JP7331540B2 - SET OF SURFACE TREATMENT LIQUID COMPOSITION AND INK, PRINTING METHOD, AND PRINTING APPARATUS - Google Patents

Description

The present invention relates to a set of a surface treatment liquid composition and ink , a printing method, and a printing apparatus.

In recent years, ink jet printers have been developed not only for home use but also for forming images on various materials such as cloth, plastic film, and hard materials.

As inks used in such inkjet printers, for example, solvent-based inks using an organic solvent as a vehicle, and UV-curable inks containing polymerizable monomers as a main component are known. The solvent-based ink is concerned about environmental impact due to solvent evaporation. For the UV curable ink, the choice of polymerizable monomers to be used may be limited in terms of safety. Therefore, water-based inks have been proposed that have less environmental impact and can record on a wide variety of substrates including impermeable substrates (see, for example, Patent Documents 1 and 2).

The ink film formed with the water-based ink generally has lower abrasion resistance than that of the ultraviolet curable ink, and depending on the application of the printed matter, the same level of abrasion resistance as that of the ultraviolet curable ink is required. For example, in printing on soft packaging materials such as food, it is required to have high abrasion resistance from the usage environment.

SUMMARY OF THE INVENTION An object of the present invention is to provide a set of a surface treatment liquid composition and an ink, which is capable of obtaining a printed material having good abrasion resistance even when printed on a non-permeable substrate.

A set of a surface treatment liquid composition and an ink of the present invention as a means for solving the above-mentioned problems comprises a surface treatment liquid composition containing a polyurethane resin A, water and an organic solvent, a polyurethane resin B, a coloring material and water. and an ink containing an organic solvent, wherein the glass transition temperature of the polyurethane resin B is higher than the glass transition temperature of the polyurethane resin A, and the breaking stress of the ink film formed with the ink is 4.0 N/ ^mm2 or more.

According to the present invention, it is possible to provide a set of a surface treatment liquid composition and an ink that can provide a printed material with good scratch resistance even when printed on a non-permeable substrate.

FIG. 1 is a perspective explanatory view showing an example of a printing apparatus. FIG. 2 is a perspective explanatory view showing an example of the main tank of the printing apparatus.

(Set of surface treatment liquid composition and ink)
The surface treatment liquid composition and ink set of the present invention comprises a surface treatment liquid composition containing polyurethane resin A, water, and an organic solvent, and an ink containing polyurethane resin B, a coloring material, water, and an organic solvent. The glass transition temperature of the polyurethane resin B is higher than the glass transition temperature of the polyurethane resin A, the breaking stress of the ink film formed with the ink is 4.0 N/mm ² or higher, and the surface treatment liquid The composition and ink may further contain other ingredients as necessary.

In the set of the surface treatment liquid composition and the ink of the present invention, the surface treatment liquid composition contains the polyurethane resin A. The ink contains polyurethane resin B. By including the polyurethane resin B in the ink, it is possible to obtain a printed matter having excellent scratch resistance. By including the polyurethane resin A in the surface treatment liquid composition, a printed matter with excellent adhesion can be obtained.
Therefore, according to the present invention, even when printing is performed on a non-permeable base material, it is possible to obtain a printed matter having good abrasion resistance.

In the present invention, the glass transition temperature of the polyurethane resin B is higher than the glass transition temperature of the polyurethane resin A. When the glass transition temperature of the polyurethane resin B is equal to or higher than the glass transition temperature of the polyurethane resin A, a printed matter having good scratch resistance can be obtained.

The breaking stress of the ink film formed from the ink is 4.0 N/mm ² or more, preferably 6 N/mm ² or more, more preferably 10 N/mm ^{2 or} more. When the breaking stress of the ink film is 4.0 N/mm ² or more, a printed matter having good scratch resistance can be obtained.
Here, the rupture stress of the ink film was measured by placing 6 g of ink in a Teflon (registered trademark) petri dish with a diameter of 50 mm, placing it in a hot air circulating constant temperature bath at 40°C for 1 day, and then placing it in a hot air circulating constant temperature bath at 70°C. Dry for 3 days to obtain an ink film. The obtained ink film is cut into a size of 5 mm×50 mm with a cutter so that the measurement can be performed under the following conditions, and the breaking stress can be measured by performing a tensile test under the following measurement conditions.
- Breaking stress measurement conditions -
・Apparatus: Autograph AG-10N manufactured by Shimadzu Corporation
・Load cell: 5kN
・Pull speed: 150 mm/minute ・Distance between chucks: 4 mm
・Sample width: 5 mm

<Ink>
The ink contains polyurethane resin B, colorant, water, and organic solvent, and further contains other components as necessary.

<Organic solvent>
The organic solvent used in the present invention is not particularly limited, and a water-soluble organic solvent can be used. Examples include ethers such as polyhydric alcohols, polyhydric alcohol alkyl ethers and polyhydric alcohol aryl ethers nitrogen-containing heterocyclic compounds, amides, amines, sulfur-containing compounds, and the like.
Examples of the water-soluble organic solvent include ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 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-1, Polyhydric alcohols such as 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 ether, etc. polyhydric alcohol alkyl ethers, ethylene glycol monophenyl ether, polyhydric alcohol aryl ethers such as ethylene glycol monobenzyl ether, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, 1 Nitrogen-containing heterocyclic compounds such as ,3-dimethyl-2-imidazolidinone, ε-caprolactam, γ-butyrolactone, formamide, N-methylformamide, N,N-dimethylformamide, 3-methoxy-N,N-dimethylpropion Amides such as amides, 3-butoxy-N,N-dimethylpropionamide, amines such as monoethanolamine, diethanolamine and triethylamine, sulfur-containing compounds such as dimethylsulfoxide, sulfolane and thiodiethanol, propylene carbonate, ethylene carbonate, etc. mentioned.
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.

