JP2017014372A - Treatment liquid composition, inkjet ink composition, and ink set - Google Patents

Abstract

[PROBLEMS] To provide a pre-treatment liquid, an ink-jet ink composition, a post-treatment liquid, and an ink set using them, which give a recorded matter excellent in bleed resistance, color developability and adhesiveness and are excellent in ejection properties. The purpose is to provide.
A cation-modified cellulose;
The cation-modified cellulose includes cellulose fibers having a diameter of 20 nm or less and a length / diameter of 20 to 1000.
Treatment liquid composition.
[Selection figure] None

Description

  The present invention relates to a treatment liquid composition, an inkjet ink composition, and an ink set.

  The ink jet recording method is capable of recording high-definition images with a relatively simple device, and has been rapidly developed in various fields. For example, Patent Document 1 discloses color bleeding that occurs between inks when a plurality of inks are recorded on a non-absorbing recording medium or a low-absorbing recording medium using an inkjet recording method. In order to prevent this, there is disclosed an ink jet recording method characterized by using a reaction liquid ink containing a flocculant composed of a polyvalent metal salt and an organic acid and an ink containing a color material as a set. Various studies have been made on ink physical properties and the like. For example, Patent Document 2 discloses a cellulose fiber having a number average fiber diameter of 2 to 150 nm for the purpose of providing a water-based coating composition excellent in water resistance of a coating film by a rheology control agent that exhibits an effect in a small amount. The cellulose has a cellulose I-type crystal structure, and the hydroxyl group at the C6 position of the glucose unit in the cellulose molecule is selectively oxidized and modified to an aldehyde group and a carboxyl group. A water-based coating composition characterized by containing cellulose fibers having a concentration of 0.6 to 2.2 mmol / g is disclosed.

JP2015-71738A JP 2011-57749 A

  However, the reaction liquid containing the flocculant composed of the polyvalent metal salt and the organic acid described in Patent Document 1 absorbs water based on the deliquescent property of the flocculant, and thus has good adhesion and tagging resistance in the long-term storage of recorded matter. There is a problem of decline. In recording on the absorbent recording medium, the pretreatment ink penetrates deep into the recording medium, so that the concentration of the polyvalent metal salt and organic acid on the surface of the recording medium is relatively reduced. Therefore, a good bleed suppressing effect is not exhibited. On the other hand, when the water-based coating composition described in Patent Document 2 is used in an ink jet system, there is a problem in that the discharge performance is extremely lowered. In addition, the use of cellulose in the pretreatment liquid and the posttreatment liquid and the effect thereof are not disclosed.

  The present invention has been made in order to solve at least a part of the above-described problems, and provides a processed liquid composition that gives a recorded matter excellent in bleed resistance, color development, and adhesion, and is excellent in ejection properties. It is an object to provide a product, an ink composition for inkjet, and an ink set using them.

  The present inventors diligently studied to solve the above problems. As a result, the inventors have found that the above-mentioned problems can be solved by using predetermined cellulose, and have completed the present invention.

That is, the present invention is as follows.
[1]
Including cation-modified cellulose,
The cation-modified cellulose includes cellulose fibers having a diameter of 20 nm or less and a length / diameter of 20 to 1000.
Treatment liquid composition.
[2]
Including cellulose fibers having a length / diameter of the cation-modified cellulose of 20 to 250,
The processing liquid composition as described in the preceding item [1].
[3]
A colorant and an anion-modified cellulose,
The anion-modified cellulose includes cellulose fibers having a diameter of 20 nm or less and a length / diameter of 20 to 250.
Ink-jet ink composition.
[4]
The treatment liquid composition according to [1] or [2], which is a pretreatment liquid,
An ink-jet ink composition as described in the preceding item [3],
Ink set.
[5]
The inkjet ink composition according to the preceding item [3];
The treatment liquid composition according to the above item [1] or [2], which is a post-treatment liquid,
Ink set.
[6]
The treatment liquid composition according to [1] or [2], which is a pretreatment liquid,
The inkjet ink composition according to the preceding item [3];
The treatment liquid composition according to the above item [1] or [2], which is a post-treatment liquid,
Ink set.

  Hereinafter, the embodiment of the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. However, the present invention is not limited to this, and various modifications are possible without departing from the scope of the present invention. It is. The “treatment liquid composition” refers to a composition used as a pretreatment liquid or a posttreatment liquid, and is applied to a recording medium by an unspecified number of coating apparatuses such as a spray or a slit coater, or an inkjet. It is a composition that can be applied. Therefore, it can include those for inkjet and coating. In addition, “for inkjet” is a composition that is ejected by inkjet and adheres to a recording medium.

