is preferred. Further, the amount of transferred to the recording medium of the pure water is preferably ^{1~30ml / m 2, 1~10ml / m} 2 is more preferable.
If the transfer amount of the ink and pure water at the contact time of 100 ms is too small, beading is likely to occur. If it is too large, the ink dot diameter after recording becomes too smaller than the desired diameter. There is.
Transfer amount of said to the recording medium of the ink of the present invention in a dynamic scanning liquid absorption contact time measured by the meter 400ms is ^{3~50ml / m 2, 4~40ml / m} 2 is preferred.
The transfer amount of pure water to the recording medium is preferably ² to 35 ml / m ² , and more preferably ² to 11 ml / m ² .
If the amount of transfer at the contact time of 400 ms is too small, the drying property is insufficient, so that spur marks are likely to occur. May become low.
Here, the dynamic scanning absorptiometer (DSA, Papa-Pagi Technical Journal, Vol. 48, May 1994, pp. 88-92, Kuju Shigenori) absorbs liquid in a very short time. It is a device that can measure accurately. The dynamic scanning absorption meter reads the liquid absorption speed directly from the movement of the meniscus in the capillary, makes the sample a disk, and then scans the liquid absorption head in a spiral shape, and the scanning speed according to a preset pattern. Is automatically changed by a method in which the number of necessary points is measured with one sample. A liquid supply head for a paper sample is connected to a capillary via a Teflon (registered trademark) tube, and the position of the meniscus in the capillary is automatically read by an optical sensor. Specifically, the transfer amount of pure water or ink was measured using a dynamic scanning absorption meter (K350 series D type, manufactured by Kyowa Seiko Co., Ltd.). The transfer amount at the contact time of 100 ms and the contact time of 400 ms can be obtained by interpolation from the measured value of the transfer amount at the contact time adjacent to each contact time. The measurement was performed at 23 ° C. and 50% RH.

<Ink adhesion amount>
In the present invention, it is necessary to strictly limit the total amount of ink in order to prevent the color material from penetrating into the ink and efficiently distribute it in the vicinity of the surface of the medium while ensuring the drying property of the ink. The total amount of ink is an important parameter when forming an image, and indicates the amount of ink per unit area when forming a solid image with the highest density. In the present invention, by defining the total amount of ink, it is possible to form a uniform image with less beading and bleeding even on media with poor ink absorption. Conversely, exceeding this upper limit and using a large amount of ink as in conventional ink jet recording, the color material separation ability of the coat layer cannot catch up, and the ink color material pigment penetrates along with the ink solvent, Since the permeation of the solvent component of the ink is not in time and the image formation is greatly hindered, a high quality image cannot be obtained.
Specifically, in the case of using the ink of the present invention, the maximum ink adhesion amount (ink total amount regulation value) at the time of image creation may be 15 g / m ² , and image formation is performed with an ink adhesion amount lower than that. It is possible to obtain a very high-quality image without any padding or bleeding. It was also found that it is desirably 12 g / m ² or less.
This is different from the combination of the conventional dye ink and the ink jet dedicated media. In the case of the pigment ink and the media of the present invention, the color material is present in the form of being deposited on the surface of the media, which is necessary to cover the surface of the media. If there is an amount of color material, not only is the color material more wasted, but even with the highly penetrating ink of the present invention, excess ink solvent interferes with adjacent dots, causing beading and bleeding. It is because it ends up.
In particular, even if the ink of the present invention is used, if the total amount regulation value of the ink is set high as in the case of the conventional ink jet recording, a large amount of ink is used in the solid portion and the shadow portion, and the color material separation of the media The image is blurred and the drying property is greatly reduced.
The total amount of ink used for image formation according to the present invention is extremely small compared to the conventional ink jet recording method even when the image density is required, and unlike the conventional ink jet media, the ink absorbability itself of the medium is low. The color material tends to spread evenly on the media surface. In other words, since the ink spreads thinly on the surface of the media, it can be dried and bleed and beading are difficult to occur even if the ink absorption capability is low.

Further, the amount of penetration of the carrier can be easily adjusted by the amount of penetrating agent (EHD) and the amount of addition of FS300 which is a fluorosurfactant. Furthermore, by reducing the total amount of ink required for printing, the capacity of the ink cartridge can be reduced compared to the conventional ink jet printer, and the apparatus can be made compact. Further, if the cartridge size is the same as the conventional one, the replacement frequency of the ink cartridge can be reduced, and printing at a lower cost is possible.
Basically, the smaller the total amount of this ink, the better the pigment separation ability of the coat layer. It is desirable to set the total amount of ink within this range.

<Total amount regulation>
Next, the “total amount restriction” process will be described.
The total amount restriction process is as shown in FIG. The total amount regulation value shown here is a result of an evaluation that does not cause a phenomenon that occurs due to excessive ink adhesion, for example, ink overflow (beading) or scraping, transfer, or paper jam that occurs due to reduced cockling resistance. This is the amount of ink droplets to be obtained.
As a method of defining the total amount regulation value, for example, it can be expressed by a droplet amount (unit: pl) in a mask size of 600 × 600 dpi 100 × 100.
As the total amount restriction value in the case where printing is performed on the recording medium, which is carried out in the present invention, the applicant has conducted an experiment, the same as the total amount restriction value of plain paper, A drop volume of about 55% of the value is reasonable. In addition, the event that the total amount restriction process is actually applied is a case where the drop amount obtained from the input value is larger than the total amount restriction value. In this case, the Bk ink drop amount is stored, and the ink drop amount of each CMY color is stored. By reducing the amount, the amount of droplets is controlled to be less than the total amount regulation value. The order of the total amount restriction processing unit and the γ table can be reversed.
In the present invention, the total amount of ink was measured using a gravimetric method. Specifically, a 5cm x 20cm rectangular solid image is printed at the highest density on Superfine exclusive paper (manufactured by Epson), which is dedicated for inkjet printing, and the weight is measured immediately after printing, and the weight before printing is subtracted. Was multiplied by 100 to obtain the total amount of ink.

<Heat treatment>
Known means can be used as the fixing device for heating in direct contact with the image. In particular, as shown in FIG. 2, at least one of the pair of rollers (1) and (2) in pressure contact with each other is unfixed by a roller pair incorporating a heater (4) having a heating filament (3) over the entire length of the roller. A heat roller fixing device that holds and conveys the paper (5) carrying the image and fixes the image on the paper is effective. The heat fixing method using a heat roller is most widely used for a copying machine or the like because of its high thermal efficiency and safety. This is because the two rollers are pressed against each other, at least one of the rollers is heated, and the image support (recording paper) is passed through the pressure-contact portion (nip portion) of the two rollers to heat and support the image. It is a method of fixing to the body. When one of the two rollers is heated, the heating roller is called a fixing roller, and the other roller is called a pressure roller. Inside the fixing roller, a heat source such as a halogen lamp or an electric heater is provided in the axial direction of the fixing roller. A temperature sensor is attached to the outer surface of the fixing roller, and the amount of power supplied to the heat source is controlled so that the temperature of the nip portion is maintained at a temperature suitable for fixing.
The heater detects the surface temperature of the roller by temperature detection means (6) such as a thermistor that contacts the peripheral surface of the roller incorporating the heater, and is controlled to blink so as to maintain a predetermined temperature. In this case, as shown in FIG. 3, the heater of the heat roller fixing device usually has a heater (4) having one heating filament (3) over its entire length in the fixing roller (1), and the length of the fixing roller. The blinking of the heating filament (3) is controlled by a signal from the temperature detection means (6) in contact with the peripheral surface of the roller near the center of the roller.
Conventionally, in such a heat-fixing type fixing device, it has been difficult to make the temperature distribution in the axial direction uniform, but a region through which a small-sized heated material such as B5 or A4 size recording paper passes In the (paper passing area), heat is consumed for heating the heated material. However, in the non-paper passing area, heat is not consumed for heating the heated material. The temperature of the nip portion of the paper becomes higher than the temperature of the nip portion in the paper passing portion area that is maintained at a predetermined temperature.
Therefore, when a large-size heated material is passed after passing a small-size heated material continuously (for example, when passing an A4-sized paper after passing an A4-sized paper continuously) There may be problems such as fixing unevenness or wrinkles on the heated material, or the coloring material melts and adheres to the fixing roller, and the surface of the heated material is soiled (this phenomenon is called hot offset).

  For the purpose of improving the above disadvantages, a heater that changes the heat generation length according to the sheet passing width and a roller using the heater can also be used. An example of the configuration is shown in FIGS. In FIG. 4A, the heater (11) whose length of the heating filament (10) is longer than the maximum size sheet passing width and the heater (13) whose length of the heating filament (12) is short and is only at the center portion. Two heaters are provided in the fixing roller (1) as shown in FIG. 5, and switching between full lighting and partial lighting is performed by switching the heater to be used. In the example shown in FIG. 4 (b), a dual filament in which a branch circuit is provided in the filament at both ends of the central portion of the heat generating filament (14), and all lighting is switched to partial lighting using the same filament. Heater (15). Also in this case, the heat generation length when all the lights are on is set longer than the width of the maximum size paper. Further, the partial lighting length is set slightly longer than the paper passing width of the small size paper.

FIG. 5 is a diagram showing the relationship between the heater of the two heater system and the sheet passing width. In either case of this method or the dual filament method, the temperature detection is performed so that the full lighting is performed when the large size paper (7) is passed, and the partial lighting circuit is provided in contact with the central portion of the roller when the small size paper (8) is passed. Flashing is controlled by means (6), for example, a thermistor.
The surface of the fixing roller is made of fluorine resin such as silicon, silicon rubber, or Teflon (registered trademark), or urethane rubber, natural rubber, or metal roller with silicone resin or fluorine resin with excellent releasability. Although what was coated is used, it should just be excellent in ink repellency and thermal stability, and is not limited to these.
These thermal fixing devices may be integrated with the printer or may be a separate housing, and can be used by connecting to the printer when necessary.

<Dry touch>
After the image is printed by the printer, the carrier in the ink needs to be permeated to some extent before the image is fixed by the above-described thermal fixing device. In particular, it is necessary to increase the viscosity so that water or a low-viscosity solvent in the ink penetrates and the color material on the medium is not transferred to the heating member. For this reason, it is necessary to ensure a dry touch time for a few seconds immediately after printing.
In the case of using the medium of the present invention, it is desirable that this finger touch drying time be secured for 5 seconds or more in an environment of 25 ° C. and 50% after ink has landed on the medium, and more desirably 15 seconds or more. This time can be long, but it has a negative impact on productivity. In order to shorten this time, it is effective to apply heat from the outside, and known non-contact heating such as a hot air dryer, a dryer, and a microwave can be used. The hot air generating device may be a commercially available device, and a hot air generating device (manufactured by Tsunashima Seisakusho) or a hair dryer can also be used.
When hot air is used, no effect can be expected at 40 ° C. or lower. On the other hand, if the air temperature is too high, the media will be damaged, so it is desirable that the temperature is 180 ° C. or lower.

<Ink fixing agent>
Further, as a condition of the pigment ink of the present invention, it is desirable that the ink contains a resin component that promotes fixing of the colorant pigment. The resin component that promotes fixing is to maintain the adhesive strength between the color material pigment and the media surface or between the color material pigments at a certain level or more, and without the resin component, the color material pigment is easily peeled off after printing. Therefore, a fixing agent should be used when higher image reliability is required. The fixing component may be contained alone in the ink or may be adsorbed and chemically bonded to the surface of the color material particles. The fixing agent may be a low molecular weight material, but is preferably a resin, a resin emulsion, or an ultraviolet curable resin.

<Ink surface tension>
In addition, as a condition of the pigment ink essential to the present invention, it must be very penetrable, and it has been found that the surface tension is 30 mN / m or less. If the surface tension is greater than 30 mN / m, a phenomenon in which the ink permeates slowly and the image blurs occurs, so that a high-quality image cannot be obtained. The lower the surface tension, the better the separation ability between the pigment and the solvent. The surface tension of the ink can be easily adjusted by the amount of penetrating agent (EHD) and the amount of fluorine surfactant FS300 added.
The ultra-high penetration ink of the present invention can be printed on a conventional void-type inkjet-dedicated medium. However, since the ink absorption speed is too high compared with the case of printing on the recording medium of the present invention, the solvent penetrates before the dots spread out after the ink droplets have landed on the medium surface, and the dot diameter becomes smaller. End up. As a result, a decrease in density and an increase in graininess are likely to occur. Therefore, in order to create a high-quality image, it is necessary to print at a higher resolution than that of the recording medium of the present invention, resulting in a decrease in printing speed and an increase in ink consumption. Therefore, it is preferable to use the recording medium of the present invention.
The ink has a surface tension at 25 ° C. of 15 to 30 mN / m, and more preferably 15 to 25 mN / m. When the surface tension is less than 15 / m, the nozzle plate of the present invention is too wet to form ink droplets (particulate), or bleeding on the recording medium of the present invention becomes remarkable and stable. Ink ejection may not be obtained, and if it exceeds 30 mN / m, ink penetration into the recording medium does not occur sufficiently, and beading may occur and drying time may be prolonged.
Here, the said surface tension can be measured at 25 degreeC using a platinum plate, for example using a surface tension measuring apparatus (Kyowa Interface Science Co., Ltd. product, CBVP-Z).

<Solid content of ink>
The solid content of the ink of the present invention is desirably 3 wt% or more. If it is lower than this concentration, the viscosity increase during drying tends to be gradual and the image tends to blur. The higher the value, the better. However, if the value is too high, nozzle clogging becomes severe, and the image is liable to be lost. Therefore, it is preferably 5 to 15 wt%.

Media coat layer-Coating layer-
The coating layer contains a pigment and a binder (binder), and further contains a surfactant and other components as necessary.
As the pigment, an inorganic pigment or a combination of an inorganic pigment and an organic pigment can be used.

Examples of the inorganic pigment include kaolin, talc, heavy calcium carbonate, light calcium carbonate, calcium sulfite, amorphous silica, titanium white, magnesium carbonate, titanium dioxide, aluminum hydroxide, calcium hydroxide, magnesium hydroxide, Examples thereof include zinc hydroxide and chlorite. Among these, kaolin is particularly preferable because it has excellent glossiness and can be made close to a paper for offset printing.
The kaolin includes delaminated kaolin, calcined kaolin, engineered kaolin by surface modification, etc. In consideration of gloss expression, the particle size distribution is such that the ratio of the particle size is 2 μm or less is 80% by mass or more. It is preferable that the kaolin which has occupies 50 mass% or more of the whole kaolin.
The amount of kaolin added is preferably 50 parts by mass or more with respect to 100 parts by mass of the total pigment in the coating layer. When the addition amount is less than 50 parts by mass, a sufficient effect on glossiness may not be obtained. The upper limit of the addition amount is not particularly limited, but is preferably 90 parts by mass or less from the viewpoint of coating suitability in consideration of the fluidity of kaolin, particularly thickening under high shear force.

Examples of the organic pigment include water-soluble dispersions such as styrene-acrylic copolymer particles, styrene-butadiene copolymer particles, polystyrene particles, and polyethylene particles. Two or more of these organic pigments may be mixed.
The addition amount of the organic pigment is preferably 2 to 20 parts by mass with respect to 100 parts by mass of the total pigment in the coating layer. Since the organic pigment is excellent in gloss expression and its specific gravity is smaller than that of an inorganic pigment, it is possible to obtain a coating layer that is bulky, high gloss, and has good surface coverage. If the addition amount is less than 2 parts by mass, the above effect is not obtained. If the addition amount exceeds 20 parts by mass, the fluidity of the coating liquid is deteriorated, leading to a decrease in coating operability, and economical in terms of cost. Not right.
The organic pigment includes a solid type, a hollow type, a donut type, and the like in terms of its form, but the average particle size is 0.2 in view of the balance of gloss development, surface coverage, and fluidity of the coating liquid. A hollow mold having a porosity of 40% or more is more preferable.

Examples of the inorganic pigment in the media coating layer used in the present invention include magnesium carbonate, talc, kaolin, illite, clay, calcium carbonate, calcium sulfite, titanium white, magnesium carbonate, and titanium dioxide. Among these pigments, the coating layer can be made thinner by using a pigment having a refractive index as high as possible. However, from the viewpoint of cost, it is preferable to use calcium carbonate or kaolin. These pigments can be used in combination as long as the effects of the present invention are not impaired, and can also be used in combination with other pigments not listed. Kaolin is preferable because it has excellent glossiness and can provide a texture for offset printing. Kaolin includes delaminated kaolin, calcined kaolin, engineered kaolin by surface modification, etc., but considering gloss development, the proportion of particle size of 2 μm or less has a particle size distribution of 80% by weight or more. It is desirable that kaolin accounts for 50% by weight or more of the entire kaolin. The blending amount of kaolin is preferably 50 parts by weight or more. When it is less than 50 parts by weight, it is difficult to expect a sufficient effect on the glossiness. The upper limit is not particularly limited, but considering the fluidity of kaolin, particularly thickening under high shear force, less than 90 parts by weight is more preferable from the viewpoint of coating suitability.
Further, these high refractive index pigments and low refractive index silica or organic pigments may be used in combination. Examples of organic pigments include water-soluble dispersions such as styrene / acrylic copolymer particles, styrene / butadiene copolymer particles, polystyrene particles, and polyethylene particles. Two or more of these organic pigments may be mixed. Since organic pigments are excellent in glossiness and their specific gravity is smaller than inorganic pigments, a coating layer with high bulkiness and high glossiness and good surface coverage can be obtained. If the amount is less than 5 parts by weight, the above effect is not achieved, and if it exceeds 5 parts by weight, the back-through tends to occur, which is not economical from the viewpoint of cost. Organic pigments include solid, hollow, and donut types in terms of their forms, but the average particle size is 0.2 to 3 in view of the balance of gloss development, surface coverage, and fluidity of the coating liquid. It is desirable to be in the range of 0.0 μm, more preferably a hollow mold having a porosity of 40% or more is employed.

<Coating layer constituent material Binder>
The binder of the colorant pigment coating layer used in the present invention is not particularly limited as long as it has a strong adhesive force with the pigment and the base paper constituting the coating layer and does not cause blocking, such as an aqueous resin or emulsion. Absent.
Examples of such an aqueous binder include starches such as polyvinyl alcohol, oxidized starch, esterified starch, enzyme-modified starch and cationized starch, casein, soy proteins, carboxymethylcellulose, and hydroxyethylcellulose. Styrene-acrylic resin, isobutylene-maleic anhydride resin, acrylic emulsion, vinyl acetate emulsion, vinylidene chloride emulsion, polyester emulsion, styrene-butadiene latex, acrylonitrile butadiene latex, and the like. Among these, it is preferable to use starch or styrene-butadiene latex from the viewpoint of cost. Styrene-butadiene latex is a copolymer commonly used for paper coating, which contains styrene and butadiene as monomers and is copolymerized with other monomers as necessary or modified by chemical reaction. Latex is good. As other monomers, vinyl monomers such as acrylic acid, methacrylic acid, acrylic acid or alkyl esters of methacrylic acid, acrylonitrile, maleic acid, fumaric acid, and vinyl acetate are often used. Further, it may contain a crosslinking agent such as methylolated melamine, methylolated urea, methylolated hydroxypropylene urea, isocyanate, etc., or a copolymer containing units such as N-methylolacrylamide and having a self-crosslinking property. Also good. These may be used individually by 1 type and may use 2 or more types together.

  The use ratio of the aqueous binder added amount (binder) in the coating layer used in the present invention is preferably 50 to 70% by weight, more preferably 55 to 60% by weight based on the total solid content of the coating layer. If the amount is too small, the adhesive strength becomes insufficient, and there is a concern that the strength of the ink receiving layer will decrease, the internal bond strength will decrease, and powder will fall off.

  In the coating layer of the present invention, other components can be added as necessary, as long as the object and effect of the present invention are not impaired. In addition to various auxiliary agents blended in ordinary coated paper pigments, such as dispersants, thickeners, water retention agents, antifoaming agents, water-proofing agents, etc. as other components, pH adjusters, preservatives, oxidation agents Additives such as inhibitors and cationic organic compounds may be used.

  There is no restriction | limiting in particular as surfactant used for a coating layer, According to the objective, it can select suitably, All of anionic surfactant, cationic surfactant, amphoteric surfactant, and nonionic surfactant should be used. Among these, nonionic active agents are particularly preferable among these. By adding the surfactant, the water resistance of the image is improved, the image density is increased, and bleeding is improved.

  Examples of the nonionic activator include higher alcohol ethylene oxide adducts, alkylphenol ethylene oxide adducts, fatty acid ethylene oxide adducts, polyhydric alcohol fatty acid ester ethylene oxide adducts, higher aliphatic amine ethylene oxide adducts, and fatty acid amides. Ethylene oxide adduct, fat ethylene oxide adduct, polypropylene glycol ethylene oxide adduct, fatty acid ester of glycerol, fatty acid ester of pentaerythritol, fatty acid ester of sorbitol and sorbitan, fatty acid ester of sucrose, alkyl ether of polyhydric alcohol, And fatty acid amides of alkanolamines. These may be used individually by 1 type and may use 2 or more types together.

  There is no restriction | limiting in particular as said polyhydric alcohol, According to the objective, it can select suitably, For example, glycerol, a trimethylol propane, a pentaerythritol, sorbitol, sucrose etc. are mentioned. As the ethylene oxide adduct, those obtained by substituting a part of ethylene oxide with an alkylene oxide such as propylene oxide or butylene oxide are also effective as long as water solubility can be maintained. The substitution rate is preferably 50% or less. 4-15 are preferable and, as for HLB (hydrophilic new oil ratio) of the said nonionic activator, 7-13 are more preferable. The addition amount of the surfactant is preferably 0 to 10 parts by mass, and more preferably 0.1 to 1.0 part by mass with respect to 100 parts by mass of the cationic organic compound.

  Other components can be further added to the coating layer as necessary, as long as the objects and effects of the present invention are not impaired. Examples of the other components include additives such as alumina powder, pH adjuster, preservative, and antioxidant.

  The cationic organic compound is not necessarily added, but is not particularly limited and can be appropriately selected and used depending on the purpose.

