JP2019214130A - Printing method, printing device, ink, and printed matter - Google Patents

Abstract

To provide a printing method or the like, having no blocking even when pressure is applied to an image, excellent in fixability of the image, and providing the image good in glossiness.SOLUTION: There is provided a printing method including an ink addition process for adding an ink to a recording medium to form an image, and a pressure addition process for adding pressure to the image, in which an ink containing water, a resin, an organic solvent, and a coloring material is used as the ink, the resin is an urethane resin having a ring structure and a non-ring structure, and logarithmic decrement in a rigid body pendulum test on the image is 0.020 to 0.060.SELECTED DRAWING: None

Description

  The present invention relates to a printing method, a printing device, an ink, and a printed matter.

  2. Description of the Related Art Conventionally, as an aqueous ink for inkjet, an ink that is printed on a special paper such as plain paper or glossy photographic paper has been developed. On the other hand, in recent years, applications of the ink jet recording system are expected to expand, and the need for printing on coated paper such as coated paper is increasing. However, it is difficult to firmly fix the pigment on a recording medium having low permeability such as coated paper, and there is a problem that the rubbing resistance of an image is deteriorated.

  In order to solve the above problem, it has been attempted to add a resin emulsion to the ink. For example, in an ink containing water, a resin, an organic solvent, and a coloring material, an ink using a urethane resin including isophorone diisocyanate, which is a cyclic isocyanate, and polyethylene glycol, which is a non-cyclic polyol, has been proposed as a resin (for example, Patent Document 1).

  SUMMARY OF THE INVENTION It is an object of the present invention to provide a printing method which does not cause blocking even when pressure is applied to an image, is excellent in image fixability, and provides an image having good gloss.

  The printing method of the present invention as means for solving the above-mentioned problems includes an ink applying step of applying an ink to a recording medium to form an image, and a pressurizing step of applying a pressure to the image, wherein the ink As water, a resin, an organic solvent, and an ink containing a coloring material, the resin is a urethane resin having a ring structure and a non-ring structure, and the logarithmic decrement of the rigid pendulum test in the image is 0.020. It is 0.060 or less.

  ADVANTAGE OF THE INVENTION According to this invention, the printing method which does not block even if pressure is applied to an image, is excellent in the fixing property of an image, and can obtain the image with favorable glossiness can be provided.

FIG. 1 is a schematic diagram illustrating an example of an image forming apparatus using continuous paper. FIG. 2 is a schematic diagram illustrating an example of the image forming apparatus of the present invention. FIG. 3 is an enlarged view of the head unit in FIG.

(Printing method and printing device)
The printing method of the present invention includes an ink applying step of applying an ink to a recording medium to form an image, and a pressurizing step of applying pressure to the image, wherein water, a resin, an organic solvent, and a coloring material are used as the ink. Is used, the resin is a urethane resin having a ring structure and an acyclic structure, and the logarithmic decrement of a rigid pendulum test in an image is 0.020 or more and 0.060 or less, and further, if necessary, Step.

  The printing apparatus of the present invention is an ink containing water, a resin, an organic solvent, and a coloring material, an ink applying unit that applies an ink to a recording medium to form an image, and a pressurizing unit that applies pressure to the image. Wherein the resin is a urethane resin having a ring structure and a non-ring structure, the logarithmic decrement of a rigid pendulum test in an image being 0.020 or more and 0.060 or less, and other means as necessary. Having.

  The printing method of the present invention can be carried out by the printing apparatus of the present invention, the ink applying step can be carried out by ink applying means, the pressurizing step can be carried out by pressurizing means, and the other steps Can be performed by other means.

  According to the printing method and the printing apparatus of the present invention, in the related art, by adding a resin emulsion to the ink, it is possible to improve the fixing property, which is a conventional problem. This is based on the finding that the elasticity is high and the tack force on the image surface increases when added. Further, in the conventional technology, the tack force on the image surface is increased, so that the image is formed at a timing when pressure is applied to the image portion such as when fixing is performed using a fixing roller after image formation, or when printing and winding on roll paper. This is based on the finding that the gloss is reduced due to blocking.

According to the study by the present inventors, if the logarithmic decrement of the rigid pendulum test in the image is 0.020 or more and 0.060 or less, the image after the image formation is 5.0 kg / cm ² or more and 10.0 kg / cm ² or less. It was found that no blocking occurred even when the pressure was applied, the fixability was good, and an image with good gloss was obtained. If the logarithmic decay rate exceeds 0.060, stickiness in the image will increase, so that blocking may occur under strong pressure.
The logarithmic decrement of the rigid pendulum test in the image can be measured as follows.

[Rigid pendulum test]
For the rigid pendulum test, the logarithmic decrement is calculated by the following method. As a method for measuring the logarithmic decay rate of an image, a rigid pendulum type physical property tester RPT-3000W (manufactured by A & D) is used. Within 3 minutes after printing, place the printing surface together with the cooling / heating block (CHB-100), and set the cylinder edge with one exclusive weight. At this time, it is necessary that all parts touching the cylinder edge be filled with the image. The measurement temperature is 30 ° C., and the logarithmic decay rate is plotted against time. The measurement time is 3 minutes, and data is measured every 6 seconds. The result of averaging all logarithmic decrements is defined as the logarithmic decrement of the image.

The glass transition temperature (Tg) of the surface of the obtained image is preferably from 0 ° C to 40 ° C, more preferably from 0 ° C to 30 ° C.
When the glass transition temperature (Tg) of the image surface is 0 ° C. or more and 40 ° C. or less, the image is not blocked even when pressure is applied to the image, and an image having excellent fixability and good gloss can be obtained. There is.
The glass transition temperature (Tg) of the image surface can be measured as follows.

[Glass transition temperature of image surface (Tg of image surface)]
The surface Tg of the image was measured using a horizontal force microscope (LFM). An image sample to be measured was placed on a Dimension Icon (manufactured by Bruker), and a temperature increase of 180 ° C to 400K at 10 ° C / min was observed to measure the lateral bias on the image surface. The temperature at which the lateral bias became the maximum value was defined as “Tg on the image surface”. The cantilever used for the measurement is ESP (manufactured by Bruker), and the measurement is performed with the indentation depth fixed at 300 nm.

<Ink applying step and ink applying means>
The ink applying step is a step of applying an ink to a recording medium to form an image, and is performed by an ink applying unit.
The ink applying means is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include a liquid discharge method and a coating method. Among these, the liquid discharge method is preferable.

  The liquid discharge method is not particularly limited and may be appropriately selected depending on the purpose. For example, the drive method of the discharge head includes a piezoelectric element actuator using PZT or the like, a method of applying thermal energy, An on-demand type head using an actuator using force or the like can be used, or a continuous injection type charge control type head can be used.

<< Ink >>
The ink contains water, a resin, an organic solvent, and a coloring material, and further contains other components as necessary.

-Resin-
The type of resin contained in the ink needs to be urethane resin.
The urethane resin is a resin having at least a urethane bond composed of an isocyanate group and an alcohol or a carboxylic acid.
The urethane resin needs to have a ring structure and a non-ring structure, and has a ring structure and a non-ring structure composed of a saturated alkane as represented by the following general formula 1. Thereby, there is an advantage that the gloss can be improved by pressure and the blocking resistance can be maintained while maintaining the fixing property.

[General Formula 1]
However, in the general formula 1, n1 to n3 represent the number of carbon atoms, and m1 to m3 represent the number of hydrogen atoms. n1 is 1 to 6, and n2 and n3 are 0 to 12. n1 to n3 and m1 to m3 may be independent or the same. Cn1Hm1, Cn2Hm2, and Cn3Hm3 are not limited to a saturated, unsaturated, or branched structure. Note that a structure in which a carbon atom in Cn1Hm1 is replaced with another element may be used.

The urethane resin used in the present invention is different from the conventional urethane resin in that the portion located between the isocyanate portion and the isocyanate portion is not the same monomer, and the cyclic structure and the non-cyclic structure need to be randomly arranged. . Although it is not necessary to be completely random, for example, it is essential that the portion located between the isocyanate portion and the isocyanate portion has the structure shown in Example 2 below, not the structure shown in Example 1 below. .
(Example 1): A-A-C-B-B-B-B-B-C-B-C-A-A-A-A-C-A-C-A-A-A-A-
(Example 2): B-A-C-A-A-A-B-A-C-A-B-C-A-B-C-A-C-A-C-A-C-A-B-A-
Here, A represents a ring structure, B represents an acyclic structure, and C represents an isocyanate moiety.

