JP2013129711A - Inkjet recording inkset, inkjet recording method, and recorded matter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an inkjet-recording inkset, wherein: density irregularities are prevented from occurring in a light-color printing part when inkjet recording is performed on an ink-nonabsorbing or ink-low-absorbing medium to be recorded, thereby showing excellent abrasion resistance in an image formed by the light-color printing part; and because a total solid concentration is not increased, missing dot and flying bend are prevented from occurring on a recorded matter even if continuous printing is performed.SOLUTION: An inkset contains dark ink of one or more colors and light ink of one or more colors, wherein the dark ink and light ink each independently contain: a pigment; a water-soluble resin; a resin emulsion; a paraffin wax emulsion; polyethylene wax emulsion; an acetylenic glycol-based surfactant; and a silicon-based surfactant. The mass ratio [(dark ink):(light ink)] of the total content of the pigment and the resin emulsion in the dark ink to the total content of the pigment and the resin emulsion in the light ink is 2:1 to 1:2. The inkjet-recording inkset is used for inkjet recording to a medium to be recorded comprising a plastic film.

Description

  The present invention relates to an ink set for ink jet recording, an ink jet recording method using the ink set, and a recorded matter obtained by the recording method.

  Conventionally, a printing method using an ink jet recording method is performed by causing ink droplets to fly and adhere to a recording medium such as paper. Due to recent advances in ink-jet recording technology, printing methods using ink-jet recording are also being used in the field of high-definition image recording (image printing), which previously used photographs and offset printing. . In particular, various proposals have been made for inks that can provide a high-quality image on an ink-absorbing recording medium such as plain paper or ink-jet recording paper (for example, glossy paper).

For example, Patent Document 1 discloses an inkjet recording in which a yellow ink set, a magenta ink set, a cyan ink set, and a black ink set are printed on glossy paper, which are made of dark ink and light ink having (almost) the same resin concentration. A method is disclosed ([0072], [0073], [0080] of Patent Document 1).
For example, Patent Document 2 includes fluororesin fine particles, modified polyester resin fine particles having a carboxyl group added to a side chain, resin fine particles composed of water and modified styrene-butadiene copolymer resin fine particles, a glycol-modified polyethylene wax emulsion, A recording liquid obtained by uniformly mixing a paraffin wax emulsion, a water-based copper phthalocyanine pigment, and diethylene glycol with stirring is applied onto plain paper and dried at room temperature to obtain a solid image on plain paper. Is disclosed (Patent Document 2 [0030], [0031]).

JP 2002-30235 A Japanese Patent Laid-Open No. 2002-80761

  However, in the ink jet recording method disclosed in Patent Document 1, in particular, in the case of film printing, density unevenness occurs in light ink, resulting in inferior image quality and inferior abrasion resistance of the light ink image, and ink non-absorptivity. In addition, it is not suitable for ink jet recording on a recording medium with low absorbency. Further, in the recording method disclosed in Patent Document 2, the printed matter is inferior in abrasion resistance of the light-colored printing portion, and the total solid content concentration is high, so that dot missing or flying curve of the recorded matter occurs when continuous printing is performed. In addition, it is not suitable for ink jet recording on a non-ink-absorbing and low-absorbing recording medium.

  Therefore, the present invention suppresses the occurrence of density unevenness in the light-colored printing portion when ink jet recording is performed on a non-ink-absorbing and low-absorbing recording medium, and is excellent in image abrasion resistance of the light-colored printing portion. In addition, an object of the present invention is to provide an ink set for ink jet recording which does not cause dot omission or flying bending of a recorded matter even when continuous printing is performed because the total solid content concentration does not increase.

  The present inventors have intensively studied to solve the above problems. As a result, Patent Document 1 discloses that the glossiness of a recorded matter obtained using an ink-absorbing recording medium such as paper is improved. It has been found that density unevenness occurs when it is used for ink jet recording on a recording medium having absorptivity and low absorptivity. This is because the amount of binder resin in the dark ink and the light ink constituting the ink set is (almost) the same. In this case, the difference in the drying speed between the dark ink and the light ink in particular. It was found that unevenness occurs with light ink. Therefore, by changing the content of the resin emulsion in the dark ink and the light ink and making the total content of the pigment and the resin emulsion in the dark ink and the light ink substantially the same, unevenness in the density does not occur, and as a result It has been found that the image quality of the recorded material is improved.

  In addition, since the recording liquid disclosed in Patent Document 2 is originally used for one color alone, various problems such as density unevenness and abrasion resistance may occur when it is used as a recording liquid set of two or more colors. I found out.

  As described above, in the recording using the ink set for ink jet recording including both the dark ink and the light ink, the ink is dried depending on whether the recording medium is ink-absorbing, ink non-absorbing or low-absorbing. We found that the mechanism is completely different. In other words, since the compatibility of dark ink and light ink differs depending on the degree of ink absorbability in the recording medium, an ink set for ink jet recording that combines dark ink and light ink prepared according to the drying mechanism of the ink may be used. It has been found that the above problems can be solved.

  Based on the above findings, the inventors of the present application have made further studies, and as a result, one or more types of dark ink and one or more types of ink used for ink jet recording on non-ink-absorbing and low-absorbing recording media. As an ink set for ink jet recording including a light ink of a color, the dark ink and the light ink are independently of each other, a pigment, a water-soluble resin, a resin emulsion, a paraffin wax emulsion, a polyethylene wax emulsion, an acetylene glycol surfactant. And a ratio of the total content of the pigment and the resin emulsion in the dark ink and the total content of the pigment and the resin emulsion in the light ink ( The above problem is caused by the ink set for inkjet recording in which the dark ink (light ink) is within a predetermined range. It found that can be determined, and have completed the present invention.