  Hereinafter, the treatment liquid composition used as the pretreatment liquid is referred to as “pretreatment liquid”, and the treatment liquid composition used as the posttreatment liquid is referred to as “posttreatment liquid”. The pretreatment liquid and the posttreatment liquid include those for inkjet.

[Pretreatment liquid]
The pretreatment liquid of this embodiment contains cation-modified cellulose, and the cation-modified cellulose contains cellulose fibers having a diameter of 20 nm or less and a length / diameter of 20 to 1000.

  Although a metal salt can be used as a cationic component for aggregating the ink component, adhesion, rubbing resistance, and water resistance may decrease due to deliquescence. In addition, when an absorbent recording medium is used as the recording medium, the pretreatment liquid penetrates to the deep part of the recording medium. The effect of aggregating and fixing objects is reduced. Therefore, the adhesion and image quality are difficult to stabilize. In contrast, in the pretreatment liquid of the present embodiment, the surface layer of the recording medium is obtained by using cation-modified cellulose that has less deliquescence and has an overwhelmingly large physical size compared to atomic and molecular cation components. Since the cation concentration increases, it is possible to efficiently obtain a recorded matter excellent in bleed resistance, color development and adhesion. This will be described in detail below.

[Cation-modified cellulose]
The cation-modified cellulose includes cellulose fibers having a diameter of 20 nm or less and a length / diameter of 20 to 1000.

In the present specification, “cation modified cellulose” refers to cellulose modified by introducing various cationic groups into the hydroxyl group of cellulose. The group that reacts with the hydroxyl group of cellulose is not particularly limited as long as it is a reactive group that reacts with the hydroxyl group to form a covalent bond. For example, an active halogen group such as an epoxy group or a halohydrin group that can form it. An active vinyl group, a methylol group, etc. are mentioned. Among these, an epoxy group or a halohydrin group capable of forming it is preferable from the viewpoint of reactivity. The quaternary ammonium group has a structure of —N ⁺ (R) ₃ (wherein R is an alkyl group, aryl group or heterocyclic group which may have a substituent). Examples of the cationizing agent include glycidyltrialkylammonium halides such as glycidyltrimethylammonium chloride, 3-chloro-2-hydroxypropyltrimethylammonium chloride, and halohydrin type thereof. Among these, the reactive group is preferably a quaternary ammonium group.

(Cellulose fiber)
Cellulose fibers contained as cation-modified cellulose are those that have been cation-modified. The diameter of the cellulose fiber is 20 nm or less, preferably 4 to 16 nm. The cellulose fiber is a single cellulose fiber having a size of about 4 nm as a basic skeleton material of a plant, and therefore 4 nm is necessarily present as a minimum unit. Moreover, since the relative surface area increases when the diameter of a cellulose fiber is 20 nm or less, it improves from a cation function. The diameter of a cellulose fiber can be measured by the method as described in an Example.

  In the case of a coating method other than inkjet, the length / diameter of the cellulose fiber is 20 to 1000, preferably 20 to 500. When the length / diameter of the cellulose fiber is 20 or more, the fixing rate to the upper layer of the recording medium is further improved. Moreover, when making an ink contain a cellulose fiber as an inkjet ink, the length / diameter of a cellulose fiber is 20-250, More preferably, it is 25-160, Most preferably, it is 20-60. When the length / diameter of the cellulose fiber is 250 or less, the discharge property is further improved. In particular, when the length / diameter of the cellulose fiber is 20 to 160, it can be suitably used as a pretreatment liquid for inkjet. The length / diameter of the cellulose fiber can be measured by the method described in Examples.

[Other ingredients]
The pretreatment liquid of this embodiment may further contain a solvent, a surfactant, a cationic resin, and the like.

(solvent)
Although it does not specifically limit as a solvent, For example, water and an organic solvent are mentioned.

  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. In addition, when water sterilized by ultraviolet irradiation or addition of hydrogen peroxide is used, generation of mold and bacteria can be prevented when the pretreatment liquid is stored for a long period of time. This tends to improve the storage stability.

  The content of water is preferably 75 to 95 parts by mass, and more preferably 80 to 95 parts by mass with respect to 100 parts by mass of the pretreatment liquid.