It is preferable that the ring structure of the urethane resin is a six-membered ring structure because a conformational structure that can be regarded as a crystal locally can be formed between the resins, and the blocking resistance is improved.
The 6-membered ring structure means that the number of atoms bonded in a ring is six, and the atoms are composed of carbon atoms, and some of the carbon atoms may be substituted with hetero atoms. , Cyclohexane and the like.
It is preferable that the ring structure of the urethane resin is a benzene ring from the viewpoint that the hardness of the resin itself can be increased.
It is preferable that the urethane resin has an alkyl group in the side chain, since it can have a moderate degree of freedom of deformation and can increase gloss when pressed.
The glass transition temperature of the urethane resin is not particularly limited and may be appropriately selected depending on the intended purpose. However, the glass transition temperature is preferably from 0 ° C to 40 ° C.
The weight average molecular weight of the urethane resin is not particularly limited and can be appropriately selected depending on the purpose, but is preferably from 4,500 to 5,500.
As a method for confirming such a resin component, there is thermal decomposition GC / MS or the like. By performing the GC / MS measurement while heating the resin at 200 ° C., the resin is decomposed and isolated for each monomer, and can be confirmed as a component in the resin.

  Examples of the method for producing the urethane resin as described above include a method in which a polyisocyanate and a polyalcohol prepolymer are copolymerized.

Corresponding urethane resin particles may be used as the urethane resin. Ink can be obtained by mixing urethane resin particles with a material such as a coloring material or an organic solvent in a state of a urethane resin emulsion in which water is used as a dispersion medium.
Further, in addition to the urethane resin, within a range that does not impair the objects and effects of the present invention, a polyester resin, an acrylic resin, a vinyl acetate resin, a styrene resin, a butadiene resin, a styrene-butadiene resin, a vinyl chloride resin, Other resins such as an acrylic styrene resin and an acrylic silicone resin can be added.

The volume average particle size of the resin particles is not particularly limited and may be appropriately selected depending on the intended purpose. However, from the viewpoint of obtaining good fixing properties and high image hardness, it is preferably from 10 nm to 1,000 nm, and more preferably from 10 nm to 1,000 nm. It is more preferably at least 200 nm and particularly preferably at least 10 nm and at most 100 nm.
The volume average particle size can be measured, for example, using a particle size analyzer (Nanotrack Wave-UT151, manufactured by Microtrack Bell Co., Ltd.).

  The content of the resin is not particularly limited and may be appropriately selected depending on the purpose. From the viewpoint of fixability and storage stability of the ink, the content is 1% by mass or more and 30% by mass or less based on the total amount of the ink. Is preferably 5% by mass or more and 20% by mass or less.

-Organic solvent-
The organic solvent used in the present invention is not particularly limited, and a water-soluble organic solvent can be used. Examples thereof include polyhydric alcohols, ethers such as polyhydric alcohol alkyl ethers and polyhydric alcohol aryl ethers, nitrogen-containing heterocyclic compounds, amides, amines, and sulfur-containing compounds.
Specific examples of the water-soluble organic solvent include, for example, ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butane Diol, 2,3-butanediol, 3-methyl-1,3-butanediol, triethylene glycol, polyethylene glycol, polypropylene glycol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol 2,4-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,3-hexanediol, 2,5-hexanediol, 1,5-hexanediol, Glycerin, 1,2,6-hexanetriol, 2-ethyl-1,3-he Polyhydric alcohols such as sundiol, ethyl-1,2,4-butanetriol, 1,2,3-butanetriol, 2,2,4-trimethyl-1,3-pentanediol and petriol, ethylene glycol mono Polyhydric alcohol alkyl ethers such as ethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monophenyl ether, ethylene glycol mono Polyhydric alcohol aryl ethers such as benzyl ether, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-hydroxyethyl- Nitrogen-containing heterocyclic compounds such as -pyrrolidone, 1,3-dimethyl-2-imidazolidinone, ε-caprolactam, γ-butyrolactone, formamide, N-methylformamide, N, N-dimethylformamide, 3-methoxy-N, Amides such as N-dimethylpropionamide and 3-butoxy-N, N-dimethylpropionamide; amines such as monoethanolamine, diethanolamine and triethylamine; sulfur-containing compounds such as dimethylsulfoxide, sulfolane and thiodiethanol; propylene carbonate; Examples include ethylene carbonate.
It is preferable to use an organic solvent having a boiling point of 250 ° C. or less, because it not only functions as a wetting agent but also provides good drying properties.

A polyol compound having 8 or more carbon atoms and a glycol ether compound are also preferably used.
Specific examples of the polyol compound having 8 or more carbon atoms include 2-ethyl-1,3-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, and the like.
Specific examples of the glycol ether compound include polyhydric alcohol alkyls such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, and propylene glycol monoethyl ether. Ethers; polyhydric alcohol aryl ethers such as ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether;

  A polyol compound having 8 or more carbon atoms and a glycol ether compound can improve ink permeability when paper is used as a recording medium.

  The content of the organic solvent in the ink is not particularly limited and may be appropriately selected depending on the intended purpose; however, from the viewpoint of drying properties and ejection reliability of the ink, the content is preferably from 10% by mass to 60% by mass, The content is more preferably from 20% by mass to 60% by mass.

−Water−
The content of water in the ink is not particularly limited and may be appropriately selected depending on the intended purpose. However, from the viewpoint of the drying property and ejection reliability of the ink, the content is preferably from 10% by mass to 90% by mass, and more preferably from 20% by mass. % Or more and 60% by mass or less.

  The water is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include pure water such as ion-exchanged water, ultrafiltration water, reverse osmosis water, and distilled water; and ultrapure water. . These may be used individually by 1 type and may use 2 or more types together.

-Coloring material-
The coloring material is not particularly limited, and pigments and dyes can be used.
As the pigment, an inorganic pigment or an organic pigment can be used. These may be used alone or in combination of two or more. Further, a mixed crystal may be used.
As the pigment, for example, a black pigment, a yellow pigment, a magenta pigment, a cyan pigment, a white pigment, a green pigment, an orange pigment, a glossy pigment such as gold or silver, a metallic pigment, and the like can be used.
As inorganic pigments, in addition to titanium oxide, iron oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, cadmium red, and chrome yellow, carbon black produced by a known method such as a contact method, a furnace method, and a thermal method Can be used.
Examples of the organic pigment include azo pigments and polycyclic pigments (for example, phthalocyanine pigment, perylene pigment, perinone pigment, anthraquinone pigment, quinacridone pigment, dioxazine pigment, indigo pigment, thioindigo pigment, isoindolinone pigment, quinophthalone pigment). Dye chelates (eg, basic dye chelates, acid dye chelates, etc.), nitro pigments, nitroso pigments, aniline black, and the like. Among these pigments, those having a good affinity for the solvent are preferably used. In addition, resin hollow particles and inorganic hollow particles can be used.
Specific examples of the pigment include carbon black (CI pigment black 7) such as furnace black, lamp black, acetylene black, and channel black, or copper and iron (CI pigment black 11) for black. And metals such as titanium oxide, and organic pigments such as aniline black (CI pigment black 1).
Further, for color, C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 17, 24, 34, 35, 37, 42 (yellow iron oxide), 53, 55, 74, 81, 83, 95, 97, 98, 100, 101, 104 , 108, 109, 110, 117, 120, 138, 150, 153, 155, 180, 185, 213, C.I. I. Pigment Orange 5, 13, 16, 17, 36, 43, 51, C.I. I. Pigment Red 1, 2, 3, 5, 17, 22, 23, 31, 38, 48: 2 (Permanent Red 2B (Ca)), 48: 3, 48: 4, 49: 1, 52: 2, 53: 1, 57: 1 (Brilliant Carmine 6B), 60: 1, 63: 1, 63: 2, 64: 1, 81, 83, 88, 101 (Bengara), 104, 105, 106, 108 (Cadmium Red), 112, 114, 122 (quinacridone magenta), 123, 146, 149, 166, 168, 170, 172, 177, 178, 179, 184, 185, 190, 193, 202, 207, 208, 209, 213, 219, 224, 254, 264, C.I. I. Pigment Violet 1 (rhodamine lake), 3, 5: 1, 16, 19, 23, 38, C.I. I. Pigment Blue 1, 2, 15 (phthalocyanine blue), 15: 1, 15: 2, 15: 3, 15: 4 (phthalocyanine blue), 16, 17: 1, 56, 60, 63, C.I. I. Pigment Green 1, 4, 7, 8, 10, 17, 18, 36 and the like.
The dye is not particularly limited, and acid dyes, direct dyes, reactive dyes, and basic dyes can be used. One type of dye may be used alone, or two or more types may be used in combination.
Examples of the dye include C.I. I. Acid Yellow 17, 23, 42, 44, 79, 142, C.I. I. Acid Red 52, 80, 82, 249, 254, 289, C.I. I. Acid Blue 9, 45, 249, C.I. I. Acid Black 1, 2, 24, 94, C.I. I. Food black 1, 2, C.I. I. Direct Yellow 1, 12, 24, 33, 50, 55, 58, 86, 132, 142, 144, 173, C.I. I. Direct Red 1,4,9,80,81,225,227, C.I. I. Direct Blue 1, 2, 15, 71, 86, 87, 98, 165, 199, 202, C.I. I. Directed black 19, 38, 51, 71, 154, 168, 171, 195, C.I. I. Reactive red 14, 32, 55, 79, 249, C.I. I. Reactive Black 3, 4, 35 and the like.

