JP2017217763A - Processing method, recording method, and ink set - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a processing method, a recording method and an ink set that improve the scratch resistance of recorded matter with respect to an ink non-absorptive recording medium containing inorganic compound particles.SOLUTION: A processing method includes the step of applying, to an ink non-absorptive recording medium containing inorganic compound particles, a process liquid containing an acid that can dissolve the inorganic compound particles.SELECTED DRAWING: None

Description

  The present invention relates to a processing method, a recording method, and an ink set.

  Conventionally, a non-ink-absorbing recording medium in which a cloth made of synthetic fiber is coated with a resin has been known. Among them, those using vinyl chloride resin for coating, such as tarpaulin, are inexpensive and have good flame retardancy, and are widely used. Such recorded matter printed on a non-ink-absorbing recording medium is used for sign displays such as a signboard, a banner, and a banner as one of its uses. For example, Patent Document 1 discloses an aqueous inkjet ink that is printed on a hydrophobic medium such as tarpaulin.

Japanese Patent Laying-Open No. 2015-21037

  However, there is a problem in that it is difficult to improve the abrasion resistance in a recorded matter printed on a non-ink-absorbing recording medium (hereinafter also referred to as a non-absorbing medium) as in the prior art. . The inventor diligently studied the cause and found that inorganic compound particles such as calcium carbonate contained in the resin of the non-absorbent medium may cause a decrease in abrasion resistance. Specifically, the inorganic compound particles such as calcium carbonate may be added as a filler (filler) or the like to the resin covering the fabric. Therefore, if the inorganic compound particles are present so as to protrude from the surface of the non-absorbent medium, a color material or the like is applied to the protruding portion by printing to form a printed layer. For this reason, when the recorded material (non-absorbent medium on which the printed layer is formed) is rubbed, the inorganic compound particles are dropped from the non-absorbent medium together with the printed layer, or the protruding portion is missing and printed on the recorded material. In some cases, there were white spots without a layer.

  SUMMARY An advantage of some aspects of the invention is to solve at least a part of the problems described above, and the invention can be implemented as the following forms or application examples.

  Application Example 1 A processing method according to this application example includes a step of applying a treatment liquid containing an acid capable of dissolving inorganic compound particles to a non-ink-absorbing recording medium containing inorganic compound particles. To do.

  According to the treatment method according to this application example, it is possible to improve the abrasion resistance of a recorded matter obtained by printing on an ink non-absorbable recording medium (non-absorbent medium) containing inorganic compound particles. . Specifically, the number of inorganic compound particles protruding on the surface of the non-absorbent medium can be reduced by applying a treatment liquid containing an acid capable of dissolving the inorganic compound particles to the non-absorbent medium. Part or all of the inorganic compound particles protruding on the surface of the non-absorbent medium are dissolved by the application of the treatment liquid. Therefore, in addition to the decrease in the number of inorganic compound particles protruding from the surface of the non-absorbent medium, the dimension protruding from the surface of the non-absorbent medium is reduced. When the protruding dimension is small, the inorganic compound particles are less likely to drop off from the surface of the non-absorbent medium when the non-absorbent medium is rubbed. When printing is performed in this state to form a printed layer and a recorded matter is produced, dropping of the inorganic compound particles and the printed layer can be suppressed. As a result, compared to a non-absorbent medium to which no treatment liquid is applied, the occurrence of white spots due to dropout of the printed layer is reduced, and the rub resistance of the recorded matter is improved. That is, it is possible to provide a processing method for improving the abrasion resistance of the recorded matter.

  Application Example 2 In the processing method according to the application example, it is preferable that the non-ink-absorbing recording medium includes a resin film.

  Thereby, a softness | flexibility and durability can be provided to a non-absorbing medium (ink non-absorbing recording medium). Therefore, it is possible to provide a processing method more suitable for sign / display applications, such as folding a recorded matter printed on the non-absorbent medium, or storing and transporting it as a roll.

  Application Example 3 In the treatment method according to the application example, it is preferable that the resin film includes any one selected from polyvinyl chloride, polyester, polyolefin, and polyamide.

  As a result, the above-described effects are further exhibited, and a processing method more suitable for sign / display applications can be provided.

