Non-permeable substrate pretreatment liquid, ink set, image recording substrate, method for producing image recording substrate, image recorded article, and image recording method

Abstract

The present invention provides a pretreatment liquid capable of further expanding the point and its use. A pretreatment liquid for a non-permeable substrate and its use, the non-permeable substrate pretreatment liquid comprising an anionic resin and an aqueous medium, wherein the anionic resin has a ClogP value of 1.40 or greater, and the content of structural units derived from an alkyl (meth)acrylate having a chain alkyl group having 2 or more carbon atoms in the anionic resin is less than 5% by mass relative to the total mass of the anionic resin.

Description

Technical Field

[0001] The present invention relates to a non-permeable substrate pretreatment liquid, an ink set, an image recording substrate, a method for producing an image recording substrate, an image recorded article, and an image recording method. Background Art

[0002] Conventionally, various studies have been conducted on image recording using ink and processing liquid.

[0003] For example, Patent Document 1 describes a receiving solution for an ink composition containing a polyvalent metal salt, a water-soluble solvent, a resin, and a surfactant, wherein the resin contains a resin emulsion as at least a part, the polyvalent metal salt contains ions and anions of a polyvalent metal, and the surfactant has an HLB value of greater than 9 and less than 19 and contains a surfactant having a specific structure.

[0004] Patent document 2 describes a primer in which a polymer of an ethylenically unsaturated monomer is dispersed in an aqueous medium using an emulsifier. The ethylenically unsaturated monomer contains a resin particle dispersion, a coagulant, a protic organic solvent, and water. The resin particle dispersion contains 15 to 40% by weight of a (meth)acrylate having an ethylene oxide chain.

[0005] Patent document 3 describes a pretreatment liquid for use with an aqueous inkjet ink containing a pigment and water. The pretreatment liquid contains resin particles, a surfactant, a coagulant, and water. The surfactant contains a polyoxyalkylene alkyl ether, the coagulant contains a polyvalent metal salt and / or a cationic polymer compound, and the water absorption rate of the coagulant at a relative humidity of 80% is 75% by mass or less.

[0006] As described in Patent Documents 1 to 3, there is known an image recording method in which a pre-treatment liquid is applied to a substrate and then ink is applied to the surface of the substrate to which the pre-treatment liquid has been applied to record an image.

[0007] Previous technical literature

[0008] Patent Literature

[0009] Patent Document 1: Japanese Patent Application Publication No. 2019-177560

[0010] Patent Document 2: Japanese Patent Application Publication No. 2019-111687

[0011] Patent Document 3: Japanese Patent Application Publication No. 2019-111763 Summary of the Invention

[0012] Technical issues to be solved by the invention

[0013] However, in image recording using a pretreatment liquid and ink, when a non-permeable substrate is used as the substrate, the expansion (dot diameter) of dots formed by fixing ink droplets on the substrate is insufficient, and streaking may occur.

[0014] Therefore, in image recording methods in which a pretreatment liquid is applied to a non-permeable substrate and then ink is applied to the surface of the substrate having the pretreatment liquid applied thereto to record an image, further dot enlargement, ie, a further increase in dot diameter, is sometimes required.

[0015] The present invention has been made in view of this situation, and one embodiment of the present invention aims to solve the problem of providing a non-permeable substrate pretreatment liquid, an ink set, an image recording substrate, a method for manufacturing an image recording substrate, and an image recording method that can further expand dots.

[0016] Another embodiment of the present invention aims to provide an image record having further expanded dots.

[0017] Means for solving technical problems

[0018] The present invention includes the following aspects.

[0019] <1> A pretreatment liquid for a non-permeable substrate, comprising an anionic resin and an aqueous medium, wherein the anionic resin has a ClogP value of 1.40 or greater, and the content of structural units derived from an alkyl (meth)acrylate having a chain alkyl group having 2 or more carbon atoms in the anionic resin is less than 5% by mass relative to the total mass of the anionic resin.

[0020] <2> according to <1> In the aforementioned pretreatment liquid for a non-permeable substrate, the anionic resin contains a structural unit derived from an anionic group-containing monomer, and the anionic group-containing monomer has a ClogP value of -4.00 or greater.

[0021] <3> according to <1> or <2> In the non-permeable substrate pretreatment liquid, the anionic resin has at least one group selected from the group consisting of a sulfonic group and a salt of a sulfonic group.

[0022] <4> according to <1> to <3> The non-permeable substrate pretreatment liquid according to any one of the preceding claims, wherein the anionic resin contains at least one structural unit selected from the group consisting of a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2).

[0023] [Chemical Formula 1]

[0024]

[0025] In formula (1) and formula (2), R1 Each independently represents a hydrogen atom or a methyl group, L 1 Each independently represents a divalent group selected from the first group consisting of an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, -O-, -NH-, -S-, -C(═O)-, and -CH(—OH)-, a divalent group composed of a combination of two or more selected from the first group, or a single bond, and M each independently represents a hydrogen atom or a cation.

[0026] <5> according to <1> to <4> The non-permeable substrate pretreatment liquid according to any one of the preceding claims, wherein the anionic resin contains a structural unit derived from a hydrogen-bonding group-containing monomer, and the hydrogen-bonding group-containing monomer has a ClogP value of 0.20 or greater.

[0027] <6> according to <5> In the non-permeable substrate pretreatment liquid, the structural unit derived from the hydrogen-bonding group-containing monomer is at least one selected from the group consisting of a structural unit represented by the following formula (3) and a structural unit represented by the following formula (4).

[0028] [Chemical Formula 2]

[0029]

[0030] In formula (3) and formula (4), R 2 Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

[0031] In formula (3),

[0032] A 2 Indicates -NH- or -N(L 4 -Y 4 )-,

[0033] L 2 represents a group selected from alkylene, alkenylene, alkynylene, arylene, -O-, -NH-, -N(L 4 -Y 4 )- and -C(=O)-, a divalent group selected from the second group consisting of, a combination of two or more selected from the second group, or a single bond,

[0034] Y 2 represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a halogen atom, -OH, or -OR 3 、-NH2、-NR 3 H, -NR 3 R 4 or -C(=O)R 3 ,

[0035] A 2 , L 2and Y 2 Two of them can be connected to each other to form a ring.

[0036] In formula (4),

[0037] L 3 represents one divalent group selected from Group 2, or a divalent group consisting of a combination of two or more divalent groups selected from Group 2,

[0038] Y 3 Represents a halogen atom, -OH, -NH2, -NR 3 H or -C(=O)R 3 ,

[0039] L 3 and Y 3 can be connected to each other to form a ring.

[0040] L 4 represents one divalent group selected from the third group consisting of an alkylene group, an alkenylene group, an alkynylene group, an arylene group, -O-, -NH-, and -C(=O)-, a divalent group consisting of a combination of two or more selected from the third group, or a single bond,

[0041] Y 4 represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a halogen atom, -OH, or -OR 3 、-NH2、-NR 3 H, -NR 3 R 4 or -C(=O)R 3 .

[0042] R 3 and R 4 Each independently represents an alkyl group, an alkenyl group, an alkynyl group or an aryl group.

[0043] In formula (3) and formula (4),

[0044] -N(L 4 -Y 4 )-L 4 and Y 4 can be connected to each other to form a ring,

[0045] -NR 3 R 4 R in 3 and R 4 can be connected to each other to form a ring.

[0046] <7> according to <6> The non-permeable substrate pretreatment liquid, wherein Y in formula (3) 2 And Y in formula (4) 3 -OH, -NH2 or -NR 3H.

[0047] <8> according to <5> to <7> In any one of the non-permeable substrate pretreatment liquids, the content of the structural unit derived from the hydrogen-bonding group-containing monomer is 5% by mass to 50% by mass based on the total mass of the anionic resin.

[0048] <9> according to <1> to <8> The non-permeable substrate pretreatment liquid according to any one of the preceding claims, wherein the anionic resin contains at least one selected from the group consisting of structural units represented by the following formulae (A) to (F).

[0049] [Chemical Formula 3]

[0050]

[0051] In formula (A) to formula (F), R 5 Each independently represents a hydrogen atom or a methyl group, R 6 Each independently represents an alkyl group, an alkenyl group or an alkynyl group, m is an integer of 0 to 5, and n is an integer of 0 to 11. 5 It represents one divalent group selected from the fourth group consisting of an alkylene group having 1 to 18 carbon atoms, an arylene group having 6 to 18 carbon atoms, -O-, -NH-, -S-, and -C(=O)-; a divalent group consisting of a combination of two or more selected from the fourth group; or a single bond.

[0052] <10> according to <1> to <9> In any one of the non-permeable substrate pretreatment liquids, the anionic resin has a glass transition temperature of -30°C or higher and lower than 100°C.

[0053] <11> An ink set comprising: <1> to <10> The non-permeable substrate pretreatment liquid according to any one of the preceding claims; and the ink, comprising a colorant and water.

[0054] <12> An image recording substrate comprising: a non-permeable substrate; and a pre-treatment layer provided on at least one surface of the non-permeable substrate and containing <1> to <10> The solid content in any one of the non-permeable substrate pretreatment liquids.

[0055] <13> An image recorded material comprising: a non-permeable substrate; and an image provided on at least one surface of the non-permeable substrate and comprising <1> to <10> A solid pretreatment layer and a colorant in any one of the non-permeable substrate pretreatment liquids.

[0056] <14> A method for producing an image recording substrate, comprising: <1> to <10> A step of applying the non-permeable substrate pretreatment liquid according to any one of the preceding claims to a non-permeable substrate.

[0057] <15> A method for recording an image, comprising: <1> to <10> a step of applying the non-permeable substrate pretreatment liquid according to any one of the preceding claims to a non-permeable substrate; and a step of recording an image by applying an ink containing a colorant and water to the surface of the non-permeable substrate applied with the non-permeable substrate pretreatment liquid using an inkjet recording method.

[0058] Effects of the Invention

[0059] According to the present invention, there are provided a non-permeable substrate pretreatment liquid capable of further enlarging dots, an ink set, an image recording substrate, a method for producing an image recording substrate, and an image recording method.

[0060] Furthermore, according to the present invention, there is provided an image recorded material on which further expanded dots are formed. DETAILED DESCRIPTION

[0061] Hereinafter, the non-permeable substrate pretreatment liquid, ink set, image recording substrate, method for producing the image recording substrate, image recorded article, and image recording method of the present invention will be described in detail.

[0062] In the present invention, a numerical range expressed by “to” indicates a range including the numerical values ​​described before and after “to” as the lower limit and the upper limit.

[0063] In the present invention, when a plurality of substances corresponding to each component are present in the composition, the amount of each component in the composition represents the total amount of the plurality of substances present in the composition unless otherwise specified.