Among the organic solvents, from the viewpoint of ensuring ejection stability from the inkjet head, it is preferable that at least one type of polyhydric alcohol is included, such as 1,2-propanediol, 1,2-butanediol, and 2,3-butanediol. -butanediol is particularly preferred.

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>
As water, for example, pure water such as ion-exchanged water, ultrafiltrated water, reverse osmosis water, distilled water, or ultrapure water can be used.
The content of water is not particularly limited and can be appropriately selected according to the purpose, but from the viewpoint of ink drying property and ejection reliability, it is preferably 10% by mass or more and 90% by mass or less, and 20% by mass or more. 60% by mass or less is more preferable.

<Color 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 the 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. 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, and is preferably 1% by mass or more and 10% by mass or less, from the viewpoints of improving image density and good fixability and ejection stability. more preferred.

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. methods and the like.
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 and Fats Co., Ltd. and sodium naphthalenesulfonate formalin condensate can also be suitably used as a dispersant.
The dispersant may be used singly or in combination of two or more.

<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 with 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. A dispersing machine is preferably used for the dispersion.
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, for example, 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.

<Polyurethane resin B>
In the present invention, the polyurethane resin B is used from the viewpoint of scratch resistance of the printed matter.
From the viewpoint of ink film strength, the polyurethane resin B preferably has a urethane group concentration of 7.5% by mass or more, more preferably 7.7% by mass or more, based on the total mass of the polyurethane resin B.
The urethane group concentration can be calculated from the charged amounts of raw materials for the polyurethane resin.
The glass transition temperature of the polyurethane resin B contained in the ink is equal to or higher than the glass transition temperature of the polyurethane resin A contained in the surface treatment liquid composition, preferably −20° C. or higher and 100° C. or lower, more preferably 40° C. or higher and 90° C. or lower. preferable.
The glass transition temperature of the polyurethane resin B can be measured, for example, using a differential scanning calorimeter (TA-60WS and DSC-60, manufactured by Shimadzu Corporation). For example, 5.0 mg of a sample is placed in an aluminum sample container, the sample container is placed on a holder unit, and set in an electric furnace. Next, in a nitrogen atmosphere, the temperature is raised from -60°C to 150°C at a rate of temperature increase of 10°C/min. After that, the temperature is lowered from 150° C. to −60° C. at a rate of temperature decrease of 5° C./min, and then the temperature is further raised to 150° C. at a rate of temperature increase of 10° C./min, and the DSC curve is measured. From the obtained DSC curve, the analysis program in the DSC-60 system can be used to analyze by the midpoint method from the inflection point at the time of temperature rise to obtain the glass transition temperature (Tg).
When two or more types of polyurethane resin B are contained, the urethane group concentration and glass transition temperature of polyurethane resin B, which has the highest content, fall within the above numerical ranges.

As the polyurethane resin B, resin particles made of the polyurethane resin B may be used. Ink can be obtained by mixing polyurethane resin particles in a resin emulsion state in which water is dispersed as a dispersion medium with a material such as a coloring material or an organic solvent.
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 polyurethane resin is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include polyurethane resins obtained by reacting polyol and polyisocyanate.
Examples of the polyols include polyether polyols, polycarbonate polyols, and polyester polyols. These may be used individually by 1 type, or may use 2 or more types together.

--Polyether polyol--
Examples of the polyether polyol include those obtained by addition polymerization of alkylene oxide using at least one compound having two or more active hydrogen atoms as a starting material.

Examples of the starting materials include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, glycerin, and trimethylolethane. , trimethylolpropane, and the like. These may be used individually by 1 type, or may use 2 or more types together.

Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran and the like. These may be used individually by 1 type, or may use 2 or more types together.

Examples of the polyether polyol include polyoxytetramethylene glycol and polyoxypropylene glycol from the viewpoint of obtaining an ink binder capable of imparting extremely excellent abrasion resistance. These may be used individually by 1 type, or may use 2 or more types together.

--Polycarbonate polyol--
Polycarbonate polyols that can be used for producing the polyurethane resin particles include, for example, those obtained by reacting carbonic acid esters with polyols, and those obtained by reacting phosgene with bisphenol A and the like. These may be used individually by 1 type, or may use 2 or more types together.

Examples of the carbonate include methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclocarbonate, diphenyl carbonate and the like. These may be used individually by 1 type, or may use 2 or more types together.

Examples of the polyol include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-butanediol, 1, 2-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,5-hexanediol, 2,5-hexanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8 -octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, hydroquinone, resorcinol , bisphenol-A, bisphenol-F, 4,4'-biphenol and other relatively low molecular weight dihydroxy compounds, polyethylene glycol, polypropylene glycol, polyether polyols such as polyoxytetramethylene glycol, polyhexamethylene adipate, polyhexamethylene Examples include polyester polyols such as succinate and polycaprolactone. These may be used individually by 1 type, or may use 2 or more types together.