  Application Example 4 In the treatment method according to the application example described above, the inorganic compound particles preferably include a calcium compound.

  Thereby, a colorless non-absorbing medium can be colored substantially white, or the whiteness of a non-absorbing medium exhibiting substantially white can be improved. The closer the recording medium is to white, the higher the color developability of the recorded matter printed on the medium, and the above method can provide a processing method for improving the color developability of the recorded matter.

  Application Example 5 In the treatment method according to the application example, it is preferable that the treatment liquid contains one or more kinds selected from carboxylic acid and hydrochloric acid as an acid.

  Thereby, it can be set as the process liquid excellent in the solubility of the inorganic compound particle | grains containing a calcium compound etc. Therefore, in addition to further reducing the number of inorganic compound particles protruding from the surface of the non-absorbent medium, the size protruding from the surface of the non-absorbent medium is further reduced. That is, it is possible to provide a processing method for further improving the abrasion resistance of the recorded matter.

  Application Example 6 In the processing method according to the application example described above, in the step of applying the treatment liquid to the non-ink-absorbing recording medium, the temperature of the portion of the non-ink-absorbing recording medium to which the treatment liquid is applied is 10. It is preferable that it is 60 degreeC or more.

  Thereby, reaction with a non-absorbable medium and a processing agent can be accelerated | stimulated, and the effect by application | coating of a processing agent can be exhibited further.

  Application Example 7 A recording method according to this application example includes a step of applying an ink composition to a non-ink-absorbing recording medium processed by the processing method according to the application example.

  According to this application example, by applying the above-described treatment to a non-absorbent medium and applying the ink composition, a recorded matter having scratch resistance (improved scratch resistance as compared with the past) is obtained. Can be manufactured.

  Application Example 8 In the recording method according to the application example described above, it is preferable that the reaction product derived from the reaction between the inorganic compound particles and the treatment liquid has an aggregating action on the ink composition.

  Thereby, at least some of the ink droplets of the ink composition applied to the non-absorbent medium are aggregated. Then, the movement of the ink droplet on the non-absorbing medium is suppressed. Therefore, it is possible to produce a recorded matter in which color bleeding and color bleeding are suppressed.

  Application Example 9 Preferably, the recording method according to the application example further includes a step of heating the non-ink-absorbing recording medium.

  Thereby, drying of the ink composition apply | coated to the nonabsorbent medium and reaction of an ink composition and a process liquid can be accelerated | stimulated.

  Application Example 10 An ink set according to this application example includes a treatment liquid containing an acid for dissolving inorganic compound particles contained in a non-ink-absorbing recording medium, and an ink composition, and includes inorganic compound particles. The reaction product derived from the reaction between the liquid and the treatment liquid has an aggregating action on the ink composition.

  According to this application example, using the ink set and a non-absorbing medium containing inorganic compound particles, it is possible to produce a recorded matter that has abrasion resistance and further suppresses color bleeding and color bleeding. .

  Hereinafter, embodiments of the present invention will be described in detail.

1. Treatment Method In the treatment method of this embodiment, a treatment liquid containing an acid capable of dissolving inorganic compound particles is applied to an ink non-absorbable recording medium containing inorganic compound particles (hereinafter also referred to as non-absorbent medium). Process.

  The treatment liquid application method is not particularly limited, but a contact method using a brush, roller, bar coater, roll coater, blade coater, or the like, or a spray, inkjet head, jet nozzle, curtain coater, etc. For example, a non-contact coating method and a non-absorbent medium impregnated with a processing solution can be used. Among these, the method of applying by the above contact method or the method of applying by the above non-contact method is preferable. These methods can be applied with a smaller amount of treatment liquid than impregnation. Further, an ink jet method by discharging droplets and applying them to the recording surface of a non-absorbent medium is more preferable. By adopting the ink jet method, the application position and the application amount of the treatment liquid can be appropriately controlled.

  The treatment liquid may be applied to the entire surface of the non-absorbent medium, or may be selectively applied to only a part. In particular, the amount of the treatment liquid to be used can be reduced by applying the treatment liquid only to the portion where the ink composition is applied.