[0064] In the numerical ranges described in stages in the present invention, the upper limit or lower limit described in a certain numerical range may be replaced by the upper limit or lower limit of another numerical range described in stages, or may be replaced by the value shown in the Examples.

[0065] In this specification, the term "process" refers not only to an independent process but also to a process that cannot be clearly distinguished from other processes as long as the intended purpose of the process is achieved.

[0066] In the present invention, a combination of preferred aspects is a more preferred aspect.

[0067] In the present invention, “(meth)acrylic acid” is a concept encompassing both acrylic acid and methacrylic acid, and “(meth)acrylate” is a concept encompassing both acrylate and methacrylate.

[0068] In the present invention, "*" in the chemical formula represents a bonding position.

[0069] In the present invention, a combination of two or more preferred aspects is a more preferred aspect.

[0070] [Pretreatment liquid for non-permeable substrates]

[0071] The pretreatment liquid for a non-permeable substrate of the present invention (hereinafter referred to as the "pretreatment liquid") contains an anionic resin and water, wherein the anionic resin has a ClogP value of 1.40 or greater, and the content of structural units derived from an alkyl (meth)acrylate having a chain alkyl group having 2 or more carbon atoms in the anionic resin is less than 5% by mass relative to the total mass of the anionic resin.

[0072] The pretreatment liquid of the present invention is used to apply to an impermeable substrate. Specifically, the pretreatment liquid of the present invention is applied to the impermeable substrate before recording an image on the impermeable substrate. The image can be recorded by applying ink to the surface of the impermeable substrate to which the pretreatment liquid has been applied.

[0073] In the present invention, an "image" refers to a film composed of a layer derived from a pretreatment liquid (hereinafter referred to as a "pretreatment layer") and a layer derived from ink (hereinafter referred to as an "ink layer"). The pretreatment layer is disposed between the impermeable substrate and the ink layer. The interface between the ink layer and the pretreatment layer does not necessarily need to be clear.

[0074] For example, the composition of the image (film) may vary continuously in the layer thickness direction.

[0075] Furthermore, in the present invention, the concept of "image" also includes solid images.

[0076] In the present invention, for example, ink is ejected as droplets from a nozzle provided in an inkjet head and lands on a non-permeable substrate. The solvent contained in the droplets composed of ink (hereinafter also referred to as "ink droplets") evaporates and becomes fixed as dots.

[0077] In the present invention, a "dot" refers to an attachment formed on a non-permeable substrate by the landing of an ink droplet. A "dot diameter" refers to the size of a dot.

[0078] The pretreatment solution of the present invention can further expand the spot. These effects are described in detail below.

[0079] Conventionally, there is known an image recording method in which a pretreatment liquid containing a resin and an aqueous medium is applied to a substrate and then ink is applied to the surface of the substrate where the pretreatment liquid has been applied to record an image (for example, see Patent Documents 1 to 3).

[0080] When recording images using a pretreatment liquid and ink, it has been found that ink droplets sometimes have difficulty spreading on a non-permeable substrate. Furthermore, with the recent demand for faster image recording speeds, the expansion of dots formed by fixing the ink droplets is insufficient, which can easily lead to uneven streaking in the image. Regarding this point, the present inventors' research has revealed that further dot expansion is possible when the pretreatment liquid contains an anionic resin and water, the anionic resin has a ClogP value of 1.40 or greater, and the content of structural units derived from an alkyl (meth)acrylate having a linear alkyl group with two or more carbon atoms in the anionic resin is less than 5% by mass relative to the total mass of the anionic resin.

[0081] When the ClogP value of the anionic resin is 1.40 or greater, mixing between the pretreatment layer formed by applying the pretreatment liquid to the impermeable substrate and the ink layer formed by applying the ink is suppressed. Suppressing mixing between the pretreatment layer and the ink layer allows ink droplets landed on the surface of the impermeable substrate to which the pretreatment liquid has been applied to spread, further increasing the dot size.

[0082] Furthermore, when the content of structural units derived from alkyl (meth)acrylates having a linear alkyl group with 2 or more carbon atoms in the anionic resin is less than 5% by mass relative to the total mass of the anionic resin, the anionic resin is less likely to be exposed to the air interface, thereby improving the wettability of the surface of the non-permeable substrate to which the pre-treatment liquid has been applied. This improved wettability allows ink droplets landed on the surface of the non-permeable substrate to which the pre-treatment liquid has been applied to spread, further increasing the size of the dot.

[0083] <Impermeable substrate>

[0084] The pretreatment solution of the present invention is intended for application to an impermeable substrate. In this context, the impermeability of an impermeable substrate refers to a 24-hour water absorption rate of 2.5% or less, as measured according to ASTM D570-98 (2018). The unit of water absorption, "%," is based on mass. The water absorption rate is preferably 1.0% or less, and more preferably 0.5% or less.

[0085] Examples of materials for the non-permeable substrate include glass, metals (e.g., aluminum, zinc, copper, etc.), and resins (e.g., polyvinyl chloride, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, nylon, acrylic resin, etc.).

[0086] The material of the non-permeable base material is preferably resin.

[0087] Among them, from the viewpoint of versatility, the material of the non-permeable substrate is preferably polypropylene, polyethylene, polyethylene terephthalate, nylon, acrylic resin, or polyvinyl chloride.

[0088] The impermeable substrate is preferably in the form of a sheet (film) or plate. Examples of such an impermeable substrate include glass plates, metal plates, resin sheets (resin films), plastic-laminated paper, metal-laminated or vapor-deposited paper, and metal-laminated or vapor-deposited plastic sheets (plastic films).

[0089] Examples of the resin-made impermeable substrate include resin sheets (resin films), and specifically, flexible packaging materials for packaging food and the like, and floor guide panels for mass retail stores.

[0090] Examples of the impermeable substrate include sheet-shaped (film-shaped) or plate-shaped impermeable substrates and textiles (woven fabrics) and nonwoven fabrics formed of impermeable fibers.

[0091] The thickness of the impermeable substrate is preferably 0.1 μm to 1,000 μm, more preferably 0.1 μm to 800 μm, and even more preferably 1 μm to 500 μm.

[0092] The non-permeable substrate may also be subjected to a hydrophilic treatment. Examples of hydrophilic treatments include, but are not limited to, corona treatment, plasma treatment, flame treatment, heat treatment, abrasion treatment, light irradiation treatment (e.g., UV treatment), and flame treatment. Corona treatment can be performed using, for example, a corona master (product name "PS-10S," manufactured by Shinko Electric & Instrumentation Co., Ltd.). The conditions for the corona treatment can be appropriately selected depending on the type of the non-permeable substrate.

[0093] The pretreatment solution of the present invention is intended for use on non-permeable substrates, but can also be used on both non-permeable and permeable substrates (e.g., permeable paper, permeable textiles, permeable nonwoven fabrics, etc.). The permeability of a permeable substrate refers to the aforementioned property of having a water absorption rate greater than 2.5%.

[0094] Next, each component contained in the pretreatment liquid of the present invention will be described.

[0095] <Aqueous medium>

[0096] The pretreatment liquid of the present invention contains an aqueous medium.

[0097] Examples of the aqueous medium include water and water-soluble organic solvents. The aqueous medium is preferably water and a water-soluble organic solvent.

[0098] Examples of water include ion-exchanged water and distilled water.

[0099] In the present invention, "water-soluble" means a property of dissolving 1 g or more (preferably 3 g or more, more preferably 10 g or more) in 100 g of water at 25°C.

[0100] The aqueous medium contained in the pretreatment liquid of the present invention may be only one kind or two or more kinds.

[0101] The content of the aqueous medium is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more, relative to the total mass of the pretreatment liquid.

[0102] The upper limit of the content of the aqueous medium also depends on the amounts of other components such as the anionic resin, but is, for example, 95% by mass, preferably 90% by mass, and more preferably 85% by mass.

[0103] When the pretreatment liquid contains water, the water content is preferably 50% by mass or more, more preferably 60% by mass or more, and more preferably 70% by mass or more, relative to the total mass of the pretreatment liquid.

[0104] The upper limit of the water content also depends on the amounts of other components such as the anionic resin, but is, for example, 95% by mass, preferably 90% by mass, and more preferably 85% by mass.

[0105] Examples of the water-soluble organic solvent include polyols such as glycerol, 1,2,6-hexanetriol, trimethylolpropane, alkanediols (e.g., ethylene glycol, propylene glycol (1,2-propylene glycol), 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, 2-butene-1,4-diol, 2-ethyl-1,3-hexanediol, 2-methyl-2,4-pentanediol, 1,2-octanediol, 1,2-hexanediol, 1,2-pentanediol, and 4-methyl-1,2-pentanediol), and polyalkylene glycols (e.g., diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, dipropylene glycol, and polyoxyethylene-polyoxypropylene glycol).

[0106] Polyol ethers such as polyalkylene glycol ethers (e.g., diethylene glycol monoalkyl ether, triethylene glycol monoalkyl ether, tripropylene glycol monoalkyl ether, polyoxypropylene glycerol ether, etc.);

[0107] Sugar alcohols described in paragraph 0116 of JP-A-2011-42150, hyaluronic acids, alkyl alcohols having 1 to 4 carbon atoms, glycol ethers, 2-pyrrolidone, and N-methyl-2-pyrrolidone.

[0108] Among them, from the viewpoint of improving blocking resistance, the water-soluble organic solvent is preferably a polyol or a polyol ether, and more preferably an alkanediol, a polyalkylene glycol, or a polyalkylene glycol ether.

[0109] When the pretreatment liquid contains a water-soluble organic solvent, the content of the water-soluble organic solvent is preferably 1 to 25% by mass, more preferably 2 to 20% by mass, and even more preferably 3 to 15% by mass relative to the total mass of the pretreatment liquid.

[0110] <Anionic resin>

[0111] The pretreatment liquid of the present invention contains an anionic resin. Anionic resin refers to a resin having at least one anionic group in its molecule. Examples of anionic groups include carboxyl groups, carboxyl salts, sulfonyl groups, sulfonyl salts, phosphate groups, phosphate salts, phosphonic acid groups, and phosphonic acid salts. Counterions in the salts include alkali metal ions such as sodium, potassium, and lithium; alkaline earth metal ions such as calcium and magnesium; and ammonium ions.

[0112] The anionic resin may have only one type of anionic group or may have two or more types. Furthermore, when the anionic group is a salt, the salt may be dissociated in the pretreatment liquid.

[0113] From the viewpoint of improving the storage stability of the pretreatment liquid, the anionic resin is preferably a polymer containing a structural unit derived from a monomer having an anionic group (hereinafter simply referred to as "anionic group-containing monomer").