  The content of the coloring material in the ink is preferably 0.1% by mass or more and 15% by mass or less, more preferably 1% by mass or more and 10% by mass from the viewpoints of improving image density, good fixability and ejection stability. It is as follows.

In order to obtain an ink by dispersing the pigment, a method of introducing a hydrophilic functional group into the pigment to form a self-dispersing pigment, a method of coating and dispersing the surface of the pigment with a resin, and dispersing using a dispersant Method, and the like.
As a method of introducing a hydrophilic functional group into a pigment to form a self-dispersing pigment, for example, a pigment (for example, carbon) is added with a functional group such as a sulfone group or a carboxyl group so that the pigment can be dispersed in water. Method.
As a method of coating and dispersing the surface of the pigment with a resin, there is a method in which the pigment is included in microcapsules so as to be dispersible in water. This can be rephrased as a resin-coated pigment. In this case, it is not necessary that all the pigments incorporated in the ink be coated on the resin, and as long as the effects of the present invention are not impaired, uncoated pigments or partially-coated pigments are dispersed in the ink. May be.
Examples of the method of dispersing using a dispersant include a method of dispersing using a known low-molecular type dispersant and a high-molecular type dispersant represented by a surfactant.
As the dispersant, for example, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a nonionic surfactant, or the like can be used depending on the pigment.
RT-100 (nonionic surfactant) manufactured by Takemoto Yushi Co., Ltd. and Na-formalin condensate of naphthalenesulfonic acid can also be suitably used as the dispersant.
One type of dispersant may be used alone, or two or more types may be used in combination.

-Pigment dispersion-
It is possible to obtain an ink by mixing a material such as water or an organic solvent with a pigment. Further, it is also possible to manufacture an ink by mixing a material such as water and an organic solvent with a pigment dispersion obtained by mixing a pigment and other water or a dispersant.
The pigment dispersion is obtained by mixing and dispersing water, a pigment, a pigment dispersant, and other components as necessary, and adjusting the particle size. The dispersion may be performed using a disperser.
The particle size of the pigment in the pigment dispersion is not particularly limited, but the dispersion frequency of the pigment is good, and the image quality such as ejection stability and image density is also high. 500 nm or less is preferable, and 20 nm or more and 150 nm or less are more preferable. The particle size of the pigment can be measured using a particle size analyzer (Nanotrac Wave-UT151, manufactured by Microtrac Bell Inc.).
The content of the pigment in the pigment dispersion is not particularly limited and may be appropriately selected depending on the intended purpose. However, from the viewpoint of obtaining good ejection stability and increasing the image density, 0.1 mass % To 50% by mass, more preferably 0.1% to 30% by mass.
The pigment dispersion is preferably degassed by filtering coarse particles with a filter, a centrifugal separator or the like, if necessary.

  The particle size of the solid content in the ink is not particularly limited and can be appropriately selected depending on the purpose.However, from the viewpoint of improving image quality such as ejection stability and image density, the maximum frequency in terms of the maximum number is considered. Is preferably from 20 nm to 1000 nm, more preferably from 20 nm to 150 nm. The solid content includes resin particles and pigment particles. The particle size can be measured using a particle size analyzer (Nanotrack Wave-UT151, manufactured by Microtrac Bell Inc.).

  If necessary, a surfactant, an antifoaming agent, an antiseptic / antifungal agent, a rust inhibitor, a pH adjuster, etc. may be added to the ink.

--- Surfactant ---
As the surfactant, any of a silicone-based surfactant, a fluorine-based surfactant, an amphoteric surfactant, a nonionic surfactant, and an anionic surfactant can be used.
The silicone surfactant is not particularly limited and can be appropriately selected depending on the purpose. Among them, those which do not decompose even at a high pH are preferable, and examples thereof include side-chain-modified polydimethylsiloxane, both-end-modified polydimethylsiloxane, one-end-modified polydimethylsiloxane, and both-end-and-end-modified polydimethylsiloxane. Those having an oxyethylene group or a polyoxyethylene polyoxypropylene group are particularly preferred because they exhibit good properties as an aqueous surfactant. Further, as the silicone-based surfactant, a polyether-modified silicone-based surfactant can also be used, and examples thereof include a compound having a polyalkylene oxide structure introduced into the side chain of the Si portion of dimethylsiloxane.
Examples of the fluorine-based surfactant include a perfluoroalkylsulfonic acid compound, a perfluoroalkylcarboxylic acid compound, a perfluoroalkylphosphate compound, a perfluoroalkylethylene oxide adduct, and a perfluoroalkylether group in the side chain. Polyoxyalkylene ether polymer compounds are particularly preferred because of their low foaming properties. Examples of the perfluoroalkylsulfonic acid compound include perfluoroalkylsulfonic acid, perfluoroalkylsulfonic acid salt, and the like. Examples of the perfluoroalkylcarboxylic acid compound include perfluoroalkylcarboxylic acid and perfluoroalkylcarboxylic acid salt. Examples of the polyoxyalkylene ether polymer compound having a perfluoroalkyl ether group in a side chain include a sulfate salt of a polyoxyalkylene ether polymer having a perfluoroalkyl ether group in a side chain, and having a perfluoroalkyl ether group in a side chain. Examples include salts of polyoxyalkylene ether polymers. The counter ions of the salts in these fluorinated surfactants include Li, Na, K, NH ₄ , NH ₃ CH ₂ CH ₂ OH, NH ₂ (CH ₂ CH ₂ OH) ₂ , and NH (CH ₂ CH ₂ OH) _{3 and the} like.
Examples of the amphoteric surfactant include lauryl aminopropionate, lauryl dimethyl betaine, stearyl dimethyl betaine, lauryl dihydroxyethyl betaine, and the like.
Examples of the nonionic surfactant include polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl ester, polyoxyethylene alkylamine, polyoxyethylene alkyl amide, polyoxyethylene propylene block polymer, sorbitan fatty acid ester, polyoxyethylene sorbitan Fatty acid esters and ethylene oxide adducts of acetylene alcohol are exemplified.
Examples of the anionic surfactant include polyoxyethylene alkyl ether acetate, dodecylbenzene sulfonate, laurylate, and polyoxyethylene alkyl ether sulfate.
These may be used alone or in combination of two or more.

As the fluorine-based surfactant, a fluorine-substituted compound having 2 to 16 carbon atoms is preferable, and a fluorine-substituted compound having 4 to 16 carbon atoms is more preferable.
Examples of the fluorine-based surfactant include a perfluoroalkyl phosphate ester compound, a perfluoroalkyl ethylene oxide adduct, and a polyoxyalkylene ether polymer compound having a perfluoroalkyl ether group in a side chain. Among these, polyoxyalkylene ether polymer compounds having a perfluoroalkyl ether group in the side chain are preferable because of their low foaming properties, and particularly, fluorine-based compounds represented by the general formulas (F-1) and (F-2). Surfactants are preferred.

General formula (F-1)
In the compound represented by the formula (F-1), m is preferably an integer of 0 to 10, and n is preferably an integer of 0 to 40 in order to impart water solubility.

General formula (F-2)
_{C n F 2n + 1- CH 2} CH (OH) CH 2 -O- (CH 2 CH 2 O) a -Y
In the compound represented by the general formula (F-2), Y is H, or _C m _{F 2m + 1} with m is an integer of 1 to 6, or _{CH 2 CH (OH) CH 2} -C m F 2m + 1 m is P is an integer of 1 to 19 at an integer of 4 to 6 or CpH _{2p + 1} . n is an integer of 1 to 6. a is an integer of 4 to 14.