  In the step of applying the treatment liquid to the non-absorbent medium, the temperature may be controlled so that at least a portion of the non-absorbent medium to which the treatment liquid is applied has a temperature within a certain range. In particular, the non-absorbent medium may be heated to a temperature within a certain range. As a control method, a conventional heating means such as an infrared heating device or a hot air heating device can be used. The temperature of the portion of the non-absorbent medium to which the treatment liquid is applied is preferably 10 ° C. or higher and 60 ° C. or lower, and more preferably 30 ° C. or higher and 60 ° C. or lower.

1.1. Ink Non-Absorbable Recording Medium The non-absorbing recording medium (non-absorbing medium) according to the present embodiment refers to a recording medium having a property of not absorbing ink or absorbing ink at all. Quantitatively, the non-absorbing medium is preferably a “recording medium having a water absorption amount of 10 mL / m ² or less from the start of contact in the Bristow method until 30 msec”. 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". Non-absorbing media having such non-absorbing properties include a recording medium that does not have an ink-receiving layer having ink absorptivity on the recording surface, and a non-ink-absorbing coating layer on the substrate. There is a recording medium provided on the recording surface.

  Preferred non-absorbent media include, for example, resin films that do not have an ink absorption layer, those in which a resin is coated on a substrate such as paper, those in which a resin film is bonded to a substrate, synthetic fibers A tarpaulin in which a resin is coated on a cloth made of a resin film to form a resin film. Examples of the resin herein include polyolefins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate, polyvinyl chloride, polystyrene, polycarbonate, and polyurethane. Among these, it is preferable to include any one selected from polyvinyl chloride, polyester, polyolefin, and polyamide, and it is more preferable to include polyvinyl chloride. As a result, a non-absorbent medium having both flexibility and durability can be obtained, and a recorded matter printed on the non-absorbent medium can be folded or stored and transported as a roll. The processing method is more suitable for sign display applications. These resins may be used alone or in combination of two or more. Further, a resin plate harder than the resin film can be used.

1.2. Inorganic compound particles The non-absorbent medium according to the present embodiment includes inorganic compound particles. Such inorganic compound particles may be contained in a non-ink-absorbing coating layer formed on the surface of the substrate, and may be filled with fillers (fillers), difficult in the resin constituting the non-absorbing medium. It may be contained as an additive such as a flame retardant or coloring material. Examples of inorganic compounds that form inorganic compound particles include alkali metal compounds such as lithium compounds, sodium compounds and potassium compounds, alkaline earth metal compounds such as magnesium compounds, calcium compounds, strontium compounds and barium compounds, aluminum Compound etc. are mentioned. These compounds are contained in the form of carbonate, sulfate, silicate, hydroxide and the like. Of these compounds, calcium compounds are often contained. Examples of the calcium compound include calcium carbonate, calcium sulfate, and calcium silicate. Of these, calcium carbonate is often contained. This is because calcium carbonate functions as a colorant (white pigment), and is inexpensive and highly safe. The average particle diameter of the inorganic compound particles is not particularly limited, but is, for example, about 0.1 μm to 20 μm.

  The inorganic compound particles may be kneaded and added to the resin film material when producing a non-absorbent medium resin film. In such a resin film, the inorganic compound particles are distributed almost uniformly from the inside to the surface of the resin film (non-absorbent medium). Therefore, innumerable inorganic compound particles protrude from the surface of the non-absorbent medium. In this state, when a printed layer is formed on the surface of the non-absorbent medium by printing and sliding is applied, the particles together with the printed layer may fall off the non-absorbent medium. For this reason, in the recorded matter, white spots may occur due to the printing layer falling off.

1.3. Treatment liquid The treatment liquid according to the present embodiment contains an acid capable of dissolving inorganic compound particles contained in the non-absorbent medium. By applying such a treatment liquid to a non-absorbent medium, the number of inorganic compound particles protruding on the surface of the non-absorbent medium is reduced, and the size of the inorganic compound particles protruding from the surface of the non-absorbent medium. Make it smaller.