[0114] From the perspective of further improving the storage stability of the pretreatment solution, the anionic resin preferably contains at least one group selected from the group consisting of a sulfonic group and a salt thereof, and more preferably contains a structural unit derived from a monomer containing at least one group selected from the group consisting of a sulfonic group and a salt thereof. If the anionic resin contains at least one group selected from the group consisting of a sulfonic group and a salt thereof, the dispersion stability of the anionic resin in the pretreatment solution is enhanced, thereby further improving the storage stability of the pretreatment solution.

[0115] (Structural unit derived from anionic group-containing monomer)

[0116] In the present invention, the anionic resin contains structural units derived from an anionic group-containing monomer. The ClogP value of the anionic group-containing monomer is preferably -4.00 or greater, more preferably -3.90 or greater, and even more preferably -3.80 or greater. The upper limit of the ClogP value of the anionic group-containing monomer is not particularly limited, but is preferably -0.50 from the perspective of production suitability.

[0117] A ClogP value of -4.00 or higher for the anionic group-containing monomer indicates high hydrophobicity. In the present invention, it is believed that by increasing the hydrophobicity of the structural units derived from the anionic group-containing monomer that constitute the anionic resin, the hydrophobicity of the anionic resin as a whole can be improved. The anionic resin contained in the pretreatment liquid has high hydrophobicity. Therefore, when the pretreatment liquid is applied to an impermeable substrate and ink is applied to the pretreatment liquid-applied surface of the impermeable substrate, mixing of the pretreatment layer and the ink layer is suppressed. Suppressing mixing between the pretreatment layer and the ink layer allows ink droplets landed on the pretreatment liquid-applied surface of the impermeable substrate to spread, further increasing the size of the dot.

[0118] In the present invention, the ClogP value is calculated using ChemDraw (registered trademark) Professional ver. 16.0.1.4 (manufactured by PerkinElmer Informatics).

[0119] Specific examples of anionic group-containing monomers and the ClogP values ​​of each monomer are shown below. Examples of anionic group-containing monomers having a ClogP value of -4.00 or greater include SEANa, SPAK, SEMNa, SPMK, MMANa, SSNa, and P-1MNa. Examples of anionic group-containing monomers having a ClogP value of -4.00 or greater and having at least one group selected from the group consisting of a sulfonic group and a salt of a sulfonic group include SEANa, SPAK, SEMNa, SPMK, and SSNa.

[0120] [Chemical Formula 4]

[0121]

[0122] From the viewpoint of further expansion, the anionic resin preferably contains at least one structural unit selected from the group consisting of a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2) as a structural unit derived from an anionic group-containing monomer.

[0123] [Chemical Formula 5]

[0124]

[0125] In formula (1) and formula (2), R 1 Each independently represents a hydrogen atom or a methyl group, L 1Each independently represents a divalent group selected from the first group consisting of an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, -O-, -NH-, -S-, -C(═O)-, and -CH(—OH)-, a divalent group consisting of a combination of two or more selected from the first group, or a single bond, and M represents a hydrogen atom or a cation.

[0126] In formula (1) and formula (2), L 1 The alkylene group having 1 to 10 carbon atoms may be linear, branched, and / or cyclic. The alkylene group preferably has 1 to 4 carbon atoms.

[0127] In formula (1) and formula (2), as L 1 Examples of the arylene group having 6 to 10 carbon atoms include phenylene and naphthyl.

[0128] In formula (1) and formula (2), L 1 The "divalent group formed by combining two or more types selected from the first group" is preferably a divalent group formed by combining at least one group selected from the group consisting of an alkylene group having 1 to 10 carbon atoms and an arylene group having 6 to 10 carbon atoms and at least one group selected from the group consisting of -O-, -NH-, -S-, -C(=O)-, and -CH(-OH)-.

[0129] L 1 An alkylene group having 1 to 10 carbon atoms or a single bond is preferred.

[0130] In formula (1) and formula (2), M each independently represents a hydrogen atom or a cation. Examples of the cation represented by M include alkali metal ions such as sodium ion, potassium ion, and lithium ion; alkaline earth metal ions such as calcium ion and magnesium ion; and ammonium ion.

[0131] M is preferably a sodium ion, a potassium ion, a lithium ion or an ammonium ion.

[0132] Examples of monomers for forming the structural unit represented by formula (1) and the structural unit represented by formula (2) include vinylsulfonic acid, p-styrenesulfonic acid, α-methylstyrenesulfonic acid, 2-sulfoethyl(meth)acrylate, 3-sulfopropyl(meth)acrylate, methacryloyloxyethylsulfonic acid, vinylbenzylsulfonic acid, 1-allyloxy-2-hydroxypropanesulfonic acid, and allyloxypolyethylene glycol (the number of repetitions of the ethylene glycol moiety is 10)sulfonic acid, as well as salts of these compounds. Examples of counterions in the salts include the cation represented by M above.

[0133] The monomers for forming the structural unit represented by formula (1) and the structural unit represented by formula (2) are preferably p-styrenesulfonic acid, a salt of p-styrenesulfonic acid, 3-sulfopropyl(meth)acrylate, or a salt of 3-sulfopropyl(meth)acrylate.

[0134] Specific examples of the structural unit represented by formula (1) and the structural unit represented by formula (2) are shown below, but the structural unit represented by formula (1) and the structural unit represented by formula (2) are not limited to the following specific examples.

[0135] [Chemical Formula 6]

[0136]

[0137] From the perspective of further expansion, the anionic resin preferably contains a structural unit derived from an anionic group-containing monomer, the ClogP value of the anionic group-containing monomer is greater than or equal to -4.00, and the structural unit derived from the anionic group-containing monomer is at least one selected from the group consisting of the structural unit represented by formula (1) and the structural unit represented by formula (2).

[0138] The anionic resin may contain only one type of structural unit derived from an anionic group-containing monomer, or may contain two or more types.

[0139] From the viewpoint of further expanding the point and improving storage stability, the content of the structural unit derived from the anionic group-containing monomer is preferably 1% by mass to 15% by mass, more preferably 2% by mass to 13% by mass, and even more preferably 3% by mass to 11% by mass relative to the total mass of the anionic resin.

[0140] Furthermore, from the viewpoint of further expanding the point and improving the storage stability, the total content of the structural unit represented by formula (1) and the structural unit represented by formula (2) is preferably 1% by mass to 15% by mass, more preferably 2% by mass to 13% by mass, and even more preferably 3% by mass to 11% by mass relative to the total mass of the anionic resin.

[0141] (Structural unit derived from a hydrogen-bonding group-containing monomer)

[0142] In the present invention, the anionic resin contains structural units derived from a monomer having a hydrogen-bonding group (hereinafter referred to as a "hydrogen-bonding group-containing monomer"). The ClogP value of the hydrogen-bonding group-containing monomer is preferably 0.20 or greater, more preferably 0.25 or greater, and even more preferably 0.30 or greater. There is no particular upper limit on the ClogP value of the hydrogen-bonding group-containing monomer; however, higher ClogP values ​​tend to prevent emulsification polymerization. Therefore, the ClogP value of the hydrogen-bonding group-containing monomer is preferably 12.00 or less, more preferably 11.00 or less.

[0143] A ClogP value of 0.20 or greater for a hydrogen-bonding group-containing monomer indicates high hydrophobicity. In the present invention, it is believed that by increasing the hydrophobicity of the structural units derived from the hydrogen-bonding group-containing monomers that comprise the anionic resin, the hydrophobicity of the anionic resin as a whole can be improved. The anionic resin contained in the pretreatment liquid has high hydrophobicity. Therefore, when the pretreatment liquid is applied to an impermeable substrate and ink is applied to the surface of the substrate that has been applied with the pretreatment liquid, mixing of the pretreatment layer and the ink layer is suppressed. Suppressing mixing between the pretreatment layer and the ink layer allows ink droplets that land on the surface of the impermeable substrate that has been applied with the pretreatment liquid to spread, further increasing the size of the dot.

[0144] The hydrogen-bonding group refers to a group that interacts with each other via a hydrogen atom. Examples of the hydrogen-bonding group include -CONH-, -OH, -NHCONH-, and -NHCOO-.

[0145] Specific examples of hydrogen-bonding group-containing monomers and the ClogP values ​​of the respective monomers are shown below.

[0146] [Chemical Formula 7]

[0147]

[0148] From the perspective of improving the adhesion of the image to the non-permeable substrate, the structural unit derived from the monomer containing a hydrogen-bonding group is preferably at least one selected from the group consisting of the structural unit represented by formula (3) and the structural unit represented by formula (4). The hydrogen-bonding group in the monomer containing a hydrogen-bonding group interacts with the non-permeable substrate, thereby improving the adhesion of the image to the non-permeable substrate.

[0149] -Structural unit represented by formula (3)-

[0150] [Chemical Formula 8]

[0151]

[0152] In formula (3), R 2 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. 2 Preferred is a hydrogen atom or a methyl group.

[0153] In formula (3), A 2 Indicates -NH- or -N(L 4 -Y 4 )-. -N(L 4 -Y 4 )-L 4 and Y 4 can be connected to each other to form a ring.

[0154] About -N(L 4 -Y 4 )-, described later.

[0155] In formula (3), L 2 represents a group selected from alkylene, alkenylene, alkynylene, arylene, -O-, -NH-, -N(L 4 -Y 4 )- and -C(═O)-, a divalent group consisting of two or more selected from the second group, or a single bond.

[0156] In formula (3), Y 2 represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a halogen atom, -OH, or -OR 3 、-NH2、-NR 3 H, -NR 3 R 4 or -C(=O)R 3 . R 3 and R 4 Each independently represents an alkyl group, an alkenyl group, an alkynyl group or an aryl group. 3 R 4 R in 3 and R 4 can be connected to each other to form a ring.

[0157] In formula (3), A 2 , L 2 and Y 2 Two of them can be connected to each other to form a ring.

[0158] 〔L 2 〕

[0159] In formula (3), L 2 represents a group selected from alkylene, alkenylene, alkynylene, arylene, -O-, -NH-, -N(L 4 -Y 4 )- and -C(═O)-, a divalent group consisting of two or more selected from the second group, or a single bond.

[0160] L 2 The alkylene group, alkenylene group and alkynylene group in each may be linear, branched and / or cyclic.

[0161] The alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 4 carbon atoms, and further preferably a methylene group or a vinyl group.

[0162] The alkenylene group is preferably an alkenylene group having 2 to 10 carbon atoms, more preferably an alkenylene group having 2 to 4 carbon atoms, and further preferably an alkenylene group having 2 or 3 carbon atoms.

[0163] The alkynylene group is preferably an alkynylene group having 2 to 10 carbon atoms, more preferably an alkynylene group having 2 to 4 carbon atoms, and further preferably an alkynylene group having 2 or 3 carbon atoms.

[0164] L 2 The arylene group in is preferably an arylene group having 6 to 10 carbon atoms, more preferably a phenylene group or a naphthylene group, and further preferably a phenylene group.

