JP7159628B2 - PRINTING METHOD, PRINTING APPARATUS, INK, AND PRINTED MATERIAL MANUFACTURING METHOD - Google Patents

Description

The present invention relates to printing methods, printing apparatuses, inks, and printed matter.

Conventionally, water-based inks for inkjet have been developed for printing on special papers such as plain paper and glossy photo paper. On the other hand, in recent years, the expansion of the application of the inkjet recording method is expected, 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 the image is deteriorated.

In order to solve the above problems, attempts have been made 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 composed of isophorone diisocyanate, which is a cyclic isocyanate, and polyethylene glycol, which is an acyclic polyol, has been proposed (for example, See Patent Document 1).

SUMMARY OF THE INVENTION An object of the present invention is to provide a printing method which does not cause blocking even when pressure is applied to an image, which is excellent in image fixability, and which can obtain an image with good glossiness.

A printing method of the present invention as a means for solving the above problems includes an ink application step of applying ink to a recording medium to form an image, and a pressurization step of applying pressure to the image, wherein the ink is , an ink containing water, a resin, an organic solvent, and a coloring material is used, the resin is a urethane resin having a cyclic structure and an acyclic structure, and the logarithmic decrement of the rigid body pendulum test in the image is 0.020. 0.060 or less.

According to the present invention, it is possible to provide a printing method that does not cause blocking even when pressure is applied to an image, that is excellent in image fixability, and that provides an image with good glossiness.

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

(Printing method and printing device)
The printing method of the present invention includes an ink application step of applying ink to a recording medium to form an image, and a pressure step of applying pressure to the image. is used, the resin is a urethane resin having a cyclic structure and an acyclic structure, the logarithmic attenuation rate of the rigid pendulum test in the image is 0.020 or more and 0.060 or less, and further if necessary other including the steps of

The printing apparatus of the present invention comprises an ink containing water, a resin, an organic solvent, and a coloring material, ink application means for applying ink to a recording medium to form an image, pressure means for applying pressure to the image, The resin is a urethane resin having a cyclic structure and an acyclic structure, and the logarithmic attenuation rate of the rigid pendulum test in the image is 0.020 or more and 0.060 or less, and if necessary, other means have

The printing method of the present invention can be performed by the printing apparatus of the present invention, the ink application step can be performed by ink application means, the pressurization step can be performed by pressurization means, and other steps. can be done by other means.

The printing method and printing apparatus of the present invention can improve the fixability, which is a conventional problem, by adding a resin emulsion to the ink in the prior art, but the resin that can improve the fixability is This is based on the knowledge that the tackiness of the image surface is increased by adding it because of its high elasticity. In addition, in the conventional technology, the tack force on the surface of the image increases, so that the image can be removed at the timing when pressure is applied to the image area, such as when fixing the image using a fixing roller after image formation, or when printing on roll paper and winding it up. This is based on the finding that blocking occurs and the gloss is lowered.

According to the study of the present inventors, if the logarithmic attenuation rate of the rigid pendulum test in the image is 0.020 or more and 0.060 or less, the image after image formation has a weight of 5.0 kg/cm ² or more and 10.0 kg/cm ² or less. It has been found that blocking does not occur even when a pressure of 100 psi is applied, fixability is improved, and an image with excellent glossiness can be obtained. If the logarithmic decrement exceeds 0.060, the stickiness in the image increases, and blocking may occur under strong pressure.
The logarithmic decay rate of the rigid pendulum test in the image can be measured as follows.

[Rigid body pendulum test]
For the rigid pendulum test, the logarithmic decrement is calculated by the following method. A rigid pendulum physical property tester RPT-3000W (manufactured by A&D) is used as a method for measuring the logarithmic attenuation rate of images. Within 3 minutes after printing, set the printed surface with a cold block (CHB-100) and set the cylinder edge with one dedicated weight. At this time, all the parts touching the cylinder edge must 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 logarithmic attenuation rate of the image is obtained by averaging all the logarithmic attenuation rates.

The glass transition temperature (Tg) of the obtained image surface is preferably 0° C. or higher and 40° C. or lower, more preferably 0° C. or higher and 30° C. or lower.
When the glass transition temperature (Tg) of the image surface is 0° C. or higher and 40° C. or lower, the image is not blocked even when pressure is applied, and an image having excellent image fixability and good glossiness 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 images was measured using lateral force microscopy (LFM). An image sample to be measured was placed on Dimension Icon (manufactured by Bruker), and the temperature was raised from 180K to 400K at a rate of 10°C/min and observed to measure the lateral bias of the image surface. The temperature at which the lateral bias becomes the maximum value was defined as "Tg of the image surface". The cantilever used for the measurement is ESP (manufactured by Bruker), and the depth of indentation is fixed at 300 nm.

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

The liquid ejection method is not particularly limited and can be appropriately selected according to the purpose. It is possible to use an on-demand type head that utilizes an actuator that utilizes force, or a continuous ejection charge control type head that can be used.

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

-resin-
The type of resin contained in the ink must be urethane resin.
A urethane resin is a resin having at least a urethane bond composed of an isocyanate group and an alcohol or carboxylic acid.
A urethane resin is required to have a cyclic structure and an acyclic structure, and has a cyclic structure and an acyclic structure composed of a saturated alkane, as represented by the following general formula 1. As a result, there is an advantage that glossiness can be improved by pressurization and blocking resistance can be maintained while maintaining fixability.

ただし、前記一般式１中、ｎ１～ｎ３は炭素原子の数を表し、ｍ１～ｍ３は水素原子の数を表す。ｎ１は１～６であり、ｎ２及びｎ３は０～１２である。ｎ１～ｎ３及びｍ１～ｍ３は独立していても同一でも構わない。Ｃｎ１Ｈｍ１、Ｃｎ２Ｈｍ２、及びＣｎ３Ｈｍ３は、飽和、不飽和、又は分鎖構造を問わない。なお、Ｃｎ１Ｈｍ１における炭素原子が他の元素に置き換わった構造であってもよい。 [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 1-6, and n2 and n3 are 0-12. n1 to n3 and m1 to m3 may be independent or the same. Cn1Hm1, Cn2Hm2, and Cn3Hm3 may be saturated, unsaturated, or branched. Note that a structure in which a carbon atom in Cn1Hm1 is replaced with another element may be used.