--Polyester polyol--
Examples of the polyester polyol include those obtained by esterifying a low-molecular-weight polyol and polycarboxylic acid, polyesters obtained by ring-opening polymerization of cyclic ester compounds such as ε-caprolactone, and copolymerization thereof. Examples include polyester. These may be used individually by 1 type, or may use 2 or more types together.

Examples of the low-molecular-weight polyols include ethylene glycol and propylene glycol. These may be used individually by 1 type, or may use 2 or more types together.

Examples of the polycarboxylic acid include succinic acid, adipic acid, sebacic acid, dodecanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, and anhydrides or ester-forming derivatives thereof. These may be used individually by 1 type, or may use 2 or more types together.

-- Polyisocyanate --
Examples of the polyisocyanate include aromatic diisocyanates such as phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate and naphthalene diisocyanate; Aliphatic or alicyclic diisocyanates such as diisocyanate and 2,2,4-trimethylhexamethylene diisocyanate can be used. These may be used individually by 1 type, or may use 2 or more types together. Among these, the ink of the present invention is also used for outdoor applications such as posters and signboards, so it requires a coating film with extremely high long-term weather resistance. Alternatively, alicyclic diisocyanates are preferred.

Furthermore, the use of at least one alicyclic diisocyanate makes it easier to obtain the desired coating film strength and abrasion resistance.
Examples of the alicyclic diisocyanate include isophorone diisocyanate and dicyclohexylmethane diisocyanate.
As content of the said alicyclic diisocyanate, 60 mass % or more is preferable with respect to the isocyanate compound whole quantity.

<Method for producing polyurethane resin>
Polyurethane resins can be obtained by conventionally generally used production methods, such as the following methods.
First, in the absence of a solvent or in the presence of an organic solvent, the polyol and the polyisocyanate are reacted at an equivalent ratio in which isocyanate groups are excessive to produce an isocyanate-terminated urethane prepolymer.
Next, the anionic groups in the isocyanate-terminated urethane prepolymer are neutralized with a neutralizing agent if necessary, then reacted with a chain extender, and finally the organic solvent in the system is removed if necessary. can be obtained by

Examples of organic solvents that can be used in the production of the polyurethane resin include ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran and dioxane; acetic esters such as ethyl acetate and butyl acetate; nitriles such as acetonitrile; , N-methylpyrrolidone, and amides such as N-ethylpyrrolidone. These may be used individually by 1 type, or may use 2 or more types together.
Examples of the chain extender include polyamines and other active hydrogen group-containing compounds.

Examples of the polyamine include ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4′-dicyclohexylmethanediamine, and 1,4-cyclohexane. Diamines such as diamines; Polyamines such as diethylenetriamine, dipropylenetriamine and triethylenetetramine; Hydrazines such as hydrazine, N,N'-dimethylhydrazine and 1,6-hexamethylenebishydrazine; Dihydrazide succinate and dihydrazide adipic acid , glutaric acid dihydrazide, sebacic acid dihydrazide, isophthalic acid dihydrazide, and the like. These may be used individually by 1 type, or may use 2 or more types together.

Examples of the other active hydrogen group-containing compounds include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, Glycols such as sucrose, methylene glycol, glycerin, and sorbitol; class; water and the like. These may be used singly or in combination of two or more as long as the storage stability of the ink is not lowered.

The content of the polyurethane resin B is preferably 3% by mass or more and 10% by mass or less, more preferably 4% by mass or more and 8% by mass or less, relative to the total amount of the ink.
When the content of the polyurethane resin B is 3% by mass or more and 10% by mass or less, the storage stability and ejection reliability of the ink are improved.
In addition to the polyurethane resin B, the ink may contain the following resins.
The type of resin that can be added in addition to the polyurethane resin B is not particularly limited and can be appropriately selected depending on the purpose. Examples include polyester resins, acrylic resins, vinyl acetate resins, styrene resins. , butadiene-based resins, styrene-butadiene-based resins, vinyl chloride-based resins, acrylic-styrene-based resins, acrylic-silicone-based resins, and the like.
Resin particles made of these resins may also be used. It is possible to obtain a surface treatment liquid composition or an ink by mixing resin particles in a state of a resin emulsion dispersed with water as a dispersion medium with other materials. As the resin particles, appropriately synthesized ones may be used, or commercially available products may be used. These may be used singly or in combination of two or more resin particles.

<Additive>
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 according to the purpose. Among them, those that do not decompose even at high pH are preferred, and examples thereof include side chain modified polydimethylsiloxane, both terminal modified polydimethylsiloxane, single terminal modified polydimethylsiloxane, and side chain both terminal modified polydimethylsiloxane. Those having a polyoxyethylene group or a polyoxyethylene-polyoxypropylene group as the modifying group are particularly preferable 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 acetate, dodecylbenzene sulfonate, laurate, polyoxyethylene alkyl ether sulfate, and the like.
These may be used individually by 1 type, or may use 2 or more types together.

The silicone-based surfactant is not particularly limited and can be appropriately selected depending on the intended purpose. Examples include polydimethylsiloxane modified at both chain ends, and polyether-modified silicone-based surfactants having polyoxyethylene groups or polyoxyethylene-polyoxypropylene groups as modifying groups exhibit excellent properties as water-based surfactants. preferable.

(However, in the formula (S-1), m, n, a, and b each independently represent an integer, R represents an alkylene group, and R' represents an alkyl group.)