[0165] L 2 The alkylene, alkenylene and alkynylene groups in the formula (4) may each have a substituent. The substituent is preferably the same as Y in the formula (4) described below. 3 That is, the substituent is preferably selected from halogen atoms, -OH, -OR 3 、-NH2、-NR 3 H, -NR 3 R 4 and -C(=O)R 3 At least one of the group consisting of. 3 and R 4 Each independently represents an alkyl group, an alkenyl group, an alkynyl group or an aryl group.

[0166] L 2 The arylene group in may have a substituent. The substituent is preferably selected from an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a halogen atom, -OH, -OR 3 、-NH2、-NR 3 H, -NR 3 R 4 and -C(=O)R 3 At least one of the group consisting of. 3 and R 4 Each independently represents an alkyl group, an alkenyl group, an alkynyl group or an aryl group.

[0167] L 2 The "divalent group formed by combining two or more selected from the second group" is preferably a group formed by combining at least one of an alkylene group, an alkenylene group, an alkynylene group, and an arylene group with -O-, -NH-, -N(L 4 -Y 4 A divalent group formed by combining at least one of -C(=O)- is particularly preferably the following group (AO2).

[0168] [Chemical Formula 9]

[0169]

[0170] In the group (AO2), R1A and R 2A Each independently represents a hydrogen atom or a methyl group, n represents an integer of 1 to 8 (preferably an integer of 1 to 4, more preferably 1 or 2), and *1 represents the same as A 2 The bonding position of *2 indicates the bonding position with Y 2 The bonding position of R 1A and R 2A When one of the is a methyl group, the other is preferably a hydrogen atom.

[0171] L 2 It is preferably a single bond, an alkylene group having 1 to 6 carbon atoms (more preferably 1 to 4, further preferably 1 or 2), an alkylene group having 1 to 6 carbon atoms (more preferably 1 to 4, further preferably 1 or 2) substituted with a hydroxy group, or a group (AO2), and more preferably a single bond or an alkylene group having 1 to 6 carbon atoms (more preferably 1 to 4, further preferably 1 or 2).

[0172] 〔Y 2 〕

[0173] In formula (3), Y 2 represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a halogen atom, -OH, or -OR 3 、-NH2、-NR 3 H, -NR 3 R 4 or -C(=O)R 3 .

[0174] R 3 and R 4 Each independently represents an alkyl group, an alkenyl group, an alkynyl group or an aryl group.

[0175] Y 2 The halogen atom in is preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, more preferably a fluorine atom, a chlorine atom or a bromine atom, further preferably a fluorine atom or a chlorine atom.

[0176] Y 2 The alkyl, alkenyl and alkynyl groups in each may be linear, branched and / or cyclic.

[0177] The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and further preferably a methyl group or an ethyl group.

[0178] The alkenyl group is preferably an alkenyl group having 2 to 10 carbon atoms, more preferably an alkenyl group having 2 to 4 carbon atoms, and further preferably an alkenyl group having 2 or 3 carbon atoms.

[0179] The alkynyl group is preferably an alkynyl group having 2 to 10 carbon atoms, more preferably an alkynyl group having 2 to 4 carbon atoms, and even more preferably an alkynyl group having 2 or 3 carbon atoms.

[0180] Y 2 The aryl group in is preferably an aryl group having 6 to 10 carbon atoms, more preferably a phenyl group or a naphthyl group.

[0181] Y 2 The aryl group in may have a substituent. The substituent is preferably 2 The same group (ie, selected from alkyl, alkenyl, alkynyl, aryl, halogen, -OH, -OR 3 、-NH2、-NR 3 H, -NR 3 R 4 and -C(=O)R 3 At least one of the group consisting of 3 and R 4 each independently represents an alkyl group, an alkenyl group, an alkynyl group or an aryl group).

[0182] Y 2 Preferably, the alkyl group has 1 to 6 carbon atoms (more preferably 1 to 4, and even more preferably 1 or 2), -OH, -OR 3 、-NH2、-NR 3 H, -NR 3 R 4 or -C(=O)R 3 . R 3 and R 4 Each independently preferably has an alkyl group having 1 to 6 carbon atoms (more preferably 1 to 4, and even more preferably 1 or 2).

[0183] 〔-N(L 4 -Y 4 )-〕

[0184] Next, for A 2 and L 2 -N(L 4 -Y 4 )-for explanation.

[0185] -N(L 4 -Y 4 )-in, L 4 It represents one divalent group selected from Group 3 (i.e., Group 3 consisting of alkylene, alkenylene, alkynylene, arylene, -O-, -NH-, and -C(=O)-), a divalent group formed by combining two or more selected from Group 3, or a single bond.

[0186] Group 3 is not -N(L 4 -Y 4 )-, except for this, same as Group 2.

[0187] -N(L 4-Y 4 )-middle, Y 4 represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a halogen atom, -OH, or -OR 3 、-NH2、-NR 3 H, -NR 3 R 4 or -C(=O)R 3 . R 3 and R 4 Each independently represents an alkyl group, an alkenyl group, an alkynyl group or an aryl group. 3 R 4 R in 3 and R 4 can be connected to each other to form a ring.

[0188] -N(L 4 -Y 4 )-L 4 and Y 4 can be connected to each other to form a ring.

[0189] -N(L 4 -Y 4 )-L 4 The preferred way is to 2 The preferred method is the same.

[0190] -N(L 4 -Y 4 )-L 4 It is preferably a single bond, an alkylene group having 1 to 6 carbon atoms (more preferably 1 to 4, further preferably 1 or 2), an alkylene group having 1 to 6 carbon atoms (more preferably 1 to 4, further preferably 1 or 2) substituted with a hydroxy group, or the following group (AO4), and more preferably a single bond or an alkylene group having 1 to 6 carbon atoms (more preferably 1 to 4, further preferably 1 or 2).

[0191] [Chemical Formula 10]

[0192]

[0193] In the group (AO4), R 1A and R 2A Each independently represents a hydrogen atom or a methyl group, n represents an integer of 1 to 8 (preferably an integer of 1 to 4, more preferably 1 or 2), *1 represents the bonding position to N (nitrogen atom), *2 represents the bonding position to Y 4 bonding position.

[0194] In R 1A and R 2A When one of the is a methyl group, the other is preferably a hydrogen atom.

[0195] The number of carbon atoms contained in the structural unit represented by formula (3) is preferably 30 or less, preferably 20 or less, more preferably 12 or less, and further preferably 8 or less. Furthermore, the number of carbon atoms is preferably 3 or more, more preferably 4 or more.

[0196] Furthermore, in formula (3), “-A 2 -L 2 -Y 2 " is also preferably any one of the following groups (3A) to (3H). In the groups (3A) to (3H), * represents a bonding position.

[0197] [Chemical Formula 11]

[0198]

[0199] Specific examples of the structural unit represented by formula (3) are shown below, but the structural unit represented by formula (3) is not limited to the following specific examples.

[0200] [Chemical Formula 12]

[0201]

[0202] -Structural unit represented by formula (4)-

[0203] [Chemical Formula 13]

[0204]

[0205] In formula (4), R 2 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. 2 Preferred is a hydrogen atom or a methyl group.

[0206] In formula (4), L 3 represents a group selected from alkylene, alkenylene, alkynylene, arylene, -O-, -NH-, -N(L 4 -Y 4 )- and -C(═O)-, or a divalent group consisting of two or more selected from the third group.

[0207] In formula (4), Y 3 Represents a halogen atom, -OH, -NH2, -NR 3 H or -C(=O)R 3 .

[0208] In formula (4), L 3 and Y 3 can be connected to each other to form a ring.

[0209] 〔L 3 〕

[0210] In formula (4), L 3 represents a group selected from alkylene, alkenylene, alkynylene, arylene, -O-, -NH-, -N(L 4 -Y 4 )- and -C(═O)-, or a divalent group consisting of two or more selected from the third group.

[0211] L 3 and L in formula (3) 2 The difference is that it is not a single bond.

[0212] L 3 The alkylene group, alkenylene group and alkynylene group in each may be linear, branched and / or cyclic.

[0213] The alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 4 carbon atoms, and further preferably a methylene group or a vinyl group.

[0214] The alkenylene group is preferably an alkenylene group having 2 to 10 carbon atoms, more preferably an alkenylene group having 2 to 4 carbon atoms, and further preferably an alkenylene group having 2 or 3 carbon atoms.

[0215] The alkynylene group is preferably an alkynylene group having 2 to 10 carbon atoms, more preferably an alkynylene group having 2 to 4 carbon atoms, and further preferably an alkynylene group having 2 or 3 carbon atoms.

[0216] L 3 The arylene group in is preferably an arylene group having 6 to 10 carbon atoms, more preferably a phenylene group or a naphthylene group, and further preferably a phenylene group.

[0217] L 3 The alkylene, alkenylene and alkynylene groups in the group may each have a substituent. The substituent is preferably selected from halogen atoms, -OH, -OR 3 、-NH2、-NR 3 H, -NR 3 R 4 and -C(=O)R 3 At least one of the group consisting of. 3 and R 4 Each independently represents an alkyl group, an alkenyl group, an alkynyl group or an aryl group.

[0218] L 3 The arylene group in may have a substituent. The substituent is preferably selected from an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a halogen atom, -OH, -OR 3 、-NH2、-NR 3 H, -NR 3 R4 and -C(=O)R 3 At least one of the group consisting of. 3 and R 4 Each independently represents an alkyl group, an alkenyl group, an alkynyl group or an aryl group.

[0219] L 3 The "divalent group formed by combining two or more selected from the second group" is preferably a group formed by combining at least one of an alkylene group, an alkenylene group, an alkynylene group, and an arylene group with -O-, -NH-, -N(L 4 -Y 4 The divalent group formed by combining at least one of -C(=O)- is particularly preferably the following group (AO3) or the following group (BO1).

[0220] [Chemical Formula 14]

[0221]

[0222] In the group (AO3), R 1A and R 2A Each independently represents a hydrogen atom or a methyl group, n represents an integer of 1 to 10 (preferably an integer of 1 to 6, more preferably an integer of 3 to 6), *1 represents a bonding position to O (oxygen atom), *2 represents a bonding position to Y 3 bonding position.

[0223] In R 1A and R 2A When one of the is a methyl group, the other is preferably a hydrogen atom.

[0224] In group (BO1), R 1B and R 2B Each independently represents an alkyl group having 1 to 10 carbon atoms, n represents an integer of 1 to 10 (preferably an integer of 1 to 6, more preferably an integer of 1 to 4), *1 represents the bonding position to O (oxygen atom), *2 represents the bonding position to Y 3 bonding position.

[0225] R 1B It is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms. 2B An alkyl group having 2 to 8 carbon atoms is preferred, and an alkyl group having 3 to 7 carbon atoms is more preferred.