That is, the present invention is as follows.
[1]
An ink set for inkjet recording comprising one or more dark inks and one or more light inks, wherein the dark ink and the light ink are independently of each other a pigment, a water-soluble resin, a resin emulsion, A paraffin wax emulsion, a polyethylene wax emulsion, an acetylene glycol surfactant, and a silicone surfactant, and the total content of the pigment and resin emulsion in the dark ink, and the pigment and resin emulsion in the light ink And the mass ratio (dark ink: light ink) of 2: 1 to 1: 2, and is used for ink jet recording on a non-ink-absorbing or low-absorbing recording medium. Ink set for inkjet recording.
[2]
The pigment content in the dark ink is 1.5-6% by mass with respect to the total mass of the ink, and the pigment content in the light ink is 1 with respect to the pigment content in the dark ink. The ink set for inkjet recording according to [1], which is / 2 to 1/8.
[3]
The mass ratio of the resin emulsion content in the dark ink and the resin emulsion content in the light ink (dark ink: light ink) is 1: 3 to 1: 6 [1] or [2 ] The ink set for inkjet recording as described in any one of.
[4]
[1] to [3] The total content of the pigment and the resin emulsion in each ink included in the ink set for inkjet recording is 3 to 7% by mass independently of the total mass of the ink. ] The ink set for inkjet recording in any one of.
[5]
The content of the paraffin wax emulsion in each ink included in the ink set for inkjet recording is independently 0.3 to 1.5% by mass with respect to the total mass of the ink [1] to [ 4] The ink set for ink jet recording according to any one of [4].
[6]
The total content of the paraffin wax emulsion and the polyethylene wax emulsion in each ink contained in the ink set for inkjet recording is 0.4 to 1.6% by mass independently of the total mass of the ink. , [1] to [5] The ink set for inkjet recording according to any one of [5].
[7]
An inkjet recording method for recording on a non-ink-absorbing or low-absorbing recording medium using the ink set for inkjet recording according to any one of [1] to [6].
[8]
A recorded matter recorded by the inkjet recording method according to [7].

  Hereinafter, embodiments for carrying out the present invention will be described in detail. In addition, this invention is not restrict | limited to the following embodiment, A various deformation | transformation can be implemented within the range of the summary.

  In this specification, “dark ink” means ink having a relatively high pigment concentration among inks constituting an ink set, and “light ink” means pigment among inks constituting an ink set. Means a relatively low concentration. In this specification, the relationship between “dark ink” and “light ink” is the same color.

In this specification, “a non-ink-absorbing and low-absorbing recording medium” means “a non-ink-absorbing and low-absorbing recording medium” having a water absorption of 10 mL / m ² or less from the start of contact to 30 msec ^1/2 in the Bristow method. Recording medium ". This Bristow method is the most popular method for measuring the amount of liquid absorbed in a short time, and is also adopted by the Japan Paper Pulp Technology Association (JAPAN TAPPI). For details of the test method, refer to Standard No. of “JAPAN TAPPI Paper Pulp Test Method 2000”. 51 "Paper and paperboard-Liquid absorbency test method-Bristow method".

  In this specification, “(meth) acrylate” means at least one of acrylate and its corresponding methacrylate, and “(meth) acryl” means at least one of acryl and its corresponding methacryl.

  In the present specification, the “wax emulsion” means a product in which solid wax particles are dispersed in water mainly using a surfactant.

[Ink set for inkjet recording]
An ink set for ink-jet recording according to an embodiment of the present invention (hereinafter, also simply referred to as “ink set”) is used for ink-jet recording on a recording medium having no ink absorption or low absorption. , One or more colors of dark ink and one or more colors of light ink. The dark ink and the light ink (hereinafter collectively referred to simply as “ink”) are independently of each other, pigment, water-soluble resin, resin emulsion, paraffin wax emulsion, polyethylene wax emulsion, acetylene glycol interface. Contains an activator and a silicon-based surfactant. The mass ratio (dark ink: light ink) of the total content of the pigment and resin emulsion in the dark ink and the total content of the pigment and resin emulsion in the light ink is 2: 1 to 1. : 2.

Examples of the color of the dark ink include black, green, orange, red, and blue in addition to yellow, magenta, and cyan. Examples of the light ink color include light yellow, light magenta, light yellow, light black, light green, light orange, light red, and light blue. In addition, the light ink can adopt the color mentioned as the color of the dark ink as long as the pigment concentration is lower than that of the dark ink.
Note that the light ink in the ink set of the present embodiment also has an effect of preventing the image from being grained and causing unevenness in image quality.

  Hereinafter, additives (components) contained in or included in each ink (ink composition) constituting the ink set of the present embodiment will be described. The components contained in the dark ink and the components contained in the light ink are selected independently from each other in terms of type, physical properties, content, and the like. In addition, when there are a plurality of types of dark ink and a plurality of types of light ink, the types, physical properties, and contents of each component contained in each ink are selected independently of each other as described above. Is done. Furthermore, the type of pigment may be the same or different between the dark ink and the light ink, and is preferably the same among them.

[Pigment]
The pigment contained in the ink in the present embodiment is not only insoluble or hardly soluble in water, but also has a property of not easily fading against light or gas. Therefore, a recorded matter recorded with an ink using a pigment is excellent in water resistance, gas resistance, and light resistance, and also has good storage stability.

  As the pigment, any of inorganic pigments and organic pigments can be used. Among these, at least one of carbon black and organic pigments belonging to the inorganic pigment is preferable because it has good color developability and is difficult to settle during dispersion because of its low specific gravity.

  Although it does not specifically limit as an inorganic pigment, For example, carbon black, iron oxide, and a titanium oxide are mentioned.

  Although it does not specifically limit as said carbon black, For example, furnace black, lamp black, acetylene black, and channel black (CI pigment black 7) are mentioned. Further, as a commercially available product of carbon black, for example, No. 2300, 900, MCF88, no. 20B, no. 33, no. 40, no. 45, no. 52, MA7, MA8, MA100, no. 2200B (all trade names, manufactured by Mitsubishi Chemical Corporation), color black FW1, FW2, FW2V, FW18, FW200, S150, S160, S170, Pretex 35, U, V, 140U, Special Black 6, 5, 4A, 4, 250 (all trade names, manufactured by Degussa AG), CONDUCTEX SC, Raven 1255, 5750, 5250, 5000, 3500, 1255, 700 (all trade names, Columbia Carbon ( Columbian Carbon Japan Ltd), Regal 400R, 330R, 660R, Mogul L, Monarch 700, 800, 880, 900, 1000, 1100, 1300, 1400, Elftex 12 (all trade names, Cabot Corporation) Manufactured).

  An inorganic pigment may be used individually by 1 type, and may be used in combination of 2 or more type.

  Examples of organic pigments include, but are not limited to, quinacridone pigments, quinacridone quinone pigments, dioxazine pigments, phthalocyanine pigments, anthrapyrimidine pigments, ansanthrone pigments, indanthrone pigments, flavanthrone pigments, Examples include perylene pigments, diketopyrrolopyrrole pigments, perinone pigments, quinophthalone pigments, anthraquinone pigments, thioindigo pigments, benzimidazolone pigments, isoindolinone pigments, azomethine pigments, and azo pigments. . Specific examples of the organic pigment include the following.

  Examples of pigments used for cyan ink include C.I. I. Pigment Blue 1, 2, 3, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 15:34, 16, 18, 22, 60, 65, 66, C.I. I. Bat Blue 4 and 60 are listed. Among them, C.I. I. At least one of Pigment Blue 15: 3 and 15: 4 is preferable.