  Examples of the organic solvent include, but are not limited to, glycerin, 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 monobutyl 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, sulfur Examples include holan and 1,1,3,3-tetramethylurea. An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type.

  The content of the organic solvent is preferably 1 to 15 parts by mass and more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the pretreatment liquid. When the content of the organic solvent is within the above range, the balance between clogging and drying on the recording medium tends to be further improved.

(Surfactant)
The surfactant is not particularly limited, and examples thereof include acetylene glycol surfactants, fluorine surfactants, and polysiloxane surfactants.

  The acetylene glycol-based surfactant is not particularly limited, and examples thereof include 2,4,7,9-tetramethyl-5-decyne-4,7-diol and 2,4,7,9-tetramethyl-5- Examples include alkylene oxide adducts of decyne-4,7-diol, and alkylene oxide adducts of 2,4-dimethyl-5-decyn-4-ol and 2,4-dimethyl-5-decyn-4-ol. Although it does not specifically limit as a commercial item of acetylene glycol-type surfactant, For example, E series (A product made by Air Products Japan (Inc)) (Surfinol 465), such as Olfine 104 series and Olfine E1010, Surfynol 61 (trade name, manufactured by Nissin Chemical Industry CO., Ltd.) and the like. One acetylene glycol surfactant may be used alone, or two or more acetylene glycol surfactants may be used in combination.

  The fluorosurfactant is not particularly limited. For example, perfluoroalkyl sulfonate, perfluoroalkyl carboxylate, perfluoroalkyl phosphate, perfluoroalkyl ethylene oxide adduct, perfluoroalkyl betaine, perfluoroalkyl betaine, A fluoroalkylamine oxide compound is mentioned. Although it does not specifically limit as a commercial item of a fluorochemical surfactant, For example, S-144, S-145 (Asahi Glass Co., Ltd. product); FC-170C, FC-430, Fluorard-FC4430 (Sumitomo 3M Co., Ltd. product) FSO, FSO-100, FSN, FSN-100, FS-300 (manufactured by Dupont); FT-250, 251 (manufactured by Neos Co., Ltd.) and the like. A fluorine-type surfactant may be used individually by 1 type, and may use 2 or more types together.

  Examples of silicone surfactants include polysiloxane compounds and polyether-modified organosiloxanes. Although it does not specifically limit as a commercial item of a silicone type surfactant, Specifically, BYK-306, BYK-307, BYK-333, BYK-341, BYK-345, BYK-346, BYK-347, BYK -348, BYK-349 (above trade name, manufactured by Big Chemie Japan Co., Ltd.), 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 (all trade names, manufactured by Shin-Etsu Chemical Co., Ltd.), and the like. A silicone type surfactant may be used individually by 1 type and may use 2 or more types together.

  The content of the surfactant is preferably 0.05 to 3 parts by mass, more preferably 0.1 to 2 parts by mass with respect to 100 parts by mass of the pretreatment liquid. When the content of the surfactant is within the above range, the wettability of the pretreatment agent to the recording medium tends to be further improved.

(Other ingredients)
The pretreatment liquid has a storage aid, a viscosity adjuster, and a pH adjuster to maintain its storage stability and ejection stability from the head, to improve clogging, or to prevent deterioration of the ink composition. Various additives such as an agent, an antioxidant, an antiseptic, an antifungal agent, a corrosion inhibitor, and a chelating agent for capturing metal ions that affect the dispersion can be appropriately added.

[Inkjet ink composition]
The ink-jet ink composition of the present embodiment comprises a colorant and an anion-modified cellulose, the anion-modified cellulose having a diameter of 20 nm or less and a length / diameter of 20 to 250 cellulose fibers. Including.

[Color material]
Examples of the color material include pigments and dyes.

(Pigment)
Although it does not specifically limit as a black pigment, For example, it is No. 2300, no. 900, MCF88, No. 33, no. 40, no. 45, no. 52, MA7, MA8, MA100, no. 2200B, etc. (Mitsubishi Chemical Corporation), Raven 5750, Raven 5250, Raven 5000, Raven 3500, Raven 1255, Raven 700, etc. (above, Columbia Carbon, Carbon 1 Rubbi 400, Carbon Co. Rega1 330R, Rega1 660R, Mogul L, Monarch 700, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, etc. (Cabot Corp. CA Kol. , Color Black FW2, olor Black FW2V, Color Black FW18, Color Black FW200, Color B1ack S150, Color Black S160, Color Black S170, Printex 35, Printex U, Printex V, Printex 140U, Special Black 6, Special Black 5, Special Black 4A, Special Black 4 (manufactured by Degussa).