In the urethane resin used in the present invention, unlike conventional urethane resins, the portion located between the isocyanate portions is not the same monomer, and the ring structure and the non-ring structure must be randomly arranged. . Although it does not have to be completely random, for example, it is essential that the portion located between the isocyanate moieties has the structure shown in Example 2 below instead of the structure shown in Example 1 below. .
(Example 1): A-A-C-B-B-B-B-C-A-A-A-A-C-A-A-A-
(Example 2): B-A-C-A-A-B-A-C-A-B-A-A-C-A-B-A-
However, A represents a cyclic structure, B represents an acyclic structure, and C represents an isocyanate moiety.

It is preferable that the ring structure in the urethane resin is a six-membered ring structure, because a conformational structure that can be locally regarded as a crystal can be taken between the resins and the blocking resistance is improved.
A 6-membered ring structure means a structure in which six atoms are cyclically bonded, and the atoms consist of carbon atoms, and some of the carbon atoms may be substituted with heteroatoms, and benzene , cyclohexane, and the like.
It is preferable that the ring structure in the urethane resin is a benzene ring because the hardness of the resin itself can be increased.
It is preferable for the urethane resin to have an alkyl group in its side chain, because it can give an appropriate degree of freedom of deformation and can increase the gloss when pressurized.
The glass transition temperature of the urethane resin is not particularly limited and can be appropriately selected depending on the intended purpose.
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 4,500 or more and 5,500 or less.
As a confirmation method of such a resin component, there is a pyrolysis GC/MS or the like. By performing GC/MS measurement while heating the resin at 200° C., the resin can be decomposed and isolated for each monomer and confirmed as a component in the resin.

Examples of the method for producing the above urethane resin include a method of copolymerizing a polyisocyanate and a polyalcohol prepolymer.

Corresponding urethane resin particles may be used as the urethane resin. Ink can be obtained by mixing urethane resin particles in the form of a urethane resin emulsion in which water is dispersed as a dispersion medium with a material such as a coloring material or an organic solvent.
In addition to the urethane resin, polyester resin, acrylic resin, vinyl acetate resin, styrene resin, butadiene resin, styrene-butadiene resin, vinyl chloride resin, Other resins such as acrylic styrene resins and acrylic silicone resins can be added.

The volume average particle diameter of the resin particles is not particularly limited and can be appropriately selected according to the intended purpose. 200 nm or less is more preferable, and 10 nm or more and 100 nm or less is particularly preferable.
The volume average particle diameter 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 can be appropriately selected according to the purpose. However, 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 preferable, and 5% by mass or more and 20% by mass or less is more preferable.

-Organic solvent-
The organic solvent used in the present invention is not particularly limited, and any 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 water-soluble organic solvents include ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, and 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-hexanediol, ethyl-1,2,4-butanetriol, 1,2,3-butanetriol, 2,2,4-trimethyl- Polyhydric alcohols such as 1,3-pentanediol and petriol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, propylene glycol monoethyl Polyhydric alcohol alkyl ethers such as ethers, polyhydric alcohol aryl ethers such as ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone , 1,3-dimethyl-2-imidazolidinone, ε-caprolactam, nitrogen-containing heterocyclic compounds such as γ-butyrolactone, formamide, N-methylformamide, N,N-dimethylformamide, 3-methoxy-N,N- Amides such as 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, and ethylene carbonate. etc.
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.

Polyol compounds having 8 or more carbon atoms and glycol ether compounds are also preferably used.
Specific examples of polyol compounds having 8 or more carbon atoms include 2-ethyl-1,3-hexanediol and 2,2,4-trimethyl-1,3-pentanediol.
Specific examples of glycol ether compounds 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, ethylene glycol monobenzyl ether, and the like.

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 can be appropriately selected according to the purpose. 20% by mass or more and 60% by mass or less is more preferable.

-water-
The content of water in the ink is not particularly limited and can be appropriately selected according to the purpose. % or more and 60 mass % or less is more preferable.

The water is not particularly limited and can be appropriately selected depending on the purpose. Examples include pure water such as ion-exchanged water, ultrafiltrated water, reverse osmosis water, and distilled water; 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.
An inorganic pigment or an organic pigment can be used as the pigment. These may be used individually by 1 type, and may use 2 or more types together. Mixed crystals may also be used.
Examples of pigments that can be used include black pigments, yellow pigments, magenta pigments, cyan pigments, white pigments, green pigments, orange pigments, glossy color pigments such as gold and silver, and metallic pigments.
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 known methods such as contact method, furnace method, thermal method, etc. can be used.
Organic pigments include azo pigments, polycyclic pigments (e.g., phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, indigo pigments, thioindigo pigments, isoindolinone pigments, quinophthalone pigments, etc.). , dye chelates (eg, basic dye chelates, acid dye chelates, etc.), nitro pigments, nitroso pigments, aniline black, and the like. Among these pigments, those having good affinity with the solvent are preferably used. In addition, resin hollow particles and inorganic hollow particles can also be used.
Specific examples of pigments for black include carbon blacks (C.I. Pigment Black 7) such as furnace black, lamp black, acetylene black and channel black, or copper and iron (C.I. Pigment Black 11). , metals such as titanium oxide, and organic pigments such as aniline black (C.I. 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 (red red), 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.
Dyes are not particularly limited, and acid dyes, direct dyes, reactive dyes, and basic dyes can be used, and may be used singly or in combination of two or more.
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. Direct 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 below.