  Examples of pigments used in magenta ink include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48 (Ca), 48 (Mn), 57 (Ca), 57: 1, 88, 112, 114, 122, 123, 144, 146, 149, 150, 166, 168 170, 171, 175, 176, 177, 178, 179, 184, 185, 187, 202, 209, 219, 224, 245, 254, 264, C.I. I. Pigment violet 19, 23, 32, 33, 36, 38, 43, 50. Among them, C.I. I. Pigment red 122, C.I. I. Pigment red 202, and C.I. I. One or more selected from the group consisting of Pigment Violet 19 is preferred.

  Examples of pigments used in yellow ink include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 16, 17, 24, 34, 35, 37, 53, 55, 65, 73, 74, 75, 81, 83, 93, 94, 95, 97, 98, 99, 108, 109, 110, 113, 114, 117, 120, 124, 128, 129, 133, 138, 139, 147, 151, 153, 154, 155, 167, 172, 180, 185, 213. Among them, C.I. I. One or more selected from the group consisting of CI Pigment Yellow 74, 155, and 213 are preferred.

  In addition, as a pigment used for inks of colors other than the above, such as green ink and orange ink, conventionally known pigments can be used.

  The average particle diameter of the pigment is preferably 250 nm or less because clogging at the nozzle can be suppressed and the ejection stability is further improved. The average particle diameter in this specification is based on volume. As a measuring method, for example, it can be measured by a particle size distribution measuring apparatus using a laser diffraction scattering method as a measurement principle. Examples of the particle size distribution measuring device include a particle size distribution meter (for example, Microtrac UPA manufactured by Nikkiso Co., Ltd.) having a dynamic light scattering method as a measurement principle.

Further, since the classification of dark ink and light ink is determined by the pigment content, the pigment content differs between the dark ink and the light ink. The pigment content in the light ink is 1/2 to 1/8 of the pigment content in the dark ink of the same color (“pigment content in the light ink” / “pigment content in the dark ink”). Is preferred. When the content of the pigment in the dark ink and the light ink is within the above range, the light amount of the light color portion and the dark color portion of the image can be leveled by forming the light color portion of the image with the light ink.
The pigment content in the dark ink is preferably 1.5 to 6% by mass with respect to the total mass (100% by mass) of the ink. In this embodiment, the mass ratio of the total content of the pigment and the resin emulsion in the dark ink and the total content of the pigment and the resin emulsion in the light ink is within a predetermined range (both The content is substantially the same), which will be described later.

(Resin dispersant)
When the above pigment is contained in the ink, the pigment may be stably dispersed and held in water. Such a dispersion method is not particularly limited. For example, a dispersion method using a resin dispersant such as a water-soluble resin or a water-dispersible resin (hereinafter, a pigment treated by this method is referred to as a “resin dispersion pigment”. Say). Among these, a water-soluble resin is preferable because of excellent dispersion stability.
Here, the water-soluble resin is not limited to the resin dispersant and may be used for other purposes. In other words, the ink in the present embodiment only needs to contain a water-soluble resin regardless of the application. Therefore, the water-soluble resin may be added (pre-added) at the stage of preparing the pigment dispersion before preparing the ink (for example, when used as a resin dispersant), and added as a component when preparing the ink. (Post-addition) may be performed (for example, in the case of using for the purpose of improving fixability and abrasion resistance).

  By including the resin-dispersed pigment in the ink, among these, when the ink adheres to the recording medium, at least one of adhesion between the recording medium and the ink and between the solidified substances in the ink is achieved. It can be good.

  Examples of the water-soluble resin include, but are not limited to, polyvinyl alcohols, poly (meth) acrylic acid, (meth) acrylic acid-acrylonitrile copolymer, vinyl acetate- (meth) acrylic acid ester copolymer. , (Meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene- (meth) acrylic acid copolymer, styrene-methacrylic acid-acrylic acid ester copolymer, styrene-α-methylstyrene- (meth) Acrylic acid copolymer, styrene-α-methylstyrene- (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, styrene-maleic anhydride copolymer, vinylnaphthalene- ( (Meth) acrylic acid copolymer, vinyl naphthalene-maleic acid copolymer, vinyl acetate-maleic acid ester copolymer Examples thereof include a polymer, a vinyl acetate-crotonic acid copolymer, a vinyl acetate- (meth) acrylic acid copolymer, and salts thereof. As the form of the copolymer, any form of a random copolymer, a block copolymer, an alternating copolymer, and a graft copolymer can be used.

  Examples of the salt include, but are not limited to, for example, ammonia, ethylamine, diethylamine, triethylamine, propylamine, isopropylamine, dipropylamine, butylamine, isobutylamine, diethanolamine, triethanolamine, triisopropanolamine, aminomethylpropanol And salts with basic compounds such as morpholine. The addition amount of these basic compounds is not particularly limited as long as it is at least the neutralization equivalent of the water-soluble resin.

  The molecular weight of the resin dispersant is preferably in the range of 1,000 to 100,000 as the weight average molecular weight, and more preferably in the range of 3,000 to 10,000. When the molecular weight is within the above range, stable dispersion of the pigment in water can be obtained, and viscosity control when applied to ink becomes easy.

  Moreover, it is preferable that it is the range of 50-300 as an acid value, and it is more preferable that it is the range of 70-150. When the acid value is within the above range, the dispersibility of the pigment in water can be stably secured, and the water resistance of the recorded matter recorded using the ink containing the pigment is improved.

  In addition, you may use a commercial item for said water-soluble resin. As specific examples of the commercially available products, Joncryl 67 (weight average molecular weight: 12,500, acid value: 213), Joncryl 678 (weight average molecular weight: 8,500, acid value: 215), Joncryl 586 (weight average) Molecular weight: 4,600, acid value: 108), joncryl 611 (weight average molecular weight: 8,100, acid value: 53), joncryl 680 (weight average molecular weight: 4,900, acid value: 215), joncryl 682 (weight average molecular weight: 1,700, acid value: 238), Joncryl 683 (weight average molecular weight: 8,000, acid value: 160), Joncryl 690 (weight average molecular weight: 16,500, acid value: 240) ) (Trade name, manufactured by BASF Japan Ltd.).

  The amount of the resin dispersant added to the pigment is preferably 1 part by mass to 100 parts by mass, and more preferably 5 parts by mass to 50 parts by mass with respect to 100 parts by mass of the pigment. When the addition amount is within the above range, good dispersion stability of the pigment in water can be ensured.