Examples of the cationic organic compound include dimethylamine / epichlorohydrin polycondensate, dimethylamine / ammonia / epichlorohydrin condensate, poly (trimethylaminoethyl methacrylate / methyl sulfate), diallylamine hydrochloride / acrylamide copolymer, (Diallylamine hydrochloride / sulfur dioxide), polyallylamine hydrochloride, poly (allylamine hydrochloride / diallylamine hydrochloride), acrylamide / diallylamine copolymer, polyvinylamine copolymer, dicyandiamide, dicyandiamide / ammonium chloride / urea / formaldehyde condensate , Polyalkylene polyamine dicyandiamide ammonium salt condensate, dimethyl diallyl ammonium chloride, polydiallyl methylamine hydrochloride, poly (diallyldi Tylammonium chloride), poly (diallyldimethylammonium chloride / sulfur dioxide), poly (diallyldimethylammonium chloride / diallylamine hydrochloride derivative), acrylamide / diallyldimethylammonium chloride copolymer, acrylate / acrylamide / diallylamine Examples thereof include hydrochloride copolymer, polyethyleneimine, ethyleneimine derivatives such as acrylicamine polymer, and polyethyleneimine alkylene oxide modified products. These may be used individually by 1 type and may use 2 or more types together.
Among these, low molecular weight cationic organic compounds such as dimethylamine / epichlorohydrin polycondensate and polyallylamine hydrochloride and other relatively high molecular weight cationic organic compounds such as poly (diallyldimethylammonium chloride) Are preferably used in combination. By using in combination, the image density can be improved and feathering can be further reduced as compared with the case of single use.

The cation equivalent of the cationic organic compound by colloid titration method (using polyvinyl potassium sulfate and toluidine blue) is preferably 3 to 8 meq / g. If the cation equivalent is within this range, good results can be obtained within the dry adhesion range.
Here, in the measurement of the cation equivalent by the colloid titration method, the cationic organic compound is diluted with distilled water to a solid content of 0.1% by mass, and pH adjustment is not performed.

The dry adhesion amount of the cationic organic compound is preferably 0.3 to 2.0 g / m ² . If the dry adhesion amount of the cationic organic compound is less than 0.3 g / m ² , sufficient image density improvement and feathering reduction effects may not be obtained.

  As the support used in the present invention, chemical pulp, mechanical pulp, waste paper recovered pulp and the like are mixed and used at an arbitrary ratio, and an internal sizing agent, a yield improver, a paper strength enhancer, etc., if necessary. The raw material added with a long net former or a gap type twin wire former, or a hybrid former in which the latter half of the long net part is composed of twin wires is used.

  Pulp used in the support of the present invention is virgin chemical pulp (CP), for example, hardwood bleached kraft pulp, softwood bleached kraft pulp, hardwood unbleached kraft pulp, softwood unbleached kraft pulp, hardwood bleached sulfite pulp, softwood bleached Virgin chemical pulp made by chemically treating wood and other fiber raw materials such as sulfite pulp, hardwood unbleached sulfite pulp, softwood unbleached sulfite pulp, and virgin mechanical pulp (MP), for example, ground Virgin mechanical pulp produced by mechanically treating wood and other fiber raw materials such as pulp, chemi-ground pulp, chemimechanical pulp, semi-chemical pulp, etc. may be included. Waste paper pulp may also be used, and the raw material for waste paper pulp is white, ruled white, cream white, card, special white, medium white as shown in the waste paper standard for quality promotion of the Waste Paper Recycling Promotion Center. , Imitation, fair-skinned, Kent, white art, special top-off, separate top-off, newspaper, magazine, etc. Specifically, printer paper such as non-coating computer paper, thermal paper, and pressure-sensitive paper as information-related paper; OA waste paper such as PPC paper; coating of art paper, coated paper, finely coated paper, matte paper, etc. Paper: High quality paper, color quality, notebook, notepaper, wrapping paper, fancy paper, medium quality paper, newsprint, reprint paper, super paper, imitation paper, pure white roll paper, uncoated paper such as milk carton, etc. Examples of used paper and paperboard include chemical pulp paper and high-yield pulp-containing paper. These may be used individually by 1 type and may use 2 or more types together.

The waste paper pulp is generally produced from a combination of the following four steps.
(1) For disaggregation, waste paper is treated with mechanical force and chemicals with a pulper to loosen it into a fibrous form, and the printing ink is peeled off from the fiber.
(2) Dust removal is to remove foreign matter (plastic etc.) and dust contained in waste paper with a screen, cleaner or the like.
(3) In the deinking, the printing ink peeled off from the fiber using a surfactant is removed from the system by a flotation method or a cleaning method.
(4) Bleaching increases the whiteness of the fiber using an oxidizing action or a reducing action.
When mixing the used paper pulp, the mixing ratio of the used paper pulp in the total pulp is preferably 40% or less from the viewpoint of curling after recording.

  As a filler that can be used for the support of the present invention, calcium carbonate is effective. However, inorganic fillers such as kaolin, calcined clay, pyrophyllite, sericite, talc, and other inorganic fillers, satin white, and barium sulfate. Organic pigments such as calcium sulfate, zinc sulfide, plastic pigment and urea resin can also be used in combination.

The internal sizing agent used for the support in the present invention is not particularly limited, and can be appropriately selected from known internal sizing agents used for inkjet recording paper. Examples of preferable internal sizing agents include rosin emulsion sizing agents. Examples of the internally added sizing agent used for making the support include, for example, a neutral rosin sizing agent, alkenyl succinic anhydride (ASA), alkyl ketene dimer (AKD), and petroleum resin-based used for neutral papermaking. Examples include sizing agents. Among these, a neutral rosin sizing agent or alkenyl succinic anhydride is particularly preferable. The alkyl ketene dimer may be added in a small amount because of its high size effect, but the friction coefficient on the surface of the recording paper (media) is low and slippery, which is not preferable from the viewpoint of transportability during ink jet recording. There is.
The amount of the internally added sizing agent is 0.1 to 0.7 parts by weight with respect to 100 parts by weight of the absolutely dry pulp, but is not limited thereto.

As the internal filler used for the support, for example, a conventionally known pigment is used as a white pigment. Examples of the white pigment include light calcium carbonate, heavy calcium carbonate, kaolin, clay, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide,
White inorganic pigments such as zinc sulfide, zinc carbonate, satin white, aluminum silicate, diatomaceous earth, calcium silicate, magnesium silicate, synthetic silica, aluminum hydroxide, alumina, lithopone, zeolite, magnesium carbonate, magnesium hydroxide, etc .; styrene Examples thereof include plastic pigments, acrylic plastic pigments, polyethylene, microcapsules, organic pigments such as urea resins and melamine resins. These may be used individually by 1 type and may use 2 or more types together.

-Manufacturing method of coating layer-
The method for applying the coating layer to the support of the present invention by coating is not particularly specified, but a method of direct coating, a method of transferring a coating once applied to another base material to a base paper, a method of spraying by a spray, etc. Is available. Examples of the direct coating method include a roll coater method, an air knife coater method, a gate roll coater method, a size press method, a shim sizer method, a rod metering size press coater, etc. Can be mentioned.
Among these, from the viewpoint of cost, a method of impregnating or adhering with a conventional size press, a gate roll size press, a film transfer size press or the like installed in a paper machine and finishing on-machine is preferable.
The adhesion amount of the coating layer liquid is not particularly limited and may be appropriately selected depending on the intended purpose, the solid content is preferably ^{0.5~20g / m 2, 1~15g / m} 2 Gayori preferable. If it is less than 0.5 g / m ² , the ink cannot be sufficiently absorbed, so that the ink overflows and character blurring occurs. On the other hand, if it exceeds 20 g / m ² , the texture of the paper is impaired, resulting in problems such as difficulty in bending and difficulty in writing with a writing instrument.
After the impregnation or coating, drying may be performed as necessary. In this case, the drying temperature is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably about 100 to 250 ° C. .

  The coating layer can be dried using, for example, a hot air drying furnace, a thermal drum, or the like. Furthermore, in order to smooth the surface or increase the strength of the surface, surface finishing may be performed with a calendar device (super calendar, soft calendar, gloss calendar, etc.).

The basis weight of the recording medium of the present invention is preferably 50 to 250 g / m ² . If it is less than 50 g / m ² , there is no stiffness, and a conveyance failure such as a recording medium being clogged in the middle of the conveyance path tends to occur. If it exceeds 250 g / m ² , the stiffness becomes too large, so that the recording medium cannot be bent at the curved portion in the middle of the conveyance path, and the conveyance failure such as the recording medium being clogged is likely to occur.

-Ink-
<Ink>
The pigment ink essential for the present invention contains at least water, a coloring material on the particles, and a water-soluble organic solvent. It contains.

-Colorant-
As the colorant, it is preferable to use at least one of a pigment and colored fine particles. As the colored fine particles, an aqueous dispersion of fine polymer particles containing at least one colorant of pigment and dye is preferably used.
Here, the term “containing a color material” means either or both of a state in which the color material is enclosed in the polymer fine particles and a state in which the color material is adsorbed on the surface of the polymer fine particles. The color material is not particularly limited as long as it is water-insoluble or hardly water-soluble and can be adsorbed by the polymer, and can be appropriately selected according to the purpose. Here, the “water-insoluble or hardly water-soluble” means that the coloring material does not dissolve 10 parts by mass or more with respect to 100 parts by mass of water at 20 ° C. Further, “dissolve” means that separation or sedimentation of the coloring material is not observed in the surface layer or the lower layer of the aqueous solution visually.
The volume average particle diameter of the polymer fine particles (colored fine particles) containing the colorant is preferably 0.01 to 0.16 μm in the ink. If it is 0.01 μm or less, the particle diameter approaches that of the dye, so that light resistance and feathering are deteriorated. In addition, it easily penetrates the coat layer and causes a decrease in concentration. On the other hand, if it exceeds 0.16 μm, the nozzle is likely to be clogged, or the color developability will be deteriorated. On the other hand, if it is 0.30 μm or more, clogging of the discharge port or clogging with a filter in the printer occurs, and discharge stability cannot be obtained.
Examples of the colorant include dyes such as water-soluble dyes, oil-soluble dyes, and disperse dyes, and pigments. Oil-soluble dyes and disperse dyes are preferable from the viewpoint of good adsorptivity and encapsulation, but pigments are preferably used from the light resistance of the obtained image.
In addition, from the viewpoint of efficiently impregnating the polymer fine particles, each of the dyes is preferably dissolved in an organic solvent, for example, a ketone solvent in an amount of 2 g / liter or more, and more preferably 20 to 600 g / liter.
The water-soluble dye is a dye classified into an acid dye, a direct dye, a basic dye, a reactive dye, and a food dye in the color index, and preferably has excellent water resistance and light resistance. .

  Examples of the acid dyes and food dyes include C.I. I. Acid Yellow 17, 23, 42, 44, 79, 142; C.I. I. Acid Red 1,8,13,14,18,26,27,35,37,42,52,82,87,89,92,97,106,111,114,115,134,186,249,254 289; I. Acid Blue 9, 29, 45, 92, 249; I. Acid Black 1, 2, 7, 24, 26, 94; I. Food Yellow 3, 4; I. Food red 7, 9, 14; I. Food black 1, 2 etc. are mentioned.

  Examples of the direct dye include C.I. I. Direct yellow 1,12,24,26,33,44,50,86,120,132,142,144; I. Direct red 1,4,9,13,17,20,28,31,39,80,81,83,89,225,227; I. Direct orange 26, 29, 62, 102; I. Direct Blue 1, 2, 6, 15, 22, 25, 71, 76, 79, 86, 87, 90, 98, 163, 165, 199, 202; I. Direct black 19, 22, 32, 38, 51, 56, 71, 74, 75, 77, 154, 168, 171 and the like.

  Examples of the basic dye include C.I. I. Basic yellow 1, 2, 11, 13, 14, 15, 19, 21, 23, 24, 25, 28, 29, 32, 36, 40, 41, 45, 49, 51, 53, 63, 64, 65, 67, 70, 73, 77, 87, 91; C.I. I. Basic Red 2,12,13,14,15,18,22,23,24,27,29,35,36,38,39,46,49,51,52,54,59,68,69,70, 73, 78, 82, 102, 104, 109, 112; I. Basic blue 1,3,5,7,9,21,22,26,35,41,45,47,54,62,65,66,67,69,75,77,78,89,92,93, 105, 117, 120, 122, 124, 129, 137, 141, 147, 155; I. Basic black 2, 8 etc. are mentioned.

  Examples of the reactive dye include C.I. I. Reactive Black 3, 4, 7, 11, 12, 17; C.I. I. Reactive Yellow 1,5,11,13,14,20,21,22,25,40,47,51,55,65,67; I. Reactive Red 1,14,17,25,26,32,37,44,46,55,60,66,74,79,96,97; I. Reactive blue 1, 2, 7, 14, 15, 23, 32, 35, 38, 41, 63, 80, 95, and the like.

Examples of other colorants include pigments. There is no restriction | limiting in particular as a pigment, According to the objective, it can select suitably, For example, any of an inorganic pigment and an organic pigment may be sufficient.
Examples of the inorganic pigment include titanium oxide, iron oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, cadmium red, chrome yellow, carbon black, bitumen, and metal powder. Among these, carbon black is preferable. In addition, as said carbon black, what was manufactured by well-known methods, such as a contact method, a furnace method, and a thermal method, is mentioned, for example.

Examples of the organic pigment include azo pigments, polycyclic pigments, dye chelates, nitro pigments, nitroso pigments, and aniline black. Among these, azo pigments and polycyclic pigments are more preferable. Examples of the azo pigment include azo lakes, insoluble azo pigments, condensed azo pigments, and chelate azo pigments. Examples of the polycyclic pigment include a phthalocyanine pigment, a perylene pigment, a perinone pigment, an anthraquinone pigment, a quinacridone pigment, a dioxazine pigment, an indigo pigment, a thioindigo pigment, an isoindolinone pigment, a quinofullerone pigment, an azomethine pigment, and rhodamine B. And lake pigments. Examples of the dye chelates include basic dye chelates and acidic dye chelates.
There is no restriction | limiting in particular as a color of the said pigment, According to the objective, it can select suitably, For example, the thing for black, the thing for color, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together.

Examples of the black color include carbon black (CI pigment black 7) such as furnace black, lamp black, acetylene black, channel black, copper, iron (CI pigment black 11), oxidation, and the like. Examples thereof include metals such as titanium, organic pigments such as aniline black (CI pigment black 1), and the like.
The carbon black used in the black pigment ink is carbon black produced by the furnace method and the channel method, the primary particle size is 15 to 40 millimicrons, the specific surface area by the BET method is 50 to 300 square meters / g, The DBP oil absorption is preferably 40 to 150 ml / 100 g, the volatile content is 0.5 to 10%, and the pH value is 2 to 9. As such a thing, for example, no. 2300, no. 900, MCF-88, no. 33, no. 40, no. 45, no. 52, MA7, MA8, MA100, no. 2200B (Mitsubishi Chemical Corporation), Raven700, 5750, 5250, 5000, 3500, 1255 (Columbia), Regal400R, 330R, 660R, MoguL, Monarch700, 800, 880, 900, 1000, 1100, 1300, Monarch 1400 (manufactured by Cabot), color black FW1, FW2, FW2V, FW18, FW200, S150, S160, S170, Printex 35, U, the same V, the same 140U, the same 140V, the special black 6, the same 5, the same 4A, the same 4 (manufactured by Degussa) and the like can be used, but are not limited thereto.

  As for the color, for yellow ink, for example, C.I. I. Pigment Yellow 1 (Fast Yellow G), 2, 3, 12 (Disazo Yellow AAA), 13, 14, 16, 17, 23, 24, 34, 35, 37, 42 (Yellow Iron Oxide), 53, 55, 73 74, 75, 81, 83 (disazo yellow HR), 93, 95, 97, 98, 100, 101, 104, 108, 109, 110, 114, 117, 120, 128, 129, 138, 150, 151, 153, 154 and the like, but are not limited thereto.

For magenta, for example, C.I. I. Pigment Red 1, 2, 3, 5, 7, 12, 17, 22 (Brilliant First Scarlet), 23, 31, 38, 48: 2 (Permanent Red 2B (Ba)), 48: 2 (Permanent Red 2B (Ca )), 48: 3 (permanent red 2B (Sr)), 48: 4 (permanent red 2B (Mn)), 49: 1, 52: 2, 53: 1, 57: 1 (brilliant carmine 6B), 60: 1, 63: 1, 63: 2, 64: 1, 81 (Rhodamine 6G rake), 83, 88, 92, 101 (Bengara), 104, 105, 106, 108 (Cadmium red), 112, 114, 122 ( Dimethylquinacridone), 123, 146, 149, 166, 168, 170, 172, 177, 178, 179, 184, 185, 190, 93,202,209,219, but like, not limited thereto.

  For cyan, for example, C.I. I. Pigment Blue 1, 2, 3, 15 (copper phthalocyanine blue R), 15: 1, 15: 2, 15: 3 (phthalocyanine blue G), 15: 4, 15: 6 (phthalocyanine blue E), 15:34, 16, 17: 1, 22, 56, 60, 63, C.I. I. Examples thereof include, but are not limited to, Bat Blue 4 and 60.

  In addition, as the intermediate colors for red, green and blue, C.I. I. Pigment red 177, 194, 224, C.I. I. Pigment orange 43, C.I. I. Pigment violet 3, 19, 23, 37, C.I. I. Pigment green 7, 36, and the like.

As the pigment, a self-dispersing pigment that can be stably dispersed without using a dispersant in which at least one hydrophilic group is bonded to the surface of the pigment directly or via another atomic group is preferably used. It is done. As a result, unlike the conventional ink, a dispersant for dispersing the pigment becomes unnecessary. As the self-dispersing pigment, those having ionicity are preferable, and those having an anionic charge or those having a cationic charge are suitable.
The volume average particle diameter of the self-dispersing pigment is preferably 0.01 to 0.16 μm in the ink.

Examples of the anionic hydrophilic group, for _{example, -COOM, -SO 3 M, -PO} 3 HM, -PO 3 M 2, -SO 2 NH 2, -SO 2 NHCOR ( although, M in the formula is hydrogen R represents an alkyl group having 1 to 12 carbon atoms, a phenyl group which may have a substituent or a naphthyl group which may have a substituent. Etc. Among these, it is preferable to use those in which —COOM and —SO ₃ M are bonded to the surface of the color pigment.

  Further, “M” in the hydrophilic group includes, for example, lithium, sodium, potassium and the like as an alkali metal. Examples of the organic ammonium include mono to trimethyl ammonium, mono to triethyl ammonium, and mono to trimethanol ammonium. As a method of obtaining the anionically charged color pigment, as a method of introducing —COONa to the color pigment surface, for example, a method of oxidizing the color pigment with sodium hypochlorite, a method of sulfonation, a diazonium salt The method of making it react is mentioned.

  As the cationic hydrophilic group, for example, a quaternary ammonium group is preferable, quaternary ammonium groups listed below are more preferable, and any of these bonded to the pigment surface is suitable as a coloring material. .

  As a method for producing the cationic self-dispersing carbon black to which the hydrophilic group is bonded, for example, as a method for bonding an N-ethylpyridyl group represented by the following structural formula, carbon black is converted to 3-amino-N -Although the method of processing with an ethyl pyridium bromide is mentioned, of course, this invention is not limited to these.

In the present invention, the hydrophilic group may be bonded to the surface of carbon black via another atomic group. Examples of other atomic groups include an alkyl group having 1 to 12 carbon atoms, a phenyl group which may have a substituent, or a naphthyl group which may have a substituent. Specific examples of the case where the above-described hydrophilic group is bonded to the surface of carbon black via another atomic group include, for example, —C ₂ H ₄ COOM (where M represents an alkali metal or quaternary ammonium). , -PhSO ₃ M (where Ph represents a phenyl group, M represents an alkali metal, quaternary ammonium), -C ₅ H ₁₀ NH ₃ ^{+, and the} like.

In the present invention, a pigment dispersion using a pigment dispersant can also be used.
As the pigment dispersant, as the hydrophilic polymer compound, in the natural system, plant polymers such as gum arabic, tragan gum, guar gum, karaya gum, locust bean gum, arabinogalactone, pectin, quince seed starch, alginic acid, Examples include seaweed polymers such as carrageenan and agar, animal polymers such as gelatin, casein, albumin and collagen, and microbial polymers such as xanthene gum and dextran. In semi-synthetic systems, fiber polymers such as methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, carboxymethylcellulose, starch polymers such as sodium starch glycolate and sodium starch phosphate, sodium alginate, propylene glycol alginate And seaweed polymers such as Pure synthetic systems include polyvinyl polymers such as polyvinyl alcohol, polyvinyl pyrrolidone, and polyvinyl methyl ether, non-crosslinked polyacrylamide, polyacrylic acid or alkali metal salts thereof, acrylic resins such as water-soluble styrene acrylic resins, and water-soluble styrene malees. Acid resin, water-soluble vinyl naphthalene acrylic resin, water-soluble vinyl naphthalene maleic resin, polyvinyl pyrrolidone, polyvinyl alcohol, alkali metal salt of β-naphthalene sulfonic acid formalin condensate, cationic functional group such as quaternary ammonium and amino group Examples thereof include a polymer compound having a salt in the side chain and a natural polymer compound such as shellac. Among these, those having a carboxyl group introduced from a homopolymer of acrylic acid, methacrylic acid or styrene acrylic acid or a copolymer of a monomer having another hydrophilic group are particularly preferred as the polymer dispersant.

  The weight average molecular weight of the copolymer is preferably 3,000 to 50,000, more preferably 5,000 to 30,000, and still more preferably 7,000 to 15,000. The mixing mass ratio of the pigment and the dispersant is preferably in the range of 1: 0.06 to 1: 3, and more preferably in the range of 1: 0.125 to 1: 3.

The simultaneous use of the polymer dispersant and the self-dispersing pigment is a preferable combination because an appropriate dot diameter can be obtained. The reason is not clear, but it is thought as follows.
By containing the polymer dispersant, the penetration into the recording paper is suppressed. On the other hand, since the aggregation of the self-dispersing pigment is suppressed by containing the polymer dispersant, the self-dispersing pigment can smoothly spread in the lateral direction. Therefore, it is considered that the dots spread widely and thinly and ideal dots can be formed.