In order to disperse the pigment and obtain an ink, there are a method of introducing a hydrophilic functional group into the pigment to make it a self-dispersing pigment, a method of coating the surface of the pigment with a resin for dispersion, and a method of dispersing using a dispersant. method, etc.
As a method of making a self-dispersing pigment by introducing a hydrophilic functional group into a pigment, for example, by adding a functional group such as a sulfone group or a carboxyl group to a pigment (for example, carbon), it becomes dispersible in water. method.
As a method of coating the surface of a pigment with a resin and dispersing it, there is a method of encapsulating the pigment in microcapsules to make it dispersible in water. This can be rephrased as a resin-coated pigment. In this case, all the pigments mixed in the ink need not be coated with a resin, and uncoated pigments or partially coated pigments may be dispersed in the ink as long as the effects of the present invention are not impaired. may be
Examples of the method of dispersing using a dispersant include a method of dispersing using a known low-molecular-weight dispersant and high-molecular-weight dispersant typified by surfactants.
As the dispersant, it is possible to use, for example, anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, etc. depending on the pigment.
RT-100 (nonionic surfactant) manufactured by Takemoto Oil & Fat Co., Ltd. and sodium naphthalenesulfonate formalin condensate can also be suitably used as a dispersant.
A dispersing agent may be used individually by 1 type, or may use 2 or more types together.

-Pigment Dispersion-
Inks can be obtained by mixing materials such as water and organic solvents with pigments. Ink can also be produced by mixing a pigment, water, a dispersant, and the like to form a pigment dispersion, and then mixing materials such as water and an organic solvent.
The pigment dispersion is obtained by mixing and dispersing water, a pigment, a pigment dispersant, and optionally other components, and adjusting the particle size. Dispersion should be carried out using a disperser.
The particle diameter of the pigment in the pigment dispersion is not particularly limited, but the dispersion stability of the pigment is improved, and the image quality such as ejection stability and image density is improved. 500 nm or less is preferable, and 20 nm or more and 150 nm or less is more preferable. The particle size of the pigment can be measured using a particle size analyzer (Nanotrack Wave-UT151, manufactured by Microtrack Bell Co., Ltd.).
The content of the pigment in the pigment dispersion is not particularly limited and can be appropriately selected according to the purpose. % or more and 50 mass % or less is preferable, and 0.1 mass % or more and 30 mass % or less is more preferable.
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 according to the purpose. is preferably 20 nm or more and 1000 nm or less, more preferably 20 nm or more and 150 nm or less. The solid content includes resin particles, pigment particles, and the like. The particle size can be measured using a particle size analyzer (Nanotrack Wave-UT151, manufactured by Microtrack Bell Co., Ltd.).

Surfactants, antifoaming agents, antiseptic and antifungal agents, antirust agents, pH adjusters, etc. may be added to the ink, if necessary.

--Surfactant--
Any of silicone surfactants, fluorine surfactants, amphoteric surfactants, nonionic surfactants, and anionic surfactants can be used as surfactants.
The silicone-based surfactant is not particularly limited and can be appropriately selected depending on the purpose. Among them, those that do not decompose even at high pH are preferable. Those having an oxyethylene group or a polyoxyethylene polyoxypropylene group are particularly preferred because they exhibit good properties as water-based surfactants. As the silicone-based surfactant, a polyether-modified silicone-based surfactant can also be used, and examples thereof include compounds in which a polyalkylene oxide structure is introduced into the side chain of the Si portion of dimethylsiloxane.
Examples of fluorine-based surfactants include perfluoroalkylsulfonic acid compounds, perfluoroalkylcarboxylic acid compounds, perfluoroalkylphosphoric acid ester compounds, perfluoroalkylethylene oxide adducts, and perfluoroalkyl ether groups in side chains. Polyoxyalkylene ether polymer compounds are particularly preferred due to their low foaming properties. Examples of the perfluoroalkylsulfonic acid compound include perfluoroalkylsulfonic acid and perfluoroalkylsulfonate. Examples of the perfluoroalkylcarboxylic acid compounds include perfluoroalkylcarboxylic acids and perfluoroalkylcarboxylic acid salts. As the polyoxyalkylene ether polymer compound having a perfluoroalkyl ether group in a side chain, a sulfate ester salt of a polyoxyalkylene ether polymer having a perfluoroalkyl ether group in a side chain, and a perfluoroalkyl ether group in a side chain Examples thereof include salts of polyoxyalkylene ether polymers. Counter ions of salts in these _{fluorosurfactants} include Li, Na, K, _NH4 , _NH3CH2CH2OH , _{NH2 ( CH2CH2OH} ) ₂ , and _{NH ( CH2CH2OH} ). ₃ and the like.
Amphoteric surfactants include, for example, laurylaminopropionate, lauryldimethylbetaine, stearyldimethylbetaine, lauryldihydroxyethylbetaine and the like.
Nonionic surfactants include, for example, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl esters, polyoxyethylene alkylamines, polyoxyethylene alkylamides, polyoxyethylene propylene block polymers, sorbitan fatty acid esters, polyoxyethylene sorbitan Examples include fatty acid esters and ethylene oxide adducts of acetylene alcohol.
Examples of anionic surfactants include polyoxyethylene alkyl ether acetates, dodecylbenzene sulfonates, laurates, and salts of polyoxyethylene alkyl ether sulfates.
These may be used individually by 1 type, or may use 2 or more types together.

As the fluorosurfactant, 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 fluorine-based surfactants include perfluoroalkyl phosphate ester compounds, perfluoroalkyl ethylene oxide adducts, and polyoxyalkylene ether polymer compounds having perfluoroalkyl ether groups in side chains. Among these, a polyoxyalkylene ether polymer compound having a perfluoroalkyl ether group in a side chain is preferable because of its low foamability, and in particular, fluorine-based compounds represented by general formulas (F-1) and (F-2) Surfactants are preferred.

上記一般式（Ｆ－１）で表される化合物において、水溶性を付与するためにｍは０～１０の整数が好ましく、ｎは０～４０の整数が好ましい。 General formula (F-1)

In the compound represented by the general 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)
_{CnF2n +1-} CH2CH(OH) _{CH2 -} O-( _CH2CH2O ) _{a -} Y
In the compound represented by the general formula (F-2), Y is H, or C _m F _2m+1 and m is an integer of 1 to 6, or CH ₂ CH(OH)CH ₂ —C _m F _2m+1 and m is An integer from 4-6, or CpH _2p+1 where p is an integer from 1-19. n is an integer of 1-6. a is an integer from 4 to 14;

Commercially available products may be used as the fluorosurfactant.
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.); Fleurard FC-93, FC-95, FC-98, FC-129, FC-135, FC-170C, FC-430, FC-431 (both manufactured by Sumitomo 3M); Megafac F-470, F -1405, F-474 (both 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 , Neos Co., Ltd.), Polyfox PF-136A, PF-156A, PF-151N, PF-154, PF-159 (manufactured by Omnova), Unidyne DSN-403N (manufactured by Daikin Industries, Ltd.), and the like. Among these, FS-3100, FS-34, FS-300 manufactured by Chemours, and Neos Co., Ltd. are excellent in terms of remarkably improving good print quality, particularly color development, permeability to paper, wettability, and level dyeing. FT-110, FT-250, FT-251, FT-400S, FT-150, FT-400SW manufactured by Omnova Co., Ltd., Polyfox PF-151N manufactured by Omnova Co., Ltd., and Unidyne DSN-403N manufactured by Daikin Industries, Ltd. are particularly preferred.