A commercially available product may be used as the above-mentioned fluorine-based surfactant.
Examples of commercially available products include Surflon S-111, S-112, S-113, S-121, S-131, S-132, S-141, and S-145 (all manufactured by Asahi Glass Co., Ltd.); Fullard FC-93, FC-95, FC-98, FC-129, FC-135, FC-170C, FC-430, FC-431 (all manufactured by Sumitomo 3M Limited); Megafac F-470, F -1405, F-474 (all manufactured by DIC Corporation); Zonyl TBS, FSP, FSA, FSN-100, FSN, FSO-100, FSO, FS-300, UR, Capstone FS-30, FS-31, FS-3100, FS-34, FS-35 (all manufactured by Chemours); FT-110, FT-250, FT-251 FT-400S, FT-150, FT-400SW (all manufactured by Neos Corporation), Polyfox PF-136A, PF-156A, PF-151N, PF-154, PF-159 (manufactured by OMNOVA), Unidyne DSN -403N (manufactured by Daikin Industries, Ltd.). Among these, FS-3100, FS-34, FS-300, and Neos Co., Ltd. manufactured by Chemours Co., Ltd. from the viewpoint that the excellent printing quality, particularly the color developing property, the permeability to paper, the wettability, and the leveling property are remarkably improved. FT-110, FT-250, FT-251, FT-400S, FT-150, FT-400SW manufactured by Omnova, Polyfox PF-151N manufactured by Omnova and Unidyne DSN-403N manufactured by Daikin Industries, Ltd. are particularly preferable.

  The content of the surfactant in the ink is not particularly limited and can be appropriately selected depending on the purpose. However, from the viewpoint of excellent wettability and ejection stability and improved image quality, 0.001 mass % To 5% by mass, more preferably 0.05% to 5% by mass.

−−Defoaming agent−−
The defoaming agent is not particularly limited, and examples thereof include a silicone-based defoaming agent, a polyether-based defoaming agent, and a fatty acid ester-based defoaming agent. These may be used alone or in combination of two or more. Among these, silicone-based antifoaming agents are preferred because of their excellent foam breaking effect.

--- Antiseptic / antifungal agent ----
The antiseptic / antifungal agent is not particularly limited, and examples thereof include 1,2-benzisothiazolin-3-one.

−−rust inhibitor−−
The rust inhibitor is not particularly limited, and examples thereof include acidic sulfites and sodium thiosulfate.

--- pH adjuster ---
The pH adjuster is not particularly limited as long as the pH can be adjusted to 7 or more, and examples thereof include amines such as diethanolamine and triethanolamine.

The physical properties of the ink are not particularly limited and can be appropriately selected depending on the purpose. For example, the viscosity, surface tension, pH, and the like are preferably in the following ranges.
The viscosity of the ink at 25 ° C. is preferably 5 mPa · s or more and 30 mPa · s or less, and more preferably 5 mPa · s or more and 25 mPa · s or less, from the viewpoint of improving print density and character quality, and obtaining good ejection properties. More preferred. Here, for the viscosity, for example, a rotary viscometer (RE-80L, manufactured by Toki Sangyo Co., Ltd.) can be used. As measurement conditions, measurement can be performed at 25 ° C. with a standard cone rotor (1 ° 34 ′ × R24), a sample liquid amount of 1.2 mL, a rotation speed of 50 rpm, and 3 minutes.
The surface tension of the ink is preferably 35 mN / m or less, and more preferably 32 mN / m or less at 25 ° C., from the viewpoint that the ink is suitably leveled on the recording medium and the drying time of the ink is shortened.
The pH of the ink is preferably from 7 to 12, and more preferably from 8 to 11, from the viewpoint of preventing corrosion of the metal member that comes into contact with the ink.

<<<< recording medium >>
The recording medium is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include plain paper, glossy paper, special paper, cloth, film, OHP sheet, and general-purpose printing paper.
Among these, a recording medium that provides the effects of the present invention includes a support, and a coating layer provided on at least one surface side of the support, and further includes other And a recording medium having the above layer. The recording medium having such a support and a coating layer is generally called a coated paper, and is known as a recording medium having low ink permeability. It is difficult to firmly fix the coloring material on a recording medium having low permeability such as coated paper, and the rubbing property often deteriorates. However, as described above, the image at 30 ° C. measured by a rigid pendulum test was used. When the logarithmic decay rate is 0.020 or more and 0.060 or less, blocking or transfer does not occur even if a pressure of 5.0 kg / cm ² or more and 10.0 kg / cm ² or less is applied to the image after image formation, and gloss is further increased. This is particularly preferable because an image having good properties can be obtained.

A recording medium having a support and a coating layer, the amount of transferred onto the recording medium of pure water at a contact time 100ms measured by a dynamic scanning liquid absorption meter, 2 mL / m ² or more 35 mL / m ² or less is preferable , 2 mL / ^{m 2} or more 10 mL / ^{m 2} or less is more preferable.
If the transfer amount of the pure water at the contact time of 100 ms is too small, beading may easily occur, and if it is too large, the ink dot diameter after recording may be smaller than a desired diameter.
Transfer amount of pure water of the recording medium in a dynamic scanning liquid absorption contact time measured by the meter 400ms is, 3 mL / ^{m 2} or more 40 mL / ^{m 2} or less is preferable, 3 mL / ^{m 2} or more 10 mL / ^{m 2} or less and more preferably .
If the transfer amount of the pure water at the contact time of 400 ms is too small, the drying property is insufficient, so that spur marks may be easily generated, and if too large, the gloss of the image portion after drying becomes low. May be easier. The amount of pure water transferred to the recording medium at the contact times of 100 ms and 400 ms is measured on the surface of the recording medium on the side having the coating layer.

  Here, the dynamic scanning absorptometer (DSA, Paper Industry Association of Japan, Vol. 48, May 1994, pp. 88-92, Kuganei Shigenori) indicates the amount of liquid absorption in a very short time. Is a device that can accurately measure The dynamic scanning absorptiometer reads the speed of the liquid absorptive directly from the movement of the meniscus in the capillary, makes the sample disk-shaped, and scans the liquid-absorbing head helically on the disk, and scans the sample according to a preset pattern. Is automatically changed by a method of automatically changing the number of required points on a single sample. The liquid supply head for the paper sample is connected to the capillary via a Teflon (registered trademark) tube, and the position of the meniscus in the capillary is automatically read by an optical sensor. Specifically, the transfer amount of pure water or ink was measured using a dynamic scanning liquid absorption meter (K350 series D type, manufactured by Kyowa Seiko Co., Ltd.). The transfer amount at the contact time of 100 ms and the contact time of 400 ms can be obtained by interpolation from the measured value of the transfer amount at the contact time adjacent to each contact time.

-Support-
The support is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a paper-based material such as paper mainly composed of wood fibers and a nonwoven fabric mainly composed of wood fibers and synthetic fibers.
The paper is not particularly limited and can be appropriately selected from known ones according to the purpose. For example, wood pulp and waste paper pulp are used. Examples of the wood pulp include hardwood bleached kraft pulp (LBKP), softwood bleached kraft pulp (NBKP), NBSP, LBSP, GP, and TMP.
The raw materials for waste paper pulp are listed in the Waste Paper Standard Quality Standards Table of the Waste Paper Recycling Promotion Center, top white, ruled white, cream white, card, special white, medium white, imitation, fair white, Kent, white art , Special top cut, separate top cut, newspaper, magazine and the like. Specifically, printer paper such as uncoated computer paper, heat-sensitive paper, and pressure-sensitive paper as information-related paper; OA waste paper such as PPC paper; coating of art paper, coated paper, lightly coated paper, matte paper, etc. Paper; high-quality paper, high-quality paper, notebooks, stationery, wrapping paper, fancy paper, medium paper, newsprint, paper change, super-hanging paper, imitation paper, pure white roll paper, uncoated paper such as milk carton, etc. Used paper such as paper and paperboard, such as chemical pulp paper and high-yield pulp-containing paper. These may be used individually by 1 type and may use 2 or more types together.