  Although it does not specifically limit as a white pigment, For example, C.I. I. Pigment white 6, 18, 21, white inorganic pigments of titanium oxide, zinc oxide, zinc sulfide, antimony oxide, and zirconium oxide. In addition to the white inorganic pigment, white organic pigments such as white hollow resin particles and polymer particles can also be used.

  Although it does not specifically limit as a yellow pigment, For example, 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, 167, 172, 180.

  Although it does not specifically limit as a magenta pigment, For example, 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, or C.I. I. Pigment violet 19, 23, 32, 33, 36, 38, 43, 50.

  Although it does not specifically limit as a cyan pigment, For example, C.I. I. Pigment Blue 1, 2, 3, 15, 15: 1, 15: 2, 15: 3, 15:34, 15: 4, 16, 18, 22, 25, 60, 65, 66, C.I. I. Bat Blue 4, 60.

  In addition, the pigment used in color inks other than magenta, cyan, and yellow is not particularly limited. I. Pigment green 7,10, C.I. I. Pigment brown 3, 5, 25, 26, C.I. I. Pigment orange 1, 2, 5, 7, 13, 14, 15, 16, 24, 34, 36, 38, 40, 43, 63.

  Although it does not specifically limit as a pearl pigment, For example, the pigment which has pearl luster and interference gloss, such as titanium dioxide covering mica, fish scale foil, and bismuth acid chloride, is mentioned.

  Although it does not specifically limit as a metallic pigment, For example, the particle | grains which consist of single bodies or alloys, such as aluminum, silver, gold | metal | money, platinum, nickel, chromium, tin, zinc, indium, titanium, copper, are mentioned.

  The said pigment may be used individually by 1 type, and may use 2 or more types together. The content of the pigment is preferably 2 to 15 parts by mass, more preferably 3 to 10 parts by mass with respect to 100 parts by mass of the ink composition.

(dye)
Although it does not specifically limit as dye, For example, C.I. I. Acid Yellow, C.I. I. Acid Red, C.I. I. Acid Blue, C.I. I. Acid Orange, C.I. I. Acid Violet, C.I. I. Acid dyes such as Acid Black; C.I. I. Basic yellow, C.I. I. Basic Red, C.I. I. Basic blue, C.I. I. Basic orange, C.I. I. Basic violet, C.I. I. C. basic dyes such as basic black; I. Direct yellow, C.I. I. Direct Red, C.I. I. Direct Blue, C.I. I. Direct orange, C.I. I. Direct violet, C.I. I. Direct dyes such as Directed Black; C.I. I. Reactive Yellow, C.I. I. Reactive Red, C.I. I. Reactive Blue, C.I. I. Reactive Orange, C.I. I. Reactive Violet, C.I. I. Reactive dyes such as reactive black; C.I. I. Disperse Yellow, C.I. I. Disper thread, C.I. I. Disperse Blue, C.I. I. Disperse orange, C.I. I. Disperse Violet, C.I. I. Disperse dyes such as disperse black are listed.

  The said dye may be used individually by 1 type, and may use 2 or more types together. The content of the dye is preferably 0.1 to 20 parts by mass, more preferably 1.0 to 15 parts by mass, and further preferably 3.0 to 10 parts by mass with respect to 100 parts by mass of the ink composition. Part.

[Anion-modified cellulose]
Anion-modified cellulose includes cellulose fibers having a diameter of 20 nm or less and a length / diameter of 20 to 250.

In the present specification, “anion-modified cellulose” refers to cellulose modified by introducing various anionic groups into the hydroxyl group of cellulose. Although it does not specifically limit as an anionic group, For example, -COOH, COR (COONa ^<+> ) ₃ is mentioned. Among these, -COOH is preferable.

(Cellulose fiber)
Cellulose fibers contained as anion-modified cellulose are anion-modified. The diameter of the cellulose fiber is 20 nm or less, preferably 4 to 16 nm. The cellulose fiber is a single cellulose fiber having a size of about 4 nm as a basic skeleton material of a plant, and therefore 4 nm is necessarily present as a minimum unit. Moreover, since a relative surface area increases when the diameter of a cellulose fiber is 20 nm or less, it improves from an anion function. The diameter of a cellulose fiber can be measured by the method as described in an Example.