[0226] L 3 Preferred are alkylene groups having 1 to 6 carbon atoms (more preferably 1 to 4, and even more preferably 1 or 2), alkylene groups having 1 to 6 carbon atoms (more preferably 1 to 4, and even more preferably 1 or 2) substituted with hydroxy groups, group (AO3), or group (BO1).

[0227] 〔Y 3 〕

[0228] In formula (4), Y 3 Represents a halogen atom, -OH, -NH2, -NR 3 H or -C(=O)R 3 .

[0229] Y in formula (4) 3 and Y in formula (3) 2 The difference is that it is not an alkyl, alkenyl, alkynyl, aryl, -OR 3 and-NR 3 R 4 Any of . In addition, Y 3 The meaning of is the same as Y in formula (3) 2 The meanings are the same and the preferred methods are also the same.

[0230] From the viewpoint of further improving the adhesion to the non-permeable substrate, Y 3 Preferably -OH, -NH2 or -NR 3 H.

[0231] -N(L in formula (4) 4 -Y 4 )- has the same meaning as -N(L 4 -Y 4 )- has the same meaning and the preferred manner is also the same.

[0232] R in formula (4) 3 and R 4 The meanings of are respectively the same as R in formula (3) 3 and R 4 The meanings are the same and the preferred methods are also the same.

[0233] The number of carbon atoms contained in the structural unit represented by formula (4) is preferably 30 or less, preferably 27 or less, more preferably 25 or less, and further preferably 23 or less. Furthermore, the number of carbon atoms is preferably 3 or more, more preferably 4 or more.

[0234] Furthermore, in formula (4), “-L 3 -Y 3 " is also preferably any one of the following groups (4A) to (4I). In the groups (4A) to (4I), * represents a bonding position.

[0235] [Chemical Formula 15]

[0236]

[0237] Specific examples of the structural unit represented by formula (4) are shown below, but the structural unit represented by formula (4) is not limited to the following specific examples.

[0238] [Chemical Formula 16]

[0239]

[0240] The anionic resin may contain only one type of structural unit derived from a hydrogen-bonding group-containing monomer, or may contain two or more types.

[0241] From the viewpoint of improving the adhesion of the image to the non-permeable substrate and further expanding the point, the content of the structural unit derived from the hydrogen-bonding group-containing monomer is preferably 5% by mass to 50% by mass, more preferably 5% by mass to 40% by mass, and even more preferably 10% by mass to 35% by mass relative to the total mass of the anionic resin.

[0242] Furthermore, from the viewpoint of improving the adhesion of the image to the non-permeable substrate and further expanding the point, the total content of the structural unit represented by formula (3) and the structural unit represented by formula (4) is preferably 5% by mass to 50% by mass, more preferably 5% by mass to 40% by mass, and even more preferably 10% by mass to 35% by mass relative to the total mass of the anionic resin.

[0243] (Structural unit derived from a hydrophobic group-containing monomer)

[0244] In the present invention, the anionic resin preferably contains a structural unit derived from a monomer having a hydrophobic group (hereinafter referred to as a "hydrophobic group-containing monomer"). Examples of the hydrophobic group include chain aliphatic groups, cyclic aliphatic groups, and aromatic groups.

[0245] From the viewpoint of further broadening the scope, the structural unit derived from the hydrophobic group-containing monomer is preferably at least one selected from the group consisting of structural units represented by the following formulae (A) to (F).

[0246] [Chemical Formula 17]

[0247]

[0248] In formula (A) to formula (F), R 5 R each independently represents a hydrogen atom or a methyl group. 6 Each independently represents an alkyl group, an alkenyl group or an alkynyl group. m is an integer from 0 to 5. n is an integer from 0 to 11. L 5It represents one divalent group selected from the fourth group consisting of an alkylene group having 1 to 18 carbon atoms, an arylene group having 6 to 18 carbon atoms, -O-, -NH-, -S-, and -C(=O)-; a divalent group consisting of a combination of two or more selected from the fourth group; or a single bond.

[0249] 〔R 6 〕

[0250] In formula (A) to formula (F), R 6 Each independently represents an alkyl group, an alkenyl group or an alkynyl group.

[0251] The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and further preferably a methyl group or an ethyl group.

[0252] The alkenyl group is preferably an alkenyl group having 2 to 10 carbon atoms, more preferably an alkenyl group having 2 to 4 carbon atoms, and further preferably an alkenyl group having 2 or 3 carbon atoms.

[0253] The alkynyl group is preferably an alkynyl group having 2 to 10 carbon atoms, more preferably an alkynyl group having 2 to 4 carbon atoms, and even more preferably an alkynyl group having 2 or 3 carbon atoms.

[0254] And, R 6 It can be an unsubstituted group or a group substituted by a substituent. 6 When the group is substituted with a substituent, examples of the substituent include a halogen atom (for example, a chlorine atom, a bromine atom, etc.) and an alkyl group (for example, a methyl group, an ethyl group, etc.).

[0255] 〔m〕

[0256] In formula (A) and formula (B), m represents a substituent (R 6 ) relative to the number of benzene rings.

[0257] m is an integer of 0 to 5, preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and even more preferably 0 or 1.

[0258] 〔n〕

[0259] n in formula (C) represents a substituent (R 6 ) relative to the number of cyclohexane rings.

[0260] n is an integer of 0 to 11, preferably an integer of 0 to 6, more preferably an integer of 0 to 2, and even more preferably 0 or 1.

[0261] 〔L 5 〕

[0262] In formula (A) to formula (F), L 5It represents one divalent group selected from the fourth group consisting of an alkylene group having 1 to 18 carbon atoms, an arylene group having 6 to 18 carbon atoms, -O-, -NH-, -S-, and -C(=O)-; a divalent group consisting of a combination of two or more selected from the fourth group; or a single bond.

[0263] L 5 The alkylene group having 1 to 18 carbon atoms may be linear, branched, and / or cyclic.

[0264] L 5 The alkylene group having 1 to 18 carbon atoms preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 or 2 carbon atoms.

[0265] Examples of the arylene group having 6 to 18 carbon atoms include phenylene, naphthylene and tolyl.

[0266] L 5 The arylene group having 6 to 18 carbon atoms preferably has 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms.

[0267] L 5 The "divalent group formed by combining two or more selected from Group 4" is preferably a divalent group formed by combining at least one of an alkylene group having 1 to 18 carbon atoms and an arylene group having 6 to 18 carbon atoms.

[0268] The divalent group formed by combining at least one of -O-, -NH-, -S-, and -C(=O)- is particularly preferably the following group (AO5) or the following group (AO6).

[0269] [Chemical Formula 18]

[0270]

[0271] In group (AO5), R 1A and R 2A Each independently represents a hydrogen atom or a methyl group, n represents an integer of 1 to 8 (preferably an integer of 1 to 4, more preferably 1 or 2), *1 represents a bonding position to a carbonyl carbon atom, and *2 represents a bonding position to a non-carbonyl carbon atom.

[0272] In R 1A and R 2A When one of the is a methyl group, the other is preferably a hydrogen atom.

[0273] In group (AO6), L 6 represents an alkylene group having 1 to 8 carbon atoms (preferably 1 to 4, more preferably 1 or 2), *1 represents the bonding position to the carbonyl carbon atom, and *2 represents the bonding position to the non-carbonyl carbon atom.

[0274] L 5 Preferred is a single bond, -O-, group (AO5) or group (AO6).

[0275] Specific examples of the structural unit represented by formula (A) are shown below, but the structural unit represented by formula (A) is not limited to the following specific examples.

[0276] [Chemical Formula 19]

[0277]

[0278] Specific examples of the structural unit represented by formula (B) are shown below, but the structural unit represented by formula (B) is not limited to the following specific examples.

[0279] [Chemical Formula 20]

[0280]

[0281] Specific examples of the structural unit represented by formula (C) are shown below, but the structural unit represented by formula (C) is not limited to the following specific examples.

[0282] [Chemical Formula 21]

[0283]

[0284] Specific examples of the structural unit represented by formula (D) are shown below, but the structural unit represented by formula (D) is not limited to the following specific examples.

[0285] [Chemical Formula 22]

[0286]

[0287] Specific examples of the structural unit represented by formula (E) are shown below, but the structural unit represented by formula (E) is not limited to the following specific examples.

[0288] [Chemical Formula 23]

[0289]

[0290] Specific examples of the structural unit represented by formula (F) are shown below, but the structural unit represented by formula (F) is not limited to the following specific examples.

[0291] [Chemical Formula 24]

[0292]

[0293] The anionic resin may contain only one type of structural unit derived from a hydrophobic group-containing monomer, or may contain two or more types.

[0294] From the perspective of further expansion, the content of the structural unit derived from the hydrophobic group-containing monomer is preferably 3% by mass or more, more preferably 30% by mass to 90% by mass, further preferably 40% by mass to 85% by mass, and particularly preferably 45% by mass to 75% by mass, relative to the total mass of the anionic resin.

[0295] Furthermore, from the perspective of further expansion, the total content of the structural units represented by formula (A) to formula (F) is preferably 3% by mass or more, more preferably 30% by mass to 90% by mass, further preferably 40% by mass to 85% by mass, and particularly preferably 45% by mass to 75% by mass, relative to the total mass of the anionic resin.

[0296] (Other structural units)

[0297] In the present invention, the anionic resin may contain other structural units in addition to the structural units derived from the anionic group-containing monomer, the structural units derived from the hydrogen-bonding group-containing monomer, and the structural units derived from the hydrophobic group-containing monomer.

[0298] As other structural units, structural units derived from (meth)acrylates having a chain alkyl group (that is, a linear or branched alkyl group) can be mentioned.

[0299] Specific examples of other structural units are shown below, but other structural units are not limited to the following specific examples.

[0300] [Chemical Formula 25]

[0301]

[0302] In the present invention, the content of the structural units derived from an alkyl (meth)acrylate having a chain alkyl group with 2 or more carbon atoms is less than 5% by mass, more preferably 4% by mass or less, and even more preferably 3% by mass or less, relative to the total mass of the anionic resin. The content of the structural units derived from an alkyl (meth)acrylate having a chain alkyl group with 2 or more carbon atoms may also be 0% by mass. In other words, the anionic resin may not contain structural units derived from an alkyl (meth)acrylate having a chain alkyl group with 2 or more carbon atoms.

[0303] In the above-mentioned specific examples, the structural unit derived from methyl (meth)acrylate does not correspond to the structural unit derived from an alkyl (meth)acrylate having a chain alkyl group having 2 or more carbon atoms.

[0304] When the structural unit derived from the (meth)acrylate having a chain alkyl group with 2 or more carbon atoms is less than 5% by mass relative to the total mass of the anionic resin, the anionic resin is less likely to be exposed to the air interface, and the ink droplet landed on the surface of the non-permeable substrate to which the pretreatment liquid has been applied spreads, forming a spread dot.

