JP4414738B2 - INK JET RECORDING MEDIUM MANUFACTURING METHOD, INK JET RECORDING MEDIUM, AND INK JET RECORDING METHOD - Google Patents

Description

  The present invention relates to a method for producing an ink jet recording medium, an ink jet recording medium, and an ink jet recording method, and in particular, a method for producing an ink jet recording medium having excellent smoothness and glossiness and no tingling, and the method. The present invention relates to an ink jet recording medium and an ink jet recording method using the medium.

  Conventionally, printing gloss (end press of thermoplastic resin coating layer) and surface gloss of electrophotographic image receiving paper (fixing and gloss of thermoplastic resin toner receiving layer) by heating and pressing and cooling peeling method processing Many proposals have been made. For example, Patent Document 1 listed below can be cited as examples relating to printing glossing, and Patent Documents 2 to 5 can be cited as examples relating to surface glossing of electrophotographic image receiving paper.

  In the above prior art, as a support for various image forming and / or fixing materials such as silver salt photographic (photographic paper), ink jet image receiving paper, thermal transfer image receiving paper, electrophotographic image receiving paper, polyethylene layers on both sides of the base paper, etc. The resin-coated paper is preferably used. However, since the resin-coated paper has an equilibrium moisture content with a base paper portion, when heated at a high temperature, a blister (a coating layer accompanying evaporation and expansion of moisture ( For example, there is a problem that a blister-like state of the polyethylene layer) occurs.

  As for the ink jet recording medium, (1) an image forming method in which an image is formed on a recording medium having a porous surface layer containing a thermoplastic resin, and then smoothed by applying pressure while heating (for example, see Patent Document 6). (2) A method of recording by applying ink droplets to a recording medium and then forming a laminate layer by applying a heating and pressing means (see, for example, Patent Document 7), (3) There has been proposed a method (for example, see Patent Document 8) in which an inkjet recording image is conductively heated from the back surface of a recording paper to dry and fix the ink.

However, since all of the above conventional techniques are processing methods after forming a recorded image on the ink receiving layer, a heating / pressurizing device or a laminating layer forming mechanism or the like is used in the ink jet recording device or as a subsequent device. It is necessary to equip it, and it requires the addition of a considerably large mechanical facility, and its application range is limited.
JP 2001-49595 A Japanese Patent Laid-Open No. 04-199171 Japanese Patent Laid-Open No. 04-344680 JP 2000-56602 A JP 2001-75409 A JP-A-11-291611 Japanese Patent No. 2908518 Japanese Patent No. 3104429

This invention is made | formed in view of this present condition, and makes it a subject to solve the said various problems in the past and to achieve the following objectives. That is,
An object of the present invention is to provide a method for producing an inkjet recording medium that is excellent in smoothness and glossiness and has no tingling sensation, while being an inkjet recording medium that can be directly applied to a conventional small and simple inkjet recording printer. And
Furthermore, the present invention provides an ink jet recording medium which is excellent in smoothness, glossiness, water resistance and the like produced by the above production method and has no dustiness, and ink jet recording which is excellent in light resistance using the ink jet recording medium. It aims to provide a method.

Means of the present invention for solving the above-mentioned problems are as follows. That is,
<1> Before performing ink jet recording, an ink jet recording medium provided with an ink receiving layer on a substrate is heated and pressurized by a cooling and peeling belt fixing type smoothing processor, cooled, and then peeled off from the belt member. A method for producing an ink jet recording medium.
<2> The method for producing an inkjet recording medium according to <1>, wherein a resin layer is provided on one side or both sides of the substrate of the inkjet recording medium.
<3> The method for producing an inkjet recording medium according to <2>, wherein the resin layer is a resin layer containing a polyolefin-based resin as a main component.
<4> The inkjet according to any one of <1> to <3>, wherein the heating and pressurization is performed in a temperature range of 80 ° C. to 110 ° C., and the cooling is performed at a temperature of 80 ° C. or less. A method for manufacturing a recording medium.
<5> The method for producing an inkjet recording medium according to any one of <2> to <4>, wherein the resin layer is formed by a melt extrusion coating method.
<6> The method for producing an inkjet recording medium according to any one of <2> to <5>, wherein the resin layer contains at least one of a white pigment and a fluorescent brightening agent.
<7> The method for producing an inkjet recording medium according to any one of <1> to <6>, wherein the belt member has a three-dimensional surface roughness (Ra) of 20 μm or less.
<8> The method for producing an inkjet recording medium according to any one of <1> to <7>, wherein the belt member is an endless belt.
<9> The method for producing an inkjet recording medium according to any one of <1> to <8>, wherein a rubber layer mainly composed of fluorocarbonsiloxane is formed on a surface of the belt member.
<10> The above <1> to <9, wherein a silicone rubber layer is formed on the surface of the belt member, and a rubber layer mainly composed of fluorocarbonsiloxane is provided on the surface of the silicone rubber layer. The method for producing an ink jet recording medium according to any one of the above.
<11> The inkjet recording medium according to any one of <1> to <10>, wherein the fluorocarbon siloxane has a perfluoroalkyl ether group and / or a perfluoroalkyl group in a main chain. Way .

  According to the present invention, it is possible to provide a method for producing an inkjet recording medium that is excellent in smoothness and glossiness and has no dustiness. In addition, the ink jet recording medium of the present invention produced according to the above production method is an ink jet recording medium having excellent smoothness, glossiness, water resistance and the like, and having no tingling feeling, and is a conventional small and simple ink jet recording printer. It can be applied as it is. Furthermore, it is possible to provide an ink jet recording method having excellent light resistance using the above ink jet recording medium.

The method for producing an ink jet recording medium of the present invention is such that an ink jet recording medium in which an ink receiving layer is provided on a substrate is subjected to a heating and pressing member of a cooling and peeling type belt type smoothing machine before ink jet recording. After heating and pressurizing and cooling, it is peeled off from the belt member in the heating and pressurizing section. Here, a form having a resin layer is preferable on one side or both sides of the substrate of the inkjet recording medium, and the resin layer is preferably a resin layer containing a polyolefin-based resin as a main component. A mode in which the cooling is performed in the range of 80 ° C. to 110 ° C. and the cooling is performed at a temperature of 80 ° C. or less is preferable.
In addition, since the ink jet recording medium of the present invention is produced by the above-described production method, it is possible to provide an ink jet recording medium excellent in smoothness and glossiness and having no dustiness, and an ink jet recording method.
Hereinafter, the production method of the ink jet recording medium, the ink jet recording medium, and the ink jet recording method of the present invention will be described in detail with respect to the constituent requirements. However, the present invention is limited to these explanations and exemplary compounds. is not.

(Substrate)
The substrate of the ink jet recording medium of the present invention can withstand the above-mentioned heating and pressurization, and can satisfy the required performance in terms of smoothness, whiteness, slipperiness, friction, antistatic properties, etc. If it is, there will be no restriction | limiting in particular, According to the objective, necessity, etc., it can select suitably. In general, papers and synthetic polymers (films) described in “The Basics of Photographic Engineering—Silver Salt Photography” (Corona Co., Ltd., 1979, pp. 223-240), etc. And a recording support.

Specific examples of the substrate include synthetic paper (polyolefin-based, polystyrene-based synthetic paper), high-quality paper, art paper, (double-sided) coated paper, (double-sided) cast-coated paper, and synthetic resin pulp such as polyethylene and natural pulp. Paper supports such as mixed paper, Yankee paper, baryta paper, wallpaper, backing paper, synthetic resin or emulsion impregnated paper, synthetic rubber latex impregnated paper, synthetic resin internal paper, paperboard, cellulose fiber paper, etc. Various plastic films or sheets such as polyolefin, polyvinyl chloride, polyethylene terephthalate, polystyrene methacrylate, polyethylene naphthalate, polycarbonate polyvinyl chloride, polystyrene, polypropylene, polyimide, celluloses (for example, triacetyl cellulose), the plastic film or Treatment to impart white reflection in over preparative (e.g., processing such as to contain a pigment such as titanium oxide into the film) was subjected to a film or sheet; cloth, metal, glasses, and the like.
These may be used alone or in combination as a laminate of two or more.

  Examples of the substrate further include JP-A-62-253159 (pages 29 to 31), JP-A-1-61236 (pages 14 to 17), JP-A-63-316848, JP-A-2-22651. No. 3-56955, US Pat. No. 5,010,333 and the like can also be used.

The substrate used in the present invention preferably has a high surface smoothness. Specifically, the surface roughness (Oken type smoothness) is preferably 210 seconds or more, and more preferably 250 seconds or more. Those are more preferred. If the surface roughness (Oken smoothness) is less than 210 seconds, the image quality of the image may be poor when an image is formed.
Here, the above-mentioned Oken-type smoothness refers to JAPAN TAPPI No. 5 Smoothness defined by the B method, preferably about 600 seconds, and more preferably about 500 seconds.

There is no restriction | limiting in particular as thickness of the said base | substrate, Although it can select suitably according to the objective, Usually, about 25-300 micrometers is frequently used, 50-260 micrometers is preferable, and 75-220 micrometers is more preferable.
There is no restriction | limiting in particular as rigidity of the said base | substrate, According to the objective, it can select suitably. The density of the substrate is preferably 0.7 g / cm ³ or more from the viewpoint of fixing performance.

  The thermal conductivity of the substrate is not particularly limited and may be appropriately selected depending on the intended purpose. However, particularly when used as a support of the present invention, the temperature is 20 ° C. relative humidity from the viewpoint of image fastness. Is preferably 0.50 kcal / m · h · ° C. or higher under the condition of 65%. Here, the thermal conductivity can be measured according to the method described in JP-A-53-66279 for a support conditioned according to JIS P 8111.

  The above-mentioned substrate can contain various additives appropriately selected according to the purpose and necessity within a range not impairing the effects of the present invention. Examples of such additives include brighteners, conductive agents, fillers, pigments such as titanium oxide, ultramarine, and carbon black, and dyes.

Moreover, in order to improve adhesiveness with the layer etc. which are provided on the one side or both sides of the substrate, a known surface treatment or undercoating treatment may be applied. As such surface treatment, for example, a glossy surface, or a mold surface treatment such as a fine surface, a matte surface, or a silk surface described in JP-A-55-26507, corona discharge treatment, flame treatment, glow discharge, etc. Examples thereof include surface activation treatment such as treatment and plasma treatment. As the undercoating treatment, for example, a method described in JP-A No. 61-84443 can be used.
The above-mentioned treatment may be performed alone, or after performing the above-mentioned molding treatment or the like, the above-mentioned activation treatment may be performed, and further, the above-mentioned undercoat treatment may be performed after the surface treatment such as the above-mentioned activation treatment, Any of these can be arbitrarily combined.

  In the above substrate, a hydrophilic binder, a semiconductive metal oxide such as alumina sol or tin oxide, and carbon black or other antistatic agent may be applied on the front surface or back surface of the substrate or a combination thereof. . Examples of such a substrate include a support described in JP-A No. 63-220246.

(Resin layer)
In the ink jet recording medium of the present invention, a form having a resin layer on one side or both sides of the substrate is preferable. The resins forming the resin layer are preferably thermoplastic resins having a melting temperature or softening temperature equal to or higher than room temperature, and polyolefin resins are particularly preferable. The resin layer is disposed between the substrate and the ink receiving layer.
Specific examples of such polyolefin resins include α-olefin homopolymers such as polyethylene, polypropylene, polystyrene, polymethyl (meth) acrylate, and polyvinyl chloride, and ethylene-vinyl acetate copolymers, ethylene. -Α-olefin copolymer such as (meth) acrylate copolymer

  Among the polyolefin resins, particularly preferred polyolefin resins are high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (L-LDPE), and blends thereof.

  The resin layer in the present invention is generally formed by using low density polyethylene (LDPE). In order to improve the heat resistance of the support (substrate), polypropylene or a blend of polypropylene and polyethylene is used. It is also preferable to use high-density polyethylene or a blend of high-density polyethylene and low-density polyethylene. In particular, it is most preferable to use a blend of high-density polyethylene and low-density polyethylene from the viewpoint of material cost and coating suitability.

As a blend of the high density polyethylene and the low density polyethylene, a mass blend ratio is usually used within a range of 1/9 to 9/1. The blend ratio is preferably 2/8 to 8/2, and more preferably 3/7 to 7/3. When the resin layers are formed on both sides of the substrate (support), the back surface of the substrate is preferably formed using, for example, high-density polyethylene or a blend of high-density polyethylene and low-density polyethylene.
Moreover, there is no restriction | limiting in particular as the molecular weight of the said polyethylene, but MFR (melt flow index) is a measured value, and is the range of 1.0-40 g / 10min, and has the extrudability Is preferred.