Waste paper pulp is generally produced from a combination of the following four steps.
(1) In disintegration, used paper is treated with a mechanical force and a chemical using a pulper to loosen it into a fibrous form, and the printing ink is peeled from the fiber.
(2) In dust removal, foreign matter (such as plastic) and dust contained in waste paper are removed by a screen, a cleaner, or the like.
(3) In the deinking, the printing ink removed from the fiber using a surfactant is removed out of the system by a flotation method or a cleaning method.
(4) Bleaching increases the whiteness of the fiber by using an oxidizing action or a reducing action.
When mixing waste paper pulp, the mixing ratio of waste paper pulp in all pulp is preferably 40% or less in order to prevent curling after recording.

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

  Examples of the internal sizing agent used for forming the support include neutral rosin-based sizing agents used for neutral papermaking, alkenyl succinic anhydride (ASA), alkyl ketene dimer (AKD), and petroleum resin-based sizing agents. And a sizing agent. Of these, neutral rosin sizing agents and alkenyl succinic anhydrides are particularly preferred. Alkyl ketene dimer requires only a small amount of addition due to its high size effect. However, the friction coefficient of the surface of the recording medium is reduced and the alkyl ketene dimer is liable to slip.

-Coating layer-
The coating layer contains a pigment and a binder (binder), and further contains a surfactant and other components as necessary. In the present invention, the term “coating layer” only needs to contain a pigment and a binder (binder) as described above, and the formation method such as whether or not the layer is actually applied and provided is not limited. Not defined.

Preferably, continuous paper is used as the recording medium.
The continuous paper is a recording medium that is continuous in the transport direction at the time of image formation, and includes, for example, roll paper rolled into a roll shape, continuous paper folded at predetermined intervals, and the like.
Commercial products can be used as such continuous paper, and examples of the commercial products include LAG90, LAG130, and LAG200 (all manufactured by Stora Enso).

<Pressure process and pressure means>
The pressing step is a step of applying pressure to an image, and is performed by a pressing unit.
The method of applying pressure to the image is not particularly limited as long as pressure can be applied to the image, and a method of pressing the image using one or a plurality of pressing rollers. A method in which the continuous paper after the application and the formation of the image are wound into a roll shape by a winding device may be used.
In the method in which the continuous paper is wound into a roll by a winding device, the pressure on the image on the continuous paper can be adjusted by the tension in which the winding device winds the continuous paper.
The pressurizing step may employ a plurality of steps or one step. The pressure only needs to be applied to at least a part of the recording medium, and it is preferable that the pressure is applied to the entire recording medium.
The pressure in pressurizing step (pressure applied to the image) is preferably from 3.0 kg / cm ² or more 12.0 kg / cm ² or less, 5.0 kg / cm ² or more 10.0 kg / cm ² or less being more preferred.
When the pressure applied to the image is 3.0 kg / cm ² or more, the fixing property of the image is sufficiently obtained, and the rubbing property is improved. On the other hand, when the pressure applied to the image is 12.0 kg / cm ² or less, it is preferable because blocking resistance can be suitably suppressed.
The pressure applied to the image can be measured by, for example, a pressure distribution measurement system I-SCAN40.
In addition, you may heat with pressurization. The drying time can be shortened by heating.

<Other steps and other means>
The other steps are not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include a control step, a display step, and a recording step.
Other means are not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include a control means, a display means, and a recording means.

The ink of the present invention can be suitably used for various recording apparatuses using an ink jet recording system, for example, a printer, a facsimile apparatus, a copying apparatus, a combined printer / fax / copier machine, and a three-dimensional printing apparatus.
In the present invention, a recording device and a recording method are a device capable of discharging ink, various processing liquids, and the like onto a recording medium, and a method of performing recording using the device. The recording medium means a medium to which ink or various processing liquids can be temporarily attached.
This recording apparatus can include not only a head portion for discharging ink, but also means for feeding, transporting, and discharging a recording medium, and other devices referred to as a pre-processing device and a post-processing device. .
The recording device and the recording method may include a heating unit used in the heating step and a drying unit used in the drying step. The heating means and the drying means include, for example, means for heating and drying the printing surface or the back surface of the recording medium. The heating means and the drying means are not particularly limited, and for example, a warm air heater or an infrared heater can be used. Heating and drying can be performed before printing, during printing, after printing, and the like.
Further, the recording apparatus and the recording method are not limited to those in which a significant image such as a character or a graphic is visualized by ink. For example, those that form patterns such as geometric patterns and the like that form three-dimensional images are also included.
Further, the recording apparatus includes both a serial type apparatus that moves the ejection head and a line type apparatus that does not move the ejection head, unless otherwise limited.
Further, the recording apparatus is not limited to a desk-top type, and can also be used as a recording medium of a wide width capable of printing on a recording medium of A0 size, or a continuous paper wound in a roll shape, for example. It also includes a simple continuous printer.

The recording apparatus can include not only a portion for discharging ink but also a device called a pre-processing device or a post-processing device.
As one embodiment of the pre-processing device and the post-processing device, the pre-processing device and the post-processing device include a pre-processing liquid and a post-processing liquid as in the case of inks such as black (K), cyan (C), magenta (M), and yellow (Y). There is a mode in which a liquid storage unit and a liquid discharge head are added, and a pretreatment liquid and a post-treatment liquid are discharged by an inkjet recording method.
As another embodiment of the pre-processing device and the post-processing device, there is a mode in which a pre-processing device and a post-processing device other than the ink jet recording method, for example, by a blade coating method, a roll coating method, and a spray coating method are provided.

<Pretreatment liquid>
The pretreatment liquid contains a coagulant, an organic solvent, and water, and may contain a surfactant, an antifoaming agent, a pH adjuster, an antiseptic / antifungal agent, a rust inhibitor and the like as required.
As the organic solvent, surfactant, defoaming agent, pH adjuster, antiseptic / antifungal agent, and rust inhibitor, the same materials as those used for the ink can be used, and other materials used for known treatment liquids can be used. .
The type of the flocculant is not particularly limited, and examples thereof include a water-soluble cationic polymer, an acid, and a polyvalent metal salt.

<Post-treatment liquid>
The post-treatment liquid is not particularly limited as long as a transparent layer can be formed. The post-treatment liquid is obtained by selecting and mixing an organic solvent, water, a resin, a surfactant, an antifoaming agent, a pH adjuster, an antiseptic / antifungal agent, a rust inhibitor and the like, as necessary. Further, the post-treatment liquid may be applied to the entire recording area formed on the recording medium, or may be applied only to the area where the ink image is formed.

  Here, FIG. 1 is a schematic diagram of an image forming apparatus as an example of a printing apparatus using continuous paper. The image forming apparatus 100 shown in FIG. 1 includes a paper feeding device 1, continuous paper 2 as a recording medium, a pretreatment liquid application unit 3, an ink ejection unit head 4, a drying unit 5, a transport roller 6, and an image collection (winding) device. ) Section 7. In the image forming apparatus 100 of FIG. 1, pressure is applied to the image surface of the continuous paper 2 as the recording medium in the process of coming into contact with the transport roller 6 immediately after the drying unit 5. When continuous paper 2 is used as a recording medium and the continuous paper 2 is wound, a force in both a horizontal direction and a vertical direction is applied to the image surface at the time of winding, and blocking (transfer to a recording medium overlapping the image surface) is performed. ) And abrasion remain. This problem can be solved by including the resin in the ink, but in this case, the image is transferred (white spots) to the transport roller 6 with which the image surface contacts before winding. In particular, since it is necessary to apply tension to a continuous paper having a wide paper width and a large basis weight, the image surface is strongly pressed against the conveying roller 6 in contact with the continuous paper, and the image transfer becomes easier.

However, when an image forming apparatus using continuous paper as shown in FIG. 1 is used, a large pressure is applied near the center of the roll in the process of rewinding the printed paper into a roll, and the image is offset. That is a widespread problem. Further, in a case where the printed paper is re-wound into a roll by applying tension to the continuous paper, a large pressure is applied not only near the center of the roll but also at the outer edge of the roll, and the image may be offset.
If an image that satisfies the requirements of the logarithmic decay rate of the present invention can be formed, if the pressure is within a specified pressure range, not only offset does not occur, but also the fixability and gloss of the image can be obtained.
In addition to the pressure caused by the overlapping of continuous paper as described above, when cut paper is laminated, or when pressure is applied due to the work of cutting continuous paper or cut paper, or to improve the fixability after printing There is a case where pressure is applied by installing a roller for applying the post-treatment liquid or a roller for applying the post-treatment liquid, and such a case is also included in the scope of the present invention.