  As a method of dispersing the above resin-dispersed pigment in water, in the case of a resin-dispersed pigment, the pigment, water, and a resin dispersant, and further adding a water-soluble organic solvent and a neutralizer as necessary, are dispersed. This can be done using a machine. Examples of the disperser include those conventionally used such as a ball mill, a sand mill, an attritor, a roll mill, an agitator mill, a Henschel mixer, a colloid mill, an ultrasonic homogenizer, a jet mill, and an ang mill. As the degree of dispersion, the average particle size of the pigment is preferably dispersed until it falls within the range of 20 nm to 500 nm, more preferably within the range of 50 nm to 200 nm. In this case, the dispersion stability of the pigment in water is further improved.

[Resin emulsion]
The ink in the present embodiment includes a resin emulsion. When the recording medium is heated (described later), the resin emulsion forms a resin film together with the polyethylene wax emulsion and the paraffin wax emulsion so that the ink is sufficiently fixed on the recording medium and the image has good abrasion resistance. Demonstrate the effect. Therefore, the resin emulsion is preferably a thermoplastic resin. Due to the above effects, a recorded matter recorded using an ink containing a resin emulsion is excellent in abrasion resistance on a non-ink-absorbing or low-absorbing recording medium.

  The resin emulsion that functions as a binder is contained in the ink in an emulsion state. By including a resin functioning as a binder in the ink in an emulsion state, it is easy to adjust the viscosity of the ink to an appropriate range in the ink jet recording method, and the ink has excellent storage stability and ejection stability. .

  Examples of the resin emulsion include, but are not limited to, (meth) acrylic acid, (meth) acrylic acid ester, acrylonitrile, cyanoacrylate, acrylamide, olefin, styrene, vinyl acetate, vinyl chloride, vinyl alcohol, vinyl ether, vinyl pyrrolidone. , Vinyl pyridine, vinyl carbazole, vinyl imidazole, and vinylidene chloride homopolymers or copolymers, fluororesins, and natural resins. Among them, at least one of (meth) acrylic resin and styrene- (meth) acrylic acid copolymer resin is preferable, and at least one of acrylic resin and styrene-acrylic acid copolymer resin is more preferable, styrene. -Acrylic acid copolymer resin is more preferable. In addition, said copolymer may be any form among a random copolymer, a block copolymer, an alternating copolymer, and a graft copolymer.

  As said resin emulsion, what is obtained by a well-known material and a manufacturing method may be used, and a commercial item may be used. The commercially available products are not limited to the following, but include, for example, Microgel E-1002, Microgel E-5002 (trade names, manufactured by Nippon Paint Co., Ltd.), Boncourt 4001, Boncourt 5454 ( Product name, manufactured by DIC, SAE1014 (trade name, manufactured by Zeon Corporation), Cybinol SK-200 (trade name, manufactured by SAIDEN CHEMICAL INDUSTRY CO., LTD.), Jonkrill 7100, John Crill 390, John Crill 711, John Crill 511, John Crill 7001, John Crill 632, John Crill 741, John Crill 450, John Crill 840, John Crill 74J, John Crill HRC-1645J, John Crill 734, John Crill 852, Jongkrill 7600, Jongkuri 775, John Crill 537J, John Crill 1535, John Crill PDX-7630A, John Crill 352J, John Crill 352D, John Crill PDX-7145, John Crill 538J, John Crill 7640, John Crill 7641, John Crill 631, John Crill 790 , Jonkrill 780, Jonkrill 7610 (trade name, manufactured by BASF) and the like.

  Although said resin emulsion is not specifically limited, For example, it can obtain by the preparation method shown below, You may combine a some method as needed. As the preparation method, a polymerization catalyst (polymerization initiator) and a dispersant are mixed in a monomer of a component constituting a desired resin, and polymerization (emulsion polymerization) is performed. A resin having a hydrophilic portion is dissolved in water. A method of removing a water-soluble organic solvent by distillation after mixing a solution obtained by dissolving in a water-soluble organic solvent into water, and a solution obtained by dissolving a resin in a water-insoluble organic solvent together with a dispersant in an aqueous solution The method of mixing is mentioned.

  The dispersant that can be used when dispersing the binder resin in the emulsion state is not particularly limited, but examples include anions such as sodium dodecylbenzenesulfonate, sodium lauryl phosphate, and polyoxyethylene alkyl ether sulfate ammonium salt. And nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, polyoxyethylene sorbitan fatty acid esters, and polyoxyethylene alkylphenyl ethers. These dispersants may be used alone or in combination of two or more.

  The mechanism by which the abrasion resistance of the image is improved when the above resin emulsion is used in combination with the polyethylene wax emulsion and the paraffin wax emulsion described below is presumed as follows. The resin emulsion has a good affinity for non-ink-absorbing or low-absorbing recording media and pigments. Therefore, when the recording medium to which the ink is attached is heated to form a resin film, the resin emulsion is firmly fixed on the recording medium while wrapping the pigment. On the other hand, the polyethylene wax emulsion and the paraffin wax emulsion are also present on the surface of the resin coating and reduce the frictional resistance of the surface. This makes it possible to form a resin film that is difficult to be scraped by external rubbing and that is difficult to peel off from the recording medium, and it is presumed that the abrasion resistance of the image is improved. In addition, the said mechanism is an inventor's guess, Comprising: The thing different from the said mechanism is also in the scope of the present invention.

  The average particle diameter of the resin emulsion is preferably in the range of 5 nm to 400 nm, and more preferably in the range of 20 nm to 300 nm, in order to further improve the storage stability and ejection stability of the ink.

  In the present embodiment, the mass ratio of the total content of the pigment and the resin emulsion in the dark ink and the total content of the pigment and the resin emulsion in the light ink (dark ink: light ink) is 2: 1. ~ 1: 2. By changing the content of the resin emulsion between the dark ink and the light ink so that the mass ratio is within the above range, that is, the contents of both are substantially the same, the uneven density of the light ink printing portion is generated. Therefore, the image quality of dark ink and light ink can be made substantially equal. By making the image quality of two types of inks with different solid content concentrations of pigment, that is, dark ink and light ink, the same image quality, especially on non-ink-absorbing or low-absorbing recording media. Images can be formed.

  In addition, the total content of the pigment and the resin emulsion in each ink included in the ink set, such as dark ink and light ink, is 3 to 3 with respect to the total mass (100% by mass) of the ink. The range is preferably 7% by mass. When the total content is within the above range, the solid content concentration can be lowered, so that the discharge stability can be further improved.

  The mass ratio of the resin emulsion content in the dark ink and the resin emulsion content in the light ink (dark ink: light ink) is preferably 1: 3 to 1: 6. When the mass ratio is within the above range, the occurrence of uneven density can be more effectively prevented.