  These polyolefin-based resins have a characteristic that it is difficult to cause blocking because they have a structure that hardly interacts with other substances even though the glass transition temperature (Tg) is low. .

  In the present invention, the method for forming the resin layer on one or both sides of the substrate is not particularly limited and can be appropriately selected depending on the purpose. For example, (1) Dry lamination (bonding) of polyolefin resin film to a substrate, (2) Application of solution containing polyolefin resin, (3) Application of emulsion containing dispersion of polyolefin resin, (4) Polyolefin Although known methods such as impregnation in a resin emulsion and (5) coating by melt extrusion coating can be used, from the viewpoint of ensuring a uniform film thickness and high productivity, the melt extrusion coating method of (5) Preferably formed.

  Although there is no restriction | limiting in particular in the thickness of the said resin layer, For example, as a thickness of the resin layer which contains polyolefin resin as a main component, 1-50 micrometers is preferable and 5-15 micrometers is more preferable.

The resin layer of the present invention can contain various fillers, additives and the like according to the purpose and necessity. In particular, in order to improve light resistance, smoothness and whiteness, a form containing at least one of a white pigment and a fluorescent brightener is preferable.
The fluorescent whitening agent is a compound having absorption in the near ultraviolet region and emitting fluorescence at 400 to 500 nm, and various known fluorescent whitening agents can be used without particular limitation. Such fluorescent whitening agents include K.I. Preferable examples include compounds described in Vol. 8, Chapter 8 of “The Chemistry of Synthetic Dies” edited by Veen Rataraman. Specific examples include stilbene compounds, coumarin compounds, biphenyl compounds, benzoxazoline compounds, naphthalimide compounds, pyrazoline compounds, carbostyryl compounds, and the like. Examples of commercially available fluorescent whitening agents include “White Furfur PSN, PHR, HCS, PCS, B” manufactured by Sumitomo Chemical Co., Ltd., “UVITEX-OB” manufactured by Ciba-Geigy, and the like. Can be mentioned.

  Examples of the white pigment include titanium oxide, calcium carbonate, barium sulfate, and zinc white. Among these, titanium oxide is preferable from the viewpoint of concealability.

The content of the white pigment and / or fluorescent whitening agent is preferably 0.1 to 8 g / m ^2, 0.5 to 5 g / m ² is more preferable. If the content is less than 0.1 g / m ² , the concealability may be insufficient and the light transmittance may be too high. On the other hand, if the content exceeds 8 g / m ² , cracks and handling workability decrease. May bring.

(Cooling peeling type belt type smoothing machine)
In the present invention, before performing ink jet recording, an ink jet recording medium provided with an ink receiving layer on a substrate is heated and pressurized by a cooling and peeling type belt fixing type smoothing processor, cooled, and then removed from the belt member. A process of peeling is performed.
Here, “before ink-jet recording” means from immediately after an ink-receiving layer is provided on a substrate to produce an ink-jet recording medium to immediately before ink-jet recording is performed by ejecting ink-jet ink. Refers to any time.
Specifically, for example, after (1) the ink receiving layer coating liquid is applied to the substrate and dried, and before being wound up as a raw roll, (2) in the state of being wound up as the original roll. (3) After the raw roll is cut into a predetermined width and length and before winding or stacking again, and (4) until immediately before finally performing inkjet recording. And the like. Further, the above-described heating and pressing and cooling peeling treatment of the present invention may be carried out a plurality of times before ink jet recording is performed.

Although there is no restriction | limiting in particular as a heating-pressing member of the said belt-type smoothing processing machine of a cooling peeling system, For example, the combination system of a heating roller, a pressurizing roller, and an endless belt is mentioned.
In this way, the ink jet recording medium having the ink receiving layer provided on the substrate is softened and compressed by the heating and pressurizing member of the cooling and peeling type belt type smoothing processor, but heated under a temperature condition in which no blisters are generated. By applying pressure and quickly cooling to a temperature condition at which the ink jet recording medium is solidified and peeling off from the belt member, a useful ink jet recording medium having excellent smoothness and gloss and no tingling sensation is continuously and efficiently produced. Manufactured.

As the above-mentioned “cooling peeling type belt fixing type smoothing processing machine” used in the present invention, any processing machine system having a mechanism capable of continuous heating and pressurization and a mechanism capable of cooling and peeling by a belt conveyance method can be used. You can also use various things.
As an embodiment of such a “cooling peeling type belt fixing type smoothing processing machine”, the cooling peeling type belt fixing type smoothing processing machine (endless press) shown in FIG. 1 will be described in detail below. .

In the cooling peeling type belt fixing type smoothing processing machine (endless press) shown in FIG. 1, the smoothing processing section (1) includes a belt (2), a heating roller (3), a pressure roller (4), and a tension roller. (5) A cleaning roller (6), a cooling device (7), and a conveyance roller (8) are provided.
A belt (2) and a pair of tension rollers (5) are disposed inside the belt (2). The belt (2) is rotatably stretched by a heating roller (3) and a pair of tension rollers (5) arranged at a position away from the heating roller (3). The pressure roller (4) is disposed in contact with the heating roller (3) in contact with the belt (2). Between the pressure roller (4) and the belt (2), pressure is applied by the pressure roller (4) and the heating roller (3) to form a nip portion. The cooling device (7) includes a heating roller (3) located upstream and a tension roller (5) located downstream of the belt (2) in the rotational direction of the belt (2). Arranged between. Two transport rollers (8) are arranged so as to face the cooling device (7) through the belt (2). Here, the distance between the two conveying rollers is substantially the same as the distance between the nip portion and one of the conveying rollers (8) and the distance between the tension roller (5) and the other one of the conveying rollers (8). That's it. The cleaning roller (6) is arranged to face the opposite side of the heating roller (3) from the side facing the pressure roller (4) via the belt (2). The cleaning roller (6) and the belt (2) are pressurized by the cleaning roller (6) and the heating roller (3). The heating roller (3), the pressure roller (4), the tension roller (5), the cleaning roller (6), and the conveying roller (8) rotate in conjunction with each other to rotate the belt (2). Can be made.

In the present invention, in order to further improve the smoothness and glossiness of the ink jet recording medium and further reduce the dustiness, the processing equipment and processing conditions for the above heating and pressurization and cooling peeling are preferably as follows. .
(1) The temperature at which the ink jet recording medium is heated and pressurized is preferably in the range of 80 ° C. to 110 ° C., and the subsequent cooling is preferably performed at a temperature of 80 ° C. or less. When the heating and pressurizing temperature is less than 80 ° C., the improvement effect by the treatment may be insufficient, and when the temperature exceeds 110 ° C., blisters may be generated in some cases. Here, the heating temperature ranges from 80 ° C. to 110 ° C. because the temperature of the resin layer is particularly high when an ink-jet recording medium provided with the ink receiving layer of the object to be processed, particularly when a resin layer is provided. This means that the temperature is in the range of 80 ° C. to 110 ° C. The heating roller (3) is naturally required to be set higher than the above temperature range. In the case of the cooling treatment, it means that the temperature of the ink jet recording medium, particularly the resin layer, is 80 ° C. or less, and the cooling device (7) naturally needs to be set lower than the above temperature range. is there.
(2) Moreover, there is no restriction | limiting in particular as a pressurization method at the time of said heat pressurization, However, the system which applies nip pressure is preferable. As such a nip pressure, in order to eliminate the Chile Chile sense to improve the surface smoothness is preferably 1 to 100 kg / cm ^2, more preferably 5~30kg / cm ^2.

(3) The three-dimensional surface roughness (Ra) of the belt member heated and pressed in contact with the ink jet recording medium is 20 μm or less from the viewpoint of efficiently producing a recording material excellent in smoothness and gloss. Is preferably 10 μm or less, more preferably 5 μm or less. When the three-dimensional surface roughness (Ra) of the belt member exceeds 20 μm, the effect of the smoothing treatment may be insufficient.
Here, the above three-dimensional surface roughness (Ra) means the center plane average roughness (SRa), and the center plane average roughness (SRa) is an area SM from the roughness curved surface to the center plane. When a part is extracted, an orthogonal coordinate axis (X axis, Y axis) is placed on the center plane of the extracted part, and an axis orthogonal to the center plane is set as the Z axis, the value given by the following formula is the center plane average roughness (SRa) and expressed in μm.

上式において、ＬＸ×ＬＹ＝ＳＭ、Ｚ＝ｆ（Ｘ，Ｙ）である。

In the above formula, LX × LY = SM and Z = f (X, Y).

Such a three-dimensional surface roughness (Ra) is measured under the following measurement and analysis conditions using, for example, a surface shape measuring device “Nanometro 110F” manufactured by Kuroda Seiko Co., Ltd.
(Scanning direction): MD direction of sample (Measurement length): X direction 50 mm, Y direction 30 mm
(Measurement pitch): X direction 0.1 mm, Y direction 0.1 mm
(Scanning speed): 30 mm / second (Bandpass filter): 1 to 2 mm (1 mm or less and 2 mm or more are cut off)
(Filter inclination): -12 dB / Oct
(Effective range of filter tilt): The short wavelength side is up to 0.5 mm wavelength, and the long wavelength side is up to 4 mm wavelength.

(4) The belt member used for heating and pressing is preferably an endless belt in order to continuously and efficiently perform the heating and pressing and cooling peeling processes of the present invention.
As the belt member used for the smoothing treatment of the present invention, a thin layer made of at least one selected from the group consisting of silicone rubber, fluororubber, silicone resin and fluororesin is formed on the surface of the belt member. It is preferable that Among these, those in which a rubber layer mainly composed of fluorocarbon siloxane having a uniform thickness is formed on the surface of the belt member are preferable. In particular, a silicone rubber layer is formed on the surface of the belt member, and the silicone rubber layer is further formed. The form which provided the rubber layer which has fluorocarbon siloxane as a main component on the surface is preferable.

As the fluorocarbon siloxane, a siloxane rubber having a perfluoroalkyl ether group and / or a perfluoroalkyl group in the main chain is preferable.
Such a fluorocarbon siloxane rubber includes (A) a fluorocarbon siloxane represented by the following general formula (1) as a main component and an aliphatic unsaturated group, (B) two or more ≡SiH in the molecule. An organopolysiloxane and / or a fluorocarbon siloxane containing a group, wherein the content of the ≡SiH group is 1 to 4 times the molar amount of the aliphatic unsaturated group in the fluorocarbon siloxane rubber composition, (C) A crosslinked siloxane rubber obtained by curing a fluorocarbon siloxane rubber composition containing a filler and (D) an effective amount of a catalyst is preferably used.

  The fluorocarbon polymer of the component (A) is mainly composed of fluorocarbon siloxane having a repeating unit represented by the following general formula (1) and has an aliphatic unsaturated group.

In the general formula (1), R ¹⁰ is a substituted or unsubstituted, preferably a hydrocarbon group having 1 to 8 carbon atoms, preferably an alkyl group having 1 to 8 carbon atoms or a carbon group having 2 to 3 carbon atoms. An alkenyl group, particularly preferably a methyl group. a and e are each independently 0 or 1, b and d are each independently an integer of 1 to 4, and c is an integer of 0 to 8. Moreover, x is an integer greater than or equal to 1, Preferably it is an integer of 10-30.

  Examples of such component (A) include compounds represented by the following general formula (2).

  In the component (B), examples of the organopolysiloxane having an ≡SiH group include organohydrogenpolysiloxanes having at least two hydrogen atoms bonded to silicon atoms in the molecule.

  In the fluorocarbon siloxane rubber composition used in the present invention, when the fluorocarbon polymer as the component (A) has an aliphatic unsaturated group, the above-described organohydrogenpolysiloxane can be used as a curing agent. . That is, in this case, a cured product is formed by an addition reaction that occurs between an aliphatic unsaturated group in the fluorocarbon siloxane and a hydrogen atom bonded to a silicon atom in the organohydrogenpolysiloxane.

  As such an organohydrogenpolysiloxane, a known organohydrogenpolysiloxane used in an addition-curable silicone rubber composition can be used.

  The above-mentioned organohydrogenpolysiloxane generally has at least one ≡SiH group, preferably 1 to 5 with respect to one aliphatic unsaturated hydrocarbon group in the fluorocarbon siloxane of component (A). It is desirable to mix them in such a ratio that they become individual.

In addition, the fluorocarbon having a ≡SiH group includes a unit of the above general formula (1) or R ¹⁰ in the general formula (1) is a dialkylhydrogensiloxy group, and a terminal is a dialkylhydrogensiloxy group or a silyl group. What is a SiH group is preferable and what is shown by following General formula (3) can be mentioned.

  As the filler of the component (C), known fillers used in general silicone rubber compositions can be used. Examples include fumed silica, precipitated silica, carbon powder, titanium dioxide, aluminum oxide, quartz powder, reinforcing fillers such as talc, sericite, and bentonite, and fibrous fillers such as asbestos, glass fibers, and organic fibers. can do.