[0305] The weight average molecular weight (Mw) of the anionic resin is preferably 3,000 to 2,000,000, more preferably 10,000 to 1,500,000, further preferably 10,000 to 1,000,000, and particularly preferably 30,000 to 200,000.

[0306] When the weight average molecular weight of the anionic resin is 3,000 or more, the adhesion of the image to the non-permeable substrate is further improved. On the other hand, when the weight average molecular weight of the anionic resin is 2,000,000 or less, the anionic dispersion stability is further improved.

[0307] In the present invention, unless otherwise specified, the weight average molecular weight (Mw) represents a value measured by gel permeation chromatography (GPC). In the measurement using gel permeation chromatography (GPC), HLC (registered trademark) -8020GPC (manufactured by Tosoh Corporation) was used as a measuring apparatus, 3 TSKgel (registered trademark) Super MultiporeHZ-H (4.6 mm ID × 15 cm, manufactured by Tosoh Corporation) were used as columns, and THF (tetrahydrofuran) was used as an eluent. In addition, for the measurement, the sample concentration was set to 0.45% by mass, the flow rate was set to 0.35 mL / min, the sample injection volume was set to 10 μl, and the measurement temperature was set to 40° C., and an RI detector was used. The calibration curve was prepared using eight samples of "TSK standard, polystyrene" manufactured by Tosoh Corporation: "F-40," "F-20," "F-4," "F-1," "A-5000," "A-2500," "A-1000," and "n-propylbenzene."

[0308] The anionic resin may be a water-insoluble resin.

[0309] In the present invention, the "water-insoluble" in the water-insoluble resin means a property in which the amount of the water-insoluble resin dissolved in 100 g of water at 25°C is less than 1.0 g (more preferably less than 0.5 g).

[0310] When the anionic resin is a water-insoluble resin, the anionic resin exists in the form of resin particles in the pretreatment liquid.

[0311] When the anionic resin is in the form of resin particles, the volume average particle size of the resin particles is preferably 1 nm to 300 nm, more preferably 3 nm to 200 nm, and even more preferably 5 nm to 150 nm.

[0312] In the present invention, the volume average particle size refers to a value measured using a laser diffraction / scattering particle size distribution analyzer. Examples of the measuring apparatus include a particle size distribution analyzer "Microtrack MT-3300II" (manufactured by Nikkiso Co., Ltd.).

[0313] Regarding the resin particles, reference can also be made to paragraphs 0137 to 0171 of International Publication No. 2017 / 163738 and paragraphs 0036 to 0081 of Japanese Patent Application Laid-Open No. 2010-077218.

[0314] The anionic resin contained in the pretreatment liquid of the present invention may be only one kind or two or more kinds.

[0315] The content of the anionic resin in the pretreatment liquid of the present invention is preferably 1 to 25% by mass, more preferably 2 to 20% by mass, further preferably 3 to 15% by mass, and particularly preferably 5 to 15% by mass, relative to the total mass of the pretreatment liquid.

[0316] When the content of the anionic resin is 1% by mass or more, the adhesion of the image to the non-permeable substrate is further improved. On the other hand, when the content of the anionic resin is 25% by mass or less, the viscosity of the pre-treatment liquid is further reduced, and the imparting properties of the pre-treatment liquid are further improved.

[0317] The glass transition temperature of the anionic resin is preferably -30°C or higher and lower than 100°C, more preferably -30°C or higher and lower than 60°C, and even more preferably -20°C or higher and lower than 40°C.

[0318] When the glass transition temperature of the anionic resin is -30°C or higher and lower than 100°C, the film strength of the image is improved, and the adhesion of the image to the permeable substrate is enhanced. Furthermore, when the glass transition temperature of the anionic resin is -30°C or higher, the dispersion stability of the anionic resin in the pretreatment solution is high, further improving the storage stability of the pretreatment solution.

[0319] In the present invention, the glass transition temperature (hereinafter also referred to as Tg) of the anionic resin refers to the secondary glass transition starting temperature (hereinafter also referred to as Tig) measured using differential scanning calorimetry (DSC) according to the method described in JIS K 7121 (1987) or JIS K 6240 (2011).

[0320] The method for measuring Tg in the present invention will be described in more detail.

[0321] First, the apparatus is held at a temperature approximately 50°C lower than the expected Tg of the resin until it stabilizes. The apparatus is then heated at a heating rate of 20°C / minute to a temperature approximately 30°C higher than the temperature at which the glass transition ends. A differential thermal analysis (DTA) curve or a DSC curve is then generated. The temperature at the intersection of a line extending from the baseline on the low temperature side of the DTA or DSC curve to the high temperature side and a tangent line drawn at the point where the gradient of the curve in the step-like portion of the glass transition reaches its maximum is defined as the Tg.

[0322] Furthermore, when the pretreatment liquid contains two or more anionic resins, the glass transition temperatures of the anionic resins contained in the pretreatment liquid are weighted averaged according to the mass fraction of each anionic resin, and the obtained weighted average is used as the glass transition temperature (Tg) of the anionic resin contained in the pretreatment liquid.

[0323] <Surfactant>

[0324] The pretreatment liquid of the present invention may contain a surfactant.

[0325] Surfactants can be used as surface tension adjusters or defoamers. Examples of surfactants include nonionic surfactants, cationic surfactants, anionic surfactants, and betaine surfactants. From the perspective of ink aggregation speed, nonionic surfactants or anionic surfactants are preferred.

[0326] Examples of the surfactant include compounds listed as surfactants in JP-A-59-157636, pp. 37-38, and Research Disclosure No. 308119 (1989). Furthermore, the surfactant may be a fluorine-based surfactant or a silicone-based surfactant as described in JP-A-2003-322926, JP-A-2004-325707, and JP-A-2004-309806.

[0327] The surfactant contained in the pretreatment liquid of the present invention may be only one kind or two or more kinds.

[0328] For example, when the pretreatment liquid contains a surfactant as a defoaming agent, the content of the surfactant is preferably 0.0001 to 1% by mass, more preferably 0.001 to 0.3% by mass, relative to the total mass of the pretreatment liquid.

[0329] <Coagulant>

[0330] The pretreatment liquid of the present invention preferably contains a coagulant. Specifically, the pretreatment liquid of the present invention preferably contains an anionic resin, an aqueous medium, and a coagulant. The anionic resin preferably has a ClogP value of 1.40 or greater, and the content of structural units derived from an alkyl (meth)acrylate having a chain alkyl group having 2 or more carbon atoms in the anionic resin is less than 5% by mass relative to the total mass of the anionic resin. The coagulant is a component used to aggregate components (e.g., a colorant) in the ink used for image recording.

[0331] The coagulant is preferably at least one selected from the group consisting of a polyvalent metal compound, an organic acid, and a metal complex, and more preferably contains an organic acid.

[0332] -Polyvalent Metal Compounds-

[0333] Examples of polyvalent metal compounds include salts of alkaline earth metals of Group 2 of the periodic table (e.g., magnesium and calcium), transition metals of Group 3 of the periodic table (e.g., lanthanum), metals of Group 13 of the periodic table (e.g., aluminum), and lanthanides (e.g., neodymium).

[0334] The salts of these metals are preferably salts of organic acids described below, nitrates, chlorides, or thiocyanates.

[0335] Among them, the polyvalent metal compound is preferably a calcium salt or magnesium salt of an organic acid (eg, formic acid, acetic acid, benzoic acid, etc.); a calcium salt or magnesium salt of nitric acid; calcium chloride, magnesium chloride, or a calcium salt or magnesium salt of thiocyanate.

[0336] It is preferred that at least a portion of the polyvalent metal compound is dissociated into polyvalent metal ions and counter ions in the pretreatment liquid.

[0337] -Organic acid-

[0338] Examples of the organic acid include organic compounds having an acidic group.

[0339] Examples of the acidic group include a phosphoric acid group, a phosphonic acid group, a phosphinic acid group, a sulfuric acid group, a sulfonic acid group, a sulfonic acid group, and a carboxyl group.

[0340] Among them, from the viewpoint of the aggregation speed of the ink, the acidic group is preferably a phosphoric acid group or a carboxyl group, and more preferably a carboxyl group.

[0341] It is preferred that the acidic groups are at least partially dissociated in the pretreatment liquid.

[0342] Examples of the organic compound having a carboxyl group include (meth)acrylic acid, poly(meth)acrylic acid, acetic acid, formic acid, benzoic acid, glycolic acid, malonic acid, malic acid (preferably DL-malic acid), maleic acid, succinic acid, glutaric acid, pimelic acid, adipic acid, fumaric acid, citric acid, tartaric acid, phthalic acid, 4-methylphthalic acid, lactic acid, pyrrolidonecarboxylic acid, pyronecarboxylic acid, pyrrolecarboxylic acid, furancarboxylic acid, pyridinecarboxylic acid, coumaric acid, thiophenecarboxylic acid, and nicotinic acid.

[0343] Among them, from the viewpoint of the aggregation speed of the ink, the organic compound having a carboxyl group is preferably a divalent or higher-valent carboxylic acid (hereinafter also referred to as a polyvalent carboxylic acid), and more preferably a dicarboxylic acid.

[0344] Specifically, the polyvalent carboxylic acid is preferably malonic acid, malic acid, maleic acid, succinic acid, glutaric acid, pimelic acid, adipic acid, fumaric acid, tartaric acid, 4-methylphthalic acid or citric acid, and more preferably malonic acid, malic acid, tartaric acid, succinic acid, glutaric acid, pimelic acid, adipic acid or citric acid.

[0345] The organic acid preferably has a low pKa (eg, 1.0 to 5.0).

[0346] Thus, by contacting with an organic acid having a lower pKa, the surface charge of particles such as pigments and resin particles in the ink, which are dispersed and stabilized by weakly acidic functional groups such as carboxyl groups, can be reduced, thereby lowering the dispersion stability.

[0347] The organic acid preferably has a low pKa, high solubility in water, and a valence of 2 or more. Furthermore, the organic acid more preferably has a high buffering capacity in a pH region lower than the pKa of the functional group (eg, carboxyl group) that stabilizes particle dispersion in the ink.

[0348] -Metal Complex-

[0349] The metal complex preferably contains at least one selected from the group consisting of zirconium, aluminum, and titanium as a metal element.

[0350] The metal complex is preferably a metal complex containing at least one selected from the group consisting of acetate, acetylacetone, methyl acetoacetate, ethyl acetoacetate, octanediol, butoxyacetylacetone, lactate, lactate ammonium salt, and triethanolamine as a ligand.

[0351] The metal complex can be a commercially available product. Various organic ligands, particularly various multidentate ligands capable of forming metal chelate catalysts, are already commercially available. Therefore, the metal complex can be a metal complex prepared by combining a commercially available organic ligand with a metal.