Here, FIG. 2 is a schematic view showing an ink jet recording apparatus as an example of a printing apparatus to which the present invention is applied. An ink jet recording apparatus 300 to which the present invention is applied includes a recording medium transport unit 301, a preprocessing step unit 302 for applying a pretreatment liquid to the recording medium 203, and a preprocessing for drying the recording medium 203 to which the pretreatment liquid has been applied. A post-drying unit 303 and an image forming process unit 304; a post-processing process unit 305 that applies a post-processing liquid to the recording medium after the image forming process; and a post-processing post-drying unit 306 that dries the recording medium 203 to which the post-processing liquid has been applied. It is composed of
The recording medium transport unit 301 includes a paper feed device 307, a plurality of transport rollers, and a winding device 308. The recording medium 203 in FIG. 2 is continuous paper (rolled paper) wound in a roll shape, and the recording medium 203 is unwound from a sheet feeding device by a conveyance roller, conveyed on a platen, and wound by a winding device. Taken.
The pretreatment liquid is applied to the recording medium 203 transported from the recording medium transport unit 301 in the preprocessing step unit 302 in FIG. In the case of inkjet, when an image is formed on a recording medium other than an inkjet dedicated paper, quality problems such as bleeding, density, color tone and show-through, and problems relating to image fastness such as water resistance and weather resistance have occurred. As means for solving the problem, prior to forming an image on a recording medium, a technique for applying a pretreatment liquid having a function of aggregating ink to improve image quality is performed.
As the pretreatment step, an application method for uniformly applying the above pretreatment liquid to the printing paper surface may be used, and there is no particular limitation. Examples of such a coating method include a blade coating method, a gravure coating method, a gravure offset coating method, a bar coating method, a roll coating method, a knife coating method, an air knife coating method, a comma coating method, a U comma coating method, and an AKKU coating method. Smoothing coat method, microgravure coat method, reverse roll coat method, four to five roll coat method, dip coat method, curtain coat method, slide coat method, die coat method and the like.

  Further, the pretreatment section may be provided with a post-pretreatment drying section 303 after the coating step as shown in FIG. The post-pretreatment drying device includes, for example, heat rollers 311 and 312 as shown in FIG. According to this apparatus, the continuous paper coated with the pretreatment liquid is transported to the heat roller by the transport roller. The heat roller is heated to a high temperature of 50 to 100 ° C., and the continuous paper coated with the pretreatment liquid is dried by evaporating moisture by contact heat transfer from the heat roller.

FIG. 3 is an enlarged view of the head unit 304K-1. As shown in FIG. 3, a large number of print nozzles 310 are arranged along the longitudinal direction of the head unit 304K-1 on the nozzle surface 309 of the 304K-1 to form a nozzle row. In this embodiment, the number of nozzle rows is one, but a plurality of rows can be provided. The other recording heads 304C, 304M, and 304Y have the same configuration, and the four recording heads 304K, 304C, 304M, and 304Y are arranged in the transport direction while maintaining the same pitch. Thus, it is possible to form an image over the entire print area width by one recording operation.
The post-processing liquid is applied to the recording medium after the image forming step in the post-processing step section 305. The post-treatment liquid described below contains a component capable of forming a transparent protective layer on the recording medium.

In the post-processing step in the present embodiment, the image is applied only to a specific portion of the image forming area of the recording medium. It is preferable to apply an optimal amount of the coating according to the color of the ink forming the image. More preferably, the amount and method of application may be changed according to the type and resolution of the recording medium.
Thereafter, the method of applying the treatment liquid is not particularly limited, and various methods are appropriately selected depending on the type of the post-treatment liquid, but the same method as the method of applying the pre-treatment liquid or the above-described ink jet ink is ejected. Any of the methods similar to the method can be suitably used. Among these, a method similar to the method of ejecting the inkjet ink is particularly preferable from the viewpoint of the apparatus configuration and the storage stability of the post-treatment liquid. The post-treatment step is a step of forming a protective layer by applying a post-treatment liquid containing a transparent resin so that the dry adhesion amount is 0.5 g / m ² or more and 10 g / m ² or less on the formed image surface. is there.

  The drying device after the post-processing includes, for example, heat rollers 313 and 314 as shown in FIG. According to this drying device, the continuous paper coated with the post-treatment liquid is transported to the heat roller by the transport roller. The heat roller is heated to a high temperature, and the continuous paper coated with the post-treatment liquid evaporates moisture by contact heat transfer from the heat roller and is dried. The drying means is not limited to this, and an infrared drying apparatus, a microwave drying apparatus, a hot air and the like can also be applied.Instead of using a single apparatus, for example, a heat roller and a hot air apparatus are combined. You may.

(Printed matter)
Printed matter of the present invention, a recording medium, a printed matter having an image on the recording medium,
The image contains a coloring material, and a urethane resin having a ring structure and a non-ring structure,
The logarithmic decrement of the rigid pendulum test in the image is 0.020 or more and 0.060 or less.
The image preferably has a surface glass transition temperature (Tg) of 0 ° C. or more and 30 ° C. or less.

The use of the ink of the present invention is not particularly limited and can be appropriately selected according to the purpose. For example, the ink can be applied to printed matter, paints, coating materials, base materials, and the like. Further, it can be used not only to form two-dimensional characters and images using ink, but also as a material for three-dimensional modeling for forming a three-dimensional three-dimensional image (three-dimensional object).
A three-dimensional modeling device for modeling a three-dimensional molded object can use a known device, and is not particularly limited. For example, a device including an ink storage unit, a supply unit, a discharge unit, a drying unit, and the like is used. be able to. The three-dimensional object includes a three-dimensional object obtained by, for example, over-coating ink. Further, a molded product obtained by processing a structure obtained by applying ink on a base material such as a recording medium is also included. The molded product is obtained by, for example, applying a molding process such as a heat drawing or a punching process to a recording material or a structure formed in a sheet shape or a film shape. -It is suitably used for molding after decorating the surface, such as meters of electronic devices and cameras and panels of operation units.

  Further, image forming, recording, printing, printing and the like in the terms of the present invention are all synonymous.

  A recording medium, a medium, and a printed material are all synonyms.

  Examples of the present invention will be described below, but the present invention is not limited to these examples.

(Synthesis Example 1)
-Synthesis of urethane resin 1-
80 parts by mass of cyclohexane-1,4-dimethanol, 10 parts by mass of 1,6-hexanediol, 272.1 parts by mass of a 25% by mass aqueous solution of sodium hydroxide (NaOH), and 411.3 parts by mass of water were added to hydrosulfite 0 After melting at 60 ° C. in the presence of 0.339 parts by mass, the mixture was cooled to room temperature to obtain a raw material aqueous solution.
Next, 8.87 kg / hour of the raw material aqueous solution and 4.37 kg / hour of methylene chloride were introduced into a 1.8 L glass-made first reactor having a reflux condenser, a stirrer, and a refrigerant jacket. It was brought into contact with 0.775 kg / hour of phosgene at normal temperature which was separately supplied.
Next, the reaction solution / reaction gas was introduced into a second reactor (1.8 L) having the same shape as the next first reactor through an overflow pipe attached to the first reactor, and reacted.
Next, 0.037 kg / hour of pt-butylphenol (8% by mass methylene chloride solution) was separately introduced into the second reactor as a molecular weight regulator.
Next, the reaction solution / reaction gas was introduced into the oligomerization tank (4.5 L) having the same shape as that of the first reactor from the overflow pipe attached to the second reactor.
Next, 0.016 kg / hour of a 2% by mass aqueous solution of trimethylamine (0.00083 mol per mol of cyclohexane-1,4-dimethanol and 1,6-hexanediol) was separately introduced as a catalyst into the oligomerization tank. .
Next, the obtained oligomerized emulsion was further guided to a separation tank (settler) having an inner volume of 5.4 L, and the aqueous phase and the oil phase were separated to obtain a methylene chloride solution of the oligomer.
2.44 kg of the methylene chloride solution of the above oligomer was charged into a 6.8 L internal volume reactor equipped with paddle blades, and 2.60 kg of methylene chloride for dilution was added thereto. 245 kg, 0.953 kg of water, 8.39 g of a 2% by weight aqueous triethylamine solution, and 25.8 g of pt-butylphenol (8% by weight methylene chloride solution) as a molecular weight modifier were added, and the mixture was stirred at 10 ° C. and subjected to polycondensation for 180 minutes. The reaction was performed.
3.12 kg of the above polycondensation reaction solution was charged into a 5.4 L internal volume reactor equipped with paddle blades, and 2.54 kg of methylene chloride and 0.575 kg of water were added thereto. After stirring for 15 minutes, stirring was stopped. And the aqueous and organic phases were separated.
Next, 1.16 kg of 0.1 N hydrochloric acid was added to the separated organic phase, and the mixture was stirred for 15 minutes. After extracting triethylamine and a small amount of remaining alkaline component, the stirring was stopped, and the aqueous phase and the organic phase were separated.
Next, 1.16 kg of pure water was added to the separated organic phase, and after stirring for 15 minutes, the stirring was stopped, and the aqueous phase and the organic phase were separated. This operation was repeated three times. The obtained polycarbonate solution was powdered by feeding it into hot water at 60 ° C. to 75 ° C. and dried to obtain a powdered polycarbonate resin.