  Examples of the catalyst for the component (D) include chloroplatinic acid, alcohol-modified chloroplatinic acid, complexes of chloroplatinic acid and olefin, platinum black or palladium, which are known as addition reaction catalysts, alumina, silica, carbon, etc. Examples are those supported on the above-mentioned carriers, rhodium-olefin complexes, chlorotris (triphenylphosphine) rhodium (Wilkinson catalyst), rhodium (III) acetylacetonate, etc. However, these complexes are preferably used by being dissolved in a solvent such as an alcohol, ether, or hydrocarbon.

  In the fluorocarbon siloxane rubber composition used in the present invention, various compounding agents can be added within a range that does not impair the object of the present invention such as improvement of smoothness and suppression of dustiness. For example, diphenylsilane diol, low-polymerization degree molecular chain terminal hydroxyl-blocked dimethylpolysiloxane, dispersant such as hexamethyldisilazane, heat resistance improver such as ferrous oxide, ferric oxide, cerium oxide, iron octylate In addition, colorants such as pigments can be blended according to the purpose and necessity.

  The belt member used in the present invention is obtained by, for example, coating the surface of a heat-resistant resin or metal belt body with the above-mentioned fluorocarbon siloxane rubber composition, and heat-curing, but if necessary, further, It can be diluted with a solvent such as m-xylene hexafluoride or benzotrifluoride to form a coating solution, which can be applied by a general coating method such as spray coating, dip coating, or knife coating. Here, the temperature and time of the heat curing can be appropriately selected, and are usually selected in accordance with the type of belt body, the manufacturing method, etc. within the temperature range of 100 to 500 ° C. and the time of 5 seconds to 5 hours. The

  The layer thickness of the fluorocarbonsiloxane rubber formed on the surface of the belt member is not particularly limited, but is usually 20 to 500 μm, preferably 40 to 200 μm.

  The form of the belt member is not particularly limited, but an endless belt in a cooling and peeling type belt type smoothing machine is preferable. The belt-type smoothing processor of the cooling and peeling method is not particularly limited and can be appropriately selected according to the purpose. For example, as shown in FIG. A system that is equipped with an apparatus and that can be post-processed by a cooling peeling method that can adjust the temperature during peeling low is preferable. The cooling temperature in the cooling device is preferably a temperature of 80 ° C. or less at which the resin layer is sufficiently solidified, more preferably 80 to 20 ° C., and most preferably about room temperature (25 ° C.).

(Inkjet recording medium)
The ink jet recording medium of the present invention is efficiently produced by the above-described method for producing an ink jet recording medium of the present invention. Therefore, in particular, it has excellent surface smoothness, no tingling sensation, and good gloss.

  Further, the three-dimensional surface roughness (Ra) of the ink jet recording medium is preferably 2 μm or less, and more preferably 1 μm or less. Here, the three-dimensional surface roughness (Ra) is synonymous with the three-dimensional surface roughness (Ra) of the belt member described above, and the measurement method is also the same.

(Inkjet recording method)
In the inkjet recording method of the present invention, a yellow ink containing at least one yellow dye, a magenta ink containing at least one magenta dye, and at least one cyan dye are formed on the above-described inkjet recording medium. An image using an ink set having the cyan ink contained therein as a minimum component, wherein the magenta dye and / or cyan dye has an oxidation potential nobler than 0.8 V (vs SCE). It is characterized by forming.

In the present invention, a magenta dye and / or a cyan dye having an oxidation potential nobler than 0.8 V (vs SCE) is used. The oxidation potential is preferably as noble, more preferably noble than the oxidation potential of 1.0 V (vs SCE), more preferably noble than 1.1 V (vs SCE), 1.15 V Those more noble than (vs SCE) are particularly preferred, and those nobler than 1.2 V (vs SCE) are most preferred.
Here, when a cyan dye having an oxidation potential nobler than 0.8 V (vs SCE) is used in combination with the magenta dye, a gray balance is preferably obtained.

  The value of the oxidation potential represents the ease of transfer of electrons from the sample to the electrode. The higher the value (the oxidation potential is noble), the more difficult the transfer of electrons from the sample to the electrode, in other words, the less the oxidation is. Represents. In relation to the structure of the compound, the oxidation potential becomes more noble by introducing an electron withdrawing group, and the oxidation potential becomes lower by introducing an electron donating group.

  Although the value of the oxidation potential will be described later, it means a potential at which the compound is an anode in voltammetry, and the electron of the compound is extracted, and is considered to approximately coincide with the energy level of HOMO in the ground state of the compound.

  The inventors of the present invention have studied the ozone fastness of the colored image. As a result, there is a correlation between the oxidation potential of the compound used for the colored image and the ozone fastness, and the value of the oxidation potential is higher than that of the saturated calomel electrode (SCE). It has been found that ozone fastness is improved by using a more noble compound.

  The reason why the ozone fastness of the colored image is improved can be explained by the relationship between the HOMO (highest occupied orbit) and LUMO (lowest empty orbit) of the compound and ozone gas. That is, the colorant is oxidized by the reaction between the colorant HOMO and the ozone gas LUMO, and as a result, it is considered that the ozone fastness of the colored image is lowered. The HOMO of the agent may be lowered to reduce the reactivity with ozone gas.

  The value (Eox) of the oxidation potential can be easily measured by those skilled in the art. Regarding the measuring method, for example, P.I. Delahay, “New Instrumental Methods in Electrochemistry” (1954, Interscience Publishers) and A.D. J. et al. It is described in detail in “Electrochemical Methods” by Bard et al. (1980, John Wiley & Sons) and “Electrochemical Measurement Method” by Akira Fujishima et al. (1984, Gihodo Publishing Co., Ltd.).

Here, the measurement of the oxidation potential will be specifically described. The oxidation potential is 1 × 10 ⁻⁴ to 1 × 10 ⁻⁶ mol · dm ^{−3 in} a solvent such as dimethylformamide or acetonitrile containing a supporting electrolyte such as sodium perchlorate or tetrapropylammonium perchlorate. Dissolve and measure as a value for SCE (saturated calomel electrode) using cyclic voltammetry or direct current polarography.
The supporting electrolyte and solvent to be used can be selected appropriately depending on the oxidation potential and solubility of the test sample. The supporting electrolyte and the solvent that can be used are described in pages 101 to 118 of “Electrochemical measurement method” by Akira Fujishima et al. (1984, published by Gihodo Publishing Co., Ltd.).

  The value of the oxidation potential may be deviated by several tens of mil volts due to the influence of the inter-liquid potential difference or the liquid resistance of the sample solution, but the potential measured by calibrating with a standard sample (for example, hydroquinone). The reproducibility of the value of can be guaranteed.

In this specification, the oxidation potential is in N, N-dimethylformamide containing 0.1 mol · dm ⁻³ of tetrapropylammonium perchlorate as a supporting electrolyte (the concentration of the compound is 1 × 10 ⁻³ mol · dm ⁻³ ). Then, SCE (saturated calomel electrode) is used as a reference electrode, a graphite electrode is used as a working electrode, and a platinum electrode is used as a counter electrode, and values measured by direct current polarography are used.

The dye used in the present invention may have any structure as long as it satisfies the above oxidation potential. In particular, yellow dyes have no structural restrictions because they have noble oxidation potential (low HOMO). Hereinafter, the structure of the dye necessary for satisfying the oxidation potential will be described in detail.
In the present invention, in order to lower the reactivity with ozone as an electrophile, it is desirable to introduce an electron withdrawing group into the dye skeleton to make the oxidation potential more noble. Therefore, using Hammett's substituent constant σp value, which is a measure of the electron withdrawing property and electron donating property of the substituent, the σp value is as in nitro, cyano, sulfinyl, sulfonyl, and sulfamoyl groups. It can be said that the oxidation potential can be made more noble by introducing a large substituent.

  Hammett's substituent constant σp value will be described below. Hammett's rule is a method described in 1935 by L.L., in order to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives. P. A rule of thumb proposed by Hammett, which is widely accepted today. Substituent constants determined by Hammett's rule include a σp value and a σm value, and these values can be found in many general books. A. Dean's “Lange's Handbook of Chemistry”, 12th edition, 1979 (Mc Graw-Hill) and “Chemicals” special edition, 122, 96-103, 1979 (Nankodo).

  In addition to the above-mentioned substituents, the oxidation potential can be made noble as the number of atoms having high electronegativity generally increases as the constituent atoms of the chromophore. Therefore, for example, when an unsaturated heterocycle is used as a constituent of a chromophore rather than an aryl group, the oxidation potential can be made noble. Examples of the heteroatom having a high electronegativity include a nitrogen atom, an oxygen atom, and a sulfur atom, and a nitrogen atom is particularly preferable.

Accordingly, the dye used in the present invention is preferably one in which the chromophore is composed of a heteroatom, one containing an unsaturated heterocycle, or one containing an electron-withdrawing group.
Preferred chromophores composed of heteroatoms include azo dyes, azomethine dyes, phthalocyanine dyes and the like, with azo dyes being particularly preferred.
As the unsaturated heterocycle, a 5- or 6-membered unsaturated heterocycle is preferable, and a thiophene ring, furan ring, pyrrole ring, thiazole ring, oxazole ring, imidazole ring, isothiazole ring, isoxazole ring, pyrazole ring, thiadiazole ring. And oxadiazole ring, triazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring and the like. The unsaturated heterocycle may form a condensed ring with a hydrocarbon ring or a heterocycle. In the case of a nitrogen-containing heterocycle, the nitrogen atom may be quaternized. Further, with respect to the heterocycle that can be tautomeric, even when only one tautomer is described, other tautomers are also included. Among these, preferred are a thiazole ring, an isothiazole ring, a pyrazole ring, a thiadiazole ring, a pyridine ring, a pyrimidine ring, and a pyrazine ring. Particularly preferred are an isothiazole ring, pyrazole ring, 1,2,4-thiadiazole ring, 1,3,4-thiadiazole ring, and pyridine ring.

  As a preferred electron-withdrawing substituent, a substituent having a Hammett's σp value of 0.40 or more is preferable, a substituent of 0.45 or more is more preferable, and a substituent of 0.50 or more is particularly preferable. When a plurality of electron-withdrawing groups are present as substituents on the chromophore, the sum of the σp values of the substituents is preferably 0.50 or more, more preferably 0.60 or more, 70 or more is preferable. Specific examples of the electron-withdrawing group having σp of 0.40 or more are described in J. A. Dean's “Lange's Handbook of Chemistry”, 12th edition, 1979 (Mc Graw-Hill) and “Chemicals” special edition, 122, 96-103, 1979 (Nankodo) it can.

The dye suitably used in the present invention is a combination of dyes represented by the following general formula (1).
(Ch) − (EWG) _n ... General formula (1)

In the general formula (1), Ch represents a chromophore containing an unsaturated heterocycle, and EWG represents an electron-withdrawing substituent having a σp value of 0.40 or more, which will be described later. n is an integer from 1 to 8.
Examples of the Ch include azo dyes having an unsaturated heterocyclic ring in the chromophore, phthalocyanine dyes, azomethine dyes, quinone dyes (anthraquinone dyes, anthrapyridone dyes, etc.), carbonium dyes (triphenylmethane dyes, xanthene dyes, acridine dyes, etc.) And chromophores of azine dyes (oxazine, thiazine, etc.). Preferred are azo dyes, phthalocyanine dyes, azomethine dyes, and anthrapyridone dyes having an unsaturated heterocyclic ring in the chromophore, and particularly preferred are azo dyes and phthalocyanine dyes having an unsaturated heterocyclic ring in the chromophore.

Preferred azo dyes that can be used as magenta and yellow dyes are those represented by the following general formula (2).
Het (A) -N = N-Het (B) ......... General formula (2)

In the general formula (2), Het (A) and Het (B) represent a 5- or 6-membered unsaturated heterocycle. Examples of unsaturated heterocycles represented by Het (A) and Het (B) include thiophene ring, furan ring, pyrrole ring, thiazole ring, oxazole ring, imidazole ring, isothiazole ring, isoxazole ring, pyrazole ring, Examples include a thiadiazole ring, an oxadiazole ring, a triazole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, and a pyrazine ring. These unsaturated heterocycles may further have a substituent. When the substituents on the unsaturated heterocycle are bonded to each other, a condensed ring with a hydrocarbon ring or an unsaturated heterocycle may be formed, and further a substituent may be present on the condensed ring. In the case of a nitrogen-containing unsaturated heterocycle, the nitrogen atom may be quaternized. Moreover, about the unsaturated heterocycle which can become tautomerism, even when only one tautomer is described, other tautomers are also included.
When the dye is a water-soluble dye, it preferably has an ionic hydrophilic group as a substituent. Examples of the ionic hydrophilic group as a substituent include a sulfo group, a carboxyl group, a phosphono group, and a quaternary ammonium group.