Further, the pigment can be provided with dispersibility by coating with a resin having a hydrophilic group and encapsulating the pigment.
As a method for coating a water-insoluble pigment with an organic polymer and microencapsulating, all conventionally known methods can be used. Conventionally known methods include chemical production methods, physical production methods, physicochemical methods, mechanical production methods, and the like. In particular,
Interfacial polymerization method (a method in which two types of monomers or two types of reactants are separately dissolved in a dispersed phase and a continuous phase, and both substances are reacted at the interface between them to form a wall film);
In-situ polymerization method (method of supplying a liquid or gas monomer and catalyst, or two reactive substances from either one of the continuous phase core particles to cause a reaction to form a wall film);
・ Liquid-cured coating method (method of forming a wall film by insolubilizing droplets of a polymer solution containing core material particles in a liquid with a curing agent);
-Coacervation (phase separation) method (a method in which a polymer dispersion in which core material particles are dispersed is separated into a coacervate (concentrated phase) and a dilute phase having a high polymer concentration to form a wall film);
・ Liquid drying method (preparing a liquid in which a core material is dispersed in a solution of a wall membrane material, placing the dispersion in a liquid in which the continuous phase of this dispersion is not miscible, and forming a composite emulsion to dissolve the wall membrane material. A method of forming a wall film by gradually removing the medium in the medium);
Melt dispersion cooling method (using a wall film material that melts into a liquid state when heated and solidifies at room temperature, this material is heated and liquefied, the core material particles are dispersed in it, cooled to fine particles, and cooled to the wall. A method of forming a film);
・ Air suspension coating method (Method of forming a wall membrane by suspending powder core material particles in the air with a fluidized bed and suspending them in an air stream while spraying and mixing the coating solution of the wall membrane material) ;
-Spray drying method (a method in which the encapsulated stock solution is sprayed and contacted with hot air to evaporate and dry the volatile components to form a wall film);
-Acid precipitation method (at least a part of anionic groups of organic polymer compounds containing anionic groups is neutralized with a basic compound to give solubility in water and kneaded in an aqueous medium with a colorant. Then, neutralize or acidify with an acidic compound, deposit organic compounds and fix them on the colorant, and then neutralize and disperse))
-Phase inversion emulsification method (a mixture containing an anionic organic polymer having dispersibility in water and a colorant is used as an organic solvent phase, and water is added to the organic solvent phase or And the like).

  Examples of organic polymers (resins) used as the material constituting the microcapsule wall membrane material include polyamide, polyurethane, polyester, polyurea, epoxy resin, polycarbonate, urea resin, melamine resin, phenol resin, and polysaccharide. , Gelatin, gum arabic, dextran, casein, protein, natural rubber, carboxypolymethylene, polyvinyl alcohol, polyvinylpyrrolidone, polyvinyl acetate, polyvinyl chloride, polyvinylidene chloride, cellulose, ethyl cellulose, methyl cellulose, nitrocellulose, hydroxyethyl cellulose, acetic acid Cellulose, polyethylene, polystyrene, (meth) acrylic acid polymer or copolymer, (meth) acrylic acid ester polymer or copolymer, (meth) acrylic acid (Meth) acrylic acid ester copolymer, styrene- (meth) acrylic acid copolymer, styrene-maleic acid copolymer, sodium alginate, fatty acid, paraffin, beeswax, water wax, hardened beef tallow, carnauba wax, albumin, etc. .

  Among these, organic polymers having an anionic group such as a carboxylic acid group or a sulfonic acid group can be used. Nonionic organic polymers include, for example, polyvinyl alcohol, polyethylene glycol monomethacrylate, polypropylene glycol monomethacrylate, methoxypolyethylene glycol monomethacrylate or their (co) polymers, and 2-oxazoline cationic ring-opening polymers. Is mentioned. In particular, a complete saponified product of polyvinyl alcohol is particularly preferable because it has low water solubility and is easily dissolved in hot water but difficult to dissolve in cold water.

  Further, the amount of the organic polymer constituting the wall membrane material of the microcapsule is 1% by weight or more and 20% by weight or less based on the water-insoluble colorant such as an organic pigment or carbon black. By setting the amount of the organic polymer within the above range, the content of the organic polymer in the capsule is relatively low so that the pigment develops due to the organic polymer covering the pigment surface. Can be suppressed. If the amount of the organic polymer is less than 1% by weight, it is difficult to exert the effect of encapsulation. Conversely, if the amount exceeds 20% by weight, the color developability of the pigment is significantly reduced. In consideration of other characteristics, the amount of the organic polymer is preferably in the range of 5 to 10% by weight based on the water-insoluble colorant.

  That is, since a part of the color material is exposed without being substantially covered, it is possible to suppress a decrease in color developability, and conversely, a part of the color material is not substantially exposed without being exposed. Since it is coated, it is possible to simultaneously exhibit the effect that the pigment is coated. The number average molecular weight of the organic polymers used in the present invention is preferably 2000 or more from the viewpoint of capsule production. Here, “substantially exposed” means not the partial exposure associated with defects such as pinholes and cracks, but a state where it is intentionally exposed.

  Furthermore, if an organic pigment or self-dispersing carbon black, which is a self-dispersing pigment, is used as a colorant, the dispersibility of the pigment is improved even if the content of the organic polymer in the capsule is relatively low. In addition, since sufficient storage stability of the ink can be secured, it is more preferable for the present invention.

  It is preferable to select an organic polymer suitable for the microencapsulation method. For example, in the case of interfacial polymerization, polyester, polyamide, polyurethane, polyvinyl pyrrolidone, epoxy resin and the like are suitable. In the case of using the in-situ polymerization method, a polymer or copolymer of (meth) acrylic acid ester, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene- (meth) acrylic acid copolymer, Polyvinyl chloride, polyvinylidene chloride, polyamide and the like are suitable. In the case of the liquid curing method, sodium alginate, polyvinyl alcohol, gelatin, albumin, epoxy resin and the like are suitable. In the case of the coacervation method, gelatin, celluloses, casein and the like are suitable. In addition, in order to obtain a fine and uniform microencapsulated pigment, it is possible to use all conventionally known encapsulation methods other than those described above.

  When the phase inversion method or the acid precipitation method is selected as the microencapsulation method, anionic organic polymers are used as the organic polymers constituting the wall membrane material of the microcapsules. The phase inversion method is a composite or composite of an anionic organic polymer having self-dispersibility or solubility in water and a colorant such as a self-dispersion organic pigment or self-dispersion carbon black, or a self-dispersion method. A mixture of a colorant such as a dispersible organic pigment or self-dispersing carbon black, a curing agent, and an anionic organic polymer is used as an organic solvent phase, and water is added to the organic solvent phase, or the organic solvent is submerged in water. In this method, a solvent phase is introduced and microencapsulation is performed while self-dispersion (phase inversion emulsification) is performed. In the above phase inversion method, there is no problem even if the organic solvent phase is mixed with a recording liquid vehicle or additives. In particular, it is more preferable to mix a liquid medium of a recording liquid because a dispersion liquid for recording liquid can be directly produced.

  On the other hand, in the acid precipitation method, a part or all of the anionic group of the anionic group-containing organic polymer is neutralized with a basic compound, and a colorant such as a self-dispersing organic pigment or self-dispersing carbon black, A water-containing cake obtained by a production method comprising a step of kneading in an aqueous medium and a step of neutralizing and acidifying an acidic compound to precipitate an anionic group-containing organic polymer and fixing it to a pigment, This is a method of microencapsulation by neutralizing a part or all of an anionic group using a compound. By doing in this way, the aqueous dispersion containing the anionic microencapsulated pigment which is fine and contains many pigments can be manufactured.

  Examples of the solvent used for microencapsulation as described above include alkyl alcohols such as methanol, ethanol, propanol and butanol; aromatic hydrocarbons such as benzol, toluol and xylol; methyl acetate Esters such as ethyl acetate and butyl acetate; Chlorinated hydrocarbons such as chloroform and ethylene dichloride; Ketones such as acetone and methyl isobutyl ketone; Ethers such as tetrahydrofuran and dioxane; Cellosolves such as methyl cellosolve and butyl cellosolve Etc. The microcapsules prepared by the above method are once separated from these solvents by centrifugation or filtration, and then stirred and redispersed with water and the necessary solvent, and used for the intended present invention. A recording liquid that can be used is obtained. The average particle diameter of the encapsulated pigment obtained by the above method is preferably 50 nm to 180 nm.

  The amount of the colorant added to the ink is preferably 2 to 15% by mass, and more preferably 3 to 12% by mass. When the addition amount is less than 2% by mass, the image density may be lowered due to a decrease in coloring power, or feathering or bleeding may be deteriorated due to a decrease in viscosity. If the nozzle is left unattended, the nozzles will be easy to dry, non-ejection phenomenon will occur, the viscosity will be too high, the permeability will decrease, and the dots will not spread, so the image density will decrease. Or a blurred image.

-Penetration agent-
As the penetrant, a water-soluble organic solvent such as a polyol compound or a glycol ether compound is used. In particular, at least one of a polyol compound having 8 or more carbon atoms and a glycol ether compound is preferably used.
If the polyol compound has less than 8 carbon atoms, sufficient penetrability cannot be obtained, and the recording medium is soiled during double-sided printing, or ink spreading on the recording medium is insufficient, resulting in poor pixel filling. Therefore, character quality and image density may be reduced.
Examples of the polyol compound having 8 or more carbon atoms include 2-ethyl-1,3-hexanediol (solubility: 4.2% (25 ° C.)), 2,2,4-trimethyl-1,3-pentanediol. (Solubility: 2.0% (25 ° C.)) is preferable.

  The glycol ether compound is not particularly limited and may be appropriately selected depending on the intended purpose.For example, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, Examples include polyhydric alcohol alkyl ethers such as tetraethylene glycol monomethyl ether and propylene glycol monoethyl ether; polyhydric alcohol aryl ethers such as ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether.

  There is no restriction | limiting in particular in the addition amount of the said penetrant, Although it can select suitably according to the objective, 0.1-20 mass% is preferable, and 0.5-10 mass% is more preferable.

  The addition amount of the water-soluble organic solvent is preferably 0.1 to 20% by mass, and more preferably 0.5 to 10% by mass.

-Wetting agent-
There is no restriction | limiting in particular as said wetting agent, According to the objective, it can select suitably, For example, at least 1 sort (s) selected from a polyol compound, a lactam compound, a urea compound, and saccharides is suitable.

  Examples of the polyol compound include polyhydric alcohols, polyhydric alcohol alkyl ethers, polyhydric alcohol aryl ethers, nitrogen-containing heterocyclic compounds, amides, amines, sulfur-containing compounds, propylene carbonate, ethylene carbonate, Etc. These may be used alone or in combination of two or more.

Examples of the polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, 1,3-purpandiol, 1,3-butanediol, 1,4 butanediol, and 3-methyl- 1,3-butanediol 1,3-propanediol, 1,5-pentanediol, 1,6 hexanediol, glycerol, 1,2,6-hexanetriol, 1,2,4-butanetriol, 1,2,3 -Butanetriol, petriol and the like.
Examples of the polyhydric alcohol alkyl ethers include ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, and propylene glycol monoethyl ether. It is done.
Examples of the polyhydric alcohol aryl ethers include ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether.
Examples of the amides include formamide, N-methylformamide, formamide, N, N-dimethylformamide and the like.
Examples of the amines include monoethanolamine, diethanolamine, triethanolamine, monoethylamine, diethylamine, and triethylamine.
Examples of the sulfur-containing compounds include dimethyl sulfoxide, sulfolane, thiodiethanol, and the like.
Among these, glycerin, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1 from the viewpoint of obtaining excellent effects on solubility and prevention of poor jetting characteristics due to water evaporation , 3-butanediol, 2,3-butanediol, 1,4-butanediol, 3-methyl-1,3-butanediol 1,3-propanediol, 1,5-pentanediol, tetraethylene glycol, 1, 6-hexanediol, 2-methyl-2,4-pentanediol, polyethylene glycol, 1,2,4-butanetriol, 1,2,6-hexanetriol, thiodiglycol, 2-pyrrolidone, N-methyl-2 -Pyrrolidone, N-hydroxyethyl-2-pi Pyrrolidone is preferred.

Examples of the lactam compound include at least one selected from 2-pyrrolidone, N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, and ε-caprolactam.
Examples of the urea compound include at least one selected from urea, thiourea, ethylene urea, and 1,3-dimethyl-2-imidazolidinone. In general, the amount of urea added to the ink is preferably 0.5 to 50% by mass, and more preferably 1 to 20% by mass.

Examples of the saccharide include monosaccharides, disaccharides, oligosaccharides (including trisaccharides and tetrasaccharides), polysaccharides, and derivatives thereof. Among these, glucose, mannose, fructose, ribose, xylose, arabinose, galactose, maltose, cellobiose, lactose, sucrose, trehalose, and maltotriose are preferable, and maltose, sorbitol, gluconolactone, and maltose are particularly preferable.
The polysaccharide means a saccharide in a broad sense and can be used to include substances widely existing in nature such as α-cyclodextrin and cellulose.
Examples of the saccharide derivatives include reducing sugars of the saccharides (for example, sugar alcohols (generally represented by HOCH ₂ (CHOH) nCH ₂ OH (where n represents an integer of 2 to 5)), Examples include oxidized sugars (for example, aldonic acid, uronic acid, etc.), amino acids, thioic acids, etc. Among these, sugar alcohols are particularly preferable, and examples of the alcohol include maltitol, sorbit, and the like.

  The content of the wetting agent in the ink is preferably 10 to 50% by mass, and more preferably 20 to 35% by mass. If the content is too small, the nozzle is likely to be dried and defective ejection of droplets may occur. If the content is too large, the ink viscosity is increased, and the proper viscosity range may be exceeded.

-Surfactant-
The surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. For example, an anionic surfactant, a nonionic surfactant, an amphoteric surfactant, a nonionic surfactant, an acetylene glycol type Surfactant or fluorosurfactant is mentioned,
Examples of the anionic surfactant include polyoxyethylene alkyl ether acetate, dodecyl benzene sulfonate, laurate, polyoxyethylene alkyl ether sulfate salt, and the like.

Examples of the nonionic surfactant include acetylene glycol surfactants, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene sorbitan fatty acid esters, polyoxypropylene polyoxyethylene alkyl ethers, polyoxyethylenes. Examples thereof include alkyl esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkyl amines, polyoxyethylene alkyl amides, and the like.
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, , 5-dimethyl-1-hexyn-3-ol and the like. Examples of commercially available acetylene glycol surfactants include Surfynol 104, 82, 465, 485, and TG manufactured by Air Products (USA).

  Examples of the amphoteric surfactant include lauryl aminopropionate, lauryl dimethyl betaine, stearyl dimethyl betaine, and lauryl dihydroxyethyl betaine. Specific examples include lauryl dimethylamine oxide, myristyl dimethylamine oxide, stearyl dimethylamine oxide, dihydroxyethyl lauryl amine oxide, polyoxyethylene coconut oil alkyl dimethyl amine oxide, dimethyl alkyl (coconut) betaine, dimethyl lauryl betaine, and the like. It is done.

Among these surfactants, surfactants selected from the following general formulas (I), (II), (III), (IV), (V), and (VI) are preferable.

ただし、前記一般式（Ｉ）中、Ｒ^１は、アルキル基を表す。ｈは、３〜１２の整数を表す。Ｍは、アルカリ金属イオン、第４級アンモニウム、第４級ホスホニウム、及びアルカノールアミンから選択されるいずれかを表す。

In the general formula (I), ^{R 1} represents an alkyl group. h represents an integer of 3 to 12. M represents one selected from alkali metal ions, quaternary ammonium, quaternary phosphonium, and alkanolamine.

ただし、前記一般式（II）中、Ｒ^２は、アルキル基を表す。Ｍは、アルカリ金属イオン、第４級アンモニウム、第４級ホスホニウム、及びアルカノールアミンから選択されるいずれかを表す。

In the general formula (II), ^{R 2} represents an alkyl group. M represents one selected from alkali metal ions, quaternary ammonium, quaternary phosphonium, and alkanolamine.

ただし、前記一般式（III）中、Ｒ^３は、炭化水素基を表す。ｋは５〜２０の整数を表す。

In the general formula (III), R ³ is represents a hydrocarbon group. k represents an integer of 5 to 20.

ただし、前記一般式（IＶ）中、Ｒ^４は、炭化水素基を表す。ｊは、５〜２０の整数を表す。

In the general formula (IV), ^{R 4} represents a hydrocarbon group. j represents an integer of 5 to 20.

ただし、前記一般式（Ｖ）中、Ｒ^６は、炭化水素基を表す。Ｌ及びｐは、１〜２０の整数を表す。

In the general formula (V), ^{R 6} represents a hydrocarbon group. L and p represent an integer of 1 to 20.

ただし、前記一般式（ＶI）中、ｑ及びｒは０〜４０の整数を表す。

However, q and r represent the integer of 0-40 in the said general formula (VI).

  Hereinafter, the surfactants of the structural formulas (I) and (II) are specifically shown in free acid form.

前記フッ素系界面活性剤としては、下記一般式（II−５）で表されるものが好適である。

As the fluorosurfactant, those represented by the following general formula (II-5) are suitable.

ただし、前記一般式（II−５）中、ｍは０〜１０の整数を表す。ｎは１〜４０の整数を表す。

However, in said general formula (II-5), m represents the integer of 0-10. n represents an integer of 1 to 40.

  Examples of the fluorosurfactant include a perfluoroalkyl sulfonic acid compound, a perfluoroalkyl carboxylic compound, a perfluoroalkyl phosphate compound, a perfluoroalkyl ethylene oxide adduct, and a perfluoroalkyl ether group in the side chain. And polyoxyalkylene ether polymer compounds. Among these, the polyoxyalkylene ether polymer compound having a perfluoroalkyl ether group in the side chain has a low foaming property, and the bioaccumulation property of a fluorine compound that has been regarded as a problem in recent years is low and highly safe. Particularly preferred.

Examples of the perfluoroalkyl sulfonic acid compound include perfluoroalkyl sulfonic acid, perfluoroalkyl sulfonate, and the like.
Examples of the perfluoroalkyl carboxylic compounds include perfluoroalkyl carboxylic acids and perfluoroalkyl carboxylic acid salts.
Examples of the perfluoroalkyl phosphate compound include perfluoroalkyl phosphate esters, perfluoroalkyl phosphate salts, and the like.
The polyoxyalkylene ether polymer compound having a perfluoroalkyl ether group in the side chain includes a polyoxyalkylene ether polymer having a perfluoroalkyl ether group in the side chain, and a polyoxyalkylene ether having a perfluoroalkyl ether group in the side chain. Examples thereof include a sulfate salt of a polymer and a salt of a polyoxyalkylene ether polymer having a perfluoroalkyl ether group in the side chain.
As counter ions of salts in these fluorosurfactants, Li, Na, K, NH ₄ , NH ₃ CH ₂ CH ₂ OH, NH ₂ (CH ₂ CH ₂ OH) ₂ , NH (CH ₂ CH ₂ OH) ₃ etc. are mentioned.

As said fluorosurfactant, what was synthesize | combined suitably may be used and a commercial item may be used.
Examples of the commercially available products include Surflon S-111, S-112, S-113, S-121, S-131, S-132, S-141, and S-145 (all manufactured by Asahi Glass Co., Ltd.), Fullrad FC. -93, FC-95, FC-98, FC-129, FC-135, FC-170C, FC-430, FC-431 (all manufactured by Sumitomo 3M), MegaFuck F-470, F1405, F-474 (All manufactured by Dainippon Ink & Chemicals, Inc.), Zonyl TBS, FSP, FSA, FSN-100, FSN, FSO-100, FSO, FS-300, UR (all manufactured by DuPont), FT-110, FT- 250, FT-251, FT-400S, FT-150, FT-400SW (all manufactured by Neos Co., Ltd.), PF-151N (manufactured by Omninova), etc. I can get lost. Among these, Zonyl FS-300, FSN, FSN-100, and FSO (manufactured by DuPont) are particularly preferable from the viewpoints of reliability and color development improvement.

  The surface tension is preferably 30 mN / m or less at 25 ° C., more preferably 25 mN / m or less.

As the pigment fixing agent, any resin emulsion can be used.
-Resin emulsion-
The resin emulsion is obtained by dispersing resin fine particles in water as a continuous phase, and may contain a dispersant such as a surfactant as necessary.
The content of resin fine particles as the dispersed phase component (content of resin fine particles in the resin emulsion) is generally preferably 10 to 70% by mass. Further, the particle diameter of the resin fine particles is preferably 10 to 1000 nm, more preferably 20 to 300 nm, particularly considering use in an ink jet recording apparatus.

The resin fine particle component of the dispersed phase is not particularly limited and may be appropriately selected depending on the intended purpose. For example, acrylic resin, vinyl acetate resin, styrene resin, butadiene resin, styrene-butadiene resin , Vinyl chloride resins, acrylic styrene resins, acrylic silicone resins, and the like. Among these, acrylic silicone resins are particularly preferable.
As said resin emulsion, what was synthesize | combined suitably may be used and a commercial item may be used.
Examples of the commercially available resin emulsion include Microgel E-1002, E-5002 (styrene-acrylic resin emulsion, manufactured by Nippon Paint Co., Ltd.), and Boncoat 4001 (acrylic resin emulsion, manufactured by Dainippon Ink & Chemicals, Inc.). ), Boncoat 5454 (styrene-acrylic resin emulsion, manufactured by Dainippon Ink & Chemicals, Inc.), SAE-1014 (styrene-acrylic resin emulsion, manufactured by Nippon Zeon Co., Ltd.), Cybinol SK-200 (acrylic resin emulsion, Seiden Chemical Co., Ltd.), Primal AC-22, AC-61 (acrylic resin emulsion, manufactured by Rohm and Haas), Nanoacryl SBCX-2821, 3689 (acrylic silicone resin emulsion, Toyo Ink Co., Ltd.) Company Ltd.), # 3070 (methyl methacrylate polymer resin emulsion, manufactured by Mikuni Color Ltd.).