Commercially available products can be used as the above polyether-modified silicone-based surfactants. -1906EX (manufactured by Nippon Emulsion Co., Ltd.), FZ-2105, FZ-2118, FZ-2154, FZ-2161, FZ-2162, FZ-2163, FZ-2164 (manufactured by Dow Corning Toray Silicone Co., Ltd.), BYK -33, BYK-387 (manufactured by BYK-Chemie Co., Ltd.), TSF4440, TSF4452, TSF4453 (manufactured by Toshiba Silicon Co., Ltd.) and the like.

The content of the surfactant is not particularly limited and can be appropriately selected according to the purpose. % 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 agent -
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.

<Ink manufacturing method>
The ink can be obtained by dispersing or dissolving each of the above constituents in an aqueous medium and, if necessary, stirring and mixing. Stirring and mixing can be carried out using a stirrer using ordinary stirring blades, a magnetic stirrer, a high-speed disperser, or the like.

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 the 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.

The method of applying the ink is not particularly limited and can be appropriately selected depending on the intended purpose. A coating method, a slide coating method, a die coating method, a spray coating method, and the like can be mentioned. Among these, the inkjet method is preferable.

<Surface treatment liquid composition>
The surface treatment liquid composition contains polyurethane resin A, water, and an organic solvent, and further contains other components as necessary.

As for the water, organic solvent and other components in the surface treatment liquid composition, the same water, organic solvent and other components as in the above ink can be used.

-Polyurethane resin A-
The polyurethane resin A in the surface treatment liquid composition may be the same as the polyurethane resin B in the ink except that its glass transition temperature is lower than the glass transition temperature of the polyurethane resin B in the ink.
The glass transition temperature of the polyurethane resin A is preferably 10°C or lower, more preferably 0°C or lower.

The method for applying the surface treatment liquid composition to the material to be printed is not particularly limited and can be appropriately selected depending on the intended purpose. method, dip coating method, curtain coating method, slide coating method, die coating method, spray coating method and the like.

<Recording medium>
The recording medium is not particularly limited, and plain paper, glossy paper, special paper, cloth, and the like can be used.
The non-permeable substrate is a substrate having a surface with low water permeability and low absorbency, and includes materials that do not open to the outside even if there are many cavities inside. , refers to a substrate having a water absorption of 10 mL/m ² or less from the start of contact to 30 msec ^1/2 in the Bristow method.
As the impermeable substrate, for example, plastic films such as vinyl chloride resin films, polyethylene terephthalate (PET) films, polypropylene, polyethylene and polycarbonate films can be suitably used.
Among these, it is suitably used as a flexible packaging material in the fields of food, healthcare and industrial materials.

The recording medium is not limited to those used as general recording media, and wallpaper, floor materials, building materials such as tiles, cloth for clothing such as T-shirts, textiles, leather, and the like can be used as appropriate. Ceramics, glass, metal, etc. can also be used by adjusting the configuration of the path for conveying the recording medium.

(printed matter)
The printed material of the present invention comprises a material to be printed, a surface layer containing a polyurethane resin A on the material to be printed, and an ink layer containing a polyurethane resin B and a coloring material on the surface layer. The glass transition temperature is higher than the glass transition temperature of the polyurethane resin A.
As the polyurethane resin A, the polyurethane resin B, and the colorant, the same set of the surface treatment liquid composition and ink can be used.

<Recording device, recording method>
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, infrared heaters, radiation heating, conduction heating, high frequency drying, microwave drying, etc. 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 recording device that can print on A0 size recording media, and for example, can use continuous paper wound into a roll as a recording medium. A continuous feed printer is also included.

An example of a recording apparatus will be described with reference to FIGS. 1 and 2. FIG. FIG. 1 is a perspective explanatory view of the device. FIG. 2 is a perspective explanatory view of the main tank. An image forming apparatus 400 as an example of a recording apparatus is a serial image forming apparatus. A mechanical unit 420 is provided inside the exterior 401 of the image forming apparatus 400 . Each ink container 411 of the main tank 410 (410k, 410c, 410m, 410y) for each color of black (K), cyan (C), magenta (M), and yellow (Y) is packed with, for example, an aluminum laminated film. It is made up of members. The ink containing portion 411 is contained, for example, in a container case 414 made of plastic. Thus, the main tank 410 is used as an ink cartridge for each color.
On the other hand, a cartridge holder 404 is provided on the far side of the opening when the cover 401c of the apparatus main body is opened. A main tank 410 is detachably attached to the cartridge holder 404 . As a result, each ink discharge port 413 of the main tank 410 communicates with the ejection head 434 for each color via the supply tube 436 for each color, and ink can be ejected from the ejection head 434 onto the printing medium.

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. Unless otherwise specified, the preparation of the ink and the surface treatment liquid composition and the evaluation using them were carried out under environmental conditions of room temperature of 25° C. and humidity of 60% RH.

In the following examples and comparative examples, the glass transition temperature of the polyurethane resin was measured as follows, and the urethane group concentration was obtained as follows.

<Glass transition temperature>
The glass transition temperature was measured using a differential scanning calorimeter (TA-60WS and DSC-60, manufactured by Shimadzu Corporation). A 5.0 mg sample was placed in an aluminum sample container, the sample container was placed on a holder unit, and set in an electric furnace. Then, the temperature was raised from −60° C. to 150° C. at a heating rate of 10° C./min under a nitrogen atmosphere. After that, the temperature was lowered from 150° C. to −60° C. at a rate of temperature decrease of 5° C./min, and then the temperature was further raised to 150° C. at a rate of temperature increase of 10° C./min, and the DSC curve was measured. The obtained DSC curve was analyzed by the mid-point method from the inflection point during temperature rise using the analysis program in the DSC-60 system, and the glass transition temperature (Tg) was measured.