(Paraffin wax emulsion)
By including a paraffin wax emulsion in the ink according to the present embodiment, slip performance is imparted to the recorded matter, whereby the ink has excellent abrasion resistance. In addition, since paraffin wax has water repellency, the water resistance of the recorded matter can be improved.

  The “paraffin wax” in the present specification means a so-called petroleum wax, which is mainly composed of a linear paraffinic hydrocarbon (normal paraffin) having about 20 to 30 carbon atoms and a small amount of iso (iso). -It means a mixture of hydrocarbons containing paraffin and having a weight average molecular weight of about 300 to 500.

  When the ink in the present embodiment contains paraffin wax in an emulsion state, it is easy to adjust the viscosity of the ink to an appropriate range in the ink jet recording method, and the storage stability and ejection stability of the ink are further improved. can do.

  The melting point of the paraffin wax emulsion is preferably 110 ° C. or lower in order to further strengthen the film of the recorded material and further improve the abrasion resistance of the image. On the other hand, the lower limit of the melting point of the paraffin wax emulsion is preferably 60 ° C. or higher in order to prevent the recording surface from being dried and sticky. Further, the melting point is more preferably 70 to 95 ° C. in order to further improve the ink ejection stability.

  The average particle diameter of the paraffin wax emulsion is preferably in the range of 5 nm to 400 nm, more preferably 50 nm to 200 nm, in order to obtain a stable emulsion state and to further improve the storage stability and ejection stability of the ink. Range. A commercially available product may be used as it is as the paraffin wax emulsion. Examples of the commercially available products include, but are not limited to, AQUACER 537, AQUACER 539 (trade names, manufactured by BYK).

  The content of the paraffin wax emulsion in each ink included in the ink set (in terms of solid content) is independently from each other in the range of 0.1 to 3% by mass with respect to the total mass (100% by mass) of the ink. Preferably, the range of 0.3-3 mass% is more preferable, and the range of 0.3-1.5 mass% is more preferable. When the content is within the above range, an image having excellent abrasion resistance, blocking resistance, and water resistance can be formed on a non-ink-absorbing or low-absorbing recording medium, and The ink can be excellent in preventing clogging.

[Polyethylene wax emulsion]
By including a polyethylene wax emulsion in the ink according to the present embodiment, the ink can have excellent abrasion resistance.

  For example, a polyethylene wax emulsion is produced by polymerizing ethylene, or by producing polyethylene for general molding by reducing the molecular weight by thermal decomposition. The polyethylene wax is oxidized to add a carboxyl group or a hydroxyl group, and further emulsified using a surfactant to obtain a polyethylene wax emulsion in the form of an aqueous wax emulsion having excellent stability.

  A commercially available product may be used as it is as the polyethylene wax emulsion. Examples of the commercially available products include, but are not limited to, Nopcoat PEM17 (trade name, manufactured by SANNOPCO LIMITED), Chemipearl W4005 (trade name, manufactured by Mitsui Chemicals, Inc.), AQUACER 515, AQUACER 593 (trade name, manufactured by BYK) can be mentioned.

  The average particle size of the polyethylene wax emulsion is preferably in the range of 5 nm to 400 nm, and more preferably in the range of 50 nm to 200 nm, in order to further improve the storage stability and ejection stability of the ink.

  The content of the polyethylene wax emulsion in each ink contained in the ink set (in terms of solid content) is independently from each other in the range of 0.1 to 3% by mass with respect to the total mass (100% by mass) of the ink. Preferably, the range of 0.3-3 mass% is more preferable, and the range of 0.3-1.5 mass% is more preferable. When the content is within the above range, the ink can be solidified and fixed satisfactorily even on a non-ink-absorbing or low-absorbing recording medium, and the storage stability and ejection stability of the ink can be improved. It will be even better.

  Further, since the dark ink and the light ink included in the ink set of the present embodiment include both the paraffin wax emulsion and the polyethylene wax emulsion, the fixing between the dark ink and the light ink having different resin emulsion contents as described above is possible. The property (adhesion degree) can be made substantially equal. Two types of inks with different pigment solid content concentrations, that is, dark ink and light ink have the same degree of adhesion so that they have excellent abrasion resistance, especially on non-ink-absorbing or low-absorbing recording media. A strong image can be formed.

  The preferable content range of each of the paraffin wax emulsion and the polyethylene wax emulsion is as described above. In addition, the total content (in terms of solid content) of the paraffin wax emulsion and the polyethylene wax emulsion in each ink included in the ink set is 0 with respect to the total mass (100% by mass) of the ink independently of each other. The range of 4-1.6 mass% is preferable.

[Wax other than the above]
The ink in the present embodiment may include a wax other than the paraffin wax emulsion and the polyethylene wax emulsion (hereinafter referred to as “other wax”). The wax has a function of imparting slip performance to the surface of the formed recorded matter and improving the abrasion resistance. The wax is preferably contained in the ink in an emulsion state. Since the wax in the ink exists in an emulsion state, the viscosity of the ink can be easily adjusted to an appropriate range in the ink jet recording method, and the storage stability and ejection stability of the ink can be further improved. .

  Examples of other waxes include, but are not limited to, polyolefin waxes (excluding the above-described polyethylene wax), and polypropylene waxes are particularly preferable. As other waxes, commercially available products may be used as they are.

  The average particle diameter of other waxes is preferably in the range of 5 nm to 400 nm, and more preferably in the range of 50 nm to 200 nm, in order to further improve the storage stability and ejection stability of the ink.

[Acetylene glycol surfactant]
The ink in the present embodiment includes an acetylene glycol surfactant that belongs to a nonionic surfactant. The acetylene glycol surfactant is excellent in the ability to properly maintain the surface tension and the interfacial tension as compared with other nonionic surfactants, and hardly causes foaming. As a result, the ink containing the acetylene glycol surfactant can appropriately maintain the interfacial tension and the surface tension with the printer member in contact with the ink such as the nozzle surface of the head. Therefore, the ejection stability can be improved by using an ink containing an acetylene glycol surfactant in an ink jet recording system. In addition, since the acetylene glycol surfactant exhibits good affinity (wetability) and penetrability with respect to the recording medium, an image recorded using an ink containing the acetylene glycol surfactant has a high density with almost no unevenness of color and bleeding. It will be fine.