500 g of a powdery polycarbonate resin, 30.5 g of dimethylolpropionic acid, 241 g of isophorone diisocyanate (IPDI), and 420 g of acetone were charged into an autoclave reactor equipped with a stirrer and a jacket while introducing nitrogen. Then, it heated at 80 degreeC and performed urethanization reaction for 5 hours, and manufactured the prepolymer. The obtained prepolymer had a solid content concentration of 67% by mass and an NCO% of 1.03%.
Next, 32.2 g of a 50% by mass acetone solution of triethylamine was added thereto, and the mixture was further stirred for 30 minutes. After the temperature of the system was returned to 40 ° C., 1,450 g of ion-exchanged water was gradually introduced into a system stirred at 300 rpm under a nitrogen stream to form fine particles. After charging the whole amount, stirring was performed for 15 minutes.
Next, diethylene triamine as a chain extender was weighed such that [equivalent number of chain extender × mass of solid content of prepolymer solution / NCO equivalent number of prepolymer] was 1.0, and a 10% by mass acetone solution was added to the system. And stirred for 5 hours to carry out a chain extension reaction. Thereafter, acetone was removed using an evaporator, and then diluted with water so that the solid content concentration became 30% by mass, to obtain a urethane resin emulsion 1 containing the urethane resin 1 of Synthesis Example 1.

(Synthesis Example 2)
-Synthesis of urethane resin 2-
In Synthesis Example 1, cyclohexane-1,4-dimethanol was changed to 2,5-dimethylcyclohexane-1,4-dimethanol, and 1,6-hexanediol was changed to 3-methyl-1,5-pentanediol. A urethane resin emulsion 2 containing the urethane resin 2 of Synthesis Example 2 was obtained in the same manner as in Synthesis Example 1 except for the above.

(Synthesis Example 3)
-Synthesis of urethane resin 3-
A urethane resin emulsion 3 containing the urethane resin 3 of Synthesis Example 3 was prepared in the same manner as in Synthesis Example 1 except that cyclohexane-1,4-dimethanol was changed to benzene-1,4-dimethanol in Synthesis Example 1. Obtained.

(Synthesis example 4)
-Synthesis of urethane resin 4-
An autoclave reactor equipped with a stirrer and a jacket was charged with 500 g of polycarbonate 1,6-hexanediol having a number average molecular weight (Mn) of 1,000, 50 g of isophorone diisocyanate (IPDI), and 420 g of acetone while introducing nitrogen. Then, it heated at 80 degreeC and performed urethanization reaction for 5 hours, and manufactured the prepolymer.
The obtained prepolymer had a solid content concentration of 67% by mass and an NCO% of 1.03%.
Next, 32.2 g of a 50% by mass acetone solution of triethylamine was added thereto, and the mixture was further stirred for 30 minutes. After the temperature of the system was returned to 40 ° C., 1,450 g of ion-exchanged water was gradually introduced into a system stirred at 300 rpm under a nitrogen stream to form fine particles. After charging the whole amount, stirring was performed for 15 minutes.
Next, diethylene triamine as a chain extender was weighed such that [equivalent number of chain extender × mass of solid content of prepolymer solution / NCO equivalent number of prepolymer] was 1.0, and a 10% by mass acetone solution was added to the system. And stirred for 5 hours to carry out a chain extension reaction. Thereafter, acetone was removed using an evaporator, and then diluted with water so that the solid content concentration became 30% by mass, to obtain a urethane resin emulsion 4 containing the urethane resin 4 of Synthesis Example 4.

(Synthesis example 5)
-Synthesis of urethane resin 5-
In Synthesis Example 4, 50 g of polycarbonate 1,6-hexanediol having a number average molecular weight (Mn) of 1,000 and polycarbonate cyclohexane-1, having a number average molecular weight (Mn) of 1,000 were placed in an autoclave reactor equipped with a stirrer and a jacket. A urethane resin emulsion 5 containing the urethane resin 5 of Synthesis Example 5 was prepared in the same manner as in Synthesis Example 4 except that 450 g of 4-dimethanol, 50 g of isophorone diisocyanate (IPDI), and 420 g of acetone were charged while introducing nitrogen. Obtained.

  Next, the glass transition temperature and the weight average molecular weight of the synthesized urethane resins 1 to 5 were measured as follows. The results are shown in Table 1.

<Glass transition temperature>
The glass transition temperature of the resin was measured using a differential scanning calorimeter DSC6200 (manufactured by Seiko Instruments Inc.). The resin emulsion was evaporated to dryness, and the resin component was used as a measurement sample. After the temperature of the sample was raised to 200 ° C., the temperature of the sample cooled to 0 ° C. at a rate of 10 ° C./min was measured by raising the temperature at a rate of 10 ° C./min.

<Weight average molecular weight>
The measurement was performed using gel permeation chromatography (GPC). The resin emulsion was evaporated to dryness, and the resin component was dissolved in tetrahydrofuran (THF) to obtain a measurement sample.

(Example 1)
<Preparation of ink>
As pigments, 6% by mass of carbon black (manufactured by Degussa, Nipex160), 25% by mass of propylene glycol (manufactured by Sigma-Aldrich), 3% by mass of glycerin (manufactured by Sigma-Aldrich), 3% by mass of dipropylene glycol monomethyl ether (Sigma-Aldrich) 5% by mass, 10% by mass of urethane resin emulsion 1 (solid content concentration: 30% by mass), and the remaining amount of water was added so that the total would be 100% by mass. After mixing and stirring, water having an average pore diameter of 1.5 μm was added. The ink of Example 1 was produced by filtration with a polypropylene filter (trade name: Profile Star, manufactured by Nippon Pall Co., Ltd.).

<Image evaluation>
Using the ink of Example 1, an image printed using an inkjet printing system (RICOH Pro VC60000, manufactured by Ricoh Co., Ltd.) was evaluated.
As a recording medium, roll paper of Lumi Art Gloss 90 gsm (manufactured by Stora Enso, paper width 520.7 mm) was set, and a solid image was recorded at a resolution of 1200 dpi. The amount of pure water transferred to the recording medium at a contact time of 100 ms of “Lumi Art Gloss 90 gsm” was 4.9 g / m ² .
The winding device used was a Rewinding module RW6 (manufactured by Hunkeler). At this time, the winding tension was varied, and as shown in Table 2 below, the pressure applied to the image was changed to obtain "blocking resistance", 60 ° glossiness ”and“ fixability ”were evaluated. The results are shown in Table 2. The pressure applied to the image is a value at the time when the roll paper has a thickness of 100 mm, and was measured using a pressure distribution measurement system I-SCAN40.

<Rigid pendulum test>
As a rigid pendulum test, the logarithmic decrement was calculated by the following method. As a method for measuring the logarithmic decrement of the image, a rigid pendulum type physical property tester RPT-3000W (manufactured by A & D) was used.
Within 3 minutes after printing, the printing surface was set up with a cooling / heating block (CHB-100), and the cylinder edge was set with one exclusive weight. At this time, it is necessary that all parts touching the cylinder edge be filled with the image. The measurement temperature was 30 ° C., and the logarithmic decrement was plotted against time. The measurement time was 3 minutes, and data was measured every 6 seconds. The result of averaging all logarithmic decrements was defined as the logarithmic decrement of the image.

<Glass transition temperature of image surface (Tg of image surface)>
The surface Tg of the image was measured using a horizontal force microscope (LFM). An image sample to be measured was placed on a Dimension Icon (manufactured by Bruker), and a temperature increase of 180 ° C to 400K at 10 ° C / min was observed to measure the lateral bias on the image surface. The temperature at which the lateral bias became the maximum value was defined as “Tg on the image surface”. The cantilever used for the measurement was ESP (manufactured by Bruker), and the measurement was performed with the indentation depth fixed at 300 nm.