<Urethane group concentration>
The urethane group concentration was calculated from the charged amounts of raw materials for the polyurethane resin.

(Synthesis example 1 of polyurethane resin)
<Synthesis of polyurethane resin 1>
-Synthesis of polyester polyol 1-
While introducing nitrogen into a 0.5 L separable flask, 343 g of BA-2 (ethylene oxide adduct of bisphenol A, manufactured by Nippon Nyukazai Co., Ltd.) and 137 g of dimethyl isophthalate were charged and melted at 130°C. When these melted, 0.14 g of titanium tetraisopropoxide was added, heated to 230° C. over 3 to 4 hours while stirring, and reacted at 230° C. for 2 to 3 hours. After that, 0.07 g of titanium tetraisopropoxide was added as a catalyst, and the mixture was held for 2 hours. Then, the introduction of nitrogen was stopped, and the mixture was reacted under a reduced pressure of 1 kPa for an additional 2 hours to obtain polyester polyol 1. The obtained polyester polyol 1 had a number average molecular weight of 1,646 and a hydroxyl value of 95.6 mgKOH/g.

-Synthesis of Polyurethane Resin Particles-
First, 100 g of the above polyester polyol 1, 4.0 g of 2,2-bis(hydroxymethyl)propionic acid, and 4,4′-dicyclohexylmethane were added to a 1 L separable flask equipped with a stirrer, thermometer, and reflux tube. 38 g of diisocyanate, 3.0 g of triethylamine, and 80 g of acetone as an organic solvent were charged while introducing nitrogen. Thereafter, the temperature was lowered to 40° C. and maintained at this temperature, and after confirming the NCO% present in the system, 270 g of ion-exchanged water was slowly added while stirring at a speed of 300 rpm to form fine particles. After heating and stirring for 3 minutes, 2.0 g of diethylenetriamine was added, and the mixture was heated and stirred for 3 hours.Finally, the organic solvent was removed to obtain a dispersion of polyurethane resin particles (solid concentration: 35% by mass).
The obtained polyurethane resin 1 had a glass transition temperature of 83° C. and a urethane group concentration of 7.7 mass %.

(Synthesis example 2 of polyurethane resin)
<Synthesis of polyurethane resin 2>
First, 100 g of Duranol T-5651 (polycarbonate diol, number average molecular weight: 1,000, manufactured by Asahi Kasei Chemicals Co., Ltd.), 2,2-bis 4.7 g of (hydroxymethyl)propionic acid, 48 g of 4,4'-dicyclohexylmethane diisocyanate, 3.5 g of triethylamine, and 80 g of acetone as an organic solvent were charged while introducing nitrogen, and a catalyst (di(2-ethylhexanoic acid ) One drop of tin (II) was added, then the temperature was raised to reflux for 3 hours, the temperature was then lowered to 40° C. and maintained at this temperature, after checking the NCO% present in the system, the 290 g of ion-exchanged water was slowly added while stirring at a high speed to form fine particles, and after heating and stirring for 30 minutes, 6.1 g of isophoronediamine was added, and the mixture was heated and stirred for 3 hours.Finally, the organic solvent was removed to remove the polyurethane resin particles. was obtained (solid content concentration 36% by mass).
The obtained polyurethane resin 2 had a glass transition temperature of −18° C. and a urethane group concentration of 8.0 mass %.

(Synthesis example 3 of polyurethane resin)
<Synthesis of polyurethane resin 3>
First, 100 g of Duranol T-5651 (polycarbonate diol, number average molecular weight: 1,000, manufactured by Asahi Kasei Chemicals Co., Ltd.), 2,2-bis (Hydroxymethyl)propionic acid 4.2 g, 4,4'-dicyclohexylmethane diisocyanate 43 g, triethylamine 3.2 g, and acetone 80 g as an organic solvent were charged while introducing nitrogen, and a catalyst (di(2-ethylhexanoic acid) One drop of tin (II) was added, then the temperature was raised to reflux for 3 hours, after which the temperature was lowered to 40° C. and maintained at that temperature, after checking the NCO % present in the system, the speed was 300 rpm. 280 g of ion-exchanged water was slowly added while stirring at , to form fine particles, and after heating and stirring for 30 minutes, 2.2 g of diethylenetriamine was added, and the mixture was heated and stirred for 3 hours.Finally, the organic solvent was removed to disperse the polyurethane resin particles. A liquid was obtained (solid concentration: 35% by mass).
The obtained polyurethane resin 3 had a glass transition temperature of −15° C. and a urethane group concentration of 7.4 mass %.