The content of the surfactant in the ink is not particularly limited and can be appropriately selected according to the purpose. % or more and 5 mass % or less is preferable, and 0.05 mass % or more and 5 mass % or less is more preferable.

-- Defoamer --
The antifoaming agent is not particularly limited, and examples thereof include silicone antifoaming agents, polyether antifoaming agents, and fatty acid ester antifoaming agents. These may be used individually by 1 type, or may use 2 or more types together. Among these, silicone-based antifoaming agents are preferred because of their excellent foam breaking effect.

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

--anti-rust--
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 it can adjust the pH to 7 or higher, 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 intended purpose. For example, viscosity, surface tension, pH and the like are preferably within the following ranges.
The viscosity of the ink at 25° C. is preferably 5 mPa·s or more and 30 mPa·s or less, more preferably 5 mPa·s or more and 25 mPa·s or less, from the viewpoint of improving the print density and character quality and obtaining good ejection properties. more preferred. Here, for viscosity, for example, a rotational viscometer (RE-80L manufactured by Toki Sangyo Co., Ltd.) can be used. Measurement conditions are 25° C., standard cone rotor (1°34′×R24), sample liquid volume 1.2 mL, rotation speed 50 rpm, 3 minutes.
The surface tension of the ink is preferably 35 mN/m or less, more preferably 32 mN/m or less at 25° C., from the viewpoint that the ink is appropriately 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, more preferably from 8 to 11, from the viewpoint of preventing corrosion of metal members in contact with the liquid.

<<Recording medium>>
The recording medium is not particularly limited and can be appropriately selected according to the purpose. Examples thereof include plain paper, glossy paper, special paper, cloth, film, OHP sheet, and general-purpose printing paper.
Among these, the recording medium that can obtain the effect in the present invention comprises a support and a coating layer provided on at least one side of the support, and if necessary, other A recording medium having a layer of The recording medium having such a support and coating layer is generally called coated paper, and is known as a recording medium with low ink permeability. It is difficult to firmly fix a coloring material on a recording medium with low permeability such as coated paper, and the rubbing property is often deteriorated. If the logarithmic attenuation 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 the glossiness is improved. It is particularly preferred because an image with good properties can be obtained.

In a recording medium having a support and a coating layer, the transfer amount of pure water to the recording medium at a contact time of 100 ms measured by a dynamic scanning liquid absorber is preferably 2 mL/m ² or more and 35 mL/m ² or less. , 2 mL/m ² or more and 10 mL/m ² or less.
If the amount of pure water transferred at the contact time of 100 ms is too small, beading may easily occur.
The transfer amount of pure water to the recording medium at a contact time of 400 ms measured by a dynamic scanning liquid absorber is preferably 3 mL/m ² or more and 40 mL/m ² or less, more preferably 3 mL/m ² or more and 10 mL/m ² or less. .
If the amount of pure water transferred at the contact time of 400 ms is too small, spur marks may be likely to occur due to insufficient drying properties. It can get easier. The amounts of pure water transferred to the recording medium at the contact times of 100 ms and 400 ms are both measured on the side of the recording medium having the coating layer.

Here, the dynamic scanning absorptometer (DSA, Paper-Paper Technology Association, Vol. 48, May 1994, pp. 88-92, Shigenori Kuga) measures the amount of liquid absorbed in a very short time. It is a device that can accurately measure The dynamic scanning liquid absorption meter directly reads the speed of liquid absorption from the movement of the meniscus in the capillary. is automatically changed, and the measurement is automated by a method of measuring only the required number of points on one sample. A liquid supply head to the paper sample is connected to the capillary through 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 amount of transfer at a contact time of 100 ms and a contact time of 400 ms can be obtained by interpolation from the measured values of the amount of transfer at contact times adjacent to each contact time.

-Support-
The support is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include sheet materials such as paper mainly composed of wood fibers and non-woven fabric mainly composed of wood fibers and synthetic fibers.
The paper is not particularly limited, and can be appropriately selected from known papers according to the purpose. For example, wood pulp, used paper pulp, and the like are used. Examples of wood pulp include bleached hardwood kraft pulp (LBKP), bleached softwood kraft pulp (NBKP), NBSP, LBSP, GP, and TMP.
The raw materials for waste paper pulp are listed in the waste paper standard quality specification table of the Waste Paper Recycling Promotion Center. , Tokujogiri, Betsujogiri, newspapers, magazines, etc. Specifically, printer paper such as non-coated computer paper, thermal paper, pressure-sensitive paper, etc.; OA waste paper such as PPC paper; coated art paper, coated paper, lightly coated paper, matte paper, etc. Paper: High-quality paper, high-quality colored paper, notebooks, letter paper, wrapping paper, fancy paper, medium-quality paper, newsprint, rough paper, super hanging paper, imitation paper, pure white roll paper, non-coated paper such as milk cartons, etc. Paper and paperboard waste paper, including chemical pulp paper and paper containing high-yield pulp. 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) Defragmentation involves treating waste paper with a mechanical force and chemicals in a pulper to loosen it into fibers and strip the printing ink from the fibers.
(2) Dust removal removes foreign matter (such as plastic) and dust contained in used paper using a screen, cleaner, or the like.
(3) Deinking removes the printing ink that has been stripped from the fibers using a surfactant by a flotation method or a washing method.
(4) Bleaching enhances the whiteness of fibers by using oxidizing and reducing actions.
When the waste paper pulp is mixed, the mixing ratio of the waste paper pulp in the total pulp is preferably 40% or less in order to prevent curling after recording.