1.3.1. The acid contained in the acid treatment liquid is not particularly limited as long as it can dissolve the inorganic compound particles contained in the non-absorbent medium, but preferably contains at least one selected from carboxylic acid and hydrochloric acid. More preferably, it contains an acid. The carboxylic acid is not particularly limited, and examples thereof include formic acid, acetic acid, benzoic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, and citric acid. Among these, it is preferable to use acetic acid. By selecting such an acid, it can be set as the process liquid excellent in the solubility of the inorganic compound particle | grains containing a calcium compound etc.

  The content of the acid contained in the treatment liquid is preferably 0.20% by mass or more and 15% by mass or less, and preferably 0.50% by mass or more and 10% by mass or less with respect to 100% by mass of the treatment liquid. More preferably, it is 0.75 mass% or more and 7.0 mass% or less. When the acid content is 0.20% by mass or more, the inorganic compound particles can be further dissolved, and the abrasion resistance of the recorded matter is increased when printing is performed on a non-absorbent medium. Further, when the acid content is 15% by mass or less, damage such as corrosion of the non-absorbent medium or the treatment liquid coating apparatus by the acid can be suppressed.

1.3.2. Water The treatment liquid according to the present embodiment contains water. Although it does not specifically limit as water, For example, what removed ionic impurities as much as possible like pure water, such as ion-exchange water, ultrafiltration water, reverse osmosis water, and distilled water, and ultrapure water is mentioned. It is done. In addition, when water sterilized by ultraviolet irradiation or addition of hydrogen peroxide is used, generation of mold and bacteria can be suppressed when the treatment liquid is stored for a long period of time. This further improves the storage stability of the treatment liquid.

1.3.3. Water-soluble organic solvent The treatment liquid according to this embodiment may further contain a water-soluble organic solvent. “Water-soluble” refers to the property of being miscible with water. The water-soluble organic solvent can act as a humectant. The content of the water-soluble organic solvent is preferably 5% by mass or more and more preferably 10% by mass or more with respect to 100% by mass of the treatment liquid. Moreover, 35 mass% or less is preferable with respect to 100 mass% of process liquids, and, as for content of a water-soluble organic solvent, 30 mass% or less is more preferable. When the content of the water-soluble organic solvent is within the above range, drying of the nozzles of the inkjet head can be prevented when the treatment liquid is applied by the inkjet method.

  The water-soluble organic solvent is not particularly limited. For example, glycerin, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,2-butanediol, 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, 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 Butyl Chill 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 represented by 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 Rulsulfoxide, sulfolane, and 1,1,3,3-tetramethylurea. A water-soluble organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type.

1.3.4. Surfactant The treatment liquid according to the present embodiment may contain a surfactant. The surfactant is not particularly limited, and examples thereof include acetylene glycol surfactants, fluorine surfactants, and silicone surfactants.

  The acetylene glycol 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- Selected from 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 One or more are preferred. Although it does not specifically limit as a commercial item of an acetylene glycol type surfactant, For example, E series (all are a brand name and air products company), such as Olfine 104 series and Olfine E1010, Surfynol 465, Surfynol 61 (or more All of them are trade names, Nissin Chemical Industry Co., Ltd.). 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 (all are brand names, Asahi Glass Co., Ltd.), FC-170C, FC-430, Fluorard-FC4430 (above All are trade names, Sumitomo 3M Ltd.), FSO, FSO-100, FSN, FSN-100, FS-300 (all are trade names, Dupont), FT-250, 251 (all are trade names, stocks) Company Neos). 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 (all are trade names, Shin-Etsu Chemical Co., Ltd.), Sylface SAG002, 005, 503A, 008 ( All of these include trade names, Nissin Chemical Industry 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 0.050 mass% or more and 6.0 mass% or less, and more preferably 0.10 mass% or more and 5.0 mass% or less with respect to 100 mass% of the treatment liquid. When the content of the surfactant is within the above range, the wettability of the treatment liquid attached to the non-absorbent medium is further improved.

2. Recording Method The recording method according to this embodiment includes a step of applying an ink composition to the non-absorbent medium processed by the above-described processing method. Thereby, it is possible to produce a recorded matter with improved abrasion resistance using a non-absorbent medium.