  The addition amount of the resin fine particle component in the resin emulsion in the ink is preferably 0.1 to 50% by mass, more preferably 0.5 to 20% by mass, and still more preferably 1 to 10% by mass. If the addition amount is less than 0.1% by mass, the effect of improving clogging resistance and ejection stability may not be sufficient, and if it exceeds 50% by mass, the storage stability of the ink may be reduced. There is.

Depending on the purpose, an ultraviolet curable resin may be used in combination.
Specific examples of the ultraviolet curable resin that can be used in the present invention include those obtained by polymerizing a known acrylic photopolymerizable monomer and / or acrylic photopolymerizable oligomer.

Examples of such photopolymerizable monomers include unsaturated carboxylic acids such as acrylic acid and methacrylic acid or esters thereof such as alkyl-, cycloalkyl-, alkyl halide-, alkoxyalkyl-, hydroxyalkyl-, aminoalkyl- Tetrahydrofurfuryl-, allyl-, glycidyl-, benzyl-, phenoxy-acrylate and methacrylate, alkylene glycol, polyoxyalkylene glycol mono- or diacrylate and methacrylate, trimethylolpropane triacrylate and methacrylate, pentaerythritol tetraacrylate and Methacrylate, acrylamide, methacrylamide or derivatives thereof, for example acrylics mono- or di-substituted with alkyl or hydroxyalkyl groups Bromide and methacrylamide, diacetone acrylamide and methacrylamide, N, etc. N'- alkylene-bis acrylamide and methacrylamide, allyl compounds such as allyl alcohol, allyl isocyanate, diallyl phthalate, and the like triallyl isocyanurate. Further, for example, acrylic acid ester or methacrylic acid of diethylene glycol dicyclopentenyl monoether such as isobornyl acrylate or methacrylate, norbornyl acrylate or methacrylate, dicyclopentenoxyethyl acrylate or methacrylate, dicyclopentenoxypropyl acrylate or methacrylate. Acid esters, acrylic acid esters or polymethacrylates of polyoxyethylene or polypropylene glycol dicyclopentenyl monoether, such as dicyclopentenyl cinnamate, dicyclopentenoxyethyl cinnamate, dicyclopentenoxyethyl monofumarate or difumarate 3,9-bis (1,1-bismethyl-2-oxyethyl) -spiro [5,5] undecane, 3 9-bis (1,1-bismethyl-2-oxyethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane, 3,9-bis (2-oxyethyl) -spiro [5,5] Mono-, diacrylate or mono-, dimethacrylate, or spiroglycols such as undecane, 3,9-bis (2-oxyethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane A mono-, diacrylate, or mono-, dimethacrylate of the ethylene oxide or propylene oxide addition polymer, or methyl ether of the monoacrylate or methacrylate, 1-azabicyclo [2,2,2] -3-octenyl acrylate, or Methacrylate, bicyclo [2,2,1] -5-heptene-2,3-dicarboxyl Allyl esters can be used a photopolymerizable monomer, such as dicyclopentadienyl acrylate or methacrylate, dicyclopentadienyl oxyethyl acrylate or methacrylate, dihydrodicyclopentadienyl acrylate or methacrylate.
These photopolymerizable monomers may be used alone or in combination of two or more.

  Examples of acrylic photopolymerizable oligomers include acrylic ester of epoxy resin such as diglycidyl ether diacrylate of bisphenol A, reaction product of epoxy resin, acrylic acid and methyltetrahydrophthalic anhydride, epoxy resin and 2-hydroxyethyl. Reaction product with acrylate, ring-opening copolymerization ester of glycidyl diacrylate and phthalic anhydride, ester of methacrylic acid dimer and polyol, polyester obtained from acrylic acid, phthalic anhydride and propylene oxide, polyvinyl alcohol and Unsaturated polyester-based prepolymers such as reaction products of N-methylolacrylamide, reaction products of polyethylene glycol, maleic anhydride and glycidyl methacrylate, and polyvinyl alcohol After esterification with, a polyvinyl alcohol-based prepolymer such as a product obtained by adding glycidyl methacrylate, a reaction product of methyl vinyl ether-maleic anhydride copolymer and 2-hydroxyethyl acrylate, or further glycidyl methacrylate. In addition to polyacrylic acid or maleic acid copolymer prepolymers such as reacted ones, a polyoxyalkylene segment or a saturated polyester segment or both are connected via a urethane bond, and an acryloyl group or a methacryloyl group is connected to both ends. Examples thereof include urethane-based prepolymers.

-Other ingredients-
The other components are not particularly limited and can be appropriately selected as necessary. For example, pH adjusters, antiseptic / antifungal agents, rust preventives, antioxidants, ultraviolet absorbers, oxygen absorbers, And light stabilizers.

  Examples of the antiseptic / antifungal agent include 1,2-benzisothiazolin-3-one, sodium dehydroacetate, sodium sorbate, sodium 2-pyridinethiol-1-oxide, sodium benzoate, and sodium pentachlorophenol. Can be mentioned.

The pH adjuster is not particularly limited as long as it can adjust the pH to 7 or more without adversely affecting the ink to be prepared, and any substance can be used according to the purpose.
Examples of the pH adjusting agent include amines such as diethanolamine and triethanolamine, hydroxides of alkali metal elements such as lithium hydroxide, sodium hydroxide and potassium hydroxide; ammonium hydroxide and quaternary ammonium hydroxide. Quaternary phosphonium hydroxide, alkali metal carbonates such as lithium carbonate, sodium carbonate, potassium carbonate, and the like.

  Examples of the rust inhibitor include acidic sulfite, sodium thiosulfate, ammonium thiodiglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, and dicyclohexylammonium nitrite.

Examples of the antioxidant include phenol-based antioxidants (including hindered phenol-based antioxidants), amine-based antioxidants, sulfur-based antioxidants, phosphorus-based antioxidants, and the like.
Examples of the phenolic antioxidant (including hindered phenolic antioxidant) include butylated hydroxyanisole, 2,6-di-tert-butyl-4-ethylphenol, stearyl-β- (3,5 -Di-tert-butyl-4-hydroxyphenyl) propionate, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 3,9-bis [1,1-dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) ) Propionyloxy] ethyl] 2,4,8,10-tetrixaspiro [5,5] undecane, 1,1,3-tris ( 2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, Tetrakis [methylene-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate] methane, and the like.

  Examples of the amine-based antioxidant include phenyl-β-naphthylamine, α-naphthylamine, N, N′-di-sec-butyl-p-phenylenediamine, phenothiazine, N, N′-diphenyl-p-phenylenediamine. 2,6-di-tert-butyl-p-cresol, 2,6-di-tert-butylphenol, 2,4-dimethyl-6-tert-butyl-phenol, butylhydroxyanisole, 2,2′-methylenebis ( 4-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 4,4′-thiobis (3-methyl-6-tert-butylphenol), tetrakis [methylene -3 (3,5-di-tert-butyl-4-dihydroxyphenyl) propionate And] methane, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, and the like.

  Examples of the sulfur-based antioxidant include dilauryl 3,3′-thiodipropionate, distearyl thiodipropionate, lauryl stearyl thiodipropionate, dimyristyl 3,3′-thiodipropionate, and distearyl β. , Β′-thiodipropionate, 2-mercaptobenzimidazole, dilauryl sulfide and the like.

  Examples of the phosphorus antioxidant include triphenyl phosphite, octadecyl phosphite, triisodecyl phosphite, trilauryl trithiophosphite, trinonylphenyl phosphite, and the like.

  Examples of the ultraviolet absorber include a benzophenone ultraviolet absorber, a benzotriazole ultraviolet absorber, a salicylate ultraviolet absorber, a cyanoacrylate ultraviolet absorber, and a nickel complex ultraviolet absorber.

  Examples of the benzophenone-based ultraviolet absorber include 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2,4-dihydroxybenzophenone, and 2-hydroxy-4-methoxybenzophenone. 2,2 ′, 4,4′-tetrahydroxybenzophenone, and the like.

  Examples of the benzotriazole ultraviolet absorber include 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-4′-octoxyphenyl) benzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5′-methylphenyl) -5-chlorobenzotriazole, and the like.

  Examples of the salicylate-based ultraviolet absorber include phenyl salicylate, p-tert-butylphenyl salicylate, p-octylphenyl salicylate, and the like.

  Examples of the cyanoacrylate ultraviolet absorber include ethyl-2-cyano-3,3′-diphenyl acrylate, methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate, and butyl-2- And cyano-3-methyl-3- (p-methoxyphenyl) acrylate.

  Examples of the nickel complex ultraviolet absorber include nickel bis (octylphenyl) sulfide, 2,2′-thiobis (4-tert-octylferrate) -n-butylamine nickel (II), and 2,2′-thiobis. (4-tert-octyl ferrate) -2-ethylhexylamine nickel (II), 2,2′-thiobis (4-tert-octyl ferrate) triethanolamine nickel (II), and the like.

  In the ink of the present invention, at least water, a colorant, a water-soluble organic solvent, a wetting agent, a surfactant, and, if necessary, other components are dispersed or dissolved in an aqueous medium, and further stirred and mixed as necessary. To manufacture. The dispersion can be performed by, for example, a sand mill, a homogenizer, a ball mill, a paint shaker, an ultrasonic disperser, etc., and stirring and mixing are performed by a stirrer using a normal stirring blade, a magnetic stirrer, a high-speed disperser, or the like. be able to.

As physical properties of the ink, for example, the viscosity, surface tension, pH, and the like are preferably in the following ranges.
The viscosity of the ink is preferably 1 cps or more and 30 cps or less at 25 ° C., more preferably 2 to 20 cps. If the viscosity exceeds 20 cps, it may be difficult to ensure ejection stability.
As said pH, 7-10 are preferable, for example.

  There is no restriction | limiting in particular as coloring of the said ink, According to the objective, it can select suitably, Yellow, magenta, cyan, black etc. are mentioned. When recording is performed using an ink set in which two or more of these colorings are used in combination, a multicolor image can be formed. When recording is performed using an ink set in which all colors are combined, a full color image is formed. be able to.

<Additives, physical properties>
In order to make the recording liquid of the present invention have desired physical properties or to prevent clogging of the nozzles of the recording head due to drying, it is preferable to use a water-soluble organic solvent in addition to the coloring material. The water-soluble organic solvent includes a wetting agent and a penetrating agent. The wetting agent is added for the purpose of preventing clogging of the nozzles of the recording head due to drying. Specific examples of the wetting agent include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, 1,3-butanediol, 1,3-propanediol, and 2-methyl-1,3-propane. Diol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, glycerin, 1,2,6-hexanetriol, 2-ethyl-1,3-hexanediol, 1,2 Polyhydric alcohols such as 1,4-butanetriol, 1,2,3-butanetriol, and petriol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene Polyhydric alcohol alkyl ethers such as glycol monobutyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether and propylene glycol monoethyl ether, polyhydric alcohol aryl ethers such as ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether Forehead: Nitrogen-containing heterocyclic compounds such as N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethylimidazolidinone, ε-caprolactam; formamide, N-methyl Amides such as formamide, formamide, N, N-dimethylformamide; monoethanolamine, diethanolamine, triethanolamine, monoethylamine, diethylamine, trie Examples thereof include amines such as tilamine, sulfur-containing compounds such as dimethyl sulfoxide, sulfolane and thiodiethanol, propylene carbonate, ethylene carbonate, and γ-butyrolactone. These solvents are used alone or in combination with water.

  Further, the penetrant is added for the purpose of improving the wettability between the recording liquid and the recording material and adjusting the penetration speed. As the penetrant, those represented by the following formulas (1) to (4) are preferable. That is, a polyoxyethylene alkylphenyl ether surfactant of the following formula (1), an acetylene glycol surfactant of the formula (2), a polyoxyethylene alkyl ether surfactant of the following formula (3) and the formula (4 The polyoxyethylene polyoxypropylene alkyl ether-based surfactant (1) can reduce the surface tension of the liquid, so that the wettability can be improved and the penetration rate can be increased.

（Ｒは分岐していても良い炭素数６〜１４の炭化水素鎖、ｋ：５〜２０）

(R is an optionally branched hydrocarbon chain having 6 to 14 carbon atoms, k: 5 to 20)

（ｍ，ｎは０〜４０）

(M and n are 0 to 40)

（Ｒは分岐してもよい炭素数６〜１４の炭化水素鎖、ｎは５〜２０）

(R is a C6-C14 hydrocarbon chain which may be branched, n is 5-20)

（Ｒは炭素数６〜１４の炭化水素鎖、ｍ、ｎは２０以下の数）

(R is a hydrocarbon chain having 6 to 14 carbon atoms, m and n are numbers of 20 or less)

  Other than the compounds of the above formulas (1) to (4), for example, diethylene glycol monophenyl ether, ethylene glycol monophenyl ether, ethylene glycol monoallyl ether, diethylene glycol monophenyl ether, diethylene glycol monobutyl ether, propylene glycol monobutyl ether, tetraethylene glycol chlorophenyl Use alkyl and aryl ethers of polyhydric alcohols such as ethers, nonionic surfactants such as polyoxyethylene polyoxypropylene block copolymers, fluorine-based surfactants, lower alcohols such as ethanol and 2-propanol However, diethylene glycol monobutyl ether is particularly preferable.

The surface tension of the recording liquid of the present invention is preferably 25 dyne / cm or less, and more preferably 23 dyne / cm or less from the viewpoint of achieving both wettability with the recording material and droplet formation.
The viscosity of the recording liquid of the present invention is preferably 1.0 to 20.0 cP, and more preferably 3.0 to 10.0 cP from the viewpoint of ejection stability.
The pH of the recording liquid of the present invention is preferably from 3 to 11, and more preferably from 6 to 10 from the viewpoint of preventing corrosion of the metal member in contact with the liquid.

  The recording liquid of the present invention can contain an antiseptic / antifungal agent. By containing the antiseptic / antifungal agent, the growth of bacteria can be suppressed, and the storage stability and the image quality stability can be improved. As antiseptic / antifungal agents, benzotriazole, sodium dehydroacetate, sodium sorbate, sodium 2-pyridinethiol-1-oxide, isothiazoline compounds, sodium benzoate, sodium pentachlorophenol, and the like can be used.

  The recording liquid of the present invention can contain a rust inhibitor. By containing a rust preventive agent, a coating can be formed on the metal surface in contact with the liquid such as a head and corrosion can be prevented. As the rust inhibitor, for example, acidic sulfite, sodium thiosulfate, ammonium thiodiglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, dicyclohexylammonium nitrite and the like can be used.

  The recording liquid of the present invention can contain an antioxidant. By containing an antioxidant, even when radical species that cause corrosion are generated, the antioxidant can be prevented by eliminating the radical species. Typical examples of the antioxidant include phenolic compounds and amine compounds. Examples of the phenolic compounds include hydroquinone and gallate compounds, 2,6-di-tert-butyl-p-cresol, and stearyl. -Β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl- 6-tert-butylphenol), 4,4′-thiobis (3-methyl-6-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-4-hydroxybenzyl) benzene, Hindered materials such as lith (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, tetrakis [methylene-3 (3 ′, 5′-di-tert-butyl-4-hydroxyphenyl) propionate] methane Phenol compounds are exemplified, and amine compounds include N, N′-diphenyl-p-phenylenediamine, phenyl-β-naphthylamine, phenyl-α-naphthylamine, N, N′-β-naphthyl-p-phenylene. Examples include diamine, N, N′-diphenylethylenediamine, phenothiazine, N, N′-di-sec-butyl-p-phenylenediamine, 4,4′-tetramethyl-diaminodiphenylmethane, and the like. Further, as the latter, sulfur compounds and phosphorus compounds are representative, but as sulfur compounds, dilauryl thiodipropionate, distearyl thiodipropionate, lauryl stearyl thiodipropionate, dithiol. Examples include myristyl thiodipropionate, distearyl β, β′-thiodibutyrate, 2-mercaptobenzimidazole, dilauryl sulfide and the like, and phosphorus compounds include triphenyl phosphite, trioctadecyl phosphite, tridecyl. Examples include phosphite, trilauryl trithiophosphite, diphenylisodecyl phosphite, trinonylphenyl phosphite, distearyl pentaerythritol phosphite.

  The recording liquid of the present invention can contain a pH adjuster. Examples of the pH adjuster include hydroxides of alkali metal elements such as lithium hydroxide, sodium hydroxide, potassium hydroxide, ammonium hydroxide, quaternary ammonium hydroxide, quaternary phosphonium hydroxide, lithium carbonate, Examples include alkali metal carbonates such as sodium carbonate and potassium carbonate, amines such as diethanolamine and triethanolamine, boric acid, hydrochloric acid, nitric acid, sulfuric acid, and acetic acid.

According to this invention, even if it is the existing printing coated paper, if the said conditions are satisfy | filled, a favorable image can be formed.
Existing coated paper for printing is used for commercial printing and publishing printing such as so-called art paper (A0, A1), A2 coated paper, A3 coated paper, B2 coated paper, lightweight coated paper, and fine coated paper. Coated paper, used for offset printing, gravure printing, and the like.
Specific products include mirror-coated platinum (Oji Paper), Esprit Coat C (Nippon Paper Industries), etc. as cast-coated paper.
Art paper includes OK Kanfuji N, OK Kanfuji-R40N, SA Kanfuji N, Satin Kanfuji N, Satin Kanfuji-R40N, Ultra Satin Kanfuji N, Ultra OK Kanfuji N, Kanto One Side (Oji Paper), NPi Special Art, NPi Super Art, NPi Super Dal, NPi Dal Art (Nippon Paper), Utrillo Super Art, Utrillo Super Dal, Utrillo Premium (Daiou Paper), Fine Art A, Tohishi Art, Super Matte Art A, Luxury Dal Art A (Mitsubishi Paper) Examples include Super Art N, Thunderbird Super Art MN, Thunderbird Special Art, Thunderbird Dull Art N (Chuetsu Pulp).
As A2 coated paper, OK top coat + (plus), OK top coat S, OK Casablanca, OK Casablanca V, OK Trinity, OK Trinity NaVi, New Age, New Age W, OK Top Coat Mat N, OK Royal Coat, OK Top Coat Dull, Z Coat, OK Bulk Princess, OK Bulk King, OK Bulk King Satin, OK Top Coat +, OK Non Wrinkle, OK Court V, OK Court N Green 100, OK Matt Court Green 100, New Age Green 100 , Z Coat Green 100 (Oji Paper), Aurora Coat, Shiraoi Mat, Imperial Mat, Silver Diamond, Recycle Coat 100, Cycle Mat 100 (Nippon Paper Industries), Mu Coat, Mu White, Mu Mat, White Mu Mat (North) Papermaking), Thunderbird coat N, Regina thunderbird coat 100, Thunderbird mat coat N, Regina thunderbird mat 100 (Chuetsu Pulp Industry), Pearl coat, White pearl coat N, New V mat, White new V mat, Pearl coat REW, White pearl Examples thereof include coat NREW, new V mat REW, white new V mat REW (Mitsubishi Paper), and the like.
As A3 coated (lightweight coated) paper, OK Coat L, Royal Coat L, OK Coat LR, OK White L, OK Royal Coat LR, OK Coat L Green 100, OK Matt Coat L Green 100 (Oji Paper), Easter DX , Recycle Coat L100, Aurora L, Recycle Mat L100, <SSS> Energy White (Nippon Paper), Utrillo Coat L, Mathis Coat (Dao Paper), High Alpha, Alpha Matt, (N) Kinmari L, Kinmari HiL (Hokuetsu) Papermaking), N pearl coat L, N pearl coat LREW, swing mat REW (Mitsubishi Paper), Super Emine, Emine, Chaton (Chuetsu Pulp Industries), and the like.
Examples of the B2 coat (medium coat) paper include OK medium coat, (F) MCOP, OK Astro Ross, OK Astro Dal, OK Astro Mat (Oji Paper), King O (Nippon Paper Industries), and the like.
Finely coated paper includes OK Royal Light S Green 100, OK Everlight Coat, OK Everlight R, OK Evergreen, Clean Hit MG, OK Fine Coating Super Eco G, Eco Green Dal, OK Fine Coating Matte Eco G100, OK Starlight Coat, OK Soft Royal, OK Bright, Clean Hit G, Yamayuri Bright, Yamayuri Bright G, OK Aqua Light Coat, OK Royal Light S Green 100, OK Bright (Rough / Shiny), Snow Mat, Snow Mat DX, OK Bulk Princess, OK Bulk Lily (Oji Paper), Pyrenee DX, Pegasus Hyper 8, Aurora S, Andes DX, Super Andes DX, Space DX, Seine DX, Special Gravure DX, Pegasus, Silver Pegasus, Pegasus Harmony, Greenland X100, Super Greenland DX100, <SSS> Energy Soft, <SSS> Energy Light, EE Henry (Nippon Paper Industries), Canto Excel, Excel Super B, Excel Super C, Canto Excel Bar, Utrillo Excel, Heine Excel, Dante Excel ( Daio Paper), Cosmo Ace (Daiso Showa Paperboard), Semi Upper L, High Beta, High Gamma, Shiromari L, Hamming, White Hamming, Semi Upper HiL, Shiromari HiL (Hokuetsu Paper), Ruby Light HREW, Pearl Soft, Ruby Light H (Mitsubishi Paper), Chaton, Aliso, Smash (Chuetsu Pulp Industries), Star Cherry, Cherry Super (Maruzumi Paper) and the like.

  In addition, as a special coated paper, if it already satisfies the conditions of this patent, it can be used as a medium of this patent. For example, some coated paper for electrophotography and coated paper for gravure printing can be mentioned. Specific examples include POD gloss coat (Oji Paper), Space DX (Nippon Paper Industries), and Ace (Nippon Paper Industries). These have an appropriate pore volume of the coat layer and can be used as the media of this patent.

-Printer The ink in the ink media set of the present invention is an ink jet head that uses a piezoelectric element as pressure generating means for pressurizing the ink in the ink flow path and deforms the diaphragm that forms the wall surface of the ink flow path to generate an ink flow. A so-called piezo-type device that discharges ink droplets by changing the volume in the path (see Japanese Patent Application Laid-Open No. 2-51734), or a heating resistor is used to heat the ink in the ink flow path to generate bubbles. A so-called thermal type (see Japanese Patent Application Laid-Open No. 61-59911), a diaphragm that forms a wall surface of an ink flow path and an electrode are arranged to face each other, and the diaphragm is generated by an electrostatic force generated between the diaphragm and the electrode. By changing the volume of the ink flow path, it is possible to change any volume of the ink flow path to discharge ink droplets (see JP-A-6-71882). It can be used well for printers equipped with ink jet heads.