As the internal filler used for the support, for example, conventionally known white pigments are 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; styrene plastic pigments, acrylic plastic pigments, polyethylene, microcapsules, urea resins , organic pigments such as melamine resins, and the like. These may be used individually by 1 type, and may use 2 or more types together.

Examples of internal sizing agents used in papermaking of the support include neutral rosin-based sizing agents used in neutral papermaking, alkenyl succinic anhydride (ASA), alkylketene dimer (AKD), and petroleum resin-based sizing agents. sizing agents, and the like. Among these, neutral rosin sizing agents or alkenyl succinic anhydrides are particularly preferred. Alkyl ketene dimer has a high sizing effect, so it can be added in a small amount. However, the coefficient of friction of the surface of the recording medium decreases, making it more slippery.

-Coating layer-
The coating layer contains a pigment and a binder (binder) and, if necessary, a surfactant and other components. In the present invention, the coating layer may contain a pigment and a binder (binder) as described above. defined as none.

Continuous paper is preferably used as the recording medium.
The continuous paper is a recording medium that is continuous in the conveying direction during image formation.
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 step and pressure means>
The pressurizing step is a step of applying pressure to the image, and is carried out by pressurizing means.
The method of applying pressure to the image is not particularly limited as long as it can apply pressure to the image. Examples include a method of winding the continuous paper on which the image has been formed by application into a roll with a winding device.
In the method of winding the continuous paper into a roll using a winding device, the pressure applied to the image on the continuous paper can be adjusted by the tension with which the winding device winds up the continuous paper.
The pressurizing step may employ a plurality of steps, or may be one step. Moreover, the pressure should be applied to at least a part of the recording medium, and preferably applied to the entire recording medium.
The pressure (pressure applied to the image) in the pressing step is preferably 3.0 kg/cm ² or more and 12.0 kg/cm ² or less, more preferably 5.0 kg/cm ² or more and 10.0 kg/cm ² or less.
When the pressure applied to the image is 3.0 kg/cm ² or more, sufficient image fixability can be obtained, and the rubbing property can be improved. On the other hand, if the pressure applied to the image is 12.0 kg/cm ² or less, the anti-blocking property can be favorably suppressed, which is preferable.
The pressure applied to the image can be measured by the pressure distribution measurement system I-SCAN 40, for example.
In addition, you may heat with pressurization. Drying time can be shortened by heating.

<Other steps and other means>
Other steps are not particularly limited and can be appropriately selected according to the purpose, and examples thereof include a control step, a display step, and a recording step.
Other means are not particularly limited and can be appropriately selected according to the purpose. Examples thereof include control means, display means, recording means and the like.

The ink of the present invention can be suitably used for various inkjet recording apparatuses, such as printers, facsimile machines, copiers, printer/facsimile/copier complex machines, stereolithography machines, and the like.
In the present invention, a recording apparatus and a recording method refer to an apparatus capable of ejecting ink, various treatment liquids, and the like onto a recording medium, and a method of performing recording using the apparatus. A recording medium means a medium to which ink or various processing liquids can adhere even temporarily.
This recording apparatus can include not only a head portion for ejecting ink, but also means for feeding, conveying, and discharging a recording medium, and other devices called pre-processing devices and post-processing devices. .
The recording apparatus and recording method may have heating means used in the heating process and drying means used in the drying process. The heating means and drying means include, for example, means for heating and drying the printing surface and the back surface of the recording medium. The heating means and drying means are not particularly limited, but for example, hot air heaters and infrared heaters can be used. Heating and drying can be performed before, during, or after printing.
Also, the recording apparatus and recording method are not limited to those that visualize significant images such as characters and graphics with ink. For example, it includes those that form patterns such as geometric patterns, and those that form three-dimensional images.
In addition, unless otherwise specified, the recording apparatus includes both a serial type apparatus in which the ejection head is moved and a line type apparatus in which the ejection head is not moved.
Furthermore, this recording device can be used not only as a desktop type, but also as a wide-width recording device that can print on A0 size recording media, and for example, a roll of continuous paper can be used as a recording medium. A continuous feed printer is also included.

This recording apparatus can include not only a portion that ejects ink, but also devices called pre-processing devices and post-processing devices.
As an aspect of the pre-treatment device and the post-treatment device, it has a pre-treatment liquid and a post-treatment liquid in the same manner 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 container and a liquid ejection head are added, and the pretreatment liquid and the posttreatment liquid are ejected by an inkjet recording method.
As another aspect of the pre-treatment device and the post-treatment device, there is an aspect in which a pre-treatment device and a post-treatment device using a method other than the inkjet recording method, such as a blade coating method, a roll coating method, and a spray coating method, are provided.

<Pretreatment liquid>
The pretreatment liquid contains a flocculant, an organic solvent, and water, and if necessary, may contain a surfactant, an antifoaming agent, a pH adjuster, an antiseptic, an antifungal agent, an antirust agent, and the like.
Organic solvents, surfactants, antifoaming agents, pH adjusters, antiseptic antifungal agents, and antirust agents can be the same materials as those used for inks, and other materials used for known treatment liquids can be used. .
The type of flocculant is not particularly limited, and examples thereof include water-soluble cationic polymers, acids, polyvalent metal salts, and the like.

<Post-treatment liquid>
The post-treatment liquid is not particularly limited as long as it can form a transparent layer. The post-treatment liquid is obtained by selecting and mixing organic solvents, water, resins, surfactants, antifoaming agents, pH adjusters, antiseptic antifungal agents, anticorrosive agents, etc., as necessary. 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. ) has a portion 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 contacting the conveying roller 6 immediately after the drying unit 5 . When the continuous paper 2 is used as the recording medium and the continuous paper 2 is wound, a force is applied to the image surface in both the horizontal and vertical directions during winding, causing blocking (transfer onto the recording medium overlapping the image surface). ) and scratches remain. This problem can be solved by including a resin in the ink, but in this case, the image may be transferred (void) to the conveying roller 6 with which the image surface contacts before winding. In particular, the wider the width of the paper and the larger the basis weight of the continuous paper, the more tension it is necessary to apply.