(Synthesis example 4 of polyurethane resin)
<Synthesis of polyurethane resin 4>
First, 100 g of PTMG1000 (polytetramethylene ether glycol, number average molecular weight: 1,000, manufactured by Mitsubishi Chemical Corporation), 2,2-bis (Hydroxymethyl)propionic acid 4.2 g, 4,4'-dicyclohexylmethane diisocyanate 43 g, triethylamine 3.2 g, and acetone 80 g as an organic solvent were charged while introducing nitrogen, and a catalyst (di(2-ethylhexanoic acid ) One drop of tin (II) was added, then the temperature was raised to reflux for 3 hours, the temperature was then lowered to 40° C. and maintained at this temperature, after checking the NCO% present in the system, the 280 g of ion-exchanged water was slowly added while stirring at a high speed to form fine particles, and after heating and stirring for 30 minutes, 2.2 g of diethylenetriamine was added, and the mixture was heated and stirred for 3 hours. A dispersion was obtained (solid content concentration 35% by weight).
The obtained polyurethane resin 4 had a glass transition temperature of −57° C. and a urethane group concentration of 7.4 mass %.

(Synthesis example 5 of polyurethane resin)
<Synthesis of polyurethane resin 5>
First, 100 g of Duranol T-5651 (polycarbonate diol, number average molecular weight: 1,000, manufactured by Asahi Kasei Chemicals Co., Ltd.), 2,2-bis 4.7 g of (hydroxymethyl)propionic acid, 50 g of 4,4'-dicyclohexylmethane diisocyanate, 3.5 g of triethylamine, and 80 g of acetone as an organic solvent were charged while introducing nitrogen, and a catalyst (di(2-ethylhexanoic acid ) One drop of tin (II) was added, then the temperature was raised to reflux for 3 hours, the temperature was then lowered to 40° C. and maintained at this temperature, after checking the NCO% present in the system, the 295 g of ion-exchanged water was slowly added while stirring at a high speed to form fine particles, and after heating and stirring for 30 minutes, 3.1 g of diethylenetriamine was added, and the mixture was heated and stirred for 3 hours. A dispersion was obtained (solid content concentration 35% by weight).
The obtained polyurethane resin 5 had a glass transition temperature of −18° C. and a urethane group concentration of 8.0 mass %.

(Preparation Example 1 of White Pigment Dispersion)
25 g of titanium oxide (STR-100W, manufactured by Sakai Chemical Industry Co., Ltd.), 5 g of a pigment dispersant (TEGO Dispers 651, manufactured by Evonik), and 70 g of ion-exchanged water are mixed and milled in a bead mill (Research Labo, manufactured by Shinmaru Enterprises). , zirconia beads having a diameter of 0.3 mm were dispersed at a filling rate of 60% and 8 m/s for 5 minutes to obtain a white pigment dispersion having a volume average particle size of 285 nm (solid concentration: 25% by mass).

(Ink Preparation Example 1)
-Preparation of ink a-
Ion-exchanged water was added to the following ink formulation so that the total amount was 100 parts by mass. After preparation, the mixture was mixed and stirred, and filtered through a filter with an average pore size of 5 μm (manufactured by Sartorius, Minizart) to prepare Ink a. .
[Ink prescription]
・ White pigment dispersion (solid content: 25% by mass): 6.0 parts by mass (solid content conversion amount)
- Polyurethane resin 1 (glass transition temperature Tg: 83°C, amount of urethane groups: 7.7% by mass): 4.0 parts by mass (in terms of solid content)
Emulgen LS-106 (manufactured by Kao Corporation, surfactant): 1.0 parts by mass 1,2-propanediol: 8.0 parts by mass 3-Methoxy-N,N-dimethylpropionamide (Equamid M100, Idemitsu Kosan Co., Ltd.): 10.0 parts by mass Dipropylene glycol monomethyl ether: 10.0 parts by mass 3-Methyl-3-methylbutanol: 4.0 parts by mass Proxel LV (manufactured by Avecia, preservative) : 0.1 parts by mass High-purity water: remaining amount (total: 100 parts by mass)

(Ink preparation examples 2 to 8)
-Preparation of inks b to h-
Inks b to h were prepared in the same manner as in Ink Preparation Example 1, except that the ink formulations were changed to those shown in Tables 1-1 and 1-2. The following acrylic resins were used in Tables 1-1 and 1-2.
Acrylic resin (Boncoat CF-6140, manufactured by DIC Corporation, solid content concentration: 30% by mass)

Next, using the obtained inks a to h, the breaking strength of the ink film was measured as follows. The results are shown in Tables 1-1 and 1-2.

<Breaking stress of ink film>
The rupture stress of the ink film was measured by placing 6 g of each ink in a Teflon (registered trademark) petri dish with a diameter of 50 mm, drying in a hot air circulation constant temperature bath at 40°C for 1 day, and then drying in a hot air circulation constant temperature bath at 70°C for 3 days. to obtain an ink film. The obtained ink film was cut into a size of 5 mm×50 mm with a cutter so that the measurement can be performed under the following conditions, and a tensile test was performed under the following measurement conditions to measure the breaking stress.
- Breaking stress measurement conditions -
・Apparatus: Autograph AG-10N manufactured by Shimadzu Corporation
・Load cell: 5kN
・Pull speed: 150 mm/minute ・Distance between chucks: 4 mm
・Sample width: 5 mm

(Synthesis example 6 of polyurethane resin)
<Synthesis of polyurethane resin 6>
First, 100 g of Duranol T-5651 (polycarbonate diol, number average molecular weight: 1,000, manufactured by Asahi Kasei Chemicals Co., Ltd.), 2,2-bis 8.7 g of (hydroxymethyl)propionic acid, 53 g of 4,4'-dicyclohexylmethane diisocyanate, 6.6 g of triethylamine, and 90 g of acetone as an organic solvent were charged while introducing nitrogen, and a catalyst (di(2-ethylhexanoic acid ) One drop of tin (II) was added, then the temperature was raised to reflux for 3 hours, the temperature was then lowered to 40° C. and maintained at this temperature, after checking the NCO% present in the system, the 310 g of ion-exchanged water was slowly added while stirring at a high speed to form fine particles, and after heating and stirring for 30 minutes, 2.7 g of diethylenetriamine was added, and the mixture was heated and stirred for 3 hours. A dispersion was obtained (solid content concentration 36% by weight).
The obtained polyurethane resin 6 had a glass transition temperature of −27° C. and a urethane group concentration of 8.4 mass %.