(ink cartridge)
The ink cartridge of the present invention contains the ink in the ink media set of the present invention in a container, and further includes other members and the like appropriately selected as necessary.
The container is not particularly limited, and its shape, structure, size, material and the like can be appropriately selected according to the purpose. For example, at least an ink bag formed of an aluminum laminate film, a resin film, or the like Preferred examples include those possessed.

Next, the ink cartridge will be described with reference to FIGS. Here, FIG. 6 is a view showing an example of the ink cartridge of the present invention, and FIG. 7 is a view including a case (exterior) of the ink cartridge of FIG.
As shown in FIG. 6, the ink cartridge (200) is filled into the ink bag (241) from the ink inlet (242) and exhausted, and then the ink inlet (242) is closed by fusion. In use, the needle of the apparatus main body is pierced into the ink discharge port (243) made of a rubber member and supplied to the apparatus.
The ink bag (241) is formed of a packaging member such as a non-permeable aluminum laminate film. As shown in FIG. 7, the ink bag (241) is usually housed in a plastic cartridge case (244) and is detachably mounted on various ink jet recording apparatuses.

  The ink cartridge of the present invention contains ink in the ink media set of the present invention and can be used by being detachably attached to various ink jet recording apparatuses, and can be detachably attached to the ink jet recording apparatus of the present invention described later. It is particularly preferable to install and use.

(Inkjet recording apparatus and inkjet recording method)
The ink jet recording apparatus of the present invention includes at least ink flying means, and further includes other means appropriately selected as necessary, for example, stimulus generation means, control means, and the like.
The inkjet recording method of the present invention includes at least an ink flying process, and further includes other processes appropriately selected as necessary, for example, a stimulus generation process, a control process, and the like.
The ink jet recording method of the present invention can be preferably carried out by the ink jet recording apparatus of the present invention, and the ink flying step can be suitably carried out by the ink flying means. Moreover, the said other process can be suitably performed by the said other means.

-Ink flying process and ink flying means-
The ink flying step is a step of recording an image on a recording medium in the ink media set by applying a stimulus to the ink in the ink media set of the present invention and causing the ink to fly.
The ink flying means is means for applying a stimulus to the ink in the ink media set of the present invention and causing the ink to fly to record an image on a recording medium in the ink media set. The ink flying means is not particularly limited, and examples thereof include various nozzles for ejecting ink.
In the present invention, it is preferable that at least a part of the liquid chamber portion, the fluid resistance portion, the vibration plate, and the nozzle member of the ink jet head is formed of a material containing at least one of silicon and nickel.
The nozzle diameter of the inkjet nozzle is preferably 30 μm or less, and preferably 1 to 20 μm.
In addition, it is preferable that a sub tank for supplying ink is provided on the ink jet head, and the sub tank is replenished with ink from an ink cartridge through a supply tube.
In the ink jet recording method of the present invention, the maximum ink adhesion amount is preferably 8 to ²⁰ g / m ² at a resolution of 300 dpi or more.

  The stimulus can be generated by, for example, the stimulus generating means, and the stimulus is not particularly limited and can be appropriately selected according to the purpose, and includes heat, pressure, vibration, light, and the like. . These may be used individually by 1 type and may use 2 or more types together. Among these, heat and pressure are preferable.

  Examples of the stimulus generating means include a heating device, a pressurizing device, a piezoelectric element, a vibration generating device, an ultrasonic oscillator, a light, and the like. Specifically, for example, a piezoelectric actuator such as a piezoelectric element, Examples include thermal actuators that use phase change due to liquid film boiling using electrothermal transducers such as heating resistors, shape memory alloy actuators that use metal phase changes due to temperature changes, electrostatic actuators that use electrostatic force, etc. It is done.

  There is no particular limitation on the mode of ink flying in the ink media set, and it varies depending on the type of the stimulus. For example, when the stimulus is “heat”, a recording signal is output to the ink in the recording head. A method of applying corresponding thermal energy using, for example, a thermal head, generating bubbles in the ink by the thermal energy, and discharging and ejecting the ink as droplets from the nozzle holes of the recording head by the pressure of the bubbles , Etc. Further, when the stimulus is “pressure”, for example, by applying a voltage to a piezoelectric element bonded to a position called a pressure chamber in an ink flow path in the recording head, the piezoelectric element bends and the volume of the pressure chamber is increased. And a method of ejecting and ejecting the ink as droplets from the nozzle holes of the recording head.

  The size of the droplets of ink to be ejected is preferably 1 to 40 pl, the speed of ejection and ejection is preferably 5 to 20 m / s, and the driving frequency is 1 kHz or more. The resolution is preferably 300 dpi or more.

  The control means is not particularly limited as long as the movement of each means can be controlled, and can be appropriately selected according to the purpose. Examples thereof include devices such as sequencers and computers.

  One mode for carrying out the ink jet recording method of the present invention by the ink jet recording apparatus of the present invention will be described with reference to the drawings. The ink jet recording apparatus shown in FIG. 8 has an apparatus main body (101), a paper feed tray (102) for loading paper mounted on the apparatus main body (101), and an image mounted on the apparatus main body (101). A paper discharge tray (103) for stocking the formed paper and an ink cartridge loading section (104) are provided. On the upper surface of the ink cartridge loading section (104), an operation section (105) such as operation keys and a display is arranged. The ink cartridge loading unit (104) has an openable / closable front cover (115) for attaching and detaching the ink cartridge (201).

  As shown in FIGS. 9 and 10, the apparatus main body (101) includes a guide rod (131), which is a guide member horizontally mounted on left and right side plates (not shown), and a stay (132). 133) is slidably held in the main scanning direction, and is moved and scanned in the direction of the arrow in FIG. 10 by a main scanning motor (not shown).

The carriage (133) includes a plurality of recording heads (134) including four inkjet recording heads that eject ink droplets of each color of yellow (Y), cyan (C), magenta (M), and black (Bk). Are arranged in a direction crossing the main scanning direction, and the ink droplet ejection direction is directed downward.
As an inkjet recording head constituting the recording head (134), a piezoelectric actuator such as a piezoelectric element, a thermal actuator that utilizes a phase change caused by liquid film boiling using an electrothermal transducer such as a heating resistor, and a temperature change A shape memory alloy actuator using a metal phase change, an electrostatic actuator using an electrostatic force, or the like provided as an energy generating means for discharging ink can be used.
The carriage (133) is equipped with a sub tank (135) for each color for supplying ink of each color to the recording head (134). The sub tank (135) is supplied with ink in the ink media set of the present invention from the ink cartridge (201) of the present invention loaded in the ink cartridge loading section (105) via an ink supply tube (not shown). Is done.

  On the other hand, as a paper feeding unit for feeding the paper (142) stacked on the paper stacking unit (pressure plate) (141) of the paper feed tray (103), 1 sheet (142) is fed from the paper stacking unit (141). A half-moon roller (sheet feeding roller (143)) that separates and feeds the sheets one by one, and a sheet separation roller (144) made of a material having a large friction coefficient, facing the sheet feeding roller (143). It is biased toward the paper feed roller (143).

  A conveying belt (151) for electrostatically adsorbing and conveying the paper (142) as a conveying unit for conveying the paper (142) fed from the paper feeding unit below the recording head (134). A counter roller (152) for conveying the paper (142) sent from the paper supply unit via the guide (145) between the conveying belt (151) and a paper (substantially vertically upward) ( 142) and a leading guide roller 153 urged toward the conveying belt (151) by the holding member (154). (155) and a charging roller (156) which is a charging means for charging the surface of the conveyor belt (151).

  The conveyance belt (151) is an endless belt, is stretched between the conveyance roller (157) and the tension roller (158), and can circulate in the belt conveyance direction. The transport belt (151) includes, for example, a surface layer serving as a sheet adsorbing surface formed of a resin material having a thickness of about 40 μm without resistance control, for example, a copolymer of tetrafluoroethylene and ethylene (ETFE), It has the same material as the surface layer and a back layer (medium resistance layer, earth layer) that has been subjected to resistance control by carbon. On the back side of the conveyance belt (151), a guide member (161) is arranged corresponding to the printing area by the recording head (134). As a paper discharge unit for discharging the paper (142) recorded by the recording head (134), a separation claw (171) for separating the paper (142) from the transport belt (151), and paper discharge A roller (172) and a paper discharge roller (173) are provided, and a paper discharge tray (103) is arranged below the paper discharge roller (172).

  A double-sided paper feeding unit (181) is detachably attached to the back surface of the apparatus main body (101). The double-sided paper feeding unit (181) takes in the paper (142) returned by the reverse rotation of the transport belt (151), reverses it, and feeds it again between the counter roller (152) and the transport belt (151). . A manual paper feed unit (182) is provided on the upper surface of the double-sided paper feed unit (181).

In this ink jet recording apparatus, the sheet (142) is separated and fed one by one from the sheet feeding unit, and the sheet (142) fed substantially vertically upward is guided by the guide (145) and the transport belt (151). ) And the counter roller (152). Further, the leading end is guided by the conveying guide (153) and pressed against the conveying belt (151) by the leading end pressure roller (155), and the conveying direction is changed by about 90 °.
At this time, the conveyance belt (151) is charged by the charging roller (156), and the sheet (142) is electrostatically adsorbed to the conveyance belt (151) and conveyed. Therefore, by driving the recording head (134) according to the image signal while moving the carriage (133), ink droplets are ejected onto the stopped sheet (142) to record one line, and the sheet ( 142), the next line is recorded after a predetermined amount is conveyed. Upon receiving a recording end signal or a signal that the rear end of the paper (142) has reached the recording area, the recording operation is finished and the paper (142) is discharged to the paper discharge tray (103).
When the ink remaining amount near end in the sub tank (135) is detected, a required amount of ink is supplied from the ink cartridge (201) to the sub tank (135).

  The ink jet recording apparatus shown in FIG. 13 is obtained by mounting the finger touch drying unit and the heat fixing unit (drying unit) of the present invention on the ink jet recording apparatus shown in FIG. After the printing is completed, the medium transferred from the conveyance belt (151) to the conveyance belt (201) on the drying unit side through the discharge roller (173) is transferred from the touch drying device (203) to the thermal energy in a non-contact state as necessary. Or, it is exposed to cold air to promote dry touch. The media on which the touch drying has been completed passes through the fixing roller of the fixing device (202) in order from the leading end, and the heat treatment of the present invention is completed.

FIG. 14 shows an example of a basic layout in the case where the fixing roller of the fixing unit is provided twice in order to perform faster fixing processing. When the medium (A4) is transported by the transport belt (A1), the touch drying is performed by the infrared heater (A2). The fixing roller (A) and the pressure roller (B) are provided in a double manner. By using two rollers, processing can be performed at a speed twice that of a single roller. This unit may be provided in the printer as shown in FIG. 13 or may be provided individually as a fixing device.
Such a fixing device can be controlled by the fixing temperature control device of the present invention, and the configuration itself of this fixing temperature control device is the surface of at least one roller of a pair of rollers pressed against each other by one temperature sensor. The temperature is monitored (detected), and the heater is blinked to control the roller temperature. When the paper is passed through the roller pair, the heater detects the roller surface temperature by the temperature sensor and the heater temperature. Control is performed by switching between a full-length heat generation state and a partial heat generation state every predetermined time in the energizable range. For example, the surface temperature of each of the fixing roller and pressure roller divided areas is monitored, the monitored temperature signal is fed back to, for example, a controller, and the set temperature can be changed (can be input) in advance. It can be similar to so-called energization control means.

An example of such a fixing device with a fixing temperature control device is described in, for example, Japanese Patent Publication No. 7-82280. An example of the configuration is shown in FIGS.
FIG. 37 shows a fixing device provided with a heater (long heater) (21) having a heating filament over the entire length in the fixing roller and a heater (short heater) (20) partially having a heating filament. It is a circuit diagram of an example to which the present invention is applied. The short heater (20) and the long heater (21) can be applied with an AC voltage of 100V by relays (SSR1) and (SSR2), respectively, and the relays (SSR1) and (SSR2) have a temperature control circuit (22). Operates in response to a signal from As shown in detail in FIG. 38, the temperature control circuit (22) is a signal from a temperature sensor (23) provided only for the roller incorporating the short heater (20) and the long heater (21). And a signal (Ref) corresponding to the set temperature are compared by a comparator (24), and if there is a difference greater than a predetermined value, a temperature control signal is input to the AND gates (AND1) and (AND2). The AND gates (AND1) and (AND2) are alternately input from the timer (25), respectively, to the preset short heater (20) and long heater (21), and the timing of energization is possible from the comparator (24). And the signal from the timer (25) overlap each other, a signal for operating the relays (SSR1) and (SSR2) is output. The timer (25) may be replaced with a copy number counter.
FIG. 39 shows the control heater switching signal from the timer (25) of the above circuit, the temperature control signal from the comparator (24), and the input signals to the relays (SSR2) and (SSR1) for controlling the long and short heaters. It is a timing chart. As shown in the figure, only the long heater is controlled to blink by a temperature control signal during standby. Next, at the time of paper feeding, the timing at which the long heater can be energized and the timing at which the short heater can be energized are alternately switched (T ₁ ), (T ₂ ) time, and the temperature control signal from the comparator and the long heater Alternatively, the heaters are energized at the timing when the energization possible timings of the short heaters overlap, and the temperature control of the rollers is performed.

  In this ink jet recording apparatus, when the ink in the ink cartridge (201) of the present invention is used up, the casing of the ink cartridge (201) can be disassembled and only the ink bag inside can be replaced. Further, the ink cartridge (201) can supply ink stably even when the ink cartridge (201) is vertically placed and has a front loading configuration. Therefore, even when the upper part of the apparatus main body (101) is closed and installed, for example, even when it is stored in a rack or an object is placed on the upper surface of the apparatus main body (101), the ink The cartridge (201) can be easily replaced.

  Here, an example is described in which the present invention is applied to a serial (shuttle type) ink jet recording apparatus that is scanned by a carriage, but the present invention can be similarly applied to a line type ink jet recording apparatus having a line type head.

  Further, the ink jet recording apparatus and the ink jet recording method of the present invention can be applied to various types of recording by the ink jet recording method, and are particularly applicable to, for example, an ink jet recording printer, a facsimile apparatus, a copying apparatus, and a printer / fax / copy multifunction machine. It can be suitably applied.

Hereinafter, an inkjet head to which the present invention is applied will be described.
FIG. 11 is an enlarged view of elements of an ink jet head according to an embodiment of the present invention, and FIG. 12 is an enlarged cross-sectional view of the main part in the channel-to-channel direction of the head.
This ink-jet head includes a frame (10) formed with an engraving to be an ink supply port (not shown) and a common liquid chamber (1b), an engraving and a nozzle to be a fluid resistance portion (2a) and a pressurized liquid chamber (2b). A flow path plate (20) having a communication port (2c) communicating with (3a), a nozzle plate forming a nozzle (3a), a convex portion (6a), a diaphragm portion (6b), and an ink inflow port (6c). ), A laminated piezoelectric element (50) bonded to the diaphragm (60) via an adhesive layer (70), and a base (50) to which the laminated piezoelectric element (50) is fixed. 40).
The base (40) is made of a barium titanate ceramic, and the laminated piezoelectric elements (50) are arranged in two rows and joined.
The laminated piezoelectric element (50) is composed of a lead zirconate titanate (PZT) piezoelectric layer having a thickness of 10 to 50 μm / layer, and an internal electrode layer made of silver / palladium (AgPd) having a thickness of several μm / layer. Are stacked alternately. The internal electrode layer is connected to the external electrode at both ends.
The laminated piezoelectric element (50) is divided onto comb teeth by half-cut dicing, and each one is used as a drive part (5f) and a support part (5g) (non-drive part). The length of the outside of the external electrode is limited by cutting or the like so as to be divided by half-cut dicing, and these become a plurality of individual electrodes. The other is not divided by dicing but is conductive and becomes a common electrode.
The FPC 8 is soldered to the individual electrodes of the drive unit. In addition, the common electrode is provided with an electrode layer at the end of the laminated piezoelectric element, and is wound around and joined to the Gnd electrode of the FPC 8. A driver IC (not shown) is mounted on the FPC 8 to control application of a driving voltage to the driving unit (5f).

The diaphragm (60) is an island-shaped convex portion (island) that joins the thin film diaphragm portion (6b) and the laminated piezoelectric element (50) serving as the drive portion (5f) formed at the center portion of the diaphragm portion (6b). Part) (6a), a thick film part including a beam to be joined to the support part, and an opening serving as an ink inflow port (6c) are formed by stacking two Ni plating films by electroforming. The diaphragm portion has a thickness of 3 μm and a width of 35 μm (one side).
The island-shaped convex part (6a) of the diaphragm (60) and the drive part (5f) of the laminated piezoelectric element (50), and the coupling of the diaphragm (60) and the frame (10) are bonded layers including a gap material ( 70) is bonded by patterning.

The flow path plate (20) uses a silicon single crystal substrate, is engraved to be a fluid resistance portion (2a), a pressurized liquid chamber (2b), and a through-hole to be a communication port (2c) at a position relative to the nozzle (3a) Was patterned by an etching method.
The portion left by etching becomes the partition wall (2d) of the pressurized liquid chamber (2b). Further, in this head, a portion for narrowing the etching width was provided, and this was used as the fluid resistance portion (2a).
The nozzle plate (30) is formed of a metal material, for example, an Ni plating film by an electroforming method, and has a large number of nozzles (3a) which are fine discharge ports for flying ink droplets. . The inner shape (inner shape) of the nozzle (3a) is formed in a horn shape (may be a substantially cylindrical shape or a substantially frustum shape). The diameter of the nozzle (3a) is approximately 20 to 35 μm on the ink droplet outlet side. The nozzle pitch of each row was 150 dpi.

The frame (10) that forms the engraving that becomes the ink supply port and the common liquid chamber (1b) is made by resin molding.
In the ink jet head configured as described above, a drive waveform (pulse voltage of 10 to 50 V) is applied to the drive unit (5f) according to the recording signal, thereby causing displacement in the stacking direction in the drive unit (5f). The pressurized liquid chamber (2b) is pressurized through the diaphragm (30) to increase the pressure, and ink droplets are ejected from the nozzle (3a).
Thereafter, the ink pressure in the pressurized liquid chamber (2b) decreases with the end of ink droplet ejection, and negative pressure is generated in the pressurized liquid chamber (2b) due to the inertia of the ink flow and the discharge process of the drive pulse. Then, the process proceeds to the ink filling process. At this time, the ink supplied from the ink tank flows into the common liquid chamber (1b), passes from the common liquid chamber (1b) through the ink inlet (6c), the fluid resistance portion (2a), and the pressurized liquid chamber ( 2b) is filled.
The fluid resistance portion (2a) has an effect on the attenuation of the residual pressure vibration after the discharge, but becomes resistant to the refilling due to the surface tension. By appropriately selecting the fluid resistance portion, it is possible to balance the attenuation of the residual pressure and the refill time, and to shorten the time (drive cycle) until the transition to the next ink droplet ejection operation.

<Explanation of relationship between nozzle plate, ink and media>
When an ink having a relatively low surface tension is used like the ink used in the image forming method of the present invention, it is desirable that the nozzle plate is excellent in water repellency and ink repellency. This is because by using a nozzle plate with excellent water repellency and ink repellency, an ink meniscus can be formed normally even with low surface tension ink, and as a result, ink droplet formation (particle formation) can be improved. is there. When the meniscus is formed normally, the ink is not pulled in one direction when the ink is ejected, and as a result, there is little ink ejection bending and an image with high dot position accuracy can be obtained.
In addition, when printing on a medium having low absorbability such as a medium (paper) used in the ink media set of the present invention, the quality of the dot position is remarkably increased in image quality. In other words, since it is difficult for ink to spread on a medium with low absorbency, if the dot position accuracy is as low as possible, a portion where the ink cannot be filled with the medium, that is, a white portion is generated. This portion that cannot be filled up leads to uneven image density and reduced image density, and appears in the degradation of image quality.
However, since the ink-jet head used in the present invention has high dot position accuracy even when using low surface tension ink, the ink can fill the medium even when using low-absorbency media. A printed matter with high image quality can be obtained without deteriorating.

<Ink repellent layer>
(Surface roughness)
The surface roughness Ra of the ink repellent layer used in the present invention is preferably 0.2 μm or less. By setting the surface roughness Ra to 0.2 μm or less, it is possible to reduce wiping residue during wiping.
15 and 16 are sectional views of an ink jet head nozzle plate prepared according to the present invention.
In this embodiment, the nozzle plate (2) which is the base material of the ink jet head is produced by electroforming Ni, and the ink repellent film (1) which is a silicone resin film having a thickness of 0.1 μm or more is formed on the surface. The surface roughness is preferably Ra = 0.2 or less. The film thickness of the ink repellent film (1) is more preferably 0.5 μm or more.
When the ink (3) is filled, as shown in FIG. 16 (c), a meniscus (liquid level) P is formed at the boundary between the ink repellent film (1) and the nozzle plate (2) made of a silicone resin film.

(Round shape)
The cross-sectional area in the plane perpendicular to the center line of the ink repellent film formed on the surface of the ink jet head on which the ink discharge opening is formed is gradually increased as the distance from the substrate surface increases. It is formed to grow.

The shape of the ink repellent film in the vicinity of the opening is preferably a curved surface.
It is preferable that the radius of curvature of the curve in the vicinity of the opening of the ink repellent film in the cross section on the plane including the center line of the opening is greater than or equal to the thickness of the ink repellent film.
The curve in the vicinity of the opening from the edge of the opening of the ink repellent film in a cross section in a plane including the center line of the opening described above forms a substantially arc curve, and the radius of curvature of the arc is the thickness of the ink repellent film. The above is preferable.
It is preferable that a tangent line passing through the edge of the opening of the ink repellent film in a cross section in a plane including the center line of the opening described above has an angle of less than 90 degrees from the surface of the nozzle member including the end.