  The heterocyclic ring represented by Het (A) and Het (B) is preferably a thiazole ring, isothiazole ring, pyrazole ring, thiadiazole ring, pyridine ring or pyrazine ring. More preferably, they are an isothiazole ring, a pyrazole ring, a thiadiazole ring, and a pyridine ring. Particularly preferred are a pyrazole ring, a 1,2,4-thiadiazole ring and a pyridine ring.

  Het (A) and Het (B) may have a substituent. Substituents include halogen atoms, alkyl groups (including cycloalkyl groups), alkenyl groups (including cycloalkenyl groups), alkynyl groups, aryl groups, heterocyclic groups, cyano groups, hydroxyl groups, nitro groups, carboxyl groups, Alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy, amino group (including anilino group), acylamino group, aminocarbonylamino group, alkoxy Carbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl and Arylsulfinyl groups, alkyl and arylsulfonyl groups, acyl groups, aryloxycarbonyl groups, alkoxycarbonyl groups, carbamoyl groups, aryl and heterocyclic azo groups, imide groups, phosphino groups, phosphono groups, phosphinyl groups, phosphinyloxy groups, Examples include a phosphinylamino group and a silyl group.

Among them, halogen atom, heterocyclic group, cyano group, nitro group, carboxyl group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy, sulfamoyl group, sulfo group, alkyl and arylsulfinyl group, alkyl and arylsulfonyl Raising substituents such as groups, acyl groups, aryloxycarbonyl groups, alkoxycarbonyl groups, carbamoyl groups, imide groups, phosphoryl groups, phosphono groups, phosphinoyl groups, phosphonyl groups, phosphinoyloxy groups, phosphinoylamino groups Among them, an electron-withdrawing group is preferable, and a substituent having σp of 0.40 or more is particularly preferable. Substituents with σp of 0.40 or more include cyano group, nitro group, carboxyl group, sulfamoyl group, alkyl and arylsulfinyl group, alkyl and arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl Groups, imide groups, phosphono groups, phosphoryl groups, etc., alkyl groups substituted with electron-withdrawing groups (trihalomethyl groups, perfluoroalkyl groups, dicyanomethyl groups, iminomethyl groups, etc.), alkenyl substituted with electron-withdrawing groups Groups (such as tricyanovinyl group) and quaternary salt substituents (sulfonium group, ammonium group, phosphonium group) can also be mentioned. Among the above functional groups, those having a hydrogen atom may be substituted with the above groups by removing this. Examples of such a substituent include an alkylcarbonylaminosulfonyl group, an arylcarbonylaminosulfonyl group, an alkylsulfonylaminocarbonyl group, an arylsulfonylaminocarbonyl group, and the like.
Moreover, when the substituents on the heterocycle are bonded to each other, a heterocycle and a condensed ring may be formed, and a substituent may be further provided on the condensed ring.

Preferable magenta dyes include dyes represented by the following general formula (M-I).

In general formula (M-I), A represents a residue of a 5-membered heterocyclic diazo component A-NH ₂ . B ¹ and B ² each represent —CR ¹ ═ and CR ² ═, or one of them represents a nitrogen atom, and the other represents —CR ¹ ═ or —CR ² ═. R ⁵ and R ⁶ each independently represent a hydrogen atom, aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkyl or arylsulfonyl group, or sulfamoyl group. Each group may further have a substituent.

G, R ¹ and R ² are each independently a hydrogen atom, halogen atom, aliphatic group, aromatic group, heterocyclic group, cyano group, carboxyl group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, heterocyclic ring Oxycarbonyl group, acyl group, hydroxy group, alkoxy group, aryloxy group, heterocyclic oxy group, silyloxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (heterocyclic amino group Anilino group), acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkyl or arylsulfonylamino group, heterocyclic sulfonylamino group, nitro group, alkyl or arylthio group , It represents an alkyl or arylsulfonyl group, a heterocyclic sulfonyl group, an alkyl or arylsulfinyl group, a heterocyclic sulfinyl group, a sulfamoyl group, a sulfo group, or a heterocyclic thio group, and each group may be further substituted. R ¹ and R ⁵ , or R ⁵ and R ⁶ may combine to form a 5- or 6-membered ring.

In the general formula (M-I), A represents a residue of a 5-membered heterocyclic diazo component A-NH _2. Examples of heteroatoms for heterocycles include N, O, and S. A nitrogen-containing 5-membered heterocyclic ring is preferable, and an aliphatic ring, an aromatic ring or another heterocyclic ring may be condensed to the heterocyclic ring. Examples of preferred heterocyclic rings for A include pyrazole ring, imidazole ring, thiazole ring, isothiazole ring, thiadiazole ring, benzothiazole ring, benzoxazole ring, and benzoisothiazole ring. Each heterocyclic group may further have a substituent. Among these, pyrazole rings, imidazole rings, isothiazole rings, thiadiazole rings, and benzothiazole rings represented by the following general formulas (a) to (f) are preferable.

In the general formulas (a) to (f), R ⁷ to R ²⁰ represent the same substituents as those described for G, R ¹ and R ² . Of the general formulas (a) to (f), preferred are the pyrazole ring and isothiazole ring represented by the general formulas (a) and (b), and most preferred is the general formula (a). It is a pyrazole ring.

In the general formula (MI), B ¹ and B ² each represent —CR ¹ ═ and CR ² ═, or either one represents a nitrogen atom and the other represents —CR ¹ ═ or —CR ² ═. More preferably, -CR ¹ = and -CR ² = respectively.

R ⁵ and R ⁶ each independently represents a hydrogen atom, aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkyl or arylsulfonyl group, sulfamoyl group, Each group may further have a substituent. Preferable substituents represented by R ⁵ and R ⁶ include a hydrogen atom, aliphatic group, aromatic group, heterocyclic group, acyl group, alkyl or arylsulfonyl group. More preferred are a hydrogen atom, aromatic group, heterocyclic group, acyl group, alkyl or arylsulfonyl group. Most preferably, they are a hydrogen atom, an aryl group, and a heterocyclic group. Each group may further have a substituent. However, R ⁵ and R ⁶ are not simultaneously hydrogen atoms.

G, R ¹ and R ² are each independently a hydrogen atom, halogen atom, aliphatic group, aromatic group, heterocyclic group, cyano group, carboxyl group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, Heterocyclic oxycarbonyl group, acyl group, hydroxy group, alkoxy group, aryloxy group, heterocyclic oxy group, silyloxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (anilino group) A heterocyclic amino group), acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkyl or arylsulfonylamino group, heterocyclic sulfonylamino group, nitro group, alkyl and Arylthio group Heterocyclic thio group, an alkylsulfonyl group, a heterocyclic sulfonyl group, an alkyl- or arylsulfinyl group, heterocyclic sulfinyl group, a sulfamoyl group, a sulfo group, each group may be further substituted.

  Examples of the substituent represented by G include a hydrogen atom, halogen atom, aliphatic group, aromatic group, hydroxy group, alkoxy group, aryloxy group, acyloxy group, heterocyclic oxy group, amino group (anilino group, heterocyclic amino group). Group), an acylamino group, a ureido group, a sulfamoylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, an alkyl and arylthio group, or a heterocyclic thio group, more preferably a hydrogen atom, a halogen atom, An alkyl group, a hydroxy group, an alkoxy group, an aryloxy group, an acyloxy group, an amino group (including an anilino group and a heterocyclic amino group) or an acylamino group, and among them, a hydrogen atom, an anilino group and an acylamino group are most preferable. Each group may further have a substituent.

Preferable substituents represented by R ¹ and R ² include a hydrogen atom, an alkyl group, a halogen atom, an alkoxycarbonyl group, a carboxyl group, a carbamoyl group, a hydroxy group, an alkoxy group, and a cyano group. Each group may further have a substituent. R ¹ and R ⁵ , or R ⁵ and R ⁶ may combine to form a 5- or 6-membered ring.

Examples of the substituent in the case where each of the substituents represented by A, R ¹ , R ² , R ⁵ , R ⁶ , and G further has a substituent include the substituents exemplified for G, R ¹ , and R ² above. be able to.

When the dye of the present invention is a water-soluble dye, it may further have an ionic hydrophilic group as a substituent at any position on A, R ¹ , R ² , R ⁵ , R ⁶ and G. preferable. Examples of the ionic hydrophilic group as a substituent include a sulfo group, a carboxyl group, a phosphono group, and a quaternary ammonium group. As the ionic hydrophilic group, a carboxyl group, a phosphono group, and a sulfo group are preferable, and a carboxyl group and a sulfo group are particularly preferable. The carboxyl group, phosphono group and sulfo group may be in the form of a salt. Examples of the counter ion forming the salt include ammonium ion, alkali metal ion (eg, lithium ion, sodium ion, potassium ion) and organic cation. (Eg, tetramethylammonium ion, tetramethylguanidinium ion, tetramethylphosphonium).

  In this specification, an aliphatic group means an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group, an aralkyl group, and a substituted aralkyl group. The aliphatic group may have a branch and may form a ring. The number of carbon atoms in the aliphatic group is preferably 1-20, and more preferably 1-16. The aryl part of the aralkyl group and the substituted aralkyl group is preferably phenyl or naphthyl, particularly preferably phenyl. Examples of aliphatic groups include methyl, ethyl, butyl, isopropyl, t-butyl, hydroxyethyl, methoxyethyl, cyanoethyl, trifluoromethyl, 3-sulfopropyl, 4-sulfobutyl, cyclohexyl group, benzyl group, 2-phenethyl Groups, vinyl groups, and allyl groups.

  In the present specification, the aromatic group means an aryl group and a substituted aryl group. The aryl group is preferably phenyl or naphthyl, particularly preferably phenyl. The number of carbon atoms in the aromatic group is preferably 6 to 20, and more preferably 6 to 16. Examples of the aromatic group include phenyl, p-tolyl, p-methoxyphenyl, o-chlorophenyl and m- (3-sulfopropylamino) phenyl.

  The heterocyclic group includes a heterocyclic group having a substituent and an unsubstituted heterocyclic group. The heterocyclic ring may be condensed with an aliphatic ring, an aromatic ring or another heterocyclic ring. The heterocyclic group is preferably a 5-membered or 6-membered heterocyclic group. Examples of the substituent include aliphatic groups, halogen atoms, alkyl and arylsulfonyl groups, acyl groups, acylamino groups, sulfamoyl groups, carbamoyl groups, and ionic hydrophilic groups. Examples of the heterocyclic group include 2-pyridyl group, 2-thienyl group, 2-thiazolyl group, 2-benzothiazolyl group, 2-benzoxazolyl group and 2-furyl group.

  The alkyl and arylsulfonyl groups include substituted alkyl and arylsulfonyl groups, unsubstituted alkyl and arylsulfonyl groups. Examples of the alkyl and arylsulfonyl groups include a methylsulfonyl group and a phenylsulfonyl group, respectively.

  Alkyl and arylsulfinyl groups include substituted alkyl and arylsulfinyl groups, unsubstituted alkyl and arylsulfinyl groups. Examples of the alkyl and arylsulfinyl groups include a methylsulfinyl group and a phenylsulfinyl group, respectively.

  The acyl group includes an acyl group having a substituent and an unsubstituted acyl group. The acyl group is preferably an acyl group having 1 to 20 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the acyl group include an acetyl group and a benzoyl group.

  Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.

  The amino group includes an amino group substituted with an alkyl group, an aryl group or a heterocyclic group, and the alkyl group, aryl group and heterocyclic group may further have a substituent. As the alkylamino group, an alkylamino group having 1 to 20 carbon atoms is preferable. Examples of the substituent include an ionic hydrophilic group. Examples of the alkylamino group include a methylamino group and a diethylamino group.

  The arylamino group includes an arylamino group having a substituent and an unsubstituted arylamino group. The arylamino group is preferably an arylamino group having 6 to 20 carbon atoms. Examples of the substituent include a halogen atom and an ionic hydrophilic group. Examples of the arylamino group include a phenylamino group and a 2-chlorophenylamino group.

  The heterocyclic amino group includes a heterocyclic amino group having a substituent and an unsubstituted heterocyclic amino group. The heterocyclic amino group is preferably a heterocyclic amino group having 2 to 20 carbon atoms. Examples of the substituent include an alkyl group, a halogen atom, and an ionic hydrophilic group.

  The alkoxy group includes an alkoxy group having a substituent and an unsubstituted alkoxy group. As said alkoxy group, a C1-C20 alkoxy group is preferable. Examples of the substituent include an alkoxy group, a hydroxyl group, and an ionic hydrophilic group. Examples of the alkoxy group include a methoxy group, an ethoxy group, an isopropoxy group, a methoxyethoxy group, a hydroxyethoxy group, and a 3-carboxypropoxy group.