  A method for applying the ink composition is not particularly limited, and examples thereof include a plate printing method such as an offset printing method and a flexographic printing method, and a non-contact printing method such as an ink jet method. Among these, an inkjet method is preferable. By adopting the ink jet method, the application position and application amount of the treatment liquid can be freely controlled, which is advantageous for on-demand printing.

  The surface temperature of the non-absorbing medium when the ink composition is applied to the non-absorbing medium is preferably 70 ° C. or lower, more preferably 50 ° C. or lower, and further preferably 45 ° C. or lower. Further, the surface temperature of the recording medium when the ink composition is applied to the non-absorbent medium is preferably 20 ° C. or higher, more preferably 25 ° C. or higher, and further preferably 30 ° C. or higher. When the surface temperature is 70 ° C. or lower, rapid drying of the ink composition applied to the non-absorbent medium is suppressed, and occurrence of unevenness is reduced. In addition, when the ink composition is applied by an inkjet method, heating of the inkjet head is suppressed. This suppresses ink thickening and solidification at the nozzles of the inkjet head, and improves the continuous ejection stability of the inkjet head. Further, when the surface temperature is 20 ° C. or higher, the filling property of the ink composition with ink droplets (dots) is ensured on the non-absorbent medium, and the image quality of the recorded matter is improved.

  The recording method of this embodiment may include a step of heating the non-absorbent medium to which the ink composition is attached. As a result, when an ink composition containing resin fine particles, which will be described later, is used, the resin fine particles are melted to form a recorded material with good filling properties. The surface temperature of the non-absorbent medium in the heating step is preferably 50 ° C. or higher and 150 ° C. or lower, more preferably 70 ° C. or higher and 120 ° C. or lower, and further preferably 80 ° C. or higher and 100 ° C. or lower. When the drying temperature is within the above range, the embedding property is further improved.

2.1. Ink Composition The reaction product (salt) derived from the reaction between the inorganic compound (inorganic compound particles) contained in the non-absorbing medium and the acid in the treatment liquid has an aggregating effect on the ink composition of the present embodiment. It is preferable to have. The aggregating action here means that at least a part of the components contained in the ink composition is aggregated. With such a configuration, the ink droplets of the applied ink composition come into contact with the reaction product on the non-absorbent medium. Then, at least some of the ink droplets aggregate. Thereby, the movement of ink droplets on the non-absorbent medium is suppressed, and a recorded matter in which color bleeding and color bleeding are suppressed can be manufactured. Examples of components that can be contained in the ink composition and aggregate when contacted with the above reaction product include resin fine particles and pigments. The dispersion state of these components dispersed in the ink composition is, for example, By being broken, agglomeration occurs.

2.1.1. Resin fine particles The resin fine particles exhibit an effect of fixing the ink composition on the non-absorbent medium by forming a resin film on the non-absorbable medium. As a result, the coated resin fine particles can protect the pigment and exhibit the fixability of the ink composition on the non-absorbent medium. The resin fine particles are also referred to as “binder solids” or “resin emulsion”.

  The resin fine particles that can be contained in the ink composition are not particularly limited. For example, (meth) acrylic acid, (meth) acrylic acid ester, acrylonitrile, cyanoacrylate, acrylamide, olefin, styrene, vinyl acetate, vinyl chloride, vinyl Examples include homopolymers or copolymers of alcohol, vinyl ether, vinyl pyrrolidone, vinyl pyridine, vinyl carbazole, vinyl imidazole, and vinylidene chloride, fluororesins, and natural resins. Among these, 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. A styrene-acrylic acid copolymer resin is more preferable. The above copolymer may be in any form of a random copolymer, a block copolymer, an alternating copolymer, and a graft copolymer.

  As said resin fine particle, what is obtained by a well-known material and a manufacturing method may be used, and a commercial item may be used. Examples of the commercially available products include, but are not limited to, for example, Microgel E-1002, Microgel E-5002 (trade name, Nippon Paint), Boncourt 4001, Boncoat 5454 (tradename, DIC), SAE1014. (Trade name, Nippon Zeon Co., Ltd.), Cybinol SK-200 (trade name, Seiden Chemical Co., Ltd.), Jonkrill 7100, Jonkrill 390, Jonkrill 711, Jonkrill 511, Jonkrill 7001, Jonkrill 632, Jonkrill 741, John Krill 450, John Krill 840, John Krill 74J, John Krill HRC-1645J, John Krill 734, John Krill 852, John Krill 7600, John Krill 775, John Krill 537J, John Krill 1535, John Krill DX-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, John Crill 780, John Crill 7610 BASF).