  The length / diameter of the cellulose fiber is 20 to 250, preferably 25 to 160, and particularly preferably 25 to 60. When the length / diameter of the cellulose fiber is 20 or more, the fixing rate to the upper layer of the recording medium is further improved. Moreover, dischargeability improves more because the length / diameter of a cellulose fiber is 160 or less. The length / diameter of the cellulose fiber can be measured by the method described in Examples.

[Other ingredients]
The ink-jet ink composition of this embodiment may further contain a solvent, a surfactant, a resin emulsion, and the like. Examples of the solvent and surfactant include the same as those mentioned in the pretreatment liquid. The resin emulsion can be appropriately used from a nonionic or anionic material.

[Post-treatment liquid]
The post-treatment liquid of this embodiment includes cellulose fibers having a diameter of 20 nm or less and a length / diameter of 20 to 1000. Cellulose fibers used in the post-treatment liquid may be cation-modified, anion-modified, or unmodified.

(Cellulose fiber)
The diameter of the cellulose fiber is 20 nm or less, preferably 4 to 16 nm. The cellulose fiber is a single cellulose fiber having a size of about 4 nm as a basic skeleton material of a plant, and therefore 4 nm is necessarily present as a minimum unit. Moreover, since the relative surface area increases when the diameter of a cellulose fiber is 20 nm or less, it improves from a cation function. The diameter of a cellulose fiber can be measured by the method as described in an Example.

  In the case of a coating method other than inkjet, the length / diameter of the cellulose fiber is 20 to 1000, preferably 20 to 500. When the length / diameter of the cellulose fiber is 20 or more, the fixing rate to the upper layer of the recording medium is further improved. In addition, when the cellulose fiber is contained in the ink as the post-processing inkjet ink, the length / diameter of the cellulose fiber is 20 to 250, more preferably 25 to 160, and particularly preferably 20 to 60. When the length / diameter of the cellulose fiber is 250 or less, the dischargeability is further improved and it can be suitably used as a post-treatment liquid for inkjet. The length / diameter of the cellulose fiber can be measured by the method described in Examples.

[Other ingredients]
The post-treatment liquid of this embodiment may further include a solvent, a surfactant, a resin emulsion, and the like. Examples of the solvent, the surfactant, and the resin emulsion include the same ones as mentioned in the pretreatment liquid.

[Ink set]
The ink set of the present embodiment includes a first aspect including the pretreatment liquid and the inkjet ink composition, a second aspect including the inkjet ink composition, and an upper post-treatment liquid. There is a mode and a third mode comprising the pretreatment liquid, the ink-jet ink composition, and the post-treatment liquid. Thus, when two or more of the pretreatment liquid, the ink composition, and the posttreatment liquid contain the cellulose material, the water resistance and the friction resistance of the obtained recorded matter tend to be further improved.

(First aspect)
In the first aspect, the pretreatment liquid is attached to the recording medium to form the first recording area, and the ink-jet ink composition is attached to the first recording area to form the second recording area. As a result, a recorded matter can be obtained. The image formed in the second recording area of the recorded matter thus obtained is excellent in bleed resistance, color development, adhesion, water resistance, and friction resistance.

(Second aspect)
In the second aspect, the ink-jet ink composition is attached to the recording medium to form the second recording area, and the post-treatment liquid is attached to the second recording area to form the third recording area. As a result, a recorded matter can be obtained. The image formed in the third recording region of the recorded matter thus obtained is excellent in water resistance and friction resistance.

(Third aspect)
In the third aspect, the pretreatment liquid is attached to the recording medium to form the first recording area, and the inkjet ink composition is attached to the first recording area to form the second recording area. A recorded matter can be obtained by forming the third recording area by attaching the post-treatment liquid to the second recording area. The image formed in the third recording area of the recorded matter thus obtained is excellent in bleed resistance, color development, adhesion, water resistance, and friction resistance.

(Recording medium)
Examples of the recording medium include an absorbing or non-absorbing recording medium. Among these, an absorptive recording medium is preferable.

  The absorbent recording medium is not particularly limited. For example, plain paper such as fabric (natural fibers or synthetic fibers such as silk, cotton, wool, nylon, polyester, rayon, etc.), electrophotographic paper having high ink permeability, and the like. , Inkjet paper (ink-only paper with an ink-absorbing layer composed of silica particles or alumina particles, or an ink-absorbing layer composed of a hydrophilic polymer such as polyvinyl alcohol (PVA) or polyvinylpyrrolidone (PVP)), Art paper, coated paper, cast paper, and the like used for general offset printing with relatively low ink permeability.