  The aryloxy group includes an aryloxy group having a substituent and an unsubstituted aryloxy group. The aryloxy group is preferably an aryloxy group having 6 to 20 carbon atoms. Examples of the substituent include an alkoxy group and an ionic hydrophilic group. Examples of the aryloxy group include a phenoxy group, a p-methoxyphenoxy group, and an o-methoxyphenoxy group.

  The silyloxy group is preferably a silyloxy group substituted with an aliphatic group or aromatic group having 1 to 20 carbon atoms. Examples of the silyloxy group include trimethylsilyloxy and diphenylmethylsilyloxy.

  The heterocyclic oxy group includes a heterocyclic oxy group having a substituent and an unsubstituted heterocyclic oxy group. The heterocyclic oxy group is preferably a heterocyclic oxy group having 2 to 20 carbon atoms. Examples of the substituent include an alkyl group, an alkoxy group, and an ionic hydrophilic group. Examples of the heterocyclic oxy group include a 3-pyridyloxy group and a 3-thienyloxy group.

  The alkoxycarbonyloxy group includes an alkoxycarbonyloxy group having a substituent and an unsubstituted alkoxycarbonyloxy group. The alkoxycarbonyloxy group is preferably an alkoxycarbonyloxy group having 2 to 20 carbon atoms. Examples of the alkoxycarbonyloxy group include a methoxycarbonyloxy group and an isopropoxycarbonyloxy group.

  The aryloxycarbonyloxy group includes an aryloxycarbonyloxy group having a substituent and an unsubstituted aryloxycarbonyloxy group. The aryloxycarbonyloxy group is preferably an aryloxycarbonyloxy group having 7 to 20 carbon atoms. Examples of the aryloxycarbonyloxy group include a phenoxycarbonyloxy group.

  The acylamino group includes an acylamino group having a substituent and an unsubstituted acylamino group. The acylamino group is preferably an acylamino group having 2 to 20 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the acylamino group include an acetylamino group, a propionylamino group, a benzoylamino group, an N-phenylacetylamino group, and a 3,5-disulfobenzoylamino group.

  The ureido group includes a ureido group having a substituent and an unsubstituted ureido group. The ureido group is preferably a ureido group having 1 to 20 carbon atoms. Examples of the substituent include an alkyl group and an aryl group. Examples of the ureido group include a 3-methylureido group, a 3,3-dimethylureido group, and a 3-phenylureido group.

  The sulfamoylamino group includes a sulfamoylamino group having a substituent and an unsubstituted sulfamoylamino group. Examples of the substituent include an alkyl group. Examples of the sulfamoylamino group include N, N-dipropylsulfamoylamino group.

  The alkoxycarbonylamino group includes an alkoxycarbonylamino group having a substituent and an unsubstituted alkoxycarbonylamino group. The alkoxycarbonylamino group is preferably an alkoxycarbonylamino group having 2 to 20 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the alkoxycarbonylamino group include an ethoxycarbonylamino group.

  The alkyl and arylsulfonylamino groups include substituted alkyl and arylsulfonylamino groups, and unsubstituted alkyl and arylsulfonylamino groups. The sulfonylamino group is preferably a sulfonylamino group having 1 to 20 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the sulfonylamino group include a methylsulfonylamino group, an N-phenyl-methylsulfonylamino group, a phenylsulfonylamino group, and a 3-carboxyphenylsulfonylamino group.

  The carbamoyl group includes a carbamoyl group having a substituent and an unsubstituted carbamoyl group. Examples of the substituent include an alkyl group. Examples of the carbamoyl group include a methylcarbamoyl group and a dimethylcarbamoyl group.

  The sulfamoyl group includes a sulfamoyl group having a substituent and an unsubstituted sulfamoyl group. Examples of the substituent include an alkyl group. Examples of the sulfamoyl group include a dimethylsulfamoyl group and a di- (2-hydroxyethyl) sulfamoyl group.

  The alkoxycarbonyl group includes an alkoxycarbonyl group having a substituent and an unsubstituted alkoxycarbonyl group. The alkoxycarbonyl group is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group.

  The acyloxy group includes an acyloxy group having a substituent and an unsubstituted acyloxy group. The acyloxy group is preferably an acyloxy group having 1 to 20 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the acyloxy group include an acetoxy group and a benzoyloxy group.

  The carbamoyloxy group includes a carbamoyloxy group having a substituent and an unsubstituted carbamoyloxy group. Examples of the substituent include an alkyl group. Examples of the carbamoyloxy group include an N-methylcarbamoyloxy group.

  The aryloxycarbonyl group includes an aryloxycarbonyl group having a substituent and an unsubstituted aryloxycarbonyl group. The aryloxycarbonyl group is preferably an aryloxycarbonyl group having 7 to 20 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the aryloxycarbonyl group include a phenoxycarbonyl group.

  The aryloxycarbonylamino group includes an aryloxycarbonylamino group having a substituent and an unsubstituted aryloxycarbonylamino group. The aryloxycarbonylamino group is preferably an aryloxycarbonylamino group having 7 to 20 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the aryloxycarbonylamino group include a phenoxycarbonylamino group.

  The alkyl, aryl and heterocyclic thio groups include substituted alkyl, aryl and heterocyclic thio groups and unsubstituted alkyl, aryl and heterocyclic thio groups. The alkyl, aryl and heterocyclic thio groups are preferably those having 1 to 20 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the alkyl, aryl and heterocyclic thio groups include a methylthio group, a phenylthio group, and a 2-pyridylthio group.

  The heterocyclic oxycarbonyl group includes a heterocyclic oxycarbonyl group having a substituent and an unsubstituted heterocyclic oxycarbonyl group. The heterocyclic oxycarbonyl group is preferably a heterocyclic oxycarbonyl group having 2 to 20 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the heterocyclic oxycarbonyl group include a 2-pyridyloxycarbonyl group.

  The heterocyclic sulfonylamino group includes a substituted heterocyclic sulfonylamino group and an unsubstituted heterocyclic sulfonylamino group. The heterocyclic sulfonylamino group is preferably a heterocyclic sulfonylamino group having 1 to 12 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the heterocyclic sulfonylamino group include a 2-thiophenesulfonylamino group and a 3-pyridinesulfonylamino group.

  The heterocyclic sulfonyl group includes a heterocyclic sulfonyl group having a substituent and an unsubstituted heterocyclic sulfonyl group. The heterocyclic sulfonyl group is preferably a heterocyclic sulfonyl group having 1 to 20 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the heterocyclic sulfonyl group include a 2-thiophenesulfonyl group and a 3-pyridinesulfonyl group.

  The heterocyclic sulfinyl group includes a heterocyclic sulfinyl group having a substituent and an unsubstituted heterocyclic sulfinyl group. The heterocyclic sulfinyl group is preferably a heterocyclic sulfinyl group having 1 to 20 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the heterocyclic sulfinyl group include a 4-pyridinesulfinyl group.

  In the present invention, the dye represented by the general formula (M-I) is preferably a dye represented by the following general formula (M-II).

In the general formula (M-II), Z ₁ represents an electron-withdrawing group having a Hammett's substituent constant σp value of 0.20 or more. Z ₁ is preferably an electron-withdrawing group having a σp value of 0.30 or more, more preferably 0.45 or more, and particularly preferably an electron-withdrawing group of 0.60 or more. It is desirable not to exceed zero. Specific examples of the preferred substituent include an electron-withdrawing substituent described later. Among them, an acyl group having 2 to 20 carbon atoms, an alkyloxycarbonyl group having 2 to 20 carbon atoms, a nitro group, a cyano group, An alkylsulfonyl group having 1 to 20 carbon atoms, an arylsulfonyl group having 6 to 20 carbon atoms, a carbamoyl group having 1 to 20 carbon atoms, and a halogenated alkyl group having 1 to 20 carbon atoms are preferable. Particularly preferred are a cyano group, an alkylsulfonyl group having 1 to 20 carbon atoms, and an arylsulfonyl group having 6 to 20 carbon atoms, and most preferred is a cyano group.

R ¹ , R ² , R ⁵ and R ⁶ have the same meanings as in the general formula (MI). R ³ and R ⁴ each independently represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkyl and arylsulfonyl group, or a sulfamoyl group. . Of these, a hydrogen atom, an aromatic group, a heterocyclic group, an acyl group, an alkyl or arylsulfonyl group is preferable, and a hydrogen atom, an aromatic group, and a heterocyclic group are particularly preferable. Z ₂ represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group. Q represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group. Among them, Q is preferably a group consisting of a nonmetallic atom group necessary for forming a 5- to 8-membered ring. The 5- to 8-membered ring may be substituted, may be a saturated ring, or may have an unsaturated bond. Of these, aromatic groups and heterocyclic groups are particularly preferred. Preferred nonmetallic atoms include nitrogen atoms, oxygen atoms, sulfur atoms or carbon atoms. Specific examples of such a ring structure include, for example, a benzene ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclohexene ring, pyridine ring, pyrimidine ring, pyrazine ring, pyridazine ring, triazine ring, imidazole ring. , Benzimidazole ring, oxazole ring, benzoxazole ring, thiazole ring, benzothiazole ring, oxane ring, sulfolane ring and thiane ring.

Each group described in formula (M-II) may further have a substituent. When each of these groups further has a substituent, examples of the substituent include the substituents described in the general formula (MI), the groups exemplified for G, R ¹ and R ² , and ionic hydrophilic groups. It is done.

Examples of the electron-withdrawing group having a Hammett substituent constant σ _p value of 0.60 or more include a cyano group, a nitro group, and an alkylsulfonyl group (for example, a methanesulfonyl group and an arylsulfonyl group (for example, a benzenesulfonyl group)). it can.
In addition to the above, an electron-withdrawing group having a Hammett σ _p value of 0.45 or more includes an acyl group (for example, acetyl group), an alkoxycarbonyl group (for example, dodecyloxycarbonyl group), an aryloxycarbonyl group (for example, m-chlorophenoxy). Carbonyl), alkylsulfinyl group (for example, n-propylsulfinyl), arylsulfinyl group (for example, phenylsulfinyl), sulfamoyl group (for example, N-ethylsulfamoyl, N, N-dimethylsulfamoyl), halogenated alkyl group (For example, trifluoromethyl).

As an electron-withdrawing group having a Hammett substituent constant σ _p value of 0.30 or more, in addition to the above, an acyloxy group (for example, acetoxy), a carbamoyl group (for example, N-ethylcarbamoyl, N, N-dibutylcarbamoyl), Halogenated alkoxy groups (for example, trifluoromethyloxy), halogenated aryloxy groups (for example, pentafluorophenyloxy), sulfonyloxy groups (for example, methylsulfonyloxy group), halogenated alkylthio groups (for example, difluoromethylthio), An aryl group (for example, 2,4-dinitrophenyl, pentachlorophenyl) substituted with an electron-withdrawing group having two or more σ _p values of 0.15 or more, and a heterocycle (for example, 2-benzoxazolyl, 2-benzothiazolyl, 1-phenyl-2-benzimidazolyl) Can. Specific examples of the electron withdrawing group having a σp value of 0.20 or more include a halogen atom in addition to the above.

A particularly preferred combination of substituents as the azo dye represented by the general formula (MI) is preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a sulfonyl group, or an acyl group as R ⁵ and R ^6. And more preferably a hydrogen atom, an aryl group, a heterocyclic group or a sulfonyl group, and most preferably a hydrogen atom, an aryl group or a heterocyclic group. However, R ⁵ and R ⁶ are not both hydrogen atoms.

  G is preferably a hydrogen atom, a halogen atom, an alkyl group, a hydroxyl group, an amino group or an acylamino group, more preferably a hydrogen atom, a halogen atom, an amino group or an acylamino group, most preferably a hydrogen atom or an amino group. An acylamino group.

  Among A, a pyrazole ring, an imidazole ring, an isothiazole ring, a thiadiazole ring, and a benzothiazole ring are preferable, a pyrazole ring and an isothiazole ring are further preferable, and a pyrazole ring is most preferable.

-CR ¹ =, B ¹ and B ² are each - CR ² = Yes, R ^1, R ² are each preferably a hydrogen atom, an alkyl group, a halogen atom, a cyano group, a carbamoyl group, a carboxyl group, a hydroxyl group, an alkoxy group And an alkoxycarbonyl group, more preferably a hydrogen atom, an alkyl group, a carboxyl group, a cyano group, or a carbamoyl group.

Preferable cyan dyes include dyes represented by the following general formula (CI).