<Blocking resistance>
About the obtained image, the state of sticking of the recorded images at the time of winding was confirmed by visual observation, and "blocking resistance" was evaluated based on the following evaluation criteria.
In addition, rank 7 or more is good in quality, and rank 10 is particularly good. Further, when the rank is 3 or less, the quality is significantly reduced.
[Evaluation criteria]
10: The recorded images do not stick together, there is no image peeling, and the image is visually uniform. 9: The recorded images do not stick together, there is no image peeling, but there is a minute image omission less than 10 μm. 8: The recorded images do not stick together and there is no image peeling, but there is a minute image omission of 10 μm or more and less than 20 μm 7: The recorded images do not stick together and there is no image peeling, but a minute image of 20 μm or more and less than 30 μm Image missing 6: Recorded images do not stick together and there is no image peeling, but minute image missing of 30 μm or more and less than 40 μm 5: Recorded images do not stick together and there is no image peeling, but 40 μm or more and 60 μm or less. 4: The recorded images do not stick together and there is no image peeling, but there is a minute image loss of 60 μm or more and less than 100 μm. Yes 3: Recorded images are stuck together and image is significantly missing 2: Recorded images are stuck together, image is significantly missing, paper is partially missing 1: Recorded images are stuck together, image Is markedly chipped, and the paper is markedly chipped. 0: Recorded images are stuck together and united

<60 ° gloss>
The obtained image was measured for 60 ° gloss using a gloss meter (Micro-TRI-Gloss 4520, manufactured by BYK Gardner).

<Fixing property>
The obtained image was rubbed 20 times with a Lumi Art Gloss 90 gsm paper (manufactured by Stora Enso), which was cut into a square of 1.2 mm, to remove ink stains on the paper, using a reflection type color spectrophotometer (X). -Rite), and the transfer density of the rubbed paper from which the background color was subtracted was evaluated according to the following criteria.
[Evaluation criteria]
：: Transfer density is less than 0.05 Δ: Transfer density is 0.05 or more and less than 0.10 ×: Transfer density is 0.10 or more

(Examples 2 to 11 and Comparative Examples 1 to 4)
In Example 1, inks of Examples 2 to 11 and Comparative Examples 1 to 4 were prepared in the same manner as in Example 1 except that the ink formulations shown in Tables 2 to 5 were used. Was evaluated. The results are shown in Tables 2 to 5.

* "-" In the blocking resistance of Comparative Example 4 in Table 5 means that measurement was impossible.

Details of each component in Tables 2 to 5 are as follows.
* 1,2-butanediol: manufactured by Sigma-Aldrich * Dipropylene glycol monobutyl ether: manufactured by Sigma-Aldrich * Dipropylene glycol ethyl methyl ether: manufactured by Sigma-Aldrich

Aspects of the present invention are, for example, as follows.
<1> an ink applying step of applying an ink to a recording medium to form an image;
A pressure step of applying pressure to the image,
Including
As the ink, water, a resin, an organic solvent, and an ink containing a coloring material,
The resin is a urethane resin having a ring structure and an acyclic structure,
A printing method, wherein a logarithmic decrement of a rigid pendulum test in the image is 0.020 or more and 0.060 or less.
<2> The printing method according to <1>, wherein the ring structure in the urethane resin is a six-membered ring structure.
<3> The printing method according to any one of <1> to <2>, wherein the ring structure in the urethane resin is a benzene ring.
<4> The printing method according to any one of <1> to <3>, wherein the urethane resin has an alkyl group in a side chain.
<5> The printing method according to any one of <1> to <4>, wherein the glass transition temperature (Tg) of the image surface is 0 ° C or more and 30 ° C or less.
<6> The printing method according to any one of <1> to <5>, wherein the recording medium is coated paper.
<7> The printing method according to any one of <1> to <6>, wherein the recording medium is continuous paper.
<8> The printing method according to any one of <1> to <7>, wherein the pressure in the pressing step is 5.0 kg / cm ² or more and 10.0 kg / cm ² or less.
<9> an ink containing water, a resin, an organic solvent, and a coloring material;
Ink applying means for applying the ink to a recording medium to form an image,
Pressurizing means for applying pressure to the image,
Have
The resin is a urethane resin having a ring structure and an acyclic structure,
A printing apparatus, wherein a logarithmic decrement of a rigid pendulum test in the image is 0.020 or more and 0.060 or less.
<10> The printing device according to <9>, wherein the ring structure of the urethane resin is a six-membered ring structure.
<11> The printing apparatus according to any one of <9> to <10>, wherein the ring structure in the urethane resin is a benzene ring.
<12> The printing apparatus according to any one of <9> to <11>, wherein the urethane resin has an alkyl group in a side chain.
<13> The printing apparatus according to any one of <9> to <12>, wherein the glass transition temperature (Tg) of the image surface is 0 ° C or more and 30 ° C or less.
<14> The printing apparatus according to any one of <9> to <13>, wherein the recording medium is coated paper.
<15> The printing apparatus according to any one of <9> to <14>, wherein the recording medium is continuous paper.
<16> The printing apparatus according to any one of <9> to <15>, wherein the pressure in the pressing step is 5.0 kg / cm ² or more and 10.0 kg / cm ² or less.
<17> An ink used in the printing method according to any one of <1> to <8>,
The ink is characterized in that the ink contains water, an organic solvent, a coloring material, and a urethane resin having a cyclic structure and an acyclic structure.
<18> A printed material having a recording medium and an image on the recording medium,
The image contains a coloring material, and a urethane resin having a ring structure and a non-ring structure,
A printed matter, wherein a logarithmic decrement of a rigid pendulum test in the image is 0.020 or more and 0.060 or less.
<19> The printed matter according to <18>, wherein a glass transition temperature (Tg) of the image surface is 0 ° C or more and 30 ° C or less.

  The printing method according to any one of <1> to <8>, the printing apparatus according to any one of <9> to <16>, the ink according to <17>, and the printing method according to <18> to <8. According to the printed matter described in any one of <19>, it is possible to solve the conventional problems and achieve the object of the present invention.

DESCRIPTION OF SYMBOLS 1 Paper feeder 2 Continuous paper 3 Pretreatment liquid application part 4 Ink ejection part head 5 Drying part 6 Conveyance roller 7 Image collection (winding) part 100 Printing device

JP-A-2017-132797

Claims (12)

An ink applying step of applying an ink to a recording medium to form an image,
A pressure step of applying pressure to the image,
Including
As the ink, water, a resin, an organic solvent, and an ink containing a coloring material,
The resin is a urethane resin having a ring structure and an acyclic structure,
A printing method, wherein a logarithmic decrement of a rigid pendulum test in the image is 0.020 or more and 0.060 or less.   The printing method according to claim 1, wherein the ring structure in the urethane resin is a six-membered ring structure.   The printing method according to claim 1, wherein a ring structure of the urethane resin is a benzene ring.   The printing method according to claim 1, wherein the urethane resin has an alkyl group in a side chain.   The printing method according to any one of claims 1 to 4, wherein a glass transition temperature (Tg) of the image surface is 0C or more and 30C or less.   The printing method according to claim 1, wherein the recording medium is coated paper.   The printing method according to claim 1, wherein the recording medium is continuous paper. The printing method according to any one of claims 1 to 7, wherein the pressure in the pressing step is 5.0 kg / cm ² or more and 10.0 kg / cm ² or less. Water, a resin, an organic solvent, and an ink containing a coloring material,
Ink applying means for applying the ink to a recording medium to form an image,
Pressurizing means for applying pressure to the image,
Have
The resin is a urethane resin having a ring structure and an acyclic structure,
A printing apparatus, wherein a logarithmic decrement of a rigid pendulum test in the image is 0.020 or more and 0.060 or less. An ink used in the printing method according to any one of claims 1 to 8,
An ink characterized in that the ink contains water, an organic solvent, a coloring material, and a urethane resin having a ring structure and a non-ring structure. A recording medium, a printed matter having an image on the recording medium,
The image contains a coloring material, and a urethane resin having a ring structure and a non-ring structure,
A printed matter, wherein a logarithmic decrement of a rigid pendulum test in the image is 0.020 or more and 0.060 or less. The printed matter according to claim 11, wherein a glass transition temperature (Tg) of the image surface is 0C or more and 30C or less.