[0352] Examples of the metal complex include zirconium tetraacetylacetonate (e.g., "ORGATIX ZC-150" manufactured by Matsumoto Fine Chemical Co., Ltd.), zirconium monoacetylacetonate (e.g., "ORGATIX ZC-540" manufactured by Matsumoto Fine Chemical Co., Ltd.), zirconium bisacetylacetonate (e.g., "Matsumoto Fine Chemical Co., Ltd.

[0353] "ORGATIX ZC-550"), zirconium monoethyl acetoacetate (e.g., "ORGATIX ZC-560" manufactured by Matsumoto Fine Chemical Co., Ltd.), zirconium acetate (e.g., "ORGATIX ZC-115" manufactured by Matsumoto Fine Chemical Co., Ltd.), diisopropoxybis(acetylacetonate)titanium (e.g., "ORGATIX TC-100" manufactured by Matsumoto Fine Chemical Co., Ltd.), tetraacetylacetonate titanium (e.g., "ORGATIX TC-401" manufactured by Matsumoto Fine Chemical Co., Ltd.), dioctyloxybis(octanediol)titanium (e.g., "ORGATIX TC-200" manufactured by Matsumoto Fine Chemical Co., Ltd.), diisopropoxybis(acetylacetonate)titanium (e.g., "ORGATIX TC-750" manufactured by Matsumoto Fine Chemical Co., Ltd.), tetraacetylacetonate zirconium (e.g., "ORGATIX TC-100" manufactured by Matsumoto Fine Chemical Co., Ltd.), Co., Ltd., “ORGATIX ZC-700”), zirconium tributoxymonoacetylacetonate (e.g., “ORGATIX ZC-540” manufactured by Matsumoto Fine Chemical Co., Ltd.), zirconium monobutoxyacetylacetonate bis(ethyl acetoacetate) (e.g., “ORGATIX ZC-570” manufactured by Matsumoto Fine Chemical Co., Ltd.), zirconium dibutoxybis(ethyl acetoacetate) (e.g., “ORGATIX ZC-580” manufactured by Matsumoto Fine Chemical Co., Ltd.), aluminum triacetylacetonate (e.g., “ORGATIX AL-80” manufactured by Matsumoto Fine Chemical Co., Ltd.), titanium ammonium lactate (e.g., “ORGATIX TC-300” manufactured by Matsumoto Fine Chemical Co., Ltd.), titanium lactate (e.g., “ORGATIX TC-310, 315"), titanium triethanolamine ("ORGATIX TC-400" manufactured by Matsumoto Fine Chemical Co., Ltd.), and zirconium chloride compounds (for example, "ORGATIX ZC-126" manufactured by Matsumoto Fine Chemical Co., Ltd.).

[0354] Among them, the metal complex is preferably titanium ammonium lactate (for example, "ORGATIX TC-300" manufactured by Matsumoto Fine Chemical Co., Ltd.), titanium lactate (for example, "ORGATIX TC-310, 315" manufactured by Matsumoto Fine Chemical Co., Ltd.), titanium triethanolamine (for example, "ORGATIX TC-400" manufactured by Matsumoto Fine Chemical Co., Ltd.) or a zirconium chloride compound (for example, "ORGATIX ZC-126" manufactured by Matsumoto Fine Chemical Co., Ltd.).

[0355] The pretreatment liquid of the present invention may contain only one kind of coagulant or two or more kinds of coagulants.

[0356] When the pretreatment liquid of the present invention contains a coagulant, the content of the coagulant is preferably 0.1% to 40% by mass, more preferably 0.1% to 30% by mass, further preferably 1% to 20% by mass, and particularly preferably 1% to 10% by mass, relative to the total mass of the pretreatment liquid.

[0357] <Other ingredients>

[0358] The pretreatment liquid may contain other components besides the above-mentioned ones as needed.

[0359] Other components that may be contained in the pretreatment liquid include well-known additives such as solid wetting agents, colloidal silica, inorganic salts, anti-fading agents, emulsion stabilizers, penetration enhancers, ultraviolet absorbers, preservatives, mildew inhibitors, pH adjusters, viscosity adjusters, rust inhibitors, chelating agents, and water-soluble polymer compounds (for example, the water-soluble polymer compounds described in paragraphs 0026 to 0080 of Japanese Patent Application Publication No. 2013-001854).

[0360] -Physical properties of pretreatment solution-

[0361] From the viewpoint of the aggregation rate of the ink, the pH of the pretreatment liquid is preferably 0.1 to 4.5, and more preferably 0.2 to 4.0. The pH is a value measured at 25°C using a commercially available pH meter.

[0362] When the pH of the pretreatment liquid is 0.1 or higher, the roughness of the non-permeable substrate is further reduced, and the adhesion of the image area is further improved. On the other hand, when the pH of the pretreatment liquid is 4.0 or lower, the aggregation rate is further increased, the coalescence of dots on the surface of the non-permeable substrate is further suppressed, and the roughness of the image is further reduced.

[0363] From the perspective of ink aggregation speed, the viscosity of the pretreatment liquid is preferably 0.5 to 10 mPa·s, more preferably 1 to 5 mPa·s. The viscosity is measured at 25°C using a viscometer. For example, a VISCOMETER TV-22 viscometer (manufactured by Toki Sangyo Co., Ltd.) can be used to measure the viscosity.

[0364] The surface tension of the pretreatment liquid is preferably 60 mN / m or less, more preferably 20 mN / m to 50 mN / m, and even more preferably 30 mN / m to 45 mN / m. The surface tension is a value measured at 25°C. For example, the surface tension can be measured using an Automatic Surface Tentiometer CBVP-Z (manufactured by Kyowa Interface Science Co., Ltd.).

[0365] 〔Ink Group〕

[0366] The ink set of the present invention comprises the pre-treatment liquid of the present invention and an ink containing water and a colorant.

[0367] The ink set of the present invention allows for recording an image by applying a pretreatment liquid to an impermeable substrate and then applying ink to the surface of the impermeable substrate to which the pretreatment liquid had been applied. Therefore, the ink set of the present invention allows for recording an image with excellent adhesion to the impermeable substrate.

[0368] The ink set of the present invention may include only one type of ink or two or more types. The ink set of the present invention may include only one type of pre-treatment liquid or two or more types.

[0369] One preferred embodiment of the ink set of the present invention includes an embodiment comprising two or more inks and one or more pre-treatment liquids.

[0370] According to this method, multi-color images can be recorded.

[0371] The following two or more inks can be mentioned:

[0372] Three inks consisting of cyan ink, magenta ink, and yellow ink;

[0373] Four inks consisting of cyan ink, magenta ink, yellow ink, and black ink;

[0374] Four or more inks consisting of the three colored inks and at least one selected from the group consisting of white ink, green ink, orange ink, purple ink, bright cyan ink, bright magenta ink, and bright yellow ink; and

[0375] Five or more inks consisting of the four colored inks and at least one selected from the group consisting of white ink, green ink, orange ink, violet ink, bright cyan ink, bright magenta ink, and bright yellow ink.

[0376] However, the two or more inks are not limited to these specific examples.

[0377] <Ink>

[0378] The ink in the ink set of the present invention contains a colorant and water. The ink is preferably a water-based ink. A water-based ink is an ink in which the water content is 50% by mass or more relative to the total amount of the ink.

[0379] In the ink, the content of the organic solvent is preferably 40% by mass or less, and more preferably 30% by mass or less, relative to the total mass of the ink.

[0380] Furthermore, in the ink, the content of the polymerizable compound (eg, a cationic polymerizable compound, a radical polymerizable compound) is preferably 10% by mass or less relative to the total mass of the ink.

[0381] (colorant)

[0382] As the colorant, an organic pigment or an inorganic pigment is preferred.

[0383] Examples of organic pigments include azo pigments, polycyclic pigments, dye chelates, nitro pigments, nitroso pigments, and aniline black. Among these, the pigment is more preferably an azo pigment or a polycyclic pigment.

[0384] Examples of the inorganic pigment include titanium oxide, iron oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, cadmium red, chrome yellow, and carbon black.

[0385] The colorant may be the colorant described in paragraphs 0096 to 0100 of Japanese Patent Application Laid-Open No. 2009-241586.

[0386] The colorant contained in the ink may be only one kind or two or more kinds.

[0387] The content of the colorant is preferably 1 to 25% by mass, more preferably 2 to 20% by mass, further preferably 2 to 15% by mass, and particularly preferably 2 to 12% by mass, relative to the total mass of the ink.

[0388] (water)

[0389] The ink contains water.

[0390] The water content is preferably 50% by mass or greater, more preferably 60% by mass or greater, relative to the total mass of the ink. The upper limit of the water content also depends on the amount of other components such as the colorant, but is, for example, 90% by mass, preferably 85% by mass, and more preferably 80% by mass.

[0391] -Dispersant-

[0392] The ink may contain at least one dispersant for dispersing the colorant.

[0393] The dispersant may be a polymer dispersant or a low molecular weight surfactant-type dispersant. Furthermore, the polymer dispersant may be a water-soluble dispersant or a water-insoluble dispersant.

[0394] Preferred examples of the dispersant include those described in paragraphs 0080 to 0096 of JP-A-2016-145312.

[0395] The mixing ratio of the colorant to the dispersant is preferably 1:0.06 to 1:3, more preferably 1:0.125 to 1:2, and even more preferably 1:0.125 to 1:1.5, based on mass.

[0396] (resin particles)

[0397] The ink preferably contains at least one type of resin particles. When the ink contains resin particles, the fixability of the ink to a non-permeable substrate and the abrasion resistance of the image can be improved.

[0398] The resin particles are preferably dispersed in water or an aqueous medium. As the resin particles, for example, preferably, there are mentioned the resin particles described in paragraphs 0062 to 0076 of JP-A-2016-188345.

[0399] (Water-soluble organic solvent)

[0400] The ink preferably contains at least one water-soluble organic solvent.

[0401] When the ink contains a water-soluble organic solvent, the ejection properties of the ink from the inkjet head are further improved.

[0402] Examples of the water-soluble organic solvent include:

[0403] Alcohols (e.g., methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, pentanol, hexanol, cyclohexanol, and benzyl alcohol);

[0404] Polyols (e.g., ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexylene glycol, pentylene glycol, glycerol, hexanetriol, thiodiglycol, 2-methyl-1,3-propanediol, 1,2,6-hexanetriol, acetylene glycol derivatives, glycerol, and trimethylolpropane);

[0405] glycol derivatives (e.g., ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether, ethylene glycol diacetate, ethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and ethylene glycol monophenyl ether);

[0406] Amines (e.g., ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenetriamine, triethylenetetramine, polyethyleneimine, and tetramethylpropylenediamine); and

[0407] Other polar solvents (e.g., formamide, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, sulfolane, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, 2-oxazolidinone, 1,3-dimethyl-2-imidazolidinone, acetonitrile and acetone).