  The opening of the nozzle plate (2) is opened such that a cross section taken along a plane perpendicular to the center line indicated by the alternate long and short dash line in FIG. 16 is substantially circular with the center line as the center. In addition, the ink repellent film (1) formed on the ink ejection surface of the nozzle plate (2) gradually increases as the cross-sectional area of the opening portion by a plane perpendicular to the center line moves away from the nozzle plate (2). It is formed as follows.

More specifically, as shown in FIG. 16A, the opening portion of the ink repellent film (1) is a round whose curvature radius (r) is a curve near the opening edge from the opening edge of the nozzle plate (2). It has a shape. The curvature radius r is preferably equal to or greater than the thickness (d) other than the vicinity of the opening of the ink repellent film (1).
This thickness (d) is the thickness of the ink repellent film (1) other than the round part that is the opening, and may be the maximum thickness of the ink repellent film.

  In this way, the opening of the ink repellent film (1) connected to the opening of the nozzle plate (2) has a shape without a sharp point (smooth curve without a pointed portion) and a curve without a catching portion. Therefore, even when wiping with a wiper made of a material such as rubber, the pointed portion is caught by the wiper and the ink repellent film (1) is peeled off from the nozzle plate (2). There can be no.

  Further, as shown in FIG. 16B, the tangent line passing through the edge of the opening portion of the ink repellent film (1) in the cross section in the plane including the center line of the opening portion of the nozzle plate (2) is the opening portion. It is preferable that the angle (θ) from the surface of the nozzle plate (2) including the edge of the opening of the nozzle plate (2) connected to the edge is less than 90 degrees.

Thus, as shown in FIG. 16C, the angle (θ) between the tangent at the edge of the opening portion of the ink repellent film (1) and the nozzle plate surface (2) is less than 90 degrees. Meniscus (liquid level) (P) is stably formed at the boundary portion between the ink repellent film (1) and the nozzle plate (2), and the possibility that meniscus (P) is formed at other portions is greatly reduced. Can do.
As a result, the meniscus formation surface can be stabilized, so that the ink ejection stability when forming an image in an image forming apparatus using an ink jet head including the nozzle plate (2) is improved. be able to.

As the silicone resin used in the present embodiment, a room temperature curable liquid silicone resin is desirable, and a silicone resin with a hydrolysis reaction is particularly preferable. In the following examples, SR2411 manufactured by Toray Dow Corning Co., Ltd. was used.
Table 1 below shows the shape of the ink repellent film (1) in the ink jet head according to the present embodiment from the edge of the nozzle plate (2) to the vicinity of the edge of the nozzle, the ink pool around the nozzle, and the edge It is the result evaluated about peeling and jetting stability.

In the case where the edge portion (near the edge of the opening portion) of the ink repellent film (1) has a shape that is substantially sharp, an ink pool is seen around the nozzle, and the edge is peeled off by wiping.
In the case of the round shape, no ink accumulation occurred, but as a comparative example, r <d as illustrated in FIG. 17A, and some edge peeling occurred, and FIG. In the case of θ> 90 degrees as exemplified in FIG. 5, the ejection of droplets was unstable.

  That is, as shown in FIG. 17C, when (r) <(d) or (θ)> 90 degrees, the ink repellent film (1) and the nozzle plate are filled when the ink (3) is filled. When the meniscus (liquid level) (P) is formed at the boundary part of (2), and the convex part toward the center of the opening part in the ink repellent film (1 ′) (cross-sectional area perpendicular to the center line in the opening part) In some cases, the meniscus (Q) is formed in a portion where the value is smallest. For this reason, variation occurs in the ejection stability of the ink when the image is formed by the image forming apparatus using the ink jet head including the nozzle plate (2).

  Next, the manufacturing method of the nozzle member of the inkjet head according to the above-described embodiment will be described.

FIG. 18 is a diagram showing a configuration in which an ink repellent film (1) is formed by applying a silicone resin by application using the dispenser (4) according to the present embodiment.
A dispenser (4) for applying a silicone solution is disposed on the ink ejection surface side of the nozzle (2) by Ni electroforming, and a predetermined distance between the nozzle plate (2) and the tip of the needle (5) is predetermined. As shown in FIGS. 15 and 16, the ink is discharged from the nozzle plate (2) by scanning the dispenser (4) while discharging silicone from the tip of the needle (5). A silicone resin film could be selectively formed on the surface.

  The silicone resin used in the present embodiment was a room temperature curing type silicone resin SR2411 (manufactured by Toray Dow Corning Co., Ltd.) viscosity: 10 mPa · s. However, a slight amount of silicone was found around the nozzle holes and the back of the nozzle plate. The silicone resin film thus selectively formed had a thickness of 1.2 μm and a surface roughness (Ra) of 0.18 μm.

As shown in FIG. 19A, the application port at the tip of the needle (5) according to this embodiment has a width that is equal to the application width to the nozzle plate (2) that is the application target. Thereby, the application | coating to the whole coating object can be completed only by scanning a dispenser (4) once in an application direction.
That is, the scanning direction for the coating operation can be set to only one direction, and the necessity of changing the direction as shown in FIG. 19B or scanning in the opposite direction can be eliminated.

  Here, as shown in FIG. 17 (b), the tip of the general needle (5) is much narrower than the application width to the nozzle plate (2), which is the application target, and thus the application to the entire application target is completed. In order to achieve this, it is necessary to change the scanning direction for the coating operation by 90 degrees and move it in the opposite direction, or to scan in multiple directions, and it is difficult to apply a uniform thickness to the entire coating target. Met.

  According to the present embodiment, the width of the application port at the tip of the needle (5) is ensured only by the application width to the nozzle plate (2) that is the application target, so that the thickness to be applied over the entire application target is uniform. The surface finish can be made with high accuracy.

FIG. 20 is a diagram illustrating a coating operation using the dispenser (4) according to the present embodiment. The basic configuration is the same as in FIG. 18 described above, but silicone is applied while jetting gas (6) from the nozzle holes (openings) of the nozzle plate (2). As the gas (6), various gases may be used as long as they do not easily cause a chemical reaction with the silicone to be applied. For example, air may be used.
Thus, by performing application | coating, spraying gas (6) from a nozzle hole, a silicone resin film can be formed only in the nozzle surface except a nozzle hole of a nozzle plate (2).

Moreover, when it apply | coats using the same silicone resin without injecting gas (6) as mentioned above, and a silicone resin approachs to the predetermined depth, when gas (6) is injected from a nozzle (2), As shown in FIG. 21, an ink repellent layer of silicone resin can be formed to a desired depth (for example, about several μm) of the nozzle inner wall.
That is, in addition to the ink repellent film (1) on the ink ejection surface described above, a very thin ink repellent film (1a) from the edge of the opening of the nozzle plate (2) to a predetermined depth (ink repellent on the inner wall of the opening) Film) can be formed.

  Wiping was performed on the ink-repellent film (1) of the nozzle plate thus prepared using EPDM rubber (rubber hardness 50 degrees). As a result, the ink repellent film (1) of the nozzle plate was able to maintain good ink repellency even after 1000 times of wiping. Further, the nozzle member on which the ink repellent film was formed was immersed in ink at 70 ° C. for 14 days. As a result, it was possible to maintain the ink repellency unchanged from the initial stage.

(Water repellent layer thickness)

FIG. 22 is a view showing an embodiment of the ink jet head of the present invention, and shows a state in which nozzle holes are formed by excimer laser processing. The nozzle plate (43) is obtained by joining a resin member (121) and a high-rigidity member (125) with a thermoplastic adhesive (126). The surface of the resin member (121) is made of SiO ₂ thin film layer (122) and fluorine. A water-repellent layer (123) is sequentially laminated, a nozzle hole (44) having a required diameter is formed in the resin member (121), and the high-rigidity member (125) communicates with the nozzle hole (44). A nozzle communication port (127) is formed. The SiO ₂ thin film layer (122) is formed by a method that allows film formation at a temperature that is relatively not heated, that is, does not cause thermal influence on the resin member. Specifically, it can be said that sputtering, ion beam vapor deposition, ion plating, CVD (chemical vapor deposition), P-CVD (plasma vapor deposition) and the like are suitable.

It is advantageous from the viewpoint of process time and material cost that the SiO ₂ thin film layer (122) has a minimum necessary thickness within a range in which adhesion can be secured. This is because if the film thickness is too large, it may interfere with nozzle hole processing with an excimer laser. That is, even if the resin member (121) is cleanly processed into a nozzle hole shape, a part of the SiO ₂ thin film layer (122) may not be sufficiently processed and may remain as a processing residue. Therefore, specifically, it can be said that the range of the film thickness of 1A to 300A is suitable as the range in which the adhesion can be secured and the SiO ₂ thin film layer (122) does not remain at the time of excimer laser processing. More preferably, the range of 10A to 100A is suitable. As a result of the experiment, even when the SiO ₂ film thickness was 30 A, the adhesion was sufficient, and there was no problem with the workability by the excimer laser. In addition, a slight machining residue was observed at 300A, but it was within the usable range. When the current exceeded 300A, a considerably large machining residue was generated, and a nozzle profile that was unusable was observed.

Any material that repels ink can be used as the material of the ink repellent layer, and specific examples include a fluorine-based water repellent material and a silicone-based water repellent material.
Various materials are known as fluorine-based water repellent materials. Here, a mixture of perfluoropolyoxetane and modified perfluoropolyoxetane (manufactured by Daikin Industries, trade name: OPTOOL DSX) with a thickness of 1A to 30A is used. The necessary water repellency is obtained by vapor deposition. As a result of the experiment, there was no difference in the water repellency and wiping durability performance regardless of whether the thickness of OPTOOL DSX was 10A, 20A, or 30A. Therefore, 1A to 20A is more preferable in consideration of cost and the like. Further, an adhesive tape (124) obtained by applying an adhesive material to a resin film is attached to the surface of the fluorine-based water repellent layer (123), and serves as an auxiliary function during excimer laser processing.
Silicone water repellent materials can also be used.
Silicone water repellent materials include room temperature curable liquid silicone resins or elastomers that are applied to the surface of a substrate and polymerized and cured by leaving it in the air at room temperature to form an ink repellent film. Is preferred.
The above-mentioned silicone-based water repellent material is a heat-curable liquid silicone resin or elastomer, and may be applied to the surface of the substrate and cured by heat treatment to form an ink-repellent film.
The silicone-based water repellent material is an ultraviolet curable liquid silicone resin or elastomer, and may be applied to the surface of the substrate and cured by irradiation with ultraviolet rays to form an ink repellent film.

  The viscosity of the silicone-based water repellent material is preferably 1000 cp (centipoise) or less.

  FIG. 23 is a diagram showing the configuration of an excimer laser processing machine used when processing the nozzle hole. The excimer laser beam (82) emitted from the laser oscillator (81) is mirrors (83), (85), Reflected by (88) and guided to the processing table (90). A beam expander (84), a mask (86), a field lens (87), an optical path until the laser beam (82) reaches the processing table (90) so that an optimum beam reaches the workpiece. An imaging optical system (89) is provided at a predetermined position. The workpiece (nozzle plate) (91) is placed on the machining table (90) and receives a laser beam. The processing table (90) is composed of a well-known XYZ table or the like, and can move the workpiece (91) as necessary to irradiate a desired position with a laser beam. Here, the laser is described using an excimer laser, but various lasers can be used as long as they are short wavelength ultraviolet lasers that can be ablated.

FIG. 24 is a diagram schematically showing a nozzle plate manufacturing process in the method for manufacturing an ink jet head of the present invention, and FIG. For example, a film without particles of Kapton (trade name), which is a Dupont polyimide film, is used as the resin film (121). In general polyimide films, particles such as SiO ₂ (silica) are added to the film material from the viewpoint of handling (sliding) in a roll film handling apparatus. However, when nozzle holes are machined with an excimer laser, SiO ₂ (silica) particles have poor processability with the excimer laser, and nozzle irregularities occur. Therefore, the material of the present invention uses a film to which no SiO ₂ (silica) particles are added.

FIG. 24B shows a step of forming the SiO ₂ thin film layer (122) on the surface of the resin film (121). The formation of the SiO ₂ thin film layer (122) is performed in a vacuum chamber. The film thickness is about several A to 200 A, and here, it is formed to a thickness of 10 to 50 A. Here, as a method of sputtering, after sputtering the Si, adhesion using the method of forming the SiO ₂ film by applying the _{O 2} ions in Si surface, the resin film of the SiO ₂ film (121) As a result, it was found that a uniform and dense film was obtained, which was more effective in improving the wiping durability of the water-repellent film.

FIG. 24C shows a process of applying the fluorine-based water repellent (123a). As an application method, a spin coater, roll coater, screen printing, spray coater, or the like can be used. It has been confirmed that the film forming method is more effective because it leads to improving the adhesion of the water-repellent film. In addition, it was also found that the vacuum deposition can be performed more effectively by forming the SiO ₂ thin film layer (122) in FIG. That is, conventionally, since the work is once taken out from the vacuum chamber after forming the SiO ₂ thin film layer (122), it is considered that the adhesion is impaired by the adhesion of impurities or the like to the surface. Various materials are known for the fluorine-based water repellent material. Here, perfluoropolyoxetane or modified perfluoropolyoxetane or a mixture of both is used as the amorphous fluorine compound. Necessary water repellency was obtained. The aforementioned “Optool DSX” manufactured by Daikin Industries is sometimes referred to as “alkoxysilane-terminated modified perfluoropolyether”.

FIG. 24 (D) shows an air leaving step after water-repellent film deposition, whereby the fluorine-based water repellent (123a) and the SiO ₂ thin film layer (122) are chemically bonded through the moisture in the air. To become a fluorine-based water repellent layer (123).

  FIG. 24E shows a process of attaching the adhesive tape (124), and the adhesive tape (124) is attached to the surface to which the fluorine-based water repellent layer (123) is applied. When this adhesive tape (124) is applied, it is necessary to apply it so that no bubbles are generated. This is because if there are bubbles, the nozzle holes opened at the positions where the bubbles are present may be of poor quality due to deposits during processing.

  FIG. 24F shows a nozzle hole (44) processing step, in which the nozzle hole (44) is formed by irradiating an excimer laser from the polyimide film (121) side. After the processing of the nozzle hole (44), the adhesive tape (124) is peeled off and used. Here, the description of the high-rigidity member (125) used to increase the rigidity of the nozzle plate (43) described in FIG. 22 is omitted, but if applied to this process, the process shown in FIG. It is appropriate to carry out during the step of FIG.

FIG. 25 is a diagram showing an outline of an apparatus used when an inkjet head is manufactured by the inkjet head manufacturing method of the present invention. This apparatus (200) was developed by OCLI (OPTICAL COATING LABORATORY INC.) Of USA. It is a device that uses a method called “meta-mode process” and is used in the production of anti-reflection and anti-fouling films for displays and the like. As shown in the figure, the Si sputter (202), O ₂ ion gun (203), Nb sputter (204), and optool vapor deposition (205), which are stations, are arranged at four locations around the drum (201), and the whole is vacuumed. In a pullable chamber. First, sputtering of Si by Si sputtering (202), then, _{O 2} by ion gun (203) and SiO ₂ against the _{O 2} ions to Si. Thereafter, Nb and Optool DSX are appropriately deposited by Nb sputtering (204) and Optool vapor deposition (205). In the case of an antireflection film, Nb and SiO ₂ are deposited after a necessary number of layers are stacked with a predetermined thickness. In the case of the present invention, since the function of the antireflection film is not necessary, Nb is not necessary, and SiO ₂ and OPTOOL DSX may be provided one by one. By using this apparatus, as described above, after forming the SiO ₂ thin layer (122), it is possible to perform vacuum deposition of the OPTOOL DSX in the vacuum chamber as it is.

(Critical surface tension)
The critical surface tension of the ink repellent layer is preferably 5 to 40 mN / m. Furthermore, it is more preferable that it is 5-30 mN / m. If it exceeds 30 mN / m, a phenomenon in which the ink becomes too wet with respect to the nozzle plate occurs during long-term use. Therefore, repeated printing causes ink ejection bending and abnormal particle formation. On the other hand, if it exceeds 40 mN / m, a phenomenon in which the nozzle plate is excessively wet from the initial stage occurs, so that an ink ejection curve or abnormal particle generation occurs from the initial stage.
Ink repellent materials listed in Table 2 were applied onto an aluminum substrate and dried by heating to prepare a nozzle plate with an ink repellent layer. When the critical surface tension of the ink repellent layer was measured, it was as shown in Table 2.

  The critical surface tension can be determined by the Zisman method. That is, when a liquid with a known surface tension is placed on the ink repellent layer, the contact angle θ is measured, and the surface tension of the liquid is plotted on the x axis and COS θ is plotted on the y axis, a straight line with a downward slope is obtained. (Zisman Plot) The surface tension when this straight line becomes Y = 1 (θ = 0) can be calculated as the critical surface tension γc. As other methods, the critical surface tension can be obtained by using the Fowkes method, the Owens and Wendt method, or the Van Oss method.

<Image creation method>
The image processing method used in the present invention is not particularly limited except for the total amount restriction, but it is desirable to transfer an original image having a high resolution at a high speed and to print without impairing the resolution of the original image. In the present invention, high-speed transfer and maintenance of resolution can be ensured by a method in which image data is compressed by a control unit such as a computer, transferred to a printer at high speed, and simple image restoration is performed on the printer side.

This will be specifically described below.
If the resolution of the image to be recorded is high, and if the number of gradations of the image is high, the capacity of the input image becomes large, and the host side handling the image to be recorded, including the transfer to the recording apparatus, can also record the recording apparatus. It takes time even within. Therefore, in the present invention, for example, 4 × 2 × 2 pixels of the input image are regarded as one pixel. As a result, the information amount of the input image is reduced to a quarter, and the time required for recording is inevitably shortened. Note that the resolution is reduced by regarding 2 × 2 pixels of the input image as one pixel, and a countermeasure for the reduction will be described later.
On the other hand, when using a recording element array formed by integrating a plurality of recording elements, for example, four times using an inkjet recording element array in which 16 recording element arrays are arranged in the main scanning direction shown in FIG. The recording elements capable of recording the same pixel of the recording medium by performing the multi-pass recording are described with one of the recording element rows in FIG. 26 (6-a), the recording elements a-1-1, A total of four can be selected from a-2-1, a-3-1, and a-4-1.
As described above, in the recording method for forming a plurality of ink dots in the same pixel, taking the recording element array shown in FIG. 26 as an example, when two ink dots are recorded in the same pixel, ₄ C ₂ = 6 You can take street combinations.
Furthermore, when using a plurality of dark and light inks, when using a plurality of recording element arrays that discharge ink of the same density, when discharging ink with different ink droplet capacities such as large dots and small dots from the recording elements, The combinations described above will increase. For example, when using a combination of dark and light ink in which the optical density of dark ink on the recording medium is substantially twice that of light ink, or a combination in which the capacity of large dots is approximately twice that of small dots Is as follows.

FIG. 27 shows recording element arrays (6-a, 6-b) that can record light ink (A ink) large and small dots and recording element arrays (6-ink) that can record dark ink (B ink) large and small dots. An ink jet recording element array consisting of c, 6-d) is shown. Here, when the maximum number of ink droplets that are landed on the same pixel is a maximum of two large dots and two small dots, the gradation values that can be expressed have various combinations.
Considering the combination of which recording element is used and recording on that pixel, for example, when reproducing a certain gradation value, if a recording element row passes over the recording pixel four times, which pass Thus, there are many combinations of which ink dots are recorded. Therefore, in the present invention, a combination of which nozzles are driven is stored as a table (printing element combination table: second table), and the combination is selected according to the input image.
Here, a series of recording element combinations to be actually used is selected by centrally managing the number of dots for recording dark and light inks and which recording element is used for recording from a large number of recording element combination tables described above. .
In the printing element combination table, the number of combinations that can be selected increases as the type of ink density, the type of ink droplet size, the number of printing elements, and the number of multi-pass passes increases. It is desirable to store such a limited number of combinations, which contributes to speeding up image recording. At that time, the combination can be limited so that the total amount of ink satisfies the limitation of this patent.

FIG. 29 is an example of the combination pattern of the recording elements stored in this way. As shown in a to o of FIG. 29, each of the two grayscale values is recorded in the 2 × 2 pixels. Looking at each unit pixel, it can be seen that the gradation value is large or small. This is referred to as a density distribution in the recording pixel (density distribution pattern of the recording pixel).
The density distribution in the recording pixels is stored in the recording ink combination table together with the above-described recording ink combination table (first table), for example, in the classifications a to o shown in FIG. FIG. 30 is an example of the recording ink combination table (first table) created in this way. Here, for simplicity, there are five patterns (patterns 1 to 5). The numerical values shown in FIG. 30 are the number of ink droplets to be recorded on a unit pixel, which constitutes each pattern when a maximum of 16 ink droplets are recorded on 2 × 2 recording pixels.
By selecting which recording ink combination table to use from the pixel values of the input image, the gradation value of the unit pixel of the input image and the gradation value of the unit pixel of the recording image are matched by the combination table In some cases, it cannot be made to occur. However, even if the gradations are somewhat different, the image data can be developed by reducing the amount of information of the input image, and image recording can be performed without sacrificing resolution.
The method for selecting the pattern of the recording ink combination table from the gradation values of the pixels of the input image is not particularly limited, and examples thereof include the following methods.
When the unit pixel of interest (for example, the upper left pixel of 2 × 2 pixels) is more than a certain value from the total and average of the 2 × 2 pixel gradation values of the input image, 4 × 2 × 2 pixels Select a pattern according to the characteristics of However, there is a method of predicting that the other three pixels are not separated when the pixel of interest is not separated from the average value by a certain value or more.
From the series of printing element combination patterns selected in this way, the gradation value and printing element combination to be used are determined for each pixel based on the input image. When there are a plurality of combinations of gradation values, patterns, and recording element combinations that have substantially the same density, more specifically, three types of combinations A, B, and C have substantially the same gradation values. Then, when expressing the gradation value, three types of recording element combinations such as ABCABCABC... Are sequentially used for each pixel.
Alternatively, it is preferable to use three types of recording element combinations at random, such as ACBCBABBBCAA. This randomizing method is not particularly limited.