<Synthesis example 1 of acrylic resin>
A mixture consisting of 20 parts by mass of methyl methacrylate, 77 parts by mass of 2-ethylhexyl acrylate, 1.4 parts by mass of Aqualon HS-10 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), and 50 parts by mass of ion-exchanged water was mixed using a homomixer. Emulsification was performed to obtain a uniform milky white emulsion.
In a 1 L flask equipped with a stirrer, a thermometer, a nitrogen gas inlet tube, and a reflux tube, 87 parts by mass of water with a pH of 3 previously adjusted with ion-exchanged water and sulfuric acid was charged, and nitrogen was introduced to 70 parts by mass. °C. Next, after adding 2.8 parts by mass of 10% by mass Aqualon HS-10 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) aqueous solution and 2.7 parts by mass of 5% by mass ammonium persulfate aqueous solution, the previously prepared emulsion was added. It was added dropwise continuously over 2.5 hours. Further, 0.6 parts by mass of a 5% ammonium persulfate aqueous solution was added every hour for 3 hours from the start of dropping. After completion of dropping, the mixture was aged at 70° C. for 2 hours, cooled, and adjusted to pH 7-8 with an aqueous sodium hydroxide solution.
The obtained acrylic resin had a glass transition temperature (Tg) of −30° C. and a solid concentration of 41% by mass.

(Preparation Example 1 of Surface Treatment Liquid Composition)
-Preparation of surface treatment liquid composition A1-
Ion-exchanged water is added to the following surface treatment liquid composition formulation so that the total amount becomes 100 parts by mass. A treatment liquid composition A1 was prepared.

[Prescription of surface treatment liquid composition]
- Polyurethane resin 5 (glass transition temperature Tg: -18°C, urethane group concentration: 8.0% by mass): 6.0 parts by mass (solid content conversion value)
Emulgen LS-106 (manufactured by Kao Corporation, surfactant): 0.5 parts by mass 1,2-propanediol: 10.0 parts by mass 3-methoxy-3-methyl-1-butanol: 3.0 Parts by mass Proxel LV (manufactured by Avecia, antiseptic): 0.1 parts by mass Ion-exchanged water: remaining amount (total: 100 parts by mass)

(Preparation Examples 2 to 4 of Surface Treatment Liquid Composition)
-Preparation of surface treatment liquid compositions A2 to A4-
Based on the surface treatment liquid composition formulation shown in Table 2, surface treatment liquid compositions A2 to A4 were prepared in the same manner as in Preparation Example 1 of the surface treatment liquid composition.

Next, using the set of the surface treatment liquid composition and ink shown in Table 3, the scratch resistance was evaluated as follows. Table 3 shows the results.

<Evaluation of abrasion resistance>
A biaxially oriented polypropylene film (manufactured by Toyobo Co., Ltd., Pylen P-2161, thickness 30 μm) was coated with a surface treatment liquid composition with a bar coater so that the average thickness was 0.3 mm, and was placed in an oven at 80 ° C. for 2 hours. After drying for 1 minute, a solid patch was printed using an inkjet printer (apparatus name: IPSiO GXe5500 modified machine, manufactured by Ricoh Co., Ltd.) filled with each ink in advance. It was dried in an oven at 80°C for 2 minutes. The obtained solid patch was rubbed with dry cotton (Kanakin No. 3) with a load of 200 g applied, and the state of the image was visually observed and evaluated according to the following evaluation criteria. Note that up to C is the allowable level.
[Evaluation criteria]
A: The image did not change even after rubbing 30 times or more. B: Some scratches remained after rubbing 30 times, but the image density was not affected. C: The image density was rubbed 10 times or more and 30 times or less. D: Image density decreased with less than 10 rubbings