In the general formula (CI), X ₁ , X ₂ , X ₃ and X ₄ each independently represents an electron-withdrawing group having σp of 0.40 or more. Y ₁ , Y ₂ , Y ₃ and Y ₄ each independently represent a monovalent substituent. M represents a hydrogen atom, a metal element or an oxide, hydroxide or halide thereof. _{a 1 ~a 4, b 1 ~b} 4 are each X ₁ to X _4, and represents the number of substituents Y ₁ to Y _4. a ₁ ~a ₄ each independently represents an integer of 0 to 4, b ₁ ~b ₄ each independently represents an integer of 0-4. However, the sum of a _{1 to} a ₄ is 2 or more, preferably 3 or more, and most preferably a ₁ = a ₂ = a ₃ = a ₄ = 1. When the dye is a water-soluble dye, an ionic hydrophilic group is further added as a substituent at any position on X ₁ , X ₂ , X ₃ , X ₄ , Y ₁ , Y ₂ , Y ₃ , Y _4. It is preferable to have. Examples of the ionic hydrophilic group as a substituent include a sulfo group, a carboxyl group, a phosphono group, and a quaternary ammonium group.

以下に本発明の一般式（Ｃ−ＩＩ）で表されるフタロシアニン染料について詳しく述べる。 Among the phthalocyanine dyes represented by the general formula (CI), a phthalocyanine dye having a structure represented by the following general formula (C-II) is more preferable.

The phthalocyanine dye represented by formula (C-II) of the present invention is described in detail below.

In General Formula (C-II), X _{11 to} X ₁₄ are each independently —SO—Z, —SO ₂ —Z, —SO ₂ NR ₁ R ₂ , a sulfo group, —CONR ₁ R ₂ , or —CO _2. R ₁ is represented. Y _{11 to} Y ₁₈ each independently represent a monovalent substituent. , M is a hydrogen atom, a metal atom or an oxide, hydroxide or halide thereof. a _{11 to} a ₁₄ each represent the number of substituents X _{11 to} X _{14 and} each independently represents an integer of 1 or 2;
Z is each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, substituted or unsubstituted Represents a heterocyclic group. R ₁ and R ₂ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, substituted or unsubstituted Represents an aryl group or a substituted or unsubstituted heterocyclic group.

In the general formula (C-II), a _{11 to} a ₁₄ each independently represents an integer of 1 or 2, particularly preferably 4 ≦ a ₁₁ + a ₁₂ + a ₁₃ + a ₁₄ ≦ 6, and of these, particularly preferable Is when a ₁₁ = a ₁₂ = a ₁₃ = a ₁₄ = 1.

X ₁₁ , X ₁₂ , X ₁₃ and X ₁₄ may each be the same substituent, or, for example, X ₁₁ , X ₁₂ , X ₁₃ and X ₁₄ are all —SO ₂ —Z, but each Z is As in the case of including different ones, they may be the same type of substituents but may be partially different from each other, or, for example, —SO ₂ —Z and —SO ₂ NR ₁ R ₂ are substituted at the same time. As in the case, they may contain different substituents.

  Among the phthalocyanine dyes represented by the general formula (C-II), particularly preferred combinations of substituents are as follows.

X _{11 to} X ₁₄ are each preferably —SO—Z, —SO ₂ —Z, —SO ₂ NR ₁ R ₂ , or CONR ₁ R ₂ , particularly —SO ₂ —Z or SO ₂ NR _1. R ₂ is preferred, and —SO ₂ —Z is most preferred.

  Z is independently preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, and most preferably a substituted alkyl group, a substituted aryl group, or a substituted heterocyclic group. . In particular, the case of having an asymmetric carbon in the substituent (use in a racemic form) is preferable because of increasing the solubility of the dye and the ink stability. In addition, for the reason of increasing the association property and improving the fastness, it is preferable that a hydroxyl group, an ether group, an ester group, a cyano group, an amide group, or a sulfonamide group have in the substituent.

R ₁ and R ₂ are each independently preferably a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, and among them, a hydrogen atom, a substituted alkyl group, a substituted An aryl group and a substituted heterocyclic group are most preferred. However, it is not preferred that R ¹ and R ² are both hydrogen atoms. In particular, the case of having an asymmetric carbon in the substituent (use in a racemic form) is preferable because of increasing the solubility of the dye and the ink stability. In addition, for the reason of increasing the association property and improving the fastness, it is preferable that a hydroxyl group, an ether group, an ester group, a cyano group, an amide group, or a sulfonamide group have in the substituent.

Y _{11 to} Y ₁₈ are a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a cyano group, an alkoxy group, an amide group, a ureido group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, a carboxyl group, and a sulfo group. In particular, a hydrogen atom, a halogen atom, a cyano group, a carboxyl group, and a sulfo group are preferable, and a hydrogen atom is most preferable. a _{11 to} a ₁₄ are each independently preferably 1 or 2, particularly preferably all 1. M represents a hydrogen atom, a metal element, or an oxide, hydroxide or halide thereof, and Cu, Ni, Zn, and Al are particularly preferable, and Cu is particularly preferable.

When the phthalocyanine dye represented by the above (CI) or (C-II) is water-soluble, it preferably has an ionic hydrophilic group. Examples of the ionic hydrophilic group include a sulfo group, a carboxyl group, a phosphono group, and a quaternary ammonium group. As the ionic hydrophilic group, a carboxyl group, a phosphono group, and a sulfo group are preferable, and a carboxyl group and a sulfo group are particularly preferable. The carboxyl group, phosphono group and sulfo group may be in the form of a salt. Examples of the counter ion forming the salt include ammonium ion, alkali metal ion (eg, lithium ion, sodium ion, potassium ion) and organic cation. (Eg, tetramethylammonium ion, tetramethylguanidinium ion, tetramethylphosphonium). Among the counter ions, alkali metal salts are preferable, and lithium salts are particularly preferable because they increase the solubility of the dye and improve the ink stability.
As the number of ionic hydrophilic groups, those having at least two or more in one molecule of phthalocyanine dye are preferable, and those having at least two sulfo groups and / or carboxyl groups are particularly preferable.

  Regarding the preferred combination of substituents of the compound represented by the general formula (C-II), a compound in which at least one of various substituents is the above-mentioned preferred group is preferred, and more various substituents are preferred. More preferred are compounds that are groups, and most preferred are compounds in which all substituents are the preferred groups.

  As the chemical structure of the phthalocyanine dye preferably used in the present invention, an electron-withdrawing group such as a sulfinyl group, a sulfonyl group, and a sulfamoyl group is substituted on each of the four benzene rings of phthalocyanine to replace the entire phthalocyanine skeleton. It is preferable to introduce the group so that the total σp value of the group is 1.6 or more.

  The phthalocyanine derivative represented by the general formula (CI) inevitably has different introduction positions and introduction numbers of the substituents Xn (n = 1 to 4) and Ym (m = 1 to 4) depending on the synthesis method. It is common to be analog mixtures, and therefore the general formula often represents a statistical average of these analog mixtures. In the present invention, it has been found that a specific mixture is particularly preferable when these analog mixtures are classified into the following three types. That is, the phthalocyanine dye analog mixtures represented by the general formulas (CI) and (C-II) are defined by being classified into the following three types based on the substitution positions.

(1) β-position substitution type: phthalocyanine dye having a specific substituent at the 2 and / or 3 position, 6 and / or 7 position, 10 and / or 11 position, 14 and / or 15 position (2) α-position substitution type: Phthalocyanine dye having specific substituents at 1 and / or 4 position, 5 and / or 8 position, 9 and / or 12 position, 13 and / or 16 position (3) α, β-position mixed substitution type: ruled at 1 to 16 position Phthalocyanine dyes with specific substituents

  In the present specification, when describing derivatives of phthalocyanine dyes having different structures (particularly, different substitution positions), the β-position substitution type, α-position substitution type, and α, β-position mixed substitution type are used. .

  Examples of the phthalocyanine derivative used in the present invention include, for example, “Phthalocyanine—Chemistry and Function” by Shirai and Kobayashi (published by IPC Co., Ltd., pages 1 to 62), C.I. C. Leznoff-A. B. P. Lever co-authored “Phthalocyanines-Properties and Applications” (published by VCH, pages 1 to 54), etc. can be synthesized by combining quoted or similar methods.

  The phthalocyanine compounds represented by the general formula (CI) of the present invention are described in WO 00/17275, 00/08103, 00/08101, 98/41853, JP-A-10-36471, and the like. In addition, for example, it can be synthesized through sulfonation, sulfonyl chloride formation, and amidation reaction of an unsubstituted phthalocyanine compound. In this case, sulfonation can occur at any position of the phthalocyanine nucleus, and the number of sulfonation is difficult to control. Therefore, when a sulfo group is introduced under such reaction conditions, the position and number of the sulfo group introduced into the product cannot be specified, and a mixture in which the number of substituents and the substitution position are different is always given. Therefore, when synthesizing the compound of the present invention using it as a raw material, the number and substitution position of the heterocyclic substituted sulfamoyl group cannot be specified, so the compound of the present invention includes several types of compounds having different numbers of substituents and substitution positions. Α, β-position mixed substitution mixture.

  As described above, for example, when a large number of electron withdrawing groups such as sulfamoyl groups are introduced into the phthalocyanine nucleus, the oxidation potential becomes more noble and the ozone resistance is enhanced. According to the above synthesis method, it is inevitable that a small amount of electron-withdrawing groups are introduced, that is, a phthalocyanine dye having a lower oxidation potential is mixed. Therefore, in order to improve ozone resistance, it is more preferable to use a synthesis method that suppresses the formation of a compound having a lower oxidation potential.

  On the other hand, the phthalocyanine compound represented by the general formula (C-II) is, for example, a phthalonitrile derivative (compound P) and / or a diiminoisoindoline derivative (compound Q) represented by the following formula ( It is obtained by reacting with a metal derivative represented by C-III). Alternatively, it can be derived from a tetrasulfophthalocyanine compound obtained by reacting a 4-sulfophthalic acid derivative (compound R) represented by the following formula and a metal derivative represented by the general formula (C-III).

In the above formulas, Xp corresponds to X ₁ , X ₂ , X ₃ , or X ₄ in the general formula (C-II). Yq and Yq ′ correspond to Y ₁₁ , Y ₁₂ , Y ₁₃ , Y ₁₄ , Y ₁₅ , Y ₁₆ , Y ₁₇ , or Y ₁₈ in the general formula (C-II), respectively. In the compound R, M ′ represents a cation.

M- (Y) _d ......... General formula (C-III)
In the general formula (C-III), M is the same as M in the general formula (C-II), and Y is a monovalent or divalent coordination such as a halogen atom, acetate anion, acetylacetonate, or oxygen. Child is shown, d is an integer of 1-4.

  That is, according to the above synthesis method, a specific number of desired substituents can be introduced. In particular, when it is desired to introduce a large number of electron withdrawing groups in order to make the oxidation potential noble as in the present invention, the above synthesis method is extremely superior to the synthesis method of the general formula (CI). It is.

  The phthalocyanine compound represented by the general formula (C-II) thus obtained is usually a compound represented by the following general formula (a) -1 to (a) -4 which is an isomer at each substitution position of Xp. In the β-position substitution type.

In the above synthesis method, if the same Xp is used, a β-position-substituted phthalocyanine dye in which X ₁₁ , X ₁₂ , X ₁₃ and X ₁₄ are exactly the same substituents can be obtained. On the other hand, by using different combinations of Xp, it is possible to synthesize dyes having the same type of substituents but partially different from each other, or dyes having different types of substituents. . Among the dyes of the general formula (C-II), these dyes having different electron-withdrawing substituents are particularly preferable because they can adjust the solubility of the dye, the associability, the stability with time of the ink, and the like.

  In the present invention, it is found that it is very important to improve the fastness that the oxidation potential is noble than 0.8 V (vs SCE) in any substitution type. It was completely unpredictable from the prior art. Although the cause is unknown in detail, the β-position substitution type tends to be clearly superior in terms of hue, light fastness, ozone gas resistance, etc. than the α, β-position mixed substitution type. .

  The phthalocyanine dyes represented by the general formulas (C-I) and (C-II) can be synthesized according to the above-described patents, such as JP-A Nos. 2002-302623, 2002-294097, It can be synthesized by the methods described in JP-A-2002-249677 and JP-A-2003-012952. Further, the starting material, dye intermediate and synthetic route are not limited by these.

  Although the oxidation potential of the magenta dye and / or cyan dye used in the present invention is nobler than 0.8 V (vs SCE), phthalocyanine widely used as a cyan dye forms an aggregate. Therefore, the fastness can be compensated even if the oxidation potential is somewhat low, whereas the magenta dye does not form an association. Therefore, in order to increase the fastness, the oxidation potential should be set higher than the cyan dye. Is preferred.

  Preferred examples of the dye used in the present invention are shown below, but these are for specifically explaining the present invention, and the present invention is not limited thereby. The oxidation potential of the dye is shown in parentheses.