Next, the configuration and operation of the ink jet recording apparatus according to this embodiment will be described. Here, 600 dpi high-definition black and white 256-level medical X-ray transmission image using black ink, and up to four ink droplets can be landed on one unit pixel. A case will be described in which 2 × 2 4 unit pixels are used and a maximum of 8 ink droplets can be landed in a recording pixel.
FIG. 31 is a block diagram showing the configuration of the ink jet recording apparatus according to this embodiment.
In the figure, (1) is an image input unit, (2) is an operation unit, (3) is a central control unit (CPU) that performs various processes, and (4) is a storage medium that stores various data, and is recorded in a table format. Element combination information (4a) and various control program groups (4b) are stored. Also, (5) is a RAM, (6) is an image processing unit, (7) is a printer control unit that performs image output control, and (8) is a bus unit (bus) that transfers various data for interconnecting various components. Line).
The image input unit (1) is configured by, for example, a scanner or a digital camera. The operation unit (2) includes various keys for setting various parameters and instructing start of recording. The CPU (3) controls the entire inkjet recording apparatus according to various programs in the storage medium (4).
The storage medium (4) stores a program for operating the ink jet recording apparatus in accordance with a control program and an error processing program. All the operations of the ink jet recording apparatus are performed by this program. As the recording medium (4) for storing the program, for example, ROM, FD, CD-ROM, HD, memory card, magneto-optical disk or the like can be used.
The RAM (5) is used as a work area for various programs in the storage medium (4), a temporary save area for error processing, and a work area for image processing. The RAM (5) can also copy the various tables in the recording medium (4), change the contents of the tables, and proceed with predetermined image processing while referring to the changed tables.
The image processing unit (6) creates an ejection pattern for realizing multi-gradation by an ink jet method based on the input image. The printer unit (7) forms a dot image based on the ejection pattern created by the image processing unit (6) during image recording. The bus line (8) transmits address signals, data, control signals, and the like in the inkjet recording apparatus.
In the printing element combination information (4a), data relating to the ink to be used is further accumulated. There is one type of ink used here, but as will be described later, light ink and dark ink may be prepared for the purpose of recording ink dots of similar colors and different densities. Useful to reproduce.
When one unit pixel is formed with a maximum of four ink dots using these inks, for example, there are various recording ink combination tables that can be represented by recording pixels composed of four unit pixels in which unit pixels are arranged 2 × 2. Cross over. Therefore, in the present embodiment, for each tone value, there are four types, a pattern in which the upper left density of the 2 × 2 matrix is highly biased and a pattern in which the upper right is biased, and a pattern with little bias. A total of 144 + 1 recording ink combination tables are used with 8 + 1 values for each recording pixel unit in total.

32 to 34 show a recording ink combination table (second table) according to the present embodiment.
Among the numbers described in the figure, “1” means ejection of ink droplets. Further, for convenience, in these tables, as information regarding the position of the 2 × 2 matrix, the upper left, upper right, lower left, and lower right pixels are sequentially designated as LU, RU, LL, and RL, and the unit pixels are other A group of ink combination tables whose density is higher than that of the unit pixel is expressed as a density pattern.
The density level is not completely proportional to the number of inks ejected to one pixel and the sum of the dye content of the ink. In the media, there are no practical problems.

FIG. 32 is a flowchart showing the flow of image processing in the ink jet recording apparatus according to this embodiment.
Hereinafter, image processing unique to the present embodiment will be described with reference to FIGS. 32 to 35.
When the printing element combination tables shown in FIGS. 33 to 35 are used, it is necessary to convert the number of gradations of the input image of 256 gradations input in step S101 of FIG. 33 into 2 + 1 values (/ 600 dpi). Therefore, the image processing unit (6) in FIG. 31 performs 2 + 1 multi-value error diffusion processing (steps S102 and S103). Here, the multilevel error diffusion method is used for this processing, but the present invention is not limited to this method. For example, an arbitrary halftone processing method such as an average density storage method or a dither matrix method may be used. Can do.
The major difference between the multi-value error diffusion method and the normal error diffusion method is that there are a plurality of threshold values (two in this case) for binarization. These threshold values may usually be determined as the midpoint of the gradation value.
More specifically, the multivalued data is recorded on the recording ink shown in FIGS. 33 to 35 while referring to the recording element combination information (4a) in the storage medium (4) in the image processing unit (6). According to the combination, the ejection / non-ejection drive signal is distributed to each recording element. Here, since the original image data is 600 dpi, the multivalued data has 2 + 1 values at 600 dpi, that is, three values of “0”, “1”, and “2” (see FIG. 35 step S103).
Therefore, in step S104, it is determined whether or not there is a difference between the average value of the recording pixel of interest and the upper left dot. For example, for a 2 × 2 recording pixel of interest (represented as (I1, J1)), the gradation value of the upper left unit pixel (i1, j1) is 2, the upper right unit pixel (i1 + 1, j1) is 1, A case where the lower left unit pixel (i1, j1 + 1) is 1 and the lower right unit pixel (i1 + 1, j1 + 1) is 0 will be described. In this case, since the density gradient information has a high density at the upper left, a density pattern of “LU” corresponding to the gradation “a” shown in FIG. 29 is selected (steps S105 and S110).
Further, since the gradation value of the 2 × 2 recording pixel itself is 4/8, the density gradient information is “LU” in the recording element combination information of density 4 (gradation value 4) shown in FIG. Based on the pattern information (that is, the combination of Nos. 45 to 48), it is determined to distribute the data. Actually, these four combinations are selected sequentially or randomly (steps S115 and S116).
By performing the above processing, the processing for one pixel of the focused recording pixel is completed. The same processing is performed for the subsequent 2 × 2 recording pixels (I2, J2).
That is, the gradation value of the upper left unit pixel (i2, j2) is 2, the upper right unit pixel (i2 + 1, j2) is 2, the lower left unit pixel (i2, j2 + 1) is 2, and the lower right unit. When the pixel (i2 + 1, j2 + 1) is 1, the density gradient information corresponds to the gradation “l” shown in FIG. Since it is difficult to determine that this pattern belongs to any one of the LU, RU, LL, and RL, “AVE” is selected here for simplicity (step S114).
Further, since the gradation value of this recording pixel is 8/8, pattern information (that is, No. No.) having density inclination information “AVE” from the recording element combination information of density 8 (gradation value 8) shown in FIG. .. 141 to 144) is determined to distribute the data (steps S115 and S116).
Similarly, with respect to the other recording pixels, by repeating the above-described processing for the total number of pixels based on the density data of the image, binary of ejection / non-ejection for each pixel for each printing element array Is generated (steps S120 to S123).

FIG. 36 shows a multi (4) pass recording method, in which a recording head 6-a having a recording element array for ejecting A ink, a recording head 6-b having a recording element array for ejecting A ink, and B ink. Each pass is recorded by a recording head 6-c having a recording element array for ejecting ink and a recording head 6-d having a recording element array for ejecting B ink.
In the present embodiment, as described above, all the pixels are sequentially processed, and printing is performed by four-pass printing by the ink jet printing apparatus having the printing element arrays of FIGS. 26, 27, and 28.
As described above, according to this embodiment, an area obtained by combining adjacent unit pixels of an input image is a recording pixel, and a gradation value pattern corresponding to the input image is determined for each recording pixel. By selecting, it is possible to reduce the information amount of the image data to about one-fourth without degrading the resolution of the input image, speeding up the image recording and reducing the burden on the control unit (CPU). be able to.
In addition, it is an ink jet recording method that records double ink droplets on at least the same unit pixel, records ink droplets having at least two types of large and small dot diameters, and records at least two types of light and dark ink droplets for similar colors. Thus, in an image recording method in which single or plural ink droplets are ejected and recorded on several unit pixels constituting a recording pixel which is a constituent unit of a recording image, complicated image processing is performed. Therefore, it is effective because the control data of the drive signals for ejection and non-ejection which are patterned is handled.
Furthermore, by preparing a plurality of recording element combination information for the same gradation value and recording sequentially or randomly according to different recording element combination information, various inks can be used for a while from the same recording element. The situation where it was not discharged is reduced, and at the same time, there is no situation of forming ink dots from the same recording element over a certain area, and even when the recording head is replaced, the change in characteristics can be suppressed, It is possible to actively and effectively deal with variations in characteristics of recording elements.
In addition, with a simple signal processing algorithm, it is possible to obtain an image with good gradation and less deterioration due to “swing”, etc. by high-speed and simple processing. Even if recorded as low-resolution data as information, A good gradation image can be obtained.

(Ink record)
The ink recorded matter recorded by the ink jet recording method of the present invention is the ink recorded matter of the present invention. The ink recorded matter of the present invention comprises an image formed using the ink in the ink media set on the recording medium in the ink media set of the present invention.
The recorded matter has high image quality, no bleeding, excellent temporal stability, and can be suitably used for various purposes as a material on which various prints or images are recorded.

Examples of the present invention will be described below, but the present invention is not limited to these examples.
-Adjustment of pigment ink-
(Production Example 1)
-Preparation of copper phthalocyanine pigment-containing polymer fine particle dispersion-
After sufficiently replacing the inside of the 1 L flask equipped with a mechanical stirrer, thermometer, nitrogen gas introduction tube, reflux tube, and dropping funnel with nitrogen gas, 11.2 g of styrene, 2.8 g of acrylic acid, 12.0 g of lauryl methacrylate Then, 4.0 g of polyethylene glycol methacrylate, 4.0 g of styrene macromer (manufactured by Toa Gosei Co., Ltd., trade name: AS-6) and 0.4 g of mercaptoethanol were charged and heated to 65 ° C. Next, 100.8 g of styrene, 25.2 g of acrylic acid, 108.0 g of lauryl methacrylate, 36.0 g of polyethylene glycol methacrylate, 60.0 g of hydroxyethyl methacrylate, styrene macromer (trade name: AS-6, manufactured by Toagosei Co., Ltd.) A mixed solution of 36.0 g, mercaptoethanol 3.6 g, azobisdimethylvaleronitrile 2.4 g, and methyl ethyl ketone 18 g was dropped into the flask over 2.5 hours.
After completion of dropping, a mixed solution of 0.8 g of azobisdimethylvaleronitrile and 18 g of methyl ethyl ketone was dropped into the flask over 0.5 hours. After aging at 65 ° C. for 1 hour, 0.8 g of azobisdimethylvaleronitrile was added and further aging was performed for 1 hour. After completion of the reaction, 364 g of methyl ethyl ketone was added to the flask to obtain 800 g of a polymer solution having a concentration of 50% by mass. Next, when a part of the polymer solution was dried and measured by gel permeation chromatography (standard: polystyrene, solvent: tetrahydrofuran), the weight average molecular weight (Mw) was 15000.
Next, 28 g of the obtained polymer solution, 26 g of copper phthalocyanine pigment, 13.6 g of 1 mol / L potassium hydroxide aqueous solution, 20 g of methyl ethyl ketone, and 30 g of ion-exchanged water were sufficiently stirred. Thereafter, the mixture was kneaded 20 times using a three-roll mill (manufactured by Noritake Company, trade name: NR-84A). The obtained paste was put into 200 g of ion-exchanged water, and after sufficiently stirring, methyl ethyl ketone and water were distilled off using an evaporator to obtain 160 g of a blue polymer fine particle dispersion having a solid content of 20.0% by mass. .
About the obtained polymer microparticles | fine-particles, the average particle diameter (D50%) measured with the particle size distribution analyzer (Microtrac UPA, Nikkiso Co., Ltd.) was 93 nm.

(Production Example 2)
-Preparation of polymer fine particle dispersion containing dimethylquinacridone pigment-
A red-purple polymer fine particle dispersion was prepared in the same manner as in Production Example 1 except that the copper phthalocyanine pigment was changed to Pigment Pigment Red 122 in Production Example 1.
About the obtained polymer microparticles | fine-particles, the average particle diameter (D50%) measured with the particle size distribution analyzer (Microtrac UPA, Nikkiso Co., Ltd.) was 127 nm.

(Production Example 3)
-Preparation of monoazo yellow pigment-containing polymer fine particle dispersion-
A yellow polymer fine particle dispersion was prepared in the same manner as in Production Example 1 except that the copper phthalocyanine pigment was changed to Pigment Pigment Yellow 74 in Production Example 1.
About the obtained polymer microparticles | fine-particles, the average particle diameter (D50%) measured with the particle size distribution analyzer (Microtrac UPA, Nikkiso Co., Ltd.) was 76 nm.

(Production Example 4)
-Preparation of carbon black dispersion-
300 g of commercially available acidic carbon black having a pH of 2.5 (manufactured by Cabot, trade name: Monarch 1300) was mixed well with 1000 ml of water. Thereafter, 450 g of sodium hypochlorite (effective chlorine concentration 12%) was added dropwise, and the mixture was stirred at 100 to 105 ° C. for 8 hours. To this solution, 100 g of sodium hypochlorite (effective chlorine concentration 12%) was further added and dispersed for 3 hours with a horizontal disperser. The resulting slurry was diluted 10 times with water, pH was adjusted with lithium hydroxide, desalted and concentrated with an ultrafiltration membrane to a conductivity of 0.2 mS / cm, and a carbon black dispersion having a pigment concentration of 15% It was. Coarse particles were removed by centrifugation and further filtered through a 1 μm nylon filter to obtain a carbon black dispersion.
About the obtained polymer microparticles | fine-particles, the average particle diameter (D50%) measured with the particle size distribution analyzer (Microtrac UPA, Nikkiso Co., Ltd.) was 95 nm.

(Production Example 5)
-Preparation of polymer fine particle dispersion of carbon black-
A black polymer fine particle dispersion was prepared in the same manner as in Production Example 1 except that the copper phthalocyanine pigment was changed to carbon black (Degussa, FW100) in Production Example 1.
About the obtained polymer microparticles | fine-particles, the average particle diameter (D50%) measured with the particle size distribution analyzer (Microtrac UPA, Nikkiso Co., Ltd.) was 104 nm.

(Production Example 6)
-Preparation of carbon black dispersion treated with diazo compound-
100 g of carbon black having a surface area of 230 m ² / g and a DBP oil absorption of 70 ml / 100 g and 34 g of p-amino-N-benzoic acid are mixed and dispersed in 750 g of water, and 16 g of nitric acid is added dropwise thereto to 70 Stir at ° C. After 5 minutes, a solution of 11 g of sodium nitrite dissolved in 50 g of water was added, and the mixture was further stirred for 1 hour. The resulting slurry was diluted 10 times and centrifuged to remove coarse particles, the pH was adjusted with diethanolamine to pH 8-9, desalted and concentrated with an ultrafiltration membrane to obtain a carbon black dispersion with a pigment concentration of 15%. Then, it was filtered through a polypropylene 0.5 μm filter to obtain a carbon black dispersion. The average particle size (D50%) measured by Microtrac UPA was 99 nm.

(Production Example 7)
-Preparation of carbon black dispersion treated with sulfonating agent-
150 g of commercially available carbon black pigment (manufactured by Degussa, “Printex # 85”) was mixed well into 400 ml of sulfolane, finely dispersed with a bead mill, 15 g of amidosulfuric acid was added, and the mixture was stirred at 140 to 150 ° C. for 10 hours. The obtained slurry is put into 1000 ml of ion-exchanged water, and a surface-treated carbon black wet cake is obtained by a centrifuge at 12000 rpm. This carbon black wet cake was redispersed in 2000 ml of ion exchange water, pH was adjusted with lithium hydroxide, and desalted and concentrated with an ultrafiltration membrane to obtain a carbon black dispersion having a pigment concentration of 10% by mass. This was filtered through a 1 μm nylon filter to obtain a carbon black body. The average particle size was 80 nm.

  Next, an ink composition was produced using the polymer fine particle dispersion and the carbon black dispersion obtained in Production Examples 1 to 7.

(Production Example 8)
-Preparation of Cyan Ink Composition 1-
Copper phthalocyanine pigment-containing polymer fine particle dispersion 20.0% by mass of production example 1, 3-methyl-1,3-butanediol 23.0% by mass, glycerin 8.0% by mass, 2-ethyl-1,3-hexane Diol 2.0% by mass, FS-300 (manufactured by DuPont) 2.5% by mass, Proxel LV (manufactured by Avecia) 0.2% by mass, 2-amino-2-ethyl-1,3-propanediol An appropriate amount of 5% by mass and ion-exchanged water was added to make 100% by mass, and then filtration was performed with a membrane filter having an average pore diameter of 0.8 μm. Thereafter, ion exchange water was used to adjust the solid content to 12 wt%. The ink composition was prepared as described above. The obtained ink composition had a viscosity at 25 ° C. of 9 mPa · s and a surface tension of 25 mN / m. The measurement of the viscosity was performed at 25 ° C. using a viscosity measuring device (manufactured by Toki Sangyo Co., Ltd., R500 rotational viscometer).

(Production Example 9)
-Preparation of magenta ink composition 1-
Dimethylquinacridone pigment-containing polymer fine particle dispersion 20.0% by mass in Production Example 2, 3-methyl-1,3-butanediol 22.5% by mass, glycerin 9.0% by mass, 2-ethyl-1,3-hexane Diol 2.0% by mass, FS-300 (manufactured by DuPont) 2.5% by mass, Proxel LV (manufactured by Avecia) 0.2% by mass, 2-amino-2-ethyl-1,3-propanediol An appropriate amount of 5% by mass and ion-exchanged water was added to make 100% by mass, and then filtration was performed with a membrane filter having an average pore diameter of 0.8 μm. Thereafter, ion exchange water was used to adjust the solid content to 12 wt%. The ink composition was prepared as described above. The obtained ink composition had a viscosity at 25 ° C. of 9 mPa · s and a surface tension of 25 mN / m.

(Production Example 10)
-Preparation of yellow ink composition 1-
Monoazo yellow pigment-containing polymer fine particle dispersion of Production Example 3 20.0% by mass, 3-methyl-1,3-butanediol 24.5% by mass, glycerin 8.0% by mass, 2-ethyl-1,3-hexane Diol 2.0% by mass, FS-300 (manufactured by DuPont) 2.5% by mass, Proxel LV (manufactured by Avecia) 0.2% by mass, 2-amino-2-ethyl-1,3-propanediol An appropriate amount of 5% by mass and ion-exchanged water was added to make 100% by mass, and then filtration was performed with a membrane filter having an average pore diameter of 0.8 μm. Thereafter, ion exchange water was used to adjust the solid content to 12 wt%. The ink composition was prepared as described above. The obtained ink composition had a viscosity at 25 ° C. of 9 mPa · s and a surface tension of 25 mN / m.

(Production Example 11)
-Preparation of Black Ink Composition 1-
Carbon black dispersion of Production Example 7 20.0% by mass, 3-methyl-1,3-butanediol 22.5% by mass, glycerin 7.5% by mass, 2-pyrrolidone 2.0% by mass, 2-ethyl- 1,3-hexanediol 2.0 mass%, R- (OCH ₂ CH ₂ ) _n OH (wherein R is an alkyl group having 12 carbon atoms, n = 9) 2.0 mass%, Proxel LV ( (Avecia Co., Ltd.) 0.2 mass%, 2-amino-2-ethyl-1,3-propanediol 0.5 mass%, and an appropriate amount of ion-exchanged water were added to make 100 mass%. Filtration was performed with an 8 μm membrane filter. Thereafter, ion exchange water was used to adjust the solid content to 12 wt%. The ink composition was prepared as described above. The obtained ink composition had a viscosity at 25 ° C. of 9 mPa · s and a surface tension of 25 mN / m.

-Preparation of dye ink-
(Production Example 12)
The components shown below were mixed, sufficiently stirred and dissolved, and then filtered under pressure using a fluoropore filter having a pore size of 0.45 μm (trade name: manufactured by Sumitomo Electric Co., Ltd.) to prepare a dye ink set.
Dye ink composition:
Dye type Yellow C.I. I. Direct yellow 86
Cyan C.I. I. Direct Blue 199
Magenta C.I. I. Acid Red 285
Black C.I. I. Direct black 154
Formulation Dye 4 parts Glycerol 7 parts Thiodiglycol 7 parts Urea 7 parts Acetylene glycol 1.5 parts Water 73.5 parts The viscosity of the resulting ink composition at 25 ° C is 4 mPa · s, and the surface tension is about 35 dyne / cm.

-Production of base paper-
(Production Example 13)
-Production of support 1-
-LBKP 80 parts by mass-NBKP 20 parts by mass-Light calcium carbonate (trade name: TP-121, manufactured by Okutama Kogyo Co., Ltd.) 10 parts by mass-Aluminum sulfate ... 1.0 part by mass-Amphoteric starch (trade name: Cato3210 1.0 mass part ・ Neutral rosin sizing agent 0.3 mass part (trade name: NeuSize M-10, manufactured by Harima Kasei Co., Ltd.)
-Yield improver (trade name: NR-11LS, manufactured by Hymo Co., Ltd.) 0.02 parts by weight A 0.3% by weight slurry of the above composition is made with a long net paper machine and machine calendered to a basis weight of 79 g / m. ² support 1 was produced. In addition, in the size press process of the papermaking process, the oxidized starch aqueous solution was applied so that the solid content was 1.0 g / m ² per side.