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. is a widespread problem. Further, when tension is applied to the continuous paper and the printed paper is rewound into a roll, a large pressure is applied not only near the center of the roll but also at the outer edge of the roll, which may cause an image to be offset.
If an image satisfying the requirements of the logarithmic attenuation rate of the present invention can be formed, offset will not occur within the specified pressure range, and fixability and glossiness of the image can be obtained.
In addition to the pressure generated by overlapping continuous paper as described above, when cut paper is stacked, when pressure is applied due to the work of cutting continuous paper or cut paper, and after printing, fixability is improved. There are cases 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 cases are also included in the scope of the present invention.

Here, FIG. 2 is a schematic diagram showing an inkjet recording apparatus as an example of a printing apparatus to which the present invention is applied. An inkjet recording apparatus 300 to which the present invention is applied includes a recording medium conveying unit 301, a pretreatment processing unit 302 for applying pretreatment liquid to a recording medium 203, and a pretreatment for drying the recording medium 203 to which the pretreatment liquid has been applied. A post-drying section 303 and an image forming process section 304, a post-processing process section 305 that applies post-treatment liquid to the recording medium after the image forming process, and a post-post-treatment drying section 306 that dries the recording medium 203 to which the post-treatment liquid has been applied. consists of
The recording medium conveying unit 301 includes a paper feeding device 307 , a plurality of conveying rollers, and a winding device 308 . The recording medium 203 in FIG. 2 is a roll of continuous paper (roll paper). The recording medium 203 is unwound from a paper feeding device by a conveying roller, conveyed on a platen, and wound by a winding device. be taken.
The recording medium 203 conveyed from the recording medium conveying unit 301 is coated with the pretreatment liquid in the pretreatment process unit 302 shown in FIG. With inkjet, when images are formed on recording media other than dedicated inkjet paper, there are quality problems such as bleeding, density, color tone, and show-through, as well as problems related to image fastness such as water resistance and weather resistance. As a solution to this problem, a technique is being developed to improve image quality by applying a pretreatment liquid having a function of aggregating ink before forming an image on a recording medium.
As the pretreatment process, a coating method for uniformly applying the pretreatment liquid to the surface of the printing paper may be used, and there is no particular limitation. Examples of such coating methods include blade coating, gravure coating, gravure offset coating, bar coating, roll coating, knife coating, air knife coating, comma coating, U comma coating, and AKKU coating. , a smoothing coating method, a micro gravure coating method, a reverse roll coating method, a four or five roll coating method, a dip coating method, a curtain coating method, a slide coating method, a die coating method, and the like.

In addition, as shown in FIG. 2, the pretreatment section may be provided with a post-pretreatment drying section 303 after the coating step. The post-pretreatment drying device is composed of heat rollers 311 and 312 as shown in FIG. 2, for example. According to this apparatus, the continuous paper coated with the pretreatment liquid is conveyed to the heat roller by the conveying roller. The heat roller is heated to a high temperature of 50 to 100° C., and the continuous paper coated with the pretreatment liquid evaporates moisture and dries due to 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 304K-1 to form a nozzle row. Although the number of nozzle rows is one in this embodiment, a plurality of rows may 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. As a result, it is possible to form an image over the entire width of the print area with a single recording operation.
After the image forming process, the recording medium is applied with a post-treatment liquid in the post-treatment process section 305 . This post-treatment liquid, which will be described later, contains components capable of forming a transparent protective layer on the recording medium.

In the post-processing step in this embodiment, the toner is applied only to a specific portion of the image forming area of the recording medium. It is preferable to apply an optimum amount according to the color of the ink forming the image. More preferably, the coating amount and coating method should be changed according to the type and resolution of the recording medium.
After that, 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. Any of the similar methods can be suitably used. Among these, a method similar to the method of jetting 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 to the surface of the formed image so that the dry adhesion amount is 0.5 g/m ² or more and 10 g/m ² or less. be.

The drying device after the post-treatment consists of heat rollers 313 and 314 as shown in FIG. 2, for example. According to this drying apparatus, the continuous paper coated with the post-treatment liquid is conveyed to the heat roller by the conveying roller. The heat roller is heated to a high temperature, and the continuous paper coated with the post-treatment liquid evaporates moisture and dries due to contact heat transfer from the heat roller. The drying means is not limited to this, and infrared drying equipment, microwave drying equipment, hot air, etc. can also be applied. may

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

The use of the ink of the present invention is not particularly limited and can be appropriately selected according to the intended purpose. Furthermore, it can be used not only as an ink to form two-dimensional characters and images, but also as a three-dimensional modeling material for forming a three-dimensional three-dimensional image (three-dimensional object).
A known three-dimensional modeling apparatus for forming three-dimensional objects can be used, and is not particularly limited. be able to. The three-dimensional object includes a three-dimensional object obtained by applying ink repeatedly. It also includes a molded product obtained by processing a structure obtained by applying ink onto a base material such as a recording medium. The molded product is, for example, a sheet-shaped or film-shaped recorded matter or structure that has been subjected to molding such as heat stretching or punching.・Suitably used for applications where molding is performed after the surface is decorated, such as electronic equipment, meters for cameras, and operation panels.

In the present invention, the terms image formation, recording, printing, and printing are all synonymous.

The terms recording medium, medium, and printed material are all synonymous.