  Although it does not specifically limit as a non-absorbable recording medium, For example, films and plates of plastics, such as polyvinyl chloride, polyethylene, polypropylene, polyethylene terephthalate (PET), polycarbonate, polystyrene, polyurethane; iron, silver, copper, Metal plates such as aluminum; or metal plates produced by vapor deposition of these various metals, plastic films, stainless steel and brass alloy plates; polyvinyl chloride, polyethylene, polypropylene, polyethylene on paper substrates Examples thereof include a recording medium in which a plastic film such as terephthalate (PET), polycarbonate, polystyrene, or polyurethane is bonded (coated).

Here, the “absorbent recording medium” refers to a recording medium having a water absorption amount of 10 mL / m ² or more from the start of contact to 30 msec in the Bristow method. The details of this Bristow method are as follows: Standard No. of “JAPAN TAPPI Paper Pulp Test Method 2000”. 51 "Paper and paperboard-Liquid absorbency test method-Bristow method".

  Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. The present invention is not limited in any way by the following examples.

[material]
The main materials used in the following examples and comparative examples are as follows.

[Color material]
Titanium dioxide: Metal oxide Nanotek® Slurry CHI Kasei Cyan Pigment: C.I. I. Pigment Blue 15: 3
[Surfactant]
BYK348 (silicone surfactant, Big Chemie Japan)
[Resin emulsion]
Jonkrill 62J (acrylic styrene resin BASF)
[Cationic resin emulsion]
Arrow Base CD-1200 (Made by Unitika)
〔Organic solvent〕
Propylene glycol triethylene glycol monobutyl ether (TEGmBE)
[Humectant]
Propylene glycol Glycerin (cation-modified cellulose)
Cationic modified cellulose A (see “Production Example 1” below)
Cationic modified cellulose B (see “Production Example 2” below)
Cationic modified cellulose C (see “Production Example 3” below)
Cationic modified cellulose D (see “Production Example 4” below)
[Anion-modified cellulose]
Anion-modified cellulose E (see “Production Example 5” below)
Anion-modified cellulose F (see “Production Example 6” below)
Anion-modified cellulose G (see “Production Example 7” below)
Anion-modified cellulose H (see “Production Example 8” below)

[Production Example 1]
200 parts by mass of pulverized cellulose (manufactured by JRS, ARBOCEL UFC100), 570 parts by mass of 99% isopropyl alcohol, 12 parts by mass of sodium hydroxide, and 30 parts by mass of water were mixed at 30 ° C. for 90 minutes. Thereafter, 56 parts by mass of a 50% aqueous solution of 3-chloro-2-hydroxypropyltrimethylammonium chloride was added. And it heated up at 70 degreeC and reacted for 90 minutes. After cooling, the reaction product was taken out and washed twice with 80% methanol to obtain neutralized, washed, dried, cation-modified cellulose. An aqueous solution containing 0.1 parts by mass of the obtained cation-modified cellulose was prepared, and pulverization treatment was carried out for 10 hours using a bead mill (DMS65 manufactured by Ashizawa Finetech Co., Ltd.) and 0.03 mm zirconia beads. The obtained aqueous cellulose solution was dried, and the diameter and length / diameter of the cation-modified cellulose A are shown in Table 1.

[Production Example 2]
Cationic modified cellulose B was obtained in the same manner as in Production Example 1 except that the processing time of the bead mill was 2 hours. The diameter and length / diameter of the cation-modified cellulose B are shown in Table 1.

[Production Example 3]
A cation-modified cellulose C was obtained in the same manner as in Production Example 1 except that the bead mill was not performed. The diameter and length / diameter of the cation-modified cellulose C are shown in Table 1.

[Production Example 4]
Cationic modified cellulose B was prepared in the same manner as in Production Example 1 except that pulverized cellulose (ARBOCEL BE 600-10TG, manufactured by German JRS) was used instead of pulverized cellulose (manufactured by German JRS, ARBOCEL UFC100). Obtained. The diameter and length / diameter of the cation-modified cellulose B are shown in Table 1.