  Although it does not specifically limit as acetylene glycol type surfactant, For example, Surfynol 104,104E, 104H, 104A, 104BC, 104DPM, 104PA, 104PG-50,104S, 420,440,465,485, SE, SE- F, 504, 61, DF37, CT111, CT121, CT131, CT136, TG, GA, (all trade names, manufactured by Air Products and Chemicals. Inc.), Olphin B, Y, P, A, STG, SPC, E1004, E1010, PD-001, PD-002W, PD-003, PD-004, EXP. 4001, EXP. 4036, EXP. 4051, AF-103, AF-104, AK-02, SK-14, AE-3, DF110D (all trade names, manufactured by Nissin Chemical Industry Co., Ltd.), acetylenol E00, E00P, E40, E100 (all are trade names, manufactured by Kawaken Fine Chemical Co., Ltd.).

  One acetylene glycol surfactant may be used alone, or two or more acetylene glycol surfactants may be used in combination.

  The content of the acetylene glycol surfactant is 0.1% by mass or more and 3% by mass because the storage stability and ejection stability of the ink are further improved with respect to the total mass (100% by mass) of the ink. % Or less is preferable.

[Silicon surfactant]
The ink in the present embodiment includes a silicon-based surfactant belonging to a nonionic surfactant. Silicon-based surfactants are superior to other nonionic surfactants in their ability to uniformly spread ink so as not to cause uneven density or bleeding on the recording medium.

  Although it does not specifically limit as a silicon-type surfactant, A polysiloxane type compound is mentioned preferably. Although it does not specifically limit as the said polysiloxane type compound, For example, polyether modified organosiloxane is mentioned. Commercially available products of the polyether-modified organosiloxane include, for example, BYK-306, BYK-307, BYK-333, BYK-341, BYK-345, BYK-346, BYK-348 (above trade names, manufactured by BYK). KF-351A, KF-352A, KF-353, KF-354L, KF-355A, KF-615A, KF-945, KF-640, KF-642, KF-643, KF-6020, X-22-4515 , KF-6011, KF-6012, KF-6015, KF-6017 (trade names, manufactured by Shin-Etsu Chemical Co., Ltd.).

  The silicon surfactant preferably includes one or more compounds represented by the following formula (1) or (2).

In said formula (1), R < ¹ > -R < ⁷ > is a C1-C6 alkyl group mutually independently, Preferably it is a methyl group. j and k are each independently an integer of 1 or more, preferably 1 to 5, more preferably 1 to 4, still more preferably 1 or 2, or k = j + 1 is satisfied, Even more preferably, j = k = 1 or k = j + 1 is satisfied. Moreover, g is an integer greater than or equal to 0, Preferably it is 1-3, More preferably, it is 1. Further, m and n are each an integer of 0 or more, preferably an integer of 1 to 5. p + q is an integer of 1 or more, preferably p + q is an integer of 2 or more and 4 or less.

The polyether siloxane surfactant in the present embodiment is a compound of the above formula (1), wherein R ^{1 to} R ⁷ all represent a methyl group, j represents 1 to 2, k represents 1 to 2. It is preferable that g represents 1-2, p represents an integer of 1 to 5, and q represents 0.

  In said formula (2), R represents a hydrogen atom or a methyl group, a represents the integer of 7-11, m represents the integer of 30-50, and n represents the integer of 3-5. preferable.

Moreover, in said formula (2), R represents a hydrogen atom or a methyl group, a represents the integer of 9-13, m represents the integer of 2-4, and n represents the integer of 1-2. It is also preferable.
Moreover, in said formula (2), R represents a hydrogen atom or a methyl group, a represents the integer of 6-18, m is 0, and it is also preferable that n is 1.
Moreover, in said formula (2), R represents a hydrogen atom, a represents the integer of 2-5, m represents the integer of 20-40, and n also represents the integer of 3-5.

  By using such a specific silicon-based surfactant, even when ink is printed on a non-absorptive material such as a recording medium or an absorbent material such as printing paper, ink beading and Bleeding can be further improved.

  A silicon-type surfactant may be used individually by 1 type, and 2 or more types may be mixed and used for it.

  The content of the silicon-based surfactant improves the storage stability and ejection stability of the ink, so that it is 0.1% by mass or more and 3% by mass with respect to the total mass (100% by mass) of the ink. The following range is preferable.

  When the dark ink and the light ink included in the ink set of the present embodiment include both the acetylene glycol surfactant and the silicon surfactant, the contents of the pigment (solid content) and the resin emulsion are mutually reduced as described above. It is different and the printing stability is comparable between dark ink and light ink containing both paraffin wax emulsion and polyethylene wax emulsion.

[Surfactants other than the above]
The ink in the present embodiment may contain a surfactant other than the above (hereinafter referred to as “other surfactant”). Examples of other surfactants include, but are not limited to, nonionic surfactants other than those described above. The nonionic surfactant has an action of spreading the ink uniformly on the recording medium. For this reason, when ink jet recording is performed using an ink containing a nonionic surfactant, a high-definition image with almost no uneven density or bleeding can be obtained. Examples of such nonionic surfactants include, but are not limited to, polyoxyethylene alkyl ether-based, polyoxypropylene alkyl ether-based, polycyclic phenyl ether-based, sorbitan derivatives, and fluorine-based surfactants. Can be mentioned.
The content of the other surfactant may be in the range of 0.1% by mass to 3% by mass with respect to the total mass (100% by mass) of the ink.

〔water〕
The ink in the present embodiment may contain water. In particular, when the ink is a water-based ink, water is a main medium of the ink, and becomes a component that evaporates and scatters when the recording medium is heated in ink jet recording.

  Examples of water include water from which ionic impurities have been removed as much as possible, such as pure water such as ion exchange water, ultrafiltration water, reverse osmosis water, and distilled water, and ultrapure water. Further, when water sterilized by ultraviolet irradiation or addition of hydrogen peroxide is used, generation of mold and bacteria can be prevented when the pigment dispersion and ink using the same are stored for a long period of time.

〔Organic solvent〕
The ink in this embodiment may further contain a volatile water-soluble organic solvent. Examples of the organic solvent include, but are not limited to, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,2-butanediol, and 1,2-pentanediol. 1,2-hexanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol mono-n-propyl ether, ethylene glycol mono-iso-propyl ether, diethylene glycol mono-iso -Propyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-t-butyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol mono-n-butyl ether Ter, diethylene glycol mono-t-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-t-butyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-iso-propyl ether, propylene glycol mono- n-butyl ether, dipropylene glycol mono-n-butyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-iso-propyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol ethyl methyl ether, diethylene glycol Butylmethyl Ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, tripropylene glycol dimethyl ether, methanol, ethanol, n-propyl alcohol, iso-propyl alcohol, n-butanol, 2-butanol, alcohols or glycols such as tert-butanol, iso-butanol, n-pentanol, 2-pentanol, 3-pentanol, and tert-pentanol, N, N-dimethylformamide, N, N-dimethylacetamide, 2-pyrrolidone, N-methyl-2-pyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, Ruhoran, and 1,1,3,3-tetramethylurea and the like.