  Although said resin fine particle is not specifically limited, For example, it can obtain by the preparation method shown below, You may combine a several 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 lower limit of the content of the resin fine particles is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, further preferably 1% by mass or more, and more preferably 2% by mass or more with respect to 100% by mass of the ink composition. Is particularly preferred. Further, the upper limit of the content of the resin fine particles is preferably 15% by mass or less, more preferably 10% by mass or less, further preferably 7% by mass or less, and particularly preferably 5% by mass or less with respect to 100% by mass of the ink composition. preferable. When the content of the resin fine particles is within the above range, the fixability of the ink composition can be further improved and the viscosity of the ink composition can be kept low. Thereby, when discharging an ink composition by an inkjet system, discharge stability improves.

2.1.2. Pigment The ink composition may contain a pigment such as an inorganic pigment or an organic pigment as a coloring material. The inorganic pigment that can be contained in the ink composition is not particularly limited, and examples thereof include carbon blacks (CI pigment black 7) such as furnace black, lamp black, acetylene black, and channel black, iron oxide, and titanium oxide. Is mentioned.

  The organic pigment that can be included in the ink composition is not particularly limited, and examples thereof include quinacridone pigments, quinacridone quinone pigments, dioxazine pigments, phthalocyanine pigments, anthrapyrimidine pigments, anthanthrone pigments, and indanthrone pigments. Pigments, flavanthrone pigments, perylene pigments, diketopyrrolopyrrole pigments, perinone pigments, quinophthalone pigments, anthraquinone pigments, thioindigo pigments, benzimidazolone pigments, isoindolinone pigments, azomethine pigments, And azo pigments.

  The above-mentioned pigments may be used alone or in combination of two or more. The pigment content is preferably 0.5% by mass or more and 15% by mass or less, more preferably 1% by mass or more and 10% by mass or less, and further preferably 1% by mass or more and 5% by mass or less. When the pigment content is within the above range, the ink composition can be made excellent in color developability.

2.1.3. Water The ink composition according to this embodiment may contain water, and may be a water-based ink composition. Although it does not specifically limit as water, For example, ionic impurities, such as ion-exchange water similar to the processing liquid mentioned above, ultrafiltration water, reverse osmosis water, pure water, such as distilled water, and ultrapure water Are removed as much as possible. In addition, when water sterilized by ultraviolet irradiation or addition of hydrogen peroxide is used, generation of mold and bacteria can be suppressed when the treatment liquid is stored for a long period of time. This further improves the storage stability of the ink composition. The ink composition of this embodiment may be a non-aqueous ink composition that does not intentionally contain moisture. Examples of such non-aqueous ink compositions include hard solvent ink, soft solvent ink, ultraviolet curable ink, and electron beam curable ink.

  The water content in the water-based ink composition is preferably 40% by mass or more and 95% by mass or less, more preferably 50% by mass or more and 80% by mass or less, and further preferably 60% by mass or more and 70% by mass or less.

  In addition to the above, the ink composition used in the present embodiment includes a water-soluble resin, an organic solvent (particularly a water-soluble organic solvent), a pyrrolidone derivative, a surfactant, a dissolution aid, a viscosity modifier, a pH adjuster, and an antioxidant. Various additives such as a preservative, an antifungal agent, a corrosion inhibitor, and a chelating agent for capturing metal ions that affect the dispersion may be appropriately added.

3. Ink Set The ink set according to this embodiment includes a treatment liquid that is applied to a non-absorbent medium containing inorganic compound particles and contains an acid for dissolving the inorganic compound particles, and an ink composition. Further, the reaction product generated by the reaction between the inorganic compound particles and the treatment liquid has an aggregating action on the ink composition. By using the ink set to perform treatment and printing on a non-absorbent medium containing inorganic compound particles, it is possible to produce a recorded material that has abrasion resistance and further suppresses color bleeding and color bleeding.