First, specific examples (Y-1 to Y-35) of yellow dyes used in the present invention are listed.

Next, specific examples (M-1 to M-26) of the magenta dye used in the present invention will be given.

Furthermore, specific examples (C-1 to C-50) of cyan dyes used in the present invention are listed.

  Other examples of compounds that can be applied to the present invention include JP 2002-294097, JP 2002-249677, JP 2002-256167, JP 2002-275386, JP 2003-012952, and JP Although described also in 2001-279145 and Unexamined-Japanese-Patent No. 2002-309116, it is not limited to these. Each of the above compounds can be easily synthesized by the methods described in the above-mentioned patents.

(Inkjet recording ink)
The ink set for inkjet recording according to the present invention has a minimum configuration of a yellow ink containing at least one yellow dye, a magenta ink containing at least one magenta dye, and a cyan ink containing at least one cyan dye. Element. Here, as the dye contained in each ink, the above-mentioned various dyes are used. Usually, each ink can be prepared by dissolving and / or dispersing a dye in an oily medium or an aqueous medium. Aqueous ink using an aqueous medium is preferable from the viewpoint of working environment and resource saving.

  In addition to the above dyes, various additives may be added within the range not impairing the effects of the present invention as required and necessary. Examples of such additives include anti-drying agents (wetting agents), anti-fading agents, emulsion stabilizers, penetration enhancers, ultraviolet absorbers, preservatives, anti-fungal agents, pH adjusters, surface tension adjusters, Well-known additives, such as an antifoamer, a viscosity modifier, a dispersing agent, a dispersion stabilizer, an antirust agent, a chelating agent, are mentioned. These various additives are directly added to the ink composition liquid in the case of water-soluble ink. When an oil-soluble dye is used in the form of a dispersion, it is generally added to the ink composition liquid after the preparation of the dye dispersion. However, it may be added to the oil phase or the aqueous phase when preparing the dispersion. .

  The anti-drying agent is preferably used for the purpose of preventing clogging due to drying of the ink-jet ink at the ink ejection port of the nozzle used in the ink-jet recording method.

Such a drying inhibitor is preferably a water-soluble organic solvent having a vapor pressure lower than that of water. Specific examples include ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, thiodiglycol, dithiodiglycol, 2-methyl-1,3-propanediol, 1,2,6-hexanetriol, acetylene glycol derivatives, Polyhydric alcohols typified by glycerin, trimethylolpropane, etc., lower alkyl of polyhydric alcohols such as ethylene glycol monomethyl (or ethyl) ether, diethylene glycol monomethyl (or ethyl) ether, triethylene glycol monoethyl (or butyl) ether Ethers, 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, heterocyclic rings such as N-ethylmorpholine, sulfolane, dimethyl sulfoxide, - sulfur-containing compounds such as sulfolane, diacetone alcohol, polyfunctional compounds such as diethanolamine, and urea derivatives.
Of these, polyhydric alcohols such as glycerin and diethylene glycol are preferred. Moreover, said anti-drying agent may be used independently and may be used together 2 or more types. These drying inhibitors are preferably contained in the ink in an amount of 10 to 50% by mass.

  The penetration enhancer is suitably used for the purpose of allowing ink jet ink to penetrate better into paper. As the penetration enhancer, alcohols such as ethanol, isopropanol, butanol, di (tri) ethylene glycol monobutyl ether, 1,2-hexanediol, sodium lauryl sulfate, sodium oleate, nonionic surfactants, etc. may be used. it can. If these are contained in the ink in an amount of 5 to 30% by mass, they are usually sufficiently effective, and it is desirable to use them within a range of addition amounts that do not cause printing bleeding or paper loss (print-through).

  The ultraviolet absorber is used for the purpose of improving image storage stability. Examples of the ultraviolet absorber include benzoins described in JP-A Nos. 58-185677, 61-190537, JP-A-2-782, JP-A-5-97075, JP-A-9-34057, and the like. Triazole compounds, benzophenone compounds described in JP-A No. 46-2784, JP-A No. 5-194433, US Pat. No. 3,214,463, etc., JP-B Nos. 48-30492, 56-21141, Cinnamic acid compounds described in JP-A-10-88106, JP-A-4-298503, JP-A-8-53427, JP-A-8-239368, JP-A-10-182621, JP-A-8 No. -502911, etc., triazine compounds, Research Disclosure No. A compound described in No. 24239, a compound that emits fluorescence by absorbing ultraviolet rays typified by a stilbene-based compound or a benzoxazole-based compound, a so-called fluorescent brightening agent can also be used.

  The anti-fading agent is used for the purpose of improving image storage stability. As the anti-fading agent, various organic and metal complex anti-fading agents can be used. Organic anti-fading agents include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, thioethers, thioureas, heterocycles, etc. (For example, those described in JP-A-2002-36717 and JP-A-2002-86904), examples of metal complexes include nickel complexes and zinc complexes. Specifically, Research Disclosure No. No. 17643, Nos. VII to I, J; 15162, ibid. No. 18716, page 650, left column, ibid. No. 36544, page 527, ibid. No. 307105, page 872, ibid. The compounds described in the patent cited in No. 15162 and the compounds included in the general formulas and compound examples of the representative compounds described in JP-A-62-215272, pages 127 to 137 can be used.

  Examples of the antifungal agent include sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, p-hydroxybenzoic acid ethyl ester, 1,2-benzisothiazolin-3-one and salts thereof. These are preferably used in the ink in an amount of 0.02 to 1.00% by mass.

  As the pH adjuster, a neutralizer (organic base, inorganic alkali) can be used. For the purpose of improving the storage stability of the inkjet ink, the pH adjuster is preferably added to the inkjet ink for pH 6-10 and summer, and more preferably added to a pH of 7-10.

Examples of the surface tension adjusting agent include nonionic, cationic and anionic surfactants. The surface tension of the inkjet ink according to the present invention is preferably 25 to 70 mPa · s, and more preferably 25 to 60 mN / m. Further, the viscosity of the inkjet ink according to the present invention is preferably 30 mPa · s or less. Furthermore, it is more preferable to adjust to 20 mPa · s or less.
Examples of such surfactants include fatty acid salts, alkyl sulfate esters, alkyl benzene sulfonates, alkyl naphthalene sulfonates, dialkyl sulfosuccinates, alkyl phosphate ester salts, naphthalene sulfonate formalin condensates, polyoxy Anionic surfactants such as ethylene alkyl sulfate ester salt, polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkylamine, Nonionic surfactants such as glycerin fatty acid esters and oxyethyleneoxypropylene block copolymers are preferred. Further, SURFYNOLS (Air Products & Chemicals), which is an acetylene-based polyoxyethylene oxide surfactant, is also preferably used. Also preferred are amine oxide types such as N, N-dimethyl-N-alkylamine oxide and quaternary ammonium salt-containing betaine type amphoteric surfactants such as N, N-dimethyl-N-lauryl-carbomethylammonium. . Further, JP-A-59-157,636, pages (37) to (38), Research Disclosure No. The surfactants described in 308119 (1989) can also be used.

  As the antifoaming agent, fluorine-based, silicone-based compounds, chelating agents represented by EDTA, and the like can be used as necessary.

  When the dye used in the present invention is oil-soluble, as a method for dispersing in an aqueous medium, a dye and an oil can be used as disclosed in JP-A Nos. 11-286637, 2001-240763, 2001-262039, and 2001-247788. Colored fine particles containing a soluble polymer are dispersed in an aqueous medium or dissolved in a high-boiling organic solvent as disclosed in JP 2001-262018, JP 2001-240763, JP 2001-335734, JP 2002-080772. It is preferable to disperse the dye in the present invention in an aqueous medium. The specific method for dispersing the dye in the present invention in the aqueous medium, the oil-soluble polymer to be used, the high-boiling organic solvent, the additive, and the amount used thereof are preferably those described in the above patent. it can.

  Or you may disperse | distribute dye to a fine particle state with solid. At the time of dispersion, a dispersant or a surfactant can be used. Dispersing devices include simple stirrer, impeller stirring method, in-line stirring method, mill method (for example, colloid mill, ball mill, sand mill, attritor, roll mill, agitator mill, etc.), ultrasonic method, high-pressure emulsification dispersion method (high-pressure homogenizer) Specific examples of commercially available devices include gorin homogenizers, microfluidizers, DeBEE2000, and the like. In addition to the above-mentioned patents, the ink jet recording ink preparation method described above is disclosed in JP-A Nos. 5-148436, 5-295212, 7-97541, 7-82515, and 7-118584. Details are described in Japanese Laid-Open Patent Publication Nos. 11-286637 and 2001-271003, and can also be used for preparing the ink for inkjet recording according to the present invention.

  As the aqueous medium, a mixture containing water as a main component and optionally adding a water-miscible organic solvent can be used. Examples of the water-miscible organic solvent include alcohol (eg, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, t-butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol), polyvalent Alcohols (eg, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol), glycol derivatives (eg , Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether Ter, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether, ethylene glycol diacetate, ethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether , Triethylene glycol monoethyl ether, ethylene glycol monophenyl ether), amine (for example, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenetriamine) Triethylenetetramine, polyethyleneimine, tetramethylpropylenediamine) and other polar solvents (eg, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, sulfolane, 2-pyrrolidone, N-methyl-2) -Pyrrolidone, N-vinyl-2-pyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone, acetonitrile, acetone). The water-miscible organic solvent may be used in combination of two or more.

  The ink used in the ink set of the present invention preferably contains 0.1 to 20 parts by mass of the dye with respect to 100 parts by mass of the ink. Each of yellow and cyan inks may use two or more kinds of dyes in combination. The magenta ink may be used in combination with two or more dyes as long as the oxidation potential is nobler than 0.8V. When two or more kinds of dyes are used in combination, the total content of the dyes is preferably within the above range.

  In recent years, yellow, magenta, and cyan inks are often composed of two or more types of inks having different dye concentrations for the purpose of improving the image quality. It is desirable that the oxidation potential is noble from 0.8V. In the present invention, when two or more different inks are used as inks having the same hue, it is preferable that the density of other types of ink is 0.05 to 0.5 times the density of one type of ink.

  The ink set of the present invention is used for forming a full-color image, but in order to adjust the color tone, a black color ink may be further used. Applicable black materials include disazo, trisazo, and tetraazo dyes, as well as carbon black dispersions.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples. In the examples, “parts” and “%” represent “parts by mass” and “% by mass” unless otherwise specified.

(Production of support)
Wood pulp consisting of 100 parts of LBKP was beaten to 300 ml Canadian freeness with a double disc refiner, 0.5 parts of epoxidized behenamide, 1.0 part of anionic polyacrylamide, 0.1 part of polyamide polyamine epichlorohydrin, and 0. All 5 parts were added in an absolute dry weight comparison with respect to the pulp, and weighed with a long net paper machine to make a base paper of 170 g / m ² .

In order to adjust the surface size of the obtained base paper, 0.04% of a fluorescent whitening agent (“Whiteex BB” manufactured by Sumitomo Chemical Co., Ltd.) was added to a 4% aqueous solution of polyvinyl alcohol, and this was converted into an absolute dry mass. After impregnating the base paper so as to be 0.5 g / m ² and drying, a calender treatment was further performed to obtain a base paper adjusted to a density of 1.05 g / ml.

After the corona discharge treatment was performed on the wire surface (back surface) side of the obtained base paper, high-density polyethylene was coated to a thickness of 19 μm using a melt extruder to form a resin layer composed of a mat surface. (Hereinafter, this resin layer surface is referred to as “back surface”). After the corona discharge treatment is further applied to the back side resin layer, as an antistatic agent, aluminum oxide (“Alumina Sol 100” manufactured by Nissan Chemical Industries, Ltd.) and silicon dioxide (“Nissan Chemical Industry Co., Ltd.” “ Snowtex O ") to 1: the dispersion was dispersed in water at 2 weight ratio, dry mass was coated to a 0.2 g / m ^2.

  Furthermore, after the corona discharge treatment is applied to the felt surface (surface) side where the resin layer is not provided, anatase-type titanium dioxide 10%, a trace amount of ultramarine blue, and a fluorescent whitening agent 0.01% (vs. polyethylene) A low-density polyethylene having an MFR (melt flow rate) of 3.8 is extruded to a thickness of 29 μm using a melt extruder, and a high gloss thermoplastic resin layer is formed on the surface side of the base paper (hereinafter, This highly glossy surface is referred to as “front side”), and the desired support was obtained.

[Example 1]
(Preparation of coating liquid A for ink receiving layer)
According to the following composition, (1) gas phase method silica fine particles, (2) ion-exchanged water, and (3) “Charol DC902P” are mixed, and a disperser “KD-P” manufactured by Shinmaru Enterprises Co., Ltd. Used to disperse. Thereafter, (4) polyaluminum chloride was further added and dispersed using a disperser “KD-P”. Next, a solution containing (5) polyvinyl alcohol, (6) boric acid, (7) polyoxyethylene lauryl ether, and (8) ion-exchanged water was added to prepare an ink-receiving layer coating solution (A).