Embodiments of the present invention are, for example, as follows.
<1> A surface treatment liquid composition containing polyurethane resin A, water, and an organic solvent;
an ink containing a polyurethane resin B, a coloring material, water, and an organic solvent;
The glass transition temperature of the polyurethane resin B is equal to or higher than the glass transition temperature of the polyurethane resin A,
A set of the surface treatment liquid composition and the ink is characterized in that the breaking stress of the ink film formed from the ink is 4.0 N/mm ² or more.
<2> A set of the surface treatment liquid composition and ink according to <1>, wherein the urethane group concentration in the total mass of the polyurethane resin B is 7.5% by mass or more.
<3> The set of the surface treatment liquid composition and ink according to any one of <1> to <2>, wherein the content of the polyurethane resin B is 3% by mass or more and 10% by mass or less with respect to the total amount of the ink. is.
<4> The set of the surface treatment liquid composition and ink according to any one of <1> to <3>, wherein the content of the polyurethane resin B is 4% by mass or more and 8% by mass or less with respect to the total amount of the ink. is.
<5> A set of the surface treatment liquid composition and ink according to any one of <1> to <4>, wherein the polyurethane resin B has a glass transition temperature of −20° C. or more and 100° C. or less.
<6> A set of the surface treatment liquid composition according to any one of <1> to <5> and an ink, which is used for an impermeable substrate.
<7> A set of the surface treatment liquid composition and ink according to <6>, wherein the impermeable base material is a flexible packaging material.
<8> A surface treatment liquid composition application step of applying a surface treatment liquid composition containing polyurethane resin A, water, and an organic solvent to an object to be printed;
an ink application step of applying an ink containing a polyurethane resin B, a coloring material, water, and an organic solvent;
The glass transition temperature of the polyurethane resin B is equal to or higher than the glass transition temperature of the polyurethane resin A,
The printing method is characterized in that the breaking stress of the ink film formed from the ink is 4.0 N/mm ² or more.
<9> The printing method according to <8>, wherein the material to be printed is an impermeable substrate.
<10> The printing method according to <9>, wherein the impermeable base material is a flexible packaging material.
<11> surface treatment liquid composition application means for applying a surface treatment liquid composition containing polyurethane resin A, water, and an organic solvent to a material to be printed;
an ink applying means for applying an ink containing a polyurethane resin B, a coloring material, water, and an organic solvent;
The glass transition temperature of the polyurethane resin B is equal to or higher than the glass transition temperature of the polyurethane resin A,
The printing apparatus is characterized in that the breaking stress of the ink film formed from the ink is 4.0 N/mm ² or more.
<12> The printing apparatus according to <11>, wherein the material to be printed is an impermeable base material.
<13> The printing apparatus according to <12>, wherein the impermeable base material is a flexible packaging material.
<14> a printed material;
a surface layer containing a polyurethane resin A on the material to be printed;
and an ink layer containing a polyurethane resin B and a coloring material on the surface layer,
The printed matter is characterized in that the glass transition temperature of the polyurethane resin B is higher than the glass transition temperature of the polyurethane resin A.
<15> The printed material according to <14>, wherein the printed material is an impermeable substrate.
<16> The printed matter according to <15>, wherein the impermeable base material is a flexible packaging material.

A set of the surface treatment liquid composition and ink according to any one of <1> to <7>, the printing method according to any one of <8> to <10>, and <11> to <13>. According to the printing apparatus described in any one and the printed matter described in any one of <14> to <16>, various problems in the related art can be solved and the object of the present invention can be achieved.

400 Image forming apparatus 401 Exterior 401c Cover 404 Cartridge holder 410, 410k, 410c, 410m, 410y Main tank 411 Ink container 413 Ink outlet 414 Container case 420 Mechanism 434 Ejection head 436 Supply tube L Ink container

JP 2005-220352 A JP 2011-094082 A

Claims (7)

a surface treatment liquid composition containing polyurethane resin A, water, and an organic solvent;
an ink containing a polyurethane resin B, a coloring material, water, and an organic solvent;
The content of the polyurethane resin B is 4% by mass or more and 8% by mass or less with respect to the total amount of the ink,
The urethane group concentration in the total mass of the polyurethane resin B is 7.5% by mass or more,
The glass transition temperature of the polyurethane resin B is equal to or higher than the glass transition temperature of the polyurethane resin A,
The glass transition temperature of the polyurethane resin B is -20°C or higher and 100°C or lower,
A set of the surface treatment liquid composition and the ink , wherein the breaking stress of the ink film formed from the ink is 4.0 N/mm ² or more. 2. A set of the surface treatment liquid composition and ink according to claim 1, which is used for impermeable substrates. 3. The surface treatment liquid composition and ink set according to claim 2, wherein the impermeable substrate is a flexible packaging material. a surface treatment liquid composition applying step of applying a surface treatment liquid composition containing a polyurethane resin A, water, and an organic solvent to an object to be printed;
an ink application step of applying an ink containing a polyurethane resin B, a coloring material, water, and an organic solvent;
The content of the polyurethane resin B is 4% by mass or more and 8% by mass or less with respect to the total amount of the ink,
The urethane group concentration in the total mass of the polyurethane resin B is 7.5% by mass or more,
The glass transition temperature of the polyurethane resin B is equal to or higher than the glass transition temperature of the polyurethane resin A,
The glass transition temperature of the polyurethane resin B is -20°C or higher and 100°C or lower,
The breaking stress of the ink film formed with the ink is 4.0 N/mm ² A printing method characterized by the above. 5. The printing method according to claim 4, wherein the substrate to be printed is an impermeable substrate. a surface treatment liquid composition applying means for applying a surface treatment liquid composition containing a polyurethane resin A, water, and an organic solvent to an object to be printed;
an ink applying means for applying an ink containing a polyurethane resin B, a coloring material, water, and an organic solvent;
The content of the polyurethane resin B is 4% by mass or more and 8% by mass or less with respect to the total amount of the ink,
The urethane group concentration in the total mass of the polyurethane resin B is 7.5% by mass or more,
The glass transition temperature of the polyurethane resin B is equal to or higher than the glass transition temperature of the polyurethane resin A,
The polyurethane resin B has a glass transition temperature of −20° C. or more and 100° C. or less,
The breaking stress of the ink film formed with the ink is 4.0 N/mm ² A printing apparatus characterized by the above. 7. The printing apparatus of claim 6, wherein the substrate is a non-permeable substrate.