[Example]
EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples. “Part” and “%” in Examples and Comparative Examples are based on mass unless otherwise specified.

3.1. Preparation of treatment liquid (Example 1)
Acetic acid 1% by mass as an acid, 2-pyrrolidone 15% by mass as an organic solvent and propylene glycol 10% by mass, Silface SAG002 (Nisshin Chemical Co., Ltd.) 3% by mass and Surfynol 465 ( Nissin Chemical Industry Co., Ltd.) was stirred and mixed so that 1% by mass and the remainder became pure water (water) to obtain a treatment solution.

(Examples 2 to 5 and Comparative Examples 1 to 3)
Except having changed the kind of acid as Table 1, it carried out similarly to Example 1, and obtained the processing liquid which concerns on Example 2-Example 5. As shown in Table 1, the treatment solutions of Comparative Example 1 and Comparative Example 2 were prepared in the same manner as in Example 1 except that substances other than acids (ammonia and calcium acetate) were used. The treatment liquid of Comparative Example 3 was prepared in the same manner as in Example 1 except that the acid (acetic acid) was removed from Example 1 and supplemented with pure water as shown in Table 1. In Table 1, “-” means not contained.

3.2. Preparation of resin fine particles First, resin fine particles contained in the ink composition were prepared.
A reaction vessel was equipped with a dropping device, thermometer, water-cooled reflux condenser, and stirrer, and 100 parts of ion-exchanged water was added and 0.2 parts of polymerization initiator potassium persulfate was added at 70 ° C. in a nitrogen atmosphere while stirring. A monomer solution in which 0.05 part of sodium lauryl sulfate, 22 parts of styrene, 50 parts of n-butyl acrylate and 0.02 part of t-dodecyl mercaptan are added dropwise to 7 parts of ion-exchanged water is reacted at 70 ° C. To produce core particles. Thereafter, 2 parts of 10% ammonium persulfate solution was added and stirred, and further 30 parts of ion exchange water, 0.2 part of potassium lauryl sulfate, 17 parts of methyl acrylate, 20 parts of ethyl acrylate, 30 parts of methyl methacrylate, 5 parts of acrylic acid. , A mixture comprising 0.5 parts of t-dodecyl mercaptan was added at 70 ° C. with stirring, followed by polymerization reaction, neutralized with sodium hydroxide, adjusted to pH 8 to 8.5 and filtered with a 0.3 μm filter. By filtering, an aqueous dispersion of core-shell polymer particles (resin fine particles) was prepared.

3.3. Preparation of ink composition C.I. I. (Color Index Generic Name) Pigment Blue 15: 3 is 4% by mass, styrene-acrylic acid water-soluble resin is 1% by mass, an aqueous dispersion of resin fine particles is 3% by mass in terms of solid content of resin fine particles, 2-pyrrolidone 15% by mass, 6% by mass of 1,3-butanediol, 6% by mass of 1,2-hexanediol, 1% by mass of Sylface SAG002, and the remaining water as a balance, and stirring, An ink composition was obtained.

3.4. Manufacture of recorded matter The treatment liquid was discharged from a nozzle array of a recording apparatus (PX-G930, Seiko Epson) and applied to tarpaulin (TH-3500, Izumi Co., Ltd.) as a non-absorbent medium. The coating area of the treatment liquid was 5 cm × 5 cm, and the recording resolution was 720 × 720 dpi (Dots Per Inch). Here, the atmospheric temperature was adjusted so that the temperature of the tarpaulin when the treatment liquid was applied was 35 ° C. The above operation was performed for each of the example and the comparative example to perform the processing.

  Next, the ink composition was discharged from another nozzle row of the same recording apparatus, and was deposited on the treatment liquid deposition area. The adhesion area of the ink composition was 5 × 5 cm, and the recording resolution was 720 × 720 dpi. Thereafter, the tarpaulin was heated and dried at 95 ° C. for 2 minutes to obtain a recorded matter. Said operation was implemented about each of the Example and the comparative example.