[Other ingredients]
In addition to the above components, the ink in the present embodiment may further include a pH adjuster such as potassium hydroxide, an antiseptic / fungicide, a rust inhibitor, a chelating agent, and the like.

[Ink production method]
The ink in the present embodiment can be obtained by mixing the above-described components (materials) in an arbitrary order, performing filtration or the like as necessary, and removing impurities. Here, it is preferable to prepare the pigment in a state of being uniformly dispersed in a solvent before mixing, because the handling becomes simple.

  As a method for mixing each material, a method in which materials are sequentially added to a container equipped with a stirring device such as a mechanical stirrer or a magnetic stirrer and stirred and mixed is preferably used. As a filtration method, for example, centrifugal filtration or filter filtration can be performed as necessary.

[Recording medium]
As described above, the ink set of the present embodiment is particularly suitable for ink jet recording using a non-ink-absorbing or low-absorbing recording medium. Specifically, the content ratio of the pigment and the resin emulsion is between the dark ink and the light ink constituting the ink set so as to be suitable for ink jet recording on a non-ink-absorbing or low-absorbing recording medium. It is set within a predetermined range.

  Examples of non-ink-absorbing recording media include, but are not limited to, plastic films that have not been surface-treated for inkjet printing (that is, that have no ink-absorbing layer formed), and substrates such as paper And those coated with plastic and those with a plastic film adhered thereto. The plastic is not particularly limited, and examples thereof include polyvinyl chloride, polyethylene terephthalate, polycarbonate, polystyrene, polyurethane, polyethylene, and polypropylene. Examples of the recording medium with low ink absorption include printing paper such as art paper, coated paper, and matte paper.

  As described above, according to the present embodiment, when ink jet recording is performed on a non-ink-absorbing and low-absorbing recording medium, occurrence of density unevenness is suppressed, the image has excellent abrasion resistance, and It is possible to provide an ink set for ink-jet recording that does not cause dot missing or flying bending of a recorded matter even when continuous printing is performed.

[Inkjet recording method]
An ink jet recording method according to an embodiment of the present invention is to perform recording on the above-described non-ink-absorbing or low-absorbing recording medium using the ink set for ink-jet recording of the above-described embodiment. The ink jet recording method preferably includes heating and drying the ink set for ink jet recording discharged onto the recording medium.
Hereinafter, an example of the ink jet recording method of the present embodiment will be described in detail for each process.

[Discharge process]
The ink jet recording method of this embodiment includes a discharge step. The ejection step is an inkjet recording method in which droplets of each ink constituting the ink set for inkjet recording are ejected onto a recording medium to form an image. As a discharge method, a conventionally known method can be used, and in particular, a method of discharging a droplet by utilizing vibration of a piezoelectric element (a recording method using a head that forms an ink droplet by mechanical deformation of an electrostrictive element). Excellent recording can be performed using.

[Drying process]
The ink jet recording method of this embodiment includes a drying step. The drying step dries the ink (image) ejected and adhered onto the recording medium. By this step, moisture contained in the ink discharged onto the recording medium is quickly evaporated and scattered, and a film is formed by the resin emulsion contained in the ink. As a result, it is possible to obtain in a short time a high-quality image with little density unevenness and bleeding, in which the dried ink is firmly fixed (adhered) on the recording medium.

  Here, the drying process may be performed in parallel with the discharge process, or may be performed after the discharge process. In other words, the recording medium may be heated before recording, during recording, and after recording. Among them, the fact that the recording medium is heated before recording or during recording can form a high-quality image with little uneven density and bleeding on the recording medium that is non-absorbing or low-absorbing ink. It can be said that it is preferable.

  The heating method is not limited to the following, but includes, for example, a heater provided in the ink jet recording apparatus, a warm air mechanism provided in the ink jet recording apparatus, and a drying mechanism such as a thermostatic chamber connected to the ink jet recording apparatus. The means to use is mentioned. And these means can be used individually by 1 type or in combination of 2 or more types.

  In the drying step, the temperature of the surface of the recording medium in contact with the ink is preferably 40 to 120 ° C., although it depends on the material of the recording medium. When the temperature is 40 ° C. or higher, evaporation and scattering of the liquid medium in the ink can be effectively promoted. On the other hand, when the temperature is 120 ° C. or lower, it is possible to prevent the recording medium from being deformed or to prevent image shrinkage during heating and cooling of the recording medium.

[Recordings]
The recorded matter according to one embodiment of the present invention is obtained by performing the ink jet recording method of the above embodiment. The recorded matter is particularly excellent in image abrasion resistance.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these.

[Materials used]
The materials used in the following examples and comparative examples are as follows.
[Pigment]
・ C. I. Pigment Blue 15: 3
・ C. I. Pigment Red 122
・ C. I. Pigment Yellow 74
・ C. I. Pigment Black 7
[Resin emulsion]
-Styrene-acrylic acid copolymer resin emulsion (Tg 85 ° C, average particle size 140 nm)
(Paraffin wax emulsion)
・ AQ539 (BYK product name)
[Polyethylene wax emulsion]
・ AQ515 (BYK product name)
[Silicon surfactant]
・ BYK348 (Brand name, manufactured by BYK)
[Acetylene glycol surfactant]
・ Surfinol DF110D (trade name, manufactured by Nissin Chemical Industry Co., Ltd.)
[Others]
・ 1,2-hexanediol ・ 2-pyrrolidone

[Preparation of pigment dispersion]
Water-soluble resin (methacrylic acid / butyl acrylate / styrene / hydroxyethyl acrylate copolymerized at a mass ratio of 25/50/15/10, weight average molecular weight 12,000) 40 parts by mass, potassium hydroxide 7 parts by mass , 23 parts by mass of water and 30 parts by mass of triethylene glycol mono-n-butyl ether were added and heated at 80 ° C. with stirring to prepare an aqueous resin solution.

  The above-mentioned aqueous resin solution (solid content: 43%) was mixed with 1.75 kg of each of the above pigments and 10.25 kg of water, stirred with a mixing stirrer and premixed to obtain a mixed solution. The above mixed solution was dispersed by a multi-pass method using a horizontal type bead mill equipped with a multi-disc type impeller having an effective volume of 1.5 liters filled with 85% of 0.5 mm zirconia beads. Specifically, two passes were performed at a bead peripheral speed of 8 m / sec and a discharge amount of 30 liters per hour to obtain a pigment dispersion mixed liquid having an average particle diameter of 325 nm. Next, the pigment dispersion mixture was circulated and dispersed using a horizontal annular bead mill having an effective volume of 1.5 liters filled with 95% of 0.05 mm zirconia beads. A screen of 0.015 mm is used, a dispersion of 10 kg of pigment dispersion is performed for 4 hours at a circulation rate of 300 liters / hour at a bead peripheral speed of 10 m / second, a pigment solid content of 20%, a water-soluble resin 5 % Aqueous pigment dispersion was obtained.