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 25% by mass sodium hydroxide (NaOH) aqueous solution, and 411.3 parts by mass of water After dissolving at 60° C. in the presence of 0.339 parts by mass, it was cooled to room temperature to obtain an aqueous raw material solution.
Next, 8.87 kg/h of the raw material aqueous solution and 4.37 kg/h of methylene chloride were introduced into a 1.8 L glass first reactor equipped with a reflux condenser, stirrer, and refrigerant jacket, where Contact was made with 0.775 kg/h of phosgene at room temperature supplied separately.
Next, the reaction liquid and reaction gas were 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 modifier.
Then, the reaction liquid and reaction gas were introduced from an overflow pipe attached to the second reactor into an oligomerization tank (4.5 L) having the same shape as the first reactor.
Next, 0.016 kg/hour of a 2% by mass trimethylamine aqueous solution (0.00083 mol per 1 mol of cyclohexane-1,4-dimethanol and 1,6-hexanediol) was separately introduced into the oligomerization tank as a catalyst. .
Then, the oligomerized emulsion thus obtained was further introduced into a separatory tank (settler) having an internal volume of 5.4 L to separate the aqueous phase and the oil phase to obtain a methylene chloride solution of the oligomer.
Of the methylene chloride solution of the above oligomer, 2.44 kg was charged into a reactor with a paddle blade having an internal volume of 6.8 L, 2.60 kg of methylene chloride for dilution was added thereto, and 0.25 wt. 245 kg, 0.953 kg of water, 8.39 g of a 2% by mass triethylamine aqueous solution, and 25.8 g of pt-butylphenol (8% by mass methylene chloride solution) as a molecular weight modifier were added, stirred at 10 ° C., and polycondensed for 180 minutes. reacted.
Of the above polycondensation reaction solution, 3.12 kg was charged into a reactor with paddle blades having an internal volume of 5.4 L, 2.54 kg of methylene chloride and 0.575 kg of water were added thereto, and after stirring for 15 minutes, stirring was stopped. and separated the aqueous and organic phases.
Next, 1.16 kg of 0.1N hydrochloric acid was added to the separated organic phase, and the mixture was stirred for 15 minutes to extract triethylamine and a small amount of remaining alkaline components.
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 resulting polycarbonate solution was powdered by feeding it into hot water of 60° C. to 75° C. and dried to obtain a powdery polycarbonate resin.

An autoclave reactor equipped with a stirrer and jacket was charged with 500 g of powdered polycarbonate resin, 30.5 g of dimethylolpropionic acid, 241 g of isophorone diisocyanate (IPDI), and 420 g of acetone while introducing nitrogen. Thereafter, the mixture was heated to 80° C. and urethanized over 5 hours to produce a prepolymer. The resulting prepolymer had a solid content concentration of 67 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 system was returned to 40° C., 1,450 g of ion-exchanged water was added stepwise to the system stirred at 300 rpm under a nitrogen stream to micronize. After the entire amount was added, stirring was performed for 15 minutes.
Next, diethylenetriamine, which is a chain extender, is weighed so that [equivalent number of chain extender x solid content of prepolymer solution/NCO equivalent number of prepolymer] is 1.0, and a 10% by mass acetone solution is added to the system. , and stirred for 5 hours to carry out a chain elongation reaction. Thereafter, acetone was removed using an evaporator, and the mixture was diluted with water so that the solid content concentration was 30% by mass, to obtain urethane resin emulsion 1 containing 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 that

(Synthesis Example 3)
-Synthesis of urethane resin 3-
Urethane resin emulsion 3 containing 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 an agitator and a jacket was charged with 500 g of polycarbonate 1,6-hexanediol with a number average molecular weight (Mn) of 1,000, 50 g of isophorone diisocyanate (IPDI), and 420 g of acetone while introducing nitrogen. Thereafter, the mixture was heated to 80° C. and urethanized over 5 hours to produce a prepolymer.
The resulting prepolymer had a solid content concentration of 67 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 system was returned to 40° C., 1,450 g of ion-exchanged water was added stepwise to the system stirred at 300 rpm under a nitrogen stream to micronize. After the entire amount was added, stirring was performed for 15 minutes.
Next, diethylenetriamine, which is a chain extender, is weighed so that [equivalent number of chain extender x solid content of prepolymer solution/NCO equivalent number of prepolymer] is 1.0, and a 10% by mass acetone solution is added to the system. , and stirred for 5 hours to carry out a chain elongation reaction. Thereafter, after removing acetone using an evaporator, the mixture was diluted with water so that the solid content concentration was 30% by mass, and a urethane resin emulsion 4 containing the urethane resin 4 of Synthesis Example 4 was obtained.

(Synthesis Example 5)
-Synthesis of urethane resin 5-
In Synthesis Example 4, 50 g of polycarbonate 1,6-hexanediol with a number average molecular weight (Mn) of 1,000, polycarbonate cyclohexane-1 with a number average molecular weight (Mn) of 1,000, 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 synthesized urethane resins 1 to 5 were measured for glass transition temperature and weight average molecular weight as follows. Table 1 shows the results.

<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 heating the sample to 200° C., the sample was cooled to 0° C. at a temperature decrease rate of 10° C./min, and the temperature was increased at a temperature increase rate of 10° C./min for measurement.

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

(Example 1)
<Ink preparation>
Carbon black (manufactured by Degussa, Nipex160) as pigments 6% by weight, propylene glycol (manufactured by Sigma-Aldrich) 25% by weight, glycerin (manufactured by Sigma-Aldrich) 3% by weight, dipropylene glycol monomethyl ether (manufactured by Sigma-Aldrich) 5% by mass, urethane resin emulsion 1 10% by mass (solid content concentration 30% by mass), and the remaining amount of water so that the total is 100% by mass. The ink of Example 1 was prepared by filtering through 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 transfer amount of pure water to the recording medium was 4.9 g/m ² when the contact time of "Lumi Art Gloss 90 gsm" was 100 ms.
Rewinding module RW6 (manufactured by Hunkeler) was used as the winding device. °gloss" and "fixability" were evaluated. Table 2 shows the results. The pressure applied to the image is the value when the roll paper is overlapped to a thickness of 100 mm, and was measured using a pressure distribution measuring system I-SCAN40.

<Rigid body pendulum test>
As the rigid pendulum test, the logarithmic decrement was calculated by the following method. A rigid pendulum type physical property tester RPT-3000W (manufactured by A&D) was used as a method for measuring the logarithmic attenuation rate of the image.
Within 3 minutes after printing, the printed surface was set with a cold block (CHB-100) and the cylinder edge was set with one dedicated weight. At this time, all the parts touching the cylinder edge must be filled with the image. The measurement temperature was 30° C., and the logarithmic decay rate was plotted against time. The measurement time was 3 minutes, and data was measured every 6 seconds. The logarithmic attenuation rate of the image was obtained by averaging all the logarithmic attenuation rates.