<Composition of coating liquid (A) for ink receiving layer>
(1) Gas phase method silica fine particles (inorganic fine particles) 10.0 parts ("Leoro Seal QS-30" manufactured by Tokuyama Corporation, average primary particle size 7 nm)
(2) Ion-exchanged water: 47.6 parts
(3) “Charol DC902P”: 1.0 part (Daiichi Kogyo Seiyaku Co., Ltd., dispersant, 51% aqueous solution)
(4) Polyaluminum chloride (basicity 83%) ……… 5.0 parts
(5) Polyvinyl alcohol (water-soluble resin) 8% aqueous solution ... 27.8 parts ("PVA-224" manufactured by Kuraray Co., Ltd., saponification degree 88%, polymerization degree 2400)
(6) Boric acid (crosslinking agent) ... 0.4 parts
(7) Polyoxyethylene lauryl ether (surfactant) ... 1.2 parts ("Emulgen 109P" manufactured by Kao Corporation, 10% aqueous solution, HLB value 13.6)
(8) Ion exchange water ... 32.0 parts

  The obtained ink receiving layer coating liquid (A) has a mass ratio of silica fine particles to water-soluble resin (PB ratio = (1) / (5)) of 4.5 / 1 and a pH of 3.5. (Acidic).

(Preparation of inkjet recording medium)
The front surface of the support obtained above is subjected to corona discharge treatment, and the ink receiving layer coating solution (A) is applied to the front surface of the support so that the dry coating amount is 200 ml / m ² . The coating was applied using an extrusion die coater, and dried with a hot air dryer at 80 ° C. (wind speed 3 to 8 m / sec) until the solid content concentration of the coating layer reached 20%. During this time, the coating layer exhibited constant rate drying. Immediately after that, it was immersed in a mordant coating solution (B) having the following composition for 30 seconds to adhere to the coating layer at 20 g / m ² and further dried at a temperature of 80 ° C. for 10 minutes. Thus, an ink jet recording medium provided with an ink receiving layer having a dry layer thickness of 32 μm was produced.

<Composition of mordant coating liquid (B)>
(1) Boric acid (crosslinking agent) ……… 0.65 parts
(2) Polyallylamine “PAA-03” (20% aqueous solution) 15 parts (Mordant, manufactured by Nittobo Co., Ltd.)
(3) Ion exchange water: 75 parts
(4) "Megafac F1405" (10% aqueous solution) ... 3 parts (Fluorosurfactant, manufactured by Dainippon Ink & Chemicals, Inc.)

(Heat and pressure treatment and cooling peeling treatment)
With respect to the ink jet recording medium obtained as described above, a roller temperature of 120 ° C. is used by using a cooling peeling type belt fixing type smoothing processing machine (endless press, the surface roughness Ra of the belt member is 0.8 μm) shown in FIG. Then, a heat and pressure treatment was performed at a belt conveying speed of 15 mm / sec and a pressure between rollers (nip pressure) of 5 kgf / cm ² , and a peeling treatment was performed after cooling to obtain an ink jet recording medium (1) of the present invention. At this time, when the maximum temperature of the coated polyethylene layer was measured from the ink receiving layer side with a non-contact thermometer, it was 90 ° C., and the temperature at the time of peeling was 80 ° C. or less.

[Examples 2-3]
In Example 1, this was performed in the same manner as in Example 1 except that the roller temperature, the conveyance speed, and the nip pressure during (heating and pressing treatment and cooling peeling treatment) were changed as shown in Table 1 below. Inventive ink jet recording media (2-3) were prepared. The measured maximum temperature of the coated polyethylene layer at this time is also shown in Table 1.

[Example 4]
In Example 1, an inkjet recording medium (4) of Comparative Example was obtained in the same manner as in Example 1 except that (heat-pressing process and cooling peeling process) were not performed.

(Evaluation test for feeling of dust)
Each of the ink jet recording media (1 to 4) obtained above was subjected to an evaluation test for dustiness as follows, and the results are shown in Table 1 below.
Using a surface shape measuring device “Nanometro 110F” manufactured by Kuroda Seiko Co., Ltd., the measurement area of the sample (30 mm × 50 mm), scanning speed (30 mm / second), measurement pitch (0.1 mm), cut-off value ( The three-dimensional surface roughness (Ra) was measured under measurement conditions of 1 mm to 2 mm. The smaller the three-dimensional surface roughness (Ra), the smaller the “dirty feeling” of the ink jet recording medium, which means smoother.

  From the results of Table 1 above, the inkjet recording media (1-3) subjected to the heating and pressurizing treatment and the cooling peeling treatment according to the present invention have a three-dimensional surface roughness (Ra) as compared with those not treated. It was found to be a recording medium that is small, excellent in surface smoothness, and has little “dirty feeling”.

(Preparation of water-based ink)
Next, an example of recording an inkjet image using a water-based ink set is shown.
After adding deionized water to the following ink components to 1 L (liter), the mixture was stirred for 1 hour while being heated to a temperature of 30 to 40 ° C. Thereafter, the pH was adjusted to 9 with 10 mol / L of KOH, and further filtered under reduced pressure using a microfilter having an average pore diameter of 0.25 μm to prepare an ink liquid for light magenta.

<Ink component>
-Magenta dye represented by the following structural formula (T-1): 7.5 g / L
・ Diethylene glycol: 50g / L
・ Urea ……… 10g / L
・ Glycerin ......... 200g / L
・ Triethylene glycol monobutyl ether …… 120g / L
・ 2-Pyrrolidone ……… 20g / L
・ Triethanolamine ………… 6.9g / L
・ Benzotriazole: 0.08 g / L
・ "Surfinol 465" ......... 10.5g / L
(Surfactant made by Air Products Japan)
・ PROXEL “XL-2” …… 3.5g / L
(Disinfectant manufactured by ICI Japan)

  Next, by changing the types of dyes and additives as shown in Table 2 below, magenta ink, light cyan ink, cyan ink, yellow ink, and black ink are prepared in the same manner as the light magenta ink liquid. And an ink set (101) having the composition shown in Table 2 below was prepared.

  Further, for each of the light magenta, magenta, light cyan, cyan, and yellow inks of the ink set (101) obtained above, the dye type was changed as shown in Table 3 below, and the ink set (102) was similarly obtained. To (106) were produced. Here, when changing the dye species, the dye concentration was adjusted so that the transmission density of each ink liquid was equivalent to that of the ink set (101), based on the assumption that equimolar amounts were used. Moreover, when using together dye, it used equimolar.

[Example 5]
(Preparation of inkjet recording medium (5))
After the front surface of the support is subjected to corona discharge treatment, the ink receiving layer coating solution (A) is applied to the support surface of the support so that the dry coating amount is 200 ml / m ² . And dried with a hot air dryer at 80 ° C. (wind speed 3 to 8 m / sec) until the solid content concentration of the coating layer reached 20%. During this time, the coating layer exhibited constant rate drying. Immediately after that, it was immersed in a mordant coating solution (C) having the following composition for 30 seconds to adhere 20 g / m ² to the coating layer, and further dried at 80 ° C. for 10 minutes. Thus, an ink jet recording medium provided with an ink receiving layer having a dry layer thickness of 32 μm was produced.

<Composition of mordant coating liquid (C)>
(1) Boric acid (crosslinking agent) ……… 0.65 parts
(2) Ammonium zirconium carbonate: 6.5 parts (“Zircozol AC-7”, 28% aqueous solution manufactured by Daiichi Elemental Chemical Co., Ltd.)
(3) Ammonium carbonate (manufactured by Kanto Chemical Co., Ltd., first grade reagent) ... 6.0 parts
(4) Ion-exchanged water: 83.8 parts
(5) "Megafac F1405" (10% aqueous solution) ... 0.2 parts (Fluorine surfactant manufactured by Dainippon Ink & Chemicals, Inc.)

(Heat and pressure treatment and cooling peeling treatment)
About the ink jet recording medium obtained above, using a cooling peeling type belt fixing type smoothing processing machine (endless press) shown in FIG. 1, a roller temperature of 120 ° C., a belt conveying speed of 15 mm / sec, a nip pressure of 5 kgf / A heat and pressure treatment was performed at cm ² , and a peeling treatment was performed after cooling to obtain an inkjet recording medium (5) of the present invention. At this time, when the maximum temperature of the coated polyethylene layer was measured, it was 90 ° C., and the temperature during peeling was 80 ° C. or less.

[Example 6]
In Example 5, a comparative ink jet recording medium (6) was obtained in the same manner as in Example 5 except that (heating and pressing treatment and cooling peeling treatment) were not performed.

(Image recording and evaluation test)
The ink sets (101) to (106) were accommodated in a cartridge of an ink jet printer “PM900C” manufactured by Seiko Epson Corporation, and an image was recorded on the ink jet recording medium (5 or 6) obtained above. With respect to the recorded image, the evaluation test for the dustiness and the light resistance evaluation test were performed in the same manner as described above. The results are shown in Table 4 below.

(Evaluation of light resistance)
A magenta solid image recorded on the inkjet recording medium (5 and 6) was passed through a filter that cuts ultraviolet rays in a wavelength region of 365 nm or less, and a Xenon Weather-ometer “Ci65A” manufactured by ATLAS was used. Irradiation is performed for 3.8 hours under the environmental condition of 32% RH at 32 ° C., and then the treatment cycle is left for 1 hour under the environmental condition of 20 ° C. and 91% RH with the lamp turned off for 168 hours. I did it. The density of the solid image before and after this processing cycle was measured with a reflection densitometer “Xrite 938” manufactured by Xrite, and the residual ratio of magenta calculated from the measured value was evaluated according to the following criteria. Further, the presence or absence of a magenta color change in the solid image before and after the processing cycle was visually confirmed.
AA: The density residual ratio of the solid image exceeded 95%.
A: The density residual ratio of the solid image was 90 to 95%.
B: The density residual ratio of the solid image was 80 to 90%.
C: The density residual ratio of the solid image was 70 to 80%.
D: The density residual ratio of the solid image was less than 70.

  From the results of Table 4 above, compared to the case where the inkjet recording medium (6) of the comparative example is used, the present invention is applied on the inkjet recording medium (5) subjected to the heating and pressurizing and cooling peeling treatment according to the present invention. The ink jet recording medium on which an image was formed using the ink set of the invention was able to obtain a magenta hue image excellent in surface smoothness, having little “chrilliness”, and excellent in light resistance.

It is the schematic which shows one Embodiment of the cooling peeling process by the belt type smoothing processing machine (endless press) of the cooling peeling type of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ......... Processing part 2 ......... Belt 3 ......... Heating roller 4 ......... Pressure roller 5 ......... Tension roller 6 ......... Cleaning roller 7 ......... Cooling device 8 ......... Conveyance roller 10 ... ...... Support

Claims (11)

  Before performing ink jet recording, an ink jet recording medium provided with an ink receiving layer on a substrate is heated and pressurized by a cooling peeling belt fixing type smoothing processor, cooled, and then peeled off from the belt member. A method for producing an inkjet recording medium.   The method for producing an ink jet recording medium according to claim 1, further comprising a resin layer on one side or both sides of the base of the ink jet recording medium.   The method for producing an inkjet recording medium according to claim 2, wherein the resin layer is a resin layer containing a polyolefin-based resin as a main component.   The method for producing an ink jet recording medium according to any one of claims 1 to 3, wherein the heating and pressurizing is performed in a temperature range of 80 ° C to 110 ° C, and the cooling is performed at a temperature of 80 ° C or less. .   The method for producing an inkjet recording medium according to claim 2, wherein the resin layer is formed by a melt extrusion coating method.   The method for producing an ink jet recording medium according to claim 2, wherein the resin layer contains at least one of a white pigment and a fluorescent brightening agent.   The method for producing an ink jet recording medium according to claim 1, wherein the belt member has a three-dimensional surface roughness (Ra) of 20 μm or less.   The method for producing an ink jet recording medium according to claim 1, wherein the belt member is an endless belt.   9. The method for producing an ink jet recording medium according to claim 1, wherein a rubber layer mainly composed of fluorocarbonsiloxane is formed on the surface of the belt member.   10. A layer of silicone rubber is formed on the surface of the belt member, and a rubber layer mainly composed of fluorocarbon siloxane is further provided on the surface of the silicone rubber layer. Manufacturing method of the inkjet recording medium.   The method for producing an ink jet recording medium according to claim 1, wherein the fluorocarbon siloxane has a perfluoroalkyl ether group and / or a perfluoroalkyl group in a main chain.

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