Example 1
The prepared support 1 has 70 parts of kaolin having a particle size of 2 μm or less as a pigment of 97% by weight as a pigment, 30 parts of heavy calcium carbonate having an average particle diameter of 1.1 μm, and an adhesive having a glass transition temperature (Tg) of − 8 parts of a styrene / butadiene copolymer emulsion at 5 ° C., 1 part of phosphate esterified starch, 0.5 part of calcium stearate as an auxiliary agent, and water were further added to prepare a coating solution having a solid content concentration of 60%. .
The coating liquid is coated on both sides of the above base paper using a blade coater so that the coating layer thickness per side is 5 μm, dried with hot air, and then subjected to supercalendering to obtain the recording paper 1 of the present invention. It was.
A black, yellow, magenta, cyan, and ink set 1 made of the ink composition produced in Production Examples 1 to 14 was prepared, and the obtained ink set 1 and recording paper 1 were used, and 300 dpi, nozzle resolution 384. Printing was performed at an image resolution of 600 dpi using a drop-on-demand printer prototype having nozzles. The large droplet size was 20 pl, the medium droplet size was 10 pl, and the small droplet size was 2 pl. The total amount of secondary colors was regulated to 140%, and the amount of adhesion was regulated. During solid printing, solid images and characters were printed so that the total amount of ink in 300 dots square did not exceed 15 g / m ² . After printing, the image was faced up for 15 seconds in an environment of 23 ° C. and 50% RH, and then passed through the fixing device shown in FIG. 14 to perform nip processing at 150 ° C. for 0.8 seconds.
The image quality and image reliability of the obtained image were evaluated. The results are shown in Table 3.
Those marked with x in the evaluation result are inappropriate as an inkjet image.
In addition, a silicone resin film (room temperature curing type silicone resin SR2411, manufactured by Toray Dow Corning Co., Ltd.) is formed on the nozzle plate surface of the inkjet printer, and the thickness thereof is 1.2 μm, and the surface roughness (Ra) Was 0.18 μm and the critical surface tension was 21.6 mN / m. The ink was ejected using the cyan ink of Production Example 8. When the flight process of the ink was observed by video recording, it was confirmed that the ink droplets were formed normally and the ejection stability was good.

Example 2
Printing was carried out in the same manner as in Example 1 except that the media of Example 1 was changed to OK top coat + (Oji Paper) of commercial printing paper.

Example 3
Printing was performed in the same manner as in Example 2 except that hot air of 120 ° C. was applied during dry touch.

Example 4
Printing was performed in the same manner as in Example 2 except that the fixing temperature was changed to 180 ° C. in Example 2.

Example 5
Printing was performed in the same manner as in Example 2 except that the fixing temperature was changed to 90 ° C. in Example 2.

Example 6
Printing was performed in the same manner as in Example 2 except that the ink adhesion amount in Example 2 was changed to 15 g / m ² .

Example 7
Printing was performed in the same manner as in Example 1 except that the medium of Example 1 was changed to OK Kanto +127 g / m ² (Oji Paper Co., Ltd.), a commercial printing paper.

Example 8
Printing was carried out in the same manner as in Example 1 except that the medium of Example 1 was changed to SA Kanfuji +127 g / m ² ((Oji Paper), a commercial printing paper.

Example 9
Printing was performed in the same manner as in Example 1 except that the medium of Example 1 was changed to Super MIdal 70 g / m ² (manufactured by Nippon Paper Industries Co., Ltd.), a commercial printing paper.

Example 10
Printing was carried out in the same manner as in Example 1 except that the medium of Example 1 was changed to a commercial printing paper aurora coat 100 g / m ² (manufactured by Nippon Paper Industries Co., Ltd.).

Example 11
Printing was performed in the same manner as in Example 1 except that the medium of Example 1 was changed to alpha mat 80 g / m ² (manufactured by Hokuetsu Paper) of commercial printing paper.

Example 12
Printing was performed in the same manner as in Example 1 except that the medium of Example 1 was changed to Ricoh Business Coat Gloss 100 100 g / m ² (manufactured by Ricoh) of gel jet paper.

Comparative Example 1
Printing was performed in the same manner as in Example 2 except that touch drying was not performed in Example 2.

Comparative Example 2
Printing was performed in the same manner as in Example 2 except that the fixing device in Example 2 was changed from a heat roller to an infrared heater (USHIO).

Comparative Example 3
Printing was performed in the same manner as in Example 2 except that the ink adhesion amount in Example 2 was changed to 20 g / m ² .

Comparative Example 4
Printing was carried out in the same manner as in Example 1 except that the medium of Example 1 was changed to the ink-jet paper Chrispier (manufactured by Epson).

Comparative Example 5
Printing was carried out in the same manner as in Example 1 except that the medium of Example 1 was changed to super fine paper (manufactured by Epson) as inkjet paper.

Comparative Example 6
Printing was carried out in the same manner as in Example 1 except that the media of Example 1 was changed to 127 g / m ² (Oji Paper Co., Ltd.), which is a commercial printing paper mirror coat platinum.

Comparative Example 7
The printer of Example 2 was changed to Pixus iP4200 (Canon), printing was performed in the glossy paper clean mode, and then the same post-processing as in Example 2 was performed.

Comparative Example 8
Printing was performed in the same manner as in Example 7 except that the paper of Comparative Example 7 was changed to OK Kanto + (Oji Paper).

Comparative Example 9
Printing was performed in the same manner as in Example 1 except that the medium of Comparative Example 7 was changed to commercial printing paper SA Kanfuji + 127 g / m ² (Oji Paper).

Comparative Example 10
Printing was performed in the same manner as in Example 1 except that the medium of Comparative Example 7 was changed to Super MIdal 70 g / m ² (manufactured by Nippon Paper Industries Co., Ltd.), a commercial printing paper.

Comparative Example 11
Printing was carried out in the same manner as in Example 1 except that the medium of Comparative Example 7 was changed to an aurora coat 100 g / m ² (manufactured by Nippon Paper Industries) of commercial printing paper.

Comparative Example 12
Printing was performed in the same manner as in Example 1 except that the medium of Comparative Example 7 was changed to commercial printing paper alpha matte 80 g / m ² (made by Hokuetsu Paper).

Comparative Example 13
Printing was performed in the same manner as in Example 1 except that the medium of Comparative Example 7 was changed to Ricoh Business Coat Gloss 100 100 g / m ² (manufactured by Ricoh) of gel jet paper.

Comparative Example 14
Printing was carried out in the same manner as in Example 1 except that the medium of Comparative Example 7 was changed to the ink-jet paper Chrispier (manufactured by Epson).

Comparative Example 15
Printing was performed in the same manner as in Example 1 except that the medium of Comparative Example 7 was changed to superfine paper (manufactured by Epson) as an inkjet paper.

Comparative Example 16
Printing was performed in the same manner as in Example 1 except that the media of Comparative Example 7 was changed to 127 g / m ² (Oji Paper Co., Ltd.), which is a commercial printing paper.

(Evaluation items and measurement methods)
<Measurement of pure water transfer by dynamic scanning absorption meter>
For each recording medium, the transfer amount of pure water was measured at 25 ° C. and 50% RH using a dynamic scanning absorption meter (K350 series D type, manufactured by Kyowa Seiko Co., Ltd.). The transfer amount at the contact time of 100 ms and the contact time of 400 ms was determined by interpolation from the measured value of the transfer amount at the contact time adjacent to each contact time.

<Image density>
The optical density of the magenta image portions of the examples and comparative examples was measured with X-Rite932 and evaluated according to the following criteria.
〔Evaluation criteria〕
◎: Magenta image density 1.6 or more ○: Magenta image density 1.3 or more △: Magenta image density 1.0 or more ×: Magenta image density less than 1.0

<Blurred image>
The degree of beading of the green solid image portion of each image print and the bleed of black characters in the yellow background were visually observed and evaluated according to the following criteria.
〔Evaluation criteria〕
A: Uniform printing with no beading or bleeding.
○: Slight beading and bleeding are observed.
(Triangle | delta): Generation | occurrence | production of beading and bleeding is recognized clearly.
X: Significant beading and bleeding were observed.

<Evaluation of glossiness>
The degree of glossiness of the image portion of each image print was visually observed and evaluated according to the following criteria.
〔Evaluation criteria〕
A: High gloss.
○: Glossy.
X: A glossiness is not recognized.

<Small banding>
A gray halftone solid image was printed using small droplets, and the occurrence of banding (streaks) was visually evaluated.
〔Evaluation criteria〕
○: There is no banding or it is almost inconspicuous and the image is uniform.
X: Banding is conspicuous and inferior in uniformity.

<Image disorder>
After the processing by the fixing roller, in the discharged paper, the thin line and the blurred image were confirmed visually as x, and the unacknowledged as ◯.

<Image offset>
When the image was heat-treated with the roller, the color material transfer was transferred from the image to the roller, and whether or not the offset color image was generated when the transferred color material was re-transferred to the media was visually determined. The case where the offset was confirmed was marked with ×, and the case where the offset was not confirmed was marked with ◯.

<Fixing>
The image subjected to the fixing process was rubbed back and forth 10 times with a finger. A case where the color material was severely peeled off or smeared was marked as x, a case where slight smearing occurred was Δ, and a case where there was no smear or smearing was marked as ◯.

<Blister>
The media was visually observed after the fixing process. The case where blisters were clearly confirmed was marked with x, the case where minute blisters were confirmed in a very small part was marked with △, and the case where no blisters were confirmed was marked with ◯.

The recording method of the present invention uses a recording medium having a texture close to that of general commercial printing paper, or general commercial / publishing paper, satisfying so-called “cut” characters, It is possible to provide a high-quality glossy recording image with excellent print quality without blurring, feathering, or bleeding in the peripheral portion of the image, and to be suitably used for ink recordings, inkjet recording apparatuses, and inkjet recording methods. Can do. Further, the obtained printed matter is excellent in image abrasion resistance, and there is no problem in handling immediately after printing.
The ink jet recording method of the present invention can be applied to various types of recording by the ink jet recording method, and is particularly preferably applied to, for example, an ink jet recording printer, a facsimile machine, a copying machine, a printer / fax / copier multifunction machine, and a printing machine. can do.

It is a flowchart which shows the flow of the total amount regulation process in this invention. It is a diagram showing a conventional fixing device of a heat fixing system. It is the figure which showed the heater of the conventional heat roller fixing device. It is the figure which showed the heater of the 2 heater system of a heat roller fixing device. It is a figure which shows the relationship between the heater of a 2 heater system, and sheet passing width. It is the schematic which shows an example of the ink cartridge of this invention. FIG. 7 is a schematic view including a case (exterior) of the ink cartridge of FIG. 6. FIG. 4 is a perspective explanatory view showing a state where an ink cartridge loading unit cover of the ink jet recording apparatus is opened. It is a schematic block diagram explaining the whole structure of an inkjet recording device. It is a schematic enlarged view which shows an example of the inkjet head of this invention. It is an element enlarged view showing an example of an ink jet head of the present invention. It is a principal part expanded sectional view which shows an example of the inkjet head of this invention. 1 is a schematic configuration diagram illustrating an overall configuration of an ink jet recording apparatus and a fixing device. 1 is a schematic configuration diagram illustrating an overall configuration of an example of an external fixing device. It is sectional drawing of the inkjet head nozzle plate produced by this invention. It is another sectional drawing of the inkjet head nozzle plate created by this invention. It is another sectional drawing of the inkjet head nozzle plate produced by this invention. It is a figure which shows the structure which apply | coats a silicone resin and forms an ink repellent film | membrane by application | coating using the dispenser which concerns on this embodiment. It is explanatory drawing of the application port of the needle tip which concerns on this embodiment. It is a figure which shows the application | coating operation | movement using the dispenser which concerns on this embodiment. It is another sectional view of an ink jet head nozzle plate. It is the figure which showed one Example of the inkjet head of this invention. It is the figure which showed the structure of the excimer laser processing machine used when processing a nozzle hole. It is the figure which showed typically the nozzle plate manufacturing process in the manufacturing method of the inkjet head of this invention. It is a figure which shows an outline | summary about the apparatus used when manufacturing an inkjet head with the inkjet head manufacturing method in this invention. FIG. 4 is a diagram illustrating a recording element array. FIG. 4 is a diagram illustrating a recording element array. FIG. 4 is a diagram illustrating a recording element array. It is an example of the combination pattern of a printing element. It is an example of a recording ink combination table (first table). It is a block diagram which shows the structure of the inkjet recording device which concerns on this embodiment. 6 is a flowchart showing a flow of image processing in the ink jet recording apparatus according to the embodiment. It is a recording ink combination table (second table) according to the present embodiment. It is a recording ink combination table (second table) according to the present embodiment. It is a recording ink combination table (second table) according to the present embodiment. It is the figure which showed the multi (4) pass recording system. FIG. 3 is a circuit diagram illustrating an example of a circuit of the fixing temperature control device of the present invention. It is a circuit diagram which shows an example of the temperature control circuit. It is the timing chart.

Explanation of symbols

(FIGS. 2 to 4)
DESCRIPTION OF SYMBOLS 1 Fixing roller 2 Pressure roller 3 Heating filament 4 Heater 5 Paper 6 Temperature detection means 7 Paper 8 Paper 9
10 Heating Filament 11 Heater 12 Heating Filament 13 Heater 14 Heating Filament 15 Dual Filament Heater (FIGS. 6 and 7)
200 Ink cartridge 241 Ink bag 242 Ink inlet 243 Ink outlet 244 Cartridge exterior (FIGS. 8, 9, 10, and 13)
101 apparatus main body 102 paper feed tray 103 paper discharge tray 104 ink cartridge loading unit 105 operation unit 111 upper cover 112 front surface 115 front cover 131 guide rod 132 stay 133 carriage 134 recording head 135 sub tank 141 paper placement unit 142 paper 143 paper supply roller 144 Separation pad 145 Guide 151 Conveying belt 152 Counter roller 153 Conveying guide 155 Pressure roller 156 Charging roller 157 Conveying roller 158 Densation roller 161 Guide member 171 Separating claw 172 Discharging roller 173 Discharging roller 181 Double-sided paper feeding unit 182 Manual feeding Paper unit 201 Ink cartridge 202 Fixing device 203 Touch drying device (FIGS. 11 and 12)
DESCRIPTION OF SYMBOLS 1b Common liquid chamber 2a Liquid resistance part 2b Pressurization liquid chamber 2c Communication port 2d Partition 3a Nozzle 5f Drive part 5g Support part 6a Convex part 6b Diaphragm 6c Ink inlet 10 Frame 20 Channel plate 30 Nozzle plate 40 Base 50 Multilayer piezoelectric element 60 Diaphragm 70 Adhesive layer (FIGS. 15 to 21)
DESCRIPTION OF SYMBOLS 1 Ink repellent film 1 'Ink repellent film 1a Ink repellent film 2 Nozzle plate 3 Ink 4 Dispenser 5 Needle 6 Gas d Thickness other than near opening part r Curvature radius θ Angle from nozzle plate plane P Meniscus Q Meniscus (FIG. 22, FIG. 24)
43 Nozzle plate 44 Nozzle hole 121 Resin member 122 Thin film layer 123 Fluorine-based water repellent layer 124 Adhesive tape 125 High rigidity member 126 Thermoplastic adhesive 127 Nozzle communication port (FIG. 23)
81 Laser oscillator 82 Excimer laser beam 83, 85, 88 Mirror 84 Beam expander 86 Mask 87 Field lens 89 Imaging optical system 90 Processing table 91 Workpiece (nozzle plate)
(Fig. 25)
200 Apparatus 201 Drum 202 Si Sputter 203 O ₂ Ion Gun 204 Nb Sputter 205 Op Tool Deposition (FIG. 31)
DESCRIPTION OF SYMBOLS 1 Image input part 2 Operation part 3 Central control part (CPU)
4 Recording media 4a Recording element combination information 4b Various control program groups 5 RAM
6 Image processing unit 7 Printer control unit 8 Bus unit (bus line)
(Fig. 36)
6-a recording head 6-b recording head 6-c recording head 6-d recording head (FIGS. 37 to 39)
20 Partial heating filament heater 21 Full length heating filament heater
SSR1 relay
SSR2 Relay 22 Temperature control circuit 23 Temperature sensor
Ref set temperature signal 24 Comparator
AND1 ANDGATE
AND2 AND GATE 25 Timer T ₁ Energizable timing T ₂ Energized timing

Claims (34)

The amount of transition of pure water to the medium at a contact time of 100 ms as measured with a dynamic scanning absorptiometer, having a single or multi-layered pigment layer applied to at least one surface of a support based on cellulose pulp. There is a 1 ml / ^{m 2} or more 1 0 ml / ^{m 2} or less, and the recording medium transfer amount to the pure water medium is 2 ml / ^{m 2} or more 35 ml / ^{m 2} or less at a contact time 400 ms, particulate color Printing using ink containing a material with an ink adhesion amount of 15 g / m ² or less, drying the image by finger touching, and then fixing each of the media and a heat source by direct contact ; An ink jet recording method comprising at least water and a wetting agent, wherein the content of the wetting agent is 20 to 50% by mass .   The ink jet recording method according to claim 1, wherein the heat source uses a fixing roller which is a heat roller. The amount of transfer of pure water to the medium at a contact time of 100 ms measured with a dynamic scanning absorptiometer is preferably 1 ml / m ² or more and 10 ml / m ² or less, and the amount of transfer of pure water to the medium at a contact time of 400 ms. to but 2 ml / m ² or more 11 ml / m ² or less is a recording medium, according to claim 1 or 2, characterized in that printing with solid content of 3% or more of the ink containing a particulate colorant Inkjet recording method.   The inkjet recording method according to claim 1, wherein the fixing temperature is 100 ° C. or higher, desirably 140 ° C. or higher and 150 ° C. or lower.   The inkjet recording method according to claim 1, wherein a nip time of the fixing roller is 0.3 seconds or more.   6. The ink jet recording method according to claim 1, wherein a non-contact drying means is used for the touch drying.   Ink jet spread in an ink jet recording device equipped with a head unit equipped with a nozzle that ejects each color ink necessary for color printing onto the surface of the recording medium, and ejects ink droplets onto the surface of the recording medium 7. An ink jet recording method according to claim 1, wherein an image is formed on a recording medium that is small and agglomerated, and an ink adhesion amount is suppressed within a regulation value by a total quantity regulation process. . The recording medium is composed of at least a base material and a coating layer, and the solid content adhesion amount of the coating layer is 0.5 to 20.0 g / m ^2. Any one of the inkjet recording methods. The inkjet recording method according to claim 1, wherein the recording medium has a basis weight of 50 to 250 g / m ² .   The ink jet recording method according to claim 1, wherein the recording medium contains a pigment, and the pigment is kaolin.   The inkjet recording method according to claim 1, wherein the recording medium contains a pigment, and the pigment is heavy calcium carbonate.   The inkjet recording method according to claim 1, wherein the recording medium contains an aqueous resin.   The inkjet recording method according to claim 12, wherein the aqueous resin is a water-soluble resin or a water-dispersible resin.   The inkjet recording method according to claim 1, wherein the ink is at least one selected from cyan ink, magenta ink, yellow ink, and black ink.   The inkjet recording method according to claim 1, further comprising an ink flying step of applying a stimulus to the ink and causing the ink to fly to form an image on the recording medium.   The inkjet recording method according to claim 15, wherein the stimulus is at least one selected from heat, pressure, vibration, and light.   2. The ink jet recording method according to claim 1, wherein an ink repellent layer is formed on a surface of the ink jet head used for ink jet recording on which an ink discharge opening is formed.   18. The ink jet recording method according to claim 17, wherein the ink repellent layer is made of a fluorine material or a silicone material.   The ink jet recording method according to claim 17 or 18, wherein the ink-repellent layer has a surface roughness Ra of 0.2 µm or less.   18. The cross-sectional area in a plane perpendicular to the center line of the opening in the vicinity of the opening of the ink repellent layer is formed so as to gradually increase as the distance from the substrate surface increases. 20. The inkjet recording method according to any one of items 19 to 19.   21. The ink jet recording method according to claim 17, wherein the thickness of the ink repellent layer is 1 mm or more.   The ink jet recording method according to any one of claims 17 to 21, wherein a critical surface tension γc of the ink repellent layer is 5 to 40 mN / m. 23. The ink jet recording method according to claim 1 , wherein the ink has a volume average particle diameter of 0.01 to 0.16 [ mu] m of a pigment or colored fine particles. The inkjet recording method according to any one of claims 1 to 23, wherein the ink has a viscosity of 1 cps to 30 cps at 25 ° C. The ink jet recording method according to any one of claims 1 to 24, wherein the ink has a surface tension at 25 ° C of 30 mN / m or less. 26. The ink according to claim 1, wherein the ink contains a water-soluble organic solvent, and the water-soluble organic solvent is any one of a polyol compound and a glycol ether compound having 8 or more carbon atoms . The ink jet recording method described in 1 . 27. The polyol compound according to claim 26, wherein the polyol compound having 8 or more carbon atoms is at least one of 2-ethyl-1,3-hexanediol and 2,2,4-trimethyl-1,3-pentanediol. The inkjet recording method as described . The ink contains a surfactant, and the surfactant is at least one selected from the following general formulas (I), (II), (III), (IV), (V), and (VI) 28. The ink jet recording method according to claim 1, wherein the ink jet recording method is a seed.

In the general formula (I), ^{R 1} represents an alkyl group. h represents an integer of 3 to 12. M represents one or more bases selected from alkali metal ions, quaternary ammonium, quaternary phosphonium, and alkanolamine.

In the general formula (II), ^{R 2} represents an alkyl group. M represents one or more bases selected from alkali metal ions, quaternary ammonium, quaternary phosphonium, and alkanolamine.

In the general formula (III), R ³ is represents a hydrocarbon group. k represents an integer of 5 to 20.

In the general formula (IV), ^{R 4} represents a hydrocarbon group. j represents an integer of 5 to 20.

In the general formula (V), ^{R 6} represents a hydrocarbon group. L and p are an integer of 1 to 20

However, q and r represent the integer of 0-40 in the said general formula (VI). 29. The inkjet recording method according to claim 1, wherein the wetting agent is at least one selected from a polyol compound, a lactam compound, a urea compound, and a saccharide. The polyol compound is glycerin, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-butanediol, 2,3-butanediol, 1, 4-butanediol, 3-methyl-1,3-butanediol 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-2,4 - pentanediol, 1,2,4-butanetriol, 1,2,6-hexanetriol, serial thiodiglycol, pentaerythritol, to claim 29 is at least one selected from trimethylol ethane and trimethylol propane The method of the ink-jet recording. The inkjet recording according to claim 29 or 30, wherein the lactam compound is at least one selected from 2-pyrrolidone, N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, and ε-caprolactam. Way . 32. The ink jet recording method according to claim 29 , wherein the urea compound is at least one selected from urea, thiourea, ethylene urea, and 1,3-dimethyl-2-imidazolidinone. The inkjet recording method according to any one of claims 29 to 32, wherein the saccharide is at least one selected from maltose, sorbitol, gluconolactone, and maltose. The ink jet recording method according to claim 1, wherein the ink is filled in an ink cartridge .

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