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

<Blocking resistance>
Regarding the obtained images, the state of sticking between the recorded images at the time of winding was visually observed, and the "blocking resistance" was evaluated based on the following evaluation criteria.
In terms of quality, rank 7 or higher is good, and rank 10 is particularly good. Also, the quality is remarkably degraded at rank 3 or lower.
[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, and there is no image peeling, but there are minute image defects of less than 10 μm. 8: Recorded images do not stick to each other and there is no image peeling, but minute image omissions of 10 µm or more and less than 20 µm occur. Image missing 6: Recorded images do not stick together and there is no image peeling, but there is minute image missing of 30 μm or more and less than 40 μm 5: Recorded images do not stick together, no image peeling, but 40 μm or more and 60 μm 4: The recorded images do not stick together and there is no image peeling, but there are minute image defects of 60 μm or more and less than 100 μm. 3: The recorded images stick together and the image is remarkably missing. 2: The recorded images stick together, the image is severely missing, and the paper is partially missing. 1: The recorded images stick together, the image is severely missing, and the paper is also severely missing. stuck together and united

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

<Fixability>
The resulting image was rubbed 20 times with Lumi Art Gloss 90 gsm paper (manufactured by Stora Enso) cut into 1.2 mm squares, and the ink stains on the paper were measured using a reflective color spectrophotometric densitometer (X -Rite Co.), and the transfer density after subtracting the background color of the rubbed paper was evaluated according to the following criteria.
[Evaluation criteria]
○: Transfer density is less than 0.05 △: 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)
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 changed. was evaluated. The results are shown in Tables 2-5.

＊表５中の比較例４の耐ブロッキング性における「－」は測定不能であることを意味する。

* "-" in the anti-blocking property of Comparative Example 4 in Table 5 means that it cannot be measured.

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

Embodiments of the present invention are, for example, as follows.
<1> an ink application step of applying ink to a recording medium to form an image;
a pressing step of applying pressure to the image;
including
As the ink, using an ink containing water, a resin, an organic solvent, and a coloring material,
The resin is a urethane resin having a cyclic structure and an acyclic structure,
The printing method is characterized in that a logarithmic attenuation factor of the rigid body pendulum test for the image is 0.020 or more and 0.060 or less.
<2> The printing method according to <1>, wherein the urethane resin has a 6-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 image surface has a glass transition temperature (Tg) of 0°C or higher and 30°C or lower.
<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;
an ink applying means for applying the ink to a recording medium to form an image;
pressure means for applying pressure to the image;
has
The resin is a urethane resin having a cyclic structure and an acyclic structure,
The printing apparatus is characterized in that the image has a logarithmic attenuation factor of 0.020 or more and 0.060 or less in a rigid body pendulum test.
<10> The printing device according to <9>, wherein the ring structure in the urethane resin is a six-membered ring structure.
<11> The printing device according to any one of <9> to <10>, wherein the ring structure in the urethane resin is a benzene ring.
<12> The printing device 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 image surface has a glass transition temperature (Tg) of 0°C or higher and 30°C or lower.
<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 by containing 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 cyclic structure and an acyclic structure,
The printed matter is characterized in that the image has a logarithmic attenuation factor of 0.020 or more and 0.060 or less in a rigid body pendulum test.
<19> The printed matter according to <18>, wherein the image surface has a glass transition temperature (Tg) of 0°C or higher and 30°C or lower.

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 <18> to < 19>, it is possible to solve the conventional problems and achieve the object of the present invention.

REFERENCE SIGNS LIST 1 paper feeding device 2 continuous paper 3 pretreatment liquid application unit 4 ink discharge unit head 5 drying unit 6 conveying roller 7 image collecting (winding) unit 100 printing device

JP 2017-132979 A

Claims (13)

an ink application step of applying ink to a recording medium to form an image;
a pressing step of applying pressure to the image;
including
As the ink, using an ink containing water, a resin, an organic solvent, and a coloring material,
the organic solvent comprises propylene glycol, glycerin, and dipropylene glycol monomethyl ether;
The resin is a urethane resin having a cyclic structure and an acyclic structure,
The urethane resin has a glass transition temperature of 0° C. or higher and 40° C. or lower,
A printing method, wherein the image has a logarithmic attenuation factor of 0.020 or more and 0.060 or less in a rigid body pendulum test. 2. The printing method according to claim 1, wherein the urethane resin has a 6-membered ring structure. 3. The printing method according to claim 1, wherein the ring structure in the urethane resin is a benzene ring. The printing method according to any one of claims 1 to 3, wherein the urethane resin has an alkyl group on its side chain. The printing method according to any one of claims 1 to 4, wherein the image surface has a glass transition temperature (Tg) of 0°C or higher and 30°C or lower. 6. The printing method according to claim 1, wherein the recording medium is coated paper. 7. The printing method according to any one of claims 1 to 6, 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/ ^cm2 or more and 10.0 kg/ ^cm2 or less. The printing method according to any one of claims 1 to 8, wherein the urethane resin has a weight average molecular weight of 4,500 or more and 5,500 or less. an ink containing water, a resin, an organic solvent, and a coloring material;
an ink applying means for applying the ink to a recording medium to form an image;
pressure means for applying pressure to the image;
has
the organic solvent comprises propylene glycol, glycerin, and dipropylene glycol monomethyl ether;
The resin is a urethane resin having a cyclic structure and an acyclic structure,
The urethane resin has a glass transition temperature of 0° C. or higher and 40° C. or lower,
A printing apparatus, wherein the image has a logarithmic attenuation factor of 0.020 or more and 0.060 or less in a rigid body pendulum test. An ink used in the printing method according to any one of claims 1 to 9,
An ink comprising water, an organic solvent, a coloring material, and a urethane resin having a cyclic structure and an acyclic structure. A method for producing a printed matter obtained by the printing method according to any one of claims 1 to 9 and having a recording medium and an image on the recording medium,
The image contains a coloring material and a urethane resin having a cyclic structure and an acyclic structure,
A method for producing a printed matter, wherein the image has a logarithmic attenuation factor of 0.020 or more and 0.060 or less in a rigid body pendulum test. 13. The method for producing a printed matter according to claim 12, wherein the image surface has a glass transition temperature (Tg) of 0[deg.]C or higher and 30[deg.]C or lower.

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