[Production Example 5]
60 parts by mass of pulverized cellulose (ARBOCEL UFC100, manufactured by JRS, Germany), 150 parts by mass of sodium hydroxide, and 2850 parts by mass of water were mixed at 30 ° C. for 1 hour. Thereafter, 179 parts by mass of monochloroacetic acid was added and further stirred for 30 minutes. And after heating up to 70 degreeC, 1 hour-izing reaction was implemented. After cooling, the reaction product was taken out, neutralized, washed and dried to obtain anion-modified cellulose E. An aqueous solution containing 0.1 part by mass of the obtained anion-modified cellulose was prepared, and pulverization treatment was carried out for 10 hours using a bead mill (DMS65 manufactured by Ashizawa Finetech Co., Ltd.) and 0.03 mm zirconia beads. The obtained aqueous cellulose solution was dried, and the diameter and length / diameter of anion-modified cellulose E are shown in Table 1.

[Production Example 6]
Anion-modified cellulose F was obtained by the same method as in Production Example 5 except that the processing time of the bead mill was 2 hours. Table 1 shows the diameter and length / diameter of the anion-modified cellulose F.

[Production Example 7]
Anion-modified cellulose G was obtained in the same manner as in Production Example 5 except that the processing time of the bead mill was 60 minutes. Table 1 shows the diameter and length / diameter of the anion-modified cellulose G.

[Production Example 8]
Anion-modified cellulose H was obtained in the same manner as in Production Example 5, except that the processing time of the bead mill was 30 minutes. Table 1 shows the diameter and length / diameter of anion-modified cellulose H.

[Diameter confirmation method of cation-modified cellulose and anion-modified cellulose]
A TEM image obtained by casting the cation-modified cellulose and the anion-modified cellulose obtained as described above on a carbon membrane-coated grid that has been subjected to a hydrophilic treatment and then negatively staining with 2% uranyl acetate is shown. The average fiber diameter was calculated from the obtained TEM image and used as the diameter.

[Length confirmation method of cation-modified cellulose and anion-modified cellulose]
The cation-modified cellulose and the anion-modified cellulose obtained as described above were diluted with Olfin E1010 1% (manufactured by Air Products) and the remaining pure water so that the solid content concentration was 10 ppm (0.0001%). Each sample solution was obtained. The obtained sample solution was applied onto a silicon substrate using a bar coater # 2, and dried. And the sample on a silicon substrate was observed using the scanning electron microscope S-4800 (made by Hitachi High-Tech Fielding), and the SEM image was obtained. From the obtained SEM image, the average value of 10 cation-modified celluloses or anion-modified cellulose fibers was calculated and used as the length.

[Preparation of pretreatment liquid (inkjet pretreatment liquid) and posttreatment liquid (inkjet posttreatment liquid)]
Each material was mixed with the composition shown in Table 2 below and stirred sufficiently to obtain each pretreatment liquid and posttreatment liquid. In Table 2 below, the numerical unit is mass%, and the total is 100.0 mass%.

[Preparation of inkjet ink composition]
Each material was mixed with the composition shown in Table 3 below and stirred sufficiently to obtain each ink-jet ink composition. In Table 3 below, the numerical unit is mass%, and the total is 100.0 mass%.

[Inkjet ejection properties]
Evaluation was performed using an inkjet printer (PX-G930 manufactured by Seiko Epson Corporation). Each pre-treatment liquid, post-treatment liquid and ink-jet ink composition prepared above were filled in the head, and it was confirmed that they could be discharged from all nozzles. Thereafter, the sample was left at 40 ° C. for one week in a position outside the home position, that is, in a state where the head was displaced from the position of the cap provided in the printer and the head was not capped. Thereafter, ejection was performed, and inkjet ejection properties were evaluated according to the following evaluation criteria. The results are shown in Tables 1-2.
(Evaluation criteria)
○: Stable ejection was possible.
Δ: Nozzle missing.
X: It was not able to discharge at all with all nozzles.

[Coating uniformity]
Each inkjet treatment liquid and inkjet ink composition prepared above were applied onto a Toray PET film “Lumirror S10” using a bar coater # 4 (Daiichi Rika Co., Ltd.) and dried. The obtained sample was visually observed and evaluated according to the following evaluation criteria. The results are shown in Tables 1-2.
(Evaluation criteria)
○: A uniform coating film was obtained.
Δ: Some unevenness was confirmed in the obtained coating film.
X: The thixotropy was high and a uniform coating film could not be formed.