[Preparation of ink set]
Using the pigment dispersion prepared above, inks of dark black, dark yellow, dark magenta, dark cyan, light magenta, and light cyan were prepared with the compositions shown in Tables 1 to 12 below. . Each ink was prepared by putting each component in a container, stirring and mixing with a magnetic stirrer for 2 hours, and then filtering through a membrane filter having a pore size of 5 μm to remove impurities such as dust and coarse particles. As shown in Tables 1 to 12 below, an ink set composed of dark black, dark yellow, dark magenta, dark cyan, light magenta, and light cyan was obtained. In addition, all the numerical values in Tables 1-12 show the mass%.

[Evaluation method]
[Shading unevenness]
A part of the inkjet printer PX-G930 (manufactured by Seiko Epson Corporation) is modified so that a heater that can change the temperature is attached to the paper guide so that the recording medium can be adjusted by heating when recording an image. did. The ink set obtained in “Preparation of ink set” was applied to a dedicated cartridge of the printer.

  Using a heater attached to the paper guide section of the printer, the surface temperature of the recording medium was heated to 45 ° C. Next, while maintaining this temperature, an operation of ejecting ink droplets from the nozzles of the ink jet printer to deposit the droplets on the recording medium was performed. By performing this operation a plurality of times, a solid pattern image of each color ink constituting the ink set was recorded on the recording medium. Next, the recording medium on which the solid pattern image was recorded was allowed to stand in a thermostat kept at 60 ° C. for 1 minute to dry the solid pattern image. In this way, a sample for evaluation of image bleeding was obtained.

Note that the image recording conditions were a resolution of 720 dpi × width 720 dpi, a printing ink amount of 1.0 mg / cm ² , and a duty of 10% to 100% (changed in 5% increments).
The recording medium used is a vinyl chloride film (trade name “LLSP EX113”, manufactured by Sakurai) and a polyester film (trade name “cold laminate film PG-50L”, manufactured by Lamy Corporation).
About the obtained sample for evaluation, the presence or absence of density unevenness was observed visually for every color, and the following evaluation criteria determined. The evaluation results are shown in Tables 13-24.
A: No shading unevenness at a duty of 75%.
Δ: Duty 65%, no shading unevenness.
X: Light and dark unevenness at Duty 65%.

[Abrasion resistance]
Ink jet recording using the ink sets of each Example and each Comparative Example was performed by the same method as the above-described uneven density.
The recording medium was heated at 45 ° C. during ink jet recording. After inkjet recording, the obtained recorded matter was dried at 60 ° C. for 1 minute. Thereafter, the recorded matter was allowed to stand at room temperature for 16 hours. Then, using a Gakushin type friction fastness tester (AB-301 (manufactured by Tester Sangyo Co., Ltd.), load 500 g), the recorded material was rubbed 100 times with a cotton cloth, and the degree to which the recorded surface was rubbed was observed. . The recording medium used for the evaluation is a polyester film (trade name “Cold Laminate Film PG-50L”, manufactured by Lamy Corporation).
The evaluation criteria are as follows. The evaluation results are shown in Tables 13-24.
○: There is no scratch that exposes the base, and the cotton fabric is less colored.
Δ: There is no scratch that exposes the base, but the cotton fabric is highly colored.
X: There are scratches on which the base is exposed.

[Solution stability]
The ink of each Example and each Comparative Example was put in a sealed container and heated at 60 ° C. for 8 hours. The evaluation results are shown in Tables 13-24.
○: No oil film-like suspended matter on the ink surface.
X: Oil film-like suspended matter is present on the ink surface.

[Continuous printing stability]
Each color ink constituting the ink set of each example and each comparative example was filled in an ink cartridge, and mounted on the same printer as that used in the above-described evaluation of density unevenness. Inkjet recording was performed continuously for 10 minutes without heating during recording, and it was confirmed that all nozzles discharged normally. Thereafter, heating during ink jet recording was performed (heating temperature 45 ° C.), and ink jet recording was continuously performed. The obtained recorded matter was observed for missing dots and flying bends.
The evaluation criteria are as follows. The evaluation results are shown in Tables 13-24. The recording medium used for the evaluation is plain paper “P” (manufactured by Xerox).
○: Neither missing dots nor flying curves were observed after 1 hour.
Δ: Flight curve was slightly observed after 1 hour (no missing dots).
X: Omission of dots and bending of flight were observed after 1 hour.

Claims (8)

An ink set for inkjet recording, comprising one or more colors of dark ink and one or more colors of light ink,
The dark ink and the light ink independently of each other contain a pigment, a water-soluble resin, a resin emulsion, a paraffin wax emulsion, a polyethylene wax emulsion, an acetylene glycol surfactant, and a silicon surfactant.
The mass ratio (dark ink: light ink) of the total content of pigment and resin emulsion in the dark ink and the total content of pigment and resin emulsion in the light ink is 2: 1 to 1: 2 and
An ink set for ink-jet recording, which is used for ink-jet recording on a non-ink-absorbing or low-absorbing recording medium.   The pigment content in the dark ink is 1.5-6% by mass with respect to the total mass of the ink, and the pigment content in the light ink is 1 with respect to the pigment content in the dark ink. The ink set for inkjet recording according to claim 1, which is / 2 to 1/8.   The mass ratio of the resin emulsion content in the dark ink and the resin emulsion content in the light ink (dark ink: light ink) is 1: 3 to 1: 6. The ink set for inkjet recording as described.   The total content of the pigment and the resin emulsion in each ink included in the ink set for inkjet recording is 3 to 7% by mass with respect to the total mass of the ink, independently of each other. The ink set for inkjet recording of any one of Claims.   The content of the paraffin wax emulsion in each ink included in the ink set for inkjet recording is 0.3 to 1.5 mass% with respect to the total mass of the ink, independently of each other. The ink set for inkjet recording of any one of these.   The total content of the paraffin wax emulsion and the polyethylene wax emulsion in each ink contained in the ink set for inkjet recording is 0.4 to 1.6% by mass independently of the total mass of the ink. The ink set for inkjet recording according to any one of claims 1 to 5.   An ink jet recording method for recording on a non-ink-absorbing or low-absorbing recording medium using the ink set for ink jet recording according to claim 1.   A recorded matter recorded by the ink jet recording method according to claim 7.