3.5. Evaluation of Recorded Material The recorded materials of Examples 1 to 5 and Comparative Examples 1 to 3 obtained as described above were evaluated by the following methods.

(Rubbing resistance evaluation)
About the recorded matter obtained as described above, a test (JIS P 8136) for reciprocating 50 width of a gold cloth No. 3 with a load of 500 g using a Gakushin type friction fastness tester AB-301 (Tester Sangyo Co., Ltd.). ) The evaluation criteria are shown below.
(Evaluation criteria)
A: There are no scratches or peeling in the printed part.
B: There is a scratch or peeling of 1% or less of the stroke area.
C: There are scratches or peeling exceeding 1% of the stroke area.

[Image quality evaluation]
Observe the pattern on the printed matter obtained as described above visually, bleed (there should be a part where ink is smeared around the pattern), and graininess (the ink is not uniform inside the pattern) The presence or absence of the appearance of being crushed was determined.
(Evaluation criteria)
A: Neither bleed nor graininess was observed.
B: Bleed was not recognized and granularity was recognized.
C: Bleed and graininess were also observed.

  These evaluation results are shown in Table 1. Focusing on the evaluation results of the abrasion resistance, when the treatment liquid contains an acid (Example 1 to Example 5), the abrasion resistance evaluation is B or more, and the abrasion resistance of the recorded matter can be improved. It has been shown. Among these, when acetic acid was contained in the treatment liquid (Example 1), the evaluation of abrasion resistance was A, indicating that a recorded material with better abrasion resistance can be produced. On the other hand, when the treatment liquid did not contain an acid (Comparative Examples 1 to 3), the scuff resistance evaluation was C, which was inferior to any of Examples 1 to 5.

  Focusing on the evaluation results of the image quality, in Example 1 in which acetic acid is contained in the treatment liquid and in Example 2 in which hydrochloric acid is contained, the image quality evaluation is A, and a recorded matter excellent in image quality in addition to abrasion resistance It was shown that it can be manufactured. In Example 3 to Example 5 in which any one of citric acid, adipic acid, and sulfuric acid was contained as an acid in the treatment liquid, bleeding was improved. On the other hand, in Comparative Example 1 in which the treatment liquid did not contain acid and ammonia was added, and in Comparative Example 3 in which acid was removed from Example 1, the image quality was evaluated as C, and the effect of improving the image quality was not recognized. In Comparative Example 2, since the calcium acetate contained in the treatment liquid has an aggregating action on the ink composition, the image quality evaluation is A. However, since the treatment liquid does not contain an acid, the rub resistance of the recorded material is low. The sex evaluation was C.

Claims (10)

  A method for treating a non-ink-absorbing recording medium, comprising: applying a treatment liquid containing an acid capable of dissolving the inorganic compound particles to a non-ink-absorbing recording medium containing inorganic compound particles.   The processing method according to claim 1, wherein the non-ink-absorbing recording medium includes a resin film.   The processing method according to claim 2, wherein the resin film includes any one selected from polyvinyl chloride, polyester, polyolefin, and polyamide.   The processing method according to any one of claims 1 to 3, wherein the inorganic compound particles include a calcium compound.   The processing method according to any one of claims 1 to 4, wherein the processing liquid contains at least one selected from carboxylic acid and hydrochloric acid as the acid.   The temperature of the portion of the non-ink-absorbing recording medium to which the processing liquid is applied is 10 ° C. or more and 60 ° C. or less in the step of applying the processing liquid to the non-ink-absorbing recording medium. The processing method according to any one of claims 1 to 5.   A recording method comprising a step of applying an ink composition to a non-ink-absorbing recording medium processed by the processing method according to claim 1.   The recording method according to claim 7, wherein a reaction product derived from a reaction between the inorganic compound particles and the treatment liquid has an aggregating action on the ink composition.   The recording method according to claim 7, further comprising a step of heating the non-ink-absorbing recording medium. A treatment liquid containing an acid for dissolving inorganic compound particles contained in the non-ink-absorbing recording medium;
An ink composition,
An ink set in which a reaction product derived from a reaction between the inorganic compound particles and the treatment liquid has an aggregating action on the ink composition.