[Method for producing recorded matter]
[Pretreatment process]
As a fabric, a 100% cotton T-shirt (HANES heavy weight, black fabric) was used and cut into A4 size. Each treatment agent prepared above is uniformly applied using a spray so as to be 18 to 20 g per A4 size, or an ink jet printer (PX-G930 manufactured by Seiko Epson Corporation) is used. The recording resolution was 1440 dpi × 1440 dpi, and one layer of solid pattern image was applied and adhered at 40 mg / inch 2. The combinations of the pretreatment agent used in the pretreatment step and the coating method in each Example and each Comparative Example are as shown in Table 4 below. After application, heat treatment was performed at 160 ° C. for 1 minute using a heat press.
Note that the “solid pattern image” in the present specification means an image in which dots are recorded for all of the pixels that are the minimum recording unit area defined by the recording resolution.

[Ink adhesion process]
Each ink prepared above was attached to the fabric using an inkjet printer (PX-G930 manufactured by Seiko Epson Corporation) on the fabric that had undergone the pretreatment process. At this time, combinations of the pretreatment agent used in the pretreatment step and the deposited ink composition in each Example and each Comparative Example are as shown in Table 4 below. As recording conditions, the recording resolution was 1440 dpi × 1440 dpi, four solid pattern images were overcoated, and 180 mg / inch ² of white ink was adhered. Inkjet printing was performed in this manner. Note that the “solid pattern image” in the present specification means an image in which dots are recorded for all of the pixels that are the minimum recording unit area defined by the recording resolution.

[Post-treatment process]
The treatment liquid prepared above was attached to the fabric using an inkjet printer (PX-G930 manufactured by Seiko Epson Corporation) on the fabric that had undergone the adhesion process.

[Heat treatment process]
The fabric to which each ink adhered was heat-treated at 160 ° C. for 1 minute using a heat press machine, and the ink was fixed to the fabric. In this way, a recorded matter in which a white image was formed on the fabric (white ink was printed) was produced.

[Whiteness]
The L ^* value in the CIE / L ^* a ^* b ^* color system was measured for the fabric after recording using a commercially available colorimeter (Gretag Macbeth Spectrolino manufactured by X-Rite). The evaluation criteria are as follows. The evaluation results are shown in Table 4.
(Evaluation criteria)
A: L ^* value was 94 or more.
A: L ^* value was 92 or more and less than 94.
Δ: L ^* value was 90 or more and less than 92.
X: L ^* value was less than 90.

[Initial abrasion resistance]
Using a Gakushin type friction fastness tester (manufactured by TESTER SANGYO CO., LTD.), Each printed matter obtained above was subjected to a friction fastness test. In the test, a dry black plain woven cotton cloth was placed on the image surface, rubbed 100 times with a load of 500 g, and the rubbing condition of the plain woven cotton cloth after rubbing and the surface state of the rubbed white printed part (image). It was observed visually. The evaluation criteria are as follows. The evaluation results are shown in Table 4.
(Evaluation criteria)
A: The plain woven cotton cloth was hardly colored. The rubbing trace of the white printed part was linear and was 1 or less.
○: The plain woven cotton cloth was slightly colored. The rubbing traces of the white printed part were linear and were 2 to 4 places.
Δ: Plain woven cotton cloth was colored. The rubbing traces of the white printed part were linear and were 5 to 9 places.
X: The plain woven cotton cloth was colored. The rubbing trace of the white printed part is linear or planar, and when the rubbing trace is linear, there are 10 or more (the planar scuffing trace is the main criterion if there is at least one spot. ).

[Abrasion resistance after standing at room temperature for 2 months]
After recording, the scratch resistance was evaluated in the same manner as the initial scratch resistance evaluation, except that a recorded material left at room temperature for 2 months was used. The evaluation results are shown in Table 4.

Claims (6)

Including cation-modified cellulose,
The cation-modified cellulose includes cellulose fibers having a diameter of 20 nm or less and a length / diameter of 20 to 1000.
Treatment liquid composition. Including cellulose fibers having a length / diameter of the cation-modified cellulose of 20 to 250,
The treatment liquid composition according to claim 1. A colorant and an anion-modified cellulose,
The anion-modified cellulose includes cellulose fibers having a diameter of 20 nm or less and a length / diameter of 20 to 250.
Ink-jet ink composition. The treatment liquid composition according to claim 1 or 2, which is a pretreatment liquid,
An ink-jet ink composition according to claim 3.
Ink set. An ink-jet ink composition according to claim 3,
The treatment liquid composition according to claim 1, which is a post-treatment liquid.
Ink set. The treatment liquid composition according to claim 1 or 2, which is a pretreatment liquid,
An ink-jet ink composition according to claim 3,
The treatment liquid composition according to claim 1, which is a post-treatment liquid.
Ink set.