[0408] (Other additives)

[0409] The ink may contain other ingredients in addition to the above-mentioned ingredients. Examples of such other ingredients include anti-fading agents, emulsion stabilizers, penetration enhancers, ultraviolet absorbers, preservatives, mildew inhibitors, pH adjusters, surface tension adjusters, defoamers, viscosity adjusters, dispersants other than those mentioned above, dispersion stabilizers, rust inhibitors, and chelating agents.

[0410] [Image recording substrate]

[0411] The image recording substrate of the present invention comprises an impermeable substrate and a pretreatment layer, the pretreatment layer being provided on at least one surface of the impermeable substrate and containing the solid content of the pretreatment liquid of the present invention. The solid content of the pretreatment liquid refers to all components excluding the solvent component (at least the aqueous medium) in the pretreatment liquid. Specifically, the solid content of the pretreatment liquid contains at least an anionic resin having a ClogP value of 1.40 or greater.

[0412] By applying ink to the pre-treated layer in the image recording substrate of the present invention to record an image, an image with expanded dots can be recorded.

[0413] The image recording substrate of the present invention can be suitably produced by, for example, the method for producing an image recording substrate described below.

[0414] [Method for producing image recording substrate]

[0415] One example of a method for producing an image recording substrate of the present invention includes applying the pretreatment liquid of the present invention to a non-permeable substrate (hereinafter also referred to as the "pretreatment liquid applying step"). The method for producing an image recording substrate of the present invention may include other steps in addition to the pretreatment liquid applying step, as needed.

[0416] <Pretreatment Liquid Application Step>

[0417] The application of the pretreatment liquid in the pretreatment liquid application step can be performed by applying a known application method such as a coating method, an inkjet recording method, or a dipping method.

[0418] Examples of the coating method include known coating methods using a bar coater, an extrusion die coater, an air knife coater, a knife coater, a rod coater, a knife coater, an extrusion coater, a reverse roll coater, and the like.

[0419] The details of the inkjet recording method are the same as those of the inkjet recording method in the image recording method described later.

[0420] The amount of the pre-treatment liquid applied is not particularly limited as long as it can aggregate the ink. From the perspective of improving the adhesion of the image and suppressing the peeling of the image, the amount of the pre-treatment liquid applied after drying is preferably 0.05 g / m 2 The amount of the pretreatment liquid after drying is more preferably 0.05 g / m 2 ~1.0g / m 2 amount.

[0421] The non-permeable substrate may also be heated before applying the pre-treatment solution. The heating temperature can be appropriately set according to the type of non-permeable substrate and the composition of the pre-treatment solution. The temperature of the non-permeable substrate is preferably set to 30°C to 70°C, more preferably 30°C to 60°C.

[0422] The non-permeable substrate may be one that has been pre-surface treated. Furthermore, in the case of using an unsurface treated non-permeable substrate, a specific example of surface treatment in which the surface of the non-permeable substrate is treated before applying the pre-treatment liquid in the pre-treatment liquid application step is as described above.

[0423] In the pretreatment liquid application step, the pretreatment liquid applied to the non-permeable substrate may be heated and dried. Components for heating and drying the pretreatment liquid include well-known heating components such as heaters, well-known air supply components such as dryers, and combinations thereof.

[0424] Examples of methods for heat-drying the pretreatment liquid include a method of heating the impermeable substrate with a heater or the like from the side opposite to the surface to which the pretreatment liquid is applied, a method of blowing warm air or hot air toward the surface to which the pretreatment liquid is applied, a method of heating the impermeable substrate with an infrared heater from the surface to which the pretreatment liquid is applied or from the side opposite to the surface to which the pretreatment liquid is applied, and a method combining a plurality of these.

[0425] The heating temperature during heat drying of the pretreatment liquid is preferably 35° C. or higher, more preferably 40° C. or higher. The upper limit of the heating temperature is not particularly limited, but is preferably 100° C., more preferably 90° C., and even more preferably 70° C.

[0426] The time for heat drying is not particularly limited, but is preferably 0.5 to 60 seconds, more preferably 0.5 to 20 seconds, and even more preferably 0.5 to 10 seconds.

[0427] [Visual Records]

[0428] The image recorded article of the present invention comprises: an impermeable substrate; and an image provided on at least one surface of the impermeable substrate and containing the solid component of the pretreatment solution of the present invention (eg, an anionic resin having a ClogP value of 1.40 or greater) and a colorant.

[0429] The image recorded material of the present invention includes an image containing an anionic resin having a ClogP value of 1.40 or greater, and therefore can form a further expanded dot diameter.

[0430] The image recorded material of the present invention can be suitably produced by, for example, the image recording method described below.

[0431] [Image Recording Method]

[0432] An example of the image recording method of the present invention is an image recording method comprising the following steps: a step of applying the pretreatment liquid of the present invention to a non-permeable substrate (pretreatment liquid applying step); and a step of applying an ink containing a colorant and water to the surface of the non-permeable substrate to which the pretreatment liquid has been applied using an inkjet recording method to record an image (image recording step).

[0433] The image recording method of the present invention may include other steps in addition to the pre-treatment liquid applying step and the image recording step, as needed.

[0434] A preferred embodiment of the pre-treatment liquid applying step is the same as a preferred embodiment of the “pre-treatment liquid applying step” in the example of the method for producing the image recording substrate described above.

[0435] <Image Recording Process>

[0436] The image recording step is a step of recording an image by applying ink containing a colorant and water to the surface of the non-permeable substrate to which the pre-treatment liquid has been applied using an inkjet recording method.

[0437] The inkjet recording method is not particularly limited to the inkjet ejection method and can be any of the known methods, such as a charge control method that utilizes electrostatic attraction to eject ink, an on-demand ejection method (pressure pulse method) that utilizes the vibration pressure of a piezoelectric element, a sound inkjet method that converts an electrical signal into a sound beam and irradiates the ink to eject the ink using radiation pressure, and a thermal inkjet (Bubble Jet (registered trademark)) method that heats the ink to form bubbles and utilizes the pressure generated.

[0438] As an inkjet recording method, the method described in Japanese Patent Application Laid-Open No. 54-59936 is particularly suitable. This method effectively utilizes the rapid volume change of ink caused by thermal energy, and uses the force generated by this state change to eject the ink from the nozzle. The method described in paragraphs 0093 to 0105 of Japanese Patent Application Laid-Open No. 2003-306623 is also applicable as an inkjet recording method.

[0439] The ink is discharged from the nozzles of an inkjet head to impart the ink to the non-permeable substrate using an inkjet recording method.

[0440] As inkjet head methods, there are a reciprocating method in which a short series head records while scanning in the width direction of the recording medium, and a line method in which a line head is used in which recording elements are arranged corresponding to the entire area of ​​one side of the recording medium.

[0441] In the linear method, the image is recorded across the entire surface of the recording medium by scanning it in a direction intersecting the arrangement of the recording elements. The linear method eliminates the need for a transport system, such as a carriage for scanning short heads, as in the reciprocating method. Furthermore, compared to the reciprocating method, the linear method eliminates the need for carriage movement and complex scanning control of the recording medium; only the recording medium moves. Therefore, the linear method can achieve faster image recording speeds than the reciprocating method.

[0442] The ink is preferably applied using an inkjet head having a resolution of 300 dpi or higher (more preferably 600 dpi or higher, and even more preferably 800 dpi or higher). dpi is an abbreviation for dots per inch, where 1 inch is 2.54 cm.

[0443] To achieve high-definition images, the droplet volume of ink ejected from the nozzles of the inkjet head is preferably 1 pL (picoliter) to 10 pL, and more preferably 1.5 pL to 6 pL. Furthermore, ejecting a combination of different droplet volumes is also effective to improve image unevenness and continuity of continuous grayscale.

[0444] In the image recording process, an image can be obtained by heating and drying the ink applied to the non-permeable substrate.

[0445] As a mechanism for performing heating and drying, a known heating mechanism such as a heater, a known air blowing mechanism such as a dryer, and a combination of these mechanisms are mentioned.

[0446] Examples of methods for heat-drying the ink include a method of heating the non-permeable substrate with a heater or the like from the side opposite to the ink-applied side thereof, a method of blowing warm air or hot air toward the ink-applied side thereof, a method of heating the non-permeable substrate with an infrared heater from the ink-applied side thereof or the side opposite to the ink-applied side thereof, and a method combining a plurality of these.

[0447] The heating temperature during heat drying is preferably 55° C. or higher, more preferably 60° C. or higher, and particularly preferably 65° C. or higher. The upper limit of the heating temperature is not particularly limited, but is, for example, 100° C., preferably 90° C.

[0448] The time for heating and drying the ink is not particularly limited, but is preferably 3 seconds to 60 seconds, more preferably 5 seconds to 60 seconds, and particularly preferably 10 seconds to 45 seconds.

[0449] Furthermore, the non-permeable substrate may be heated before applying the ink.

[0450] The heating temperature may be appropriately set, and the temperature of the impermeable substrate is preferably set to 20°C to 50°C, more preferably 25°C to 40°C.

[0451] In the image recording step, two or more colors of ink may be applied to the surface of the non-permeable substrate to which the pre-treatment liquid has been applied, thereby recording an image of two or more colors.

[0452] Example

[0453] Hereinafter, examples of the present invention will be described, but the present invention is not limited to the following examples.

[0454] In addition, unless otherwise specified, "%" means mass %.

[0455] <Synthesis of Resin 1 Used in Pretreatment Liquid of Example 1>

[0456] In a 1000 mL three-necked flask equipped with a stirrer and a cooling tube, 7.5 g of sodium dodecylbenzenesulfonate (product name "NEOPELEX G-15", 16 mass % aqueous solution, manufactured by Kao Corporation) and 303.2 g of water were added and heated to 85° C. under a nitrogen atmosphere. To the mixed solution in the heated three-necked flask, Solution A, comprising 11.0 g of sulfopropyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 40 g of water; Solution B, comprising 25 g of 4-hydroxybutyl acrylate ("HB A" in the tables, manufactured by Fujifilm Wako Pure Chemical Corporation); 44 g of isobornyl methacrylate ("IBOMA" in the tables, manufactured by Fujifilm Wako Pure Chemical Corporation); and 20 g of styrene ("St" in the tables, manufactured by Fujifilm Wako Pure Chemical Corporation); and Solution C, comprising 1.8 g of sodium persulfate (manufactured by Fujifilm Wako Pure Chemical Corporation) dissolved in 50 g of water, were added dropwise simultaneously over 3 hours. After the dropwise additions were completed, the mixture was allowed to react for an additional 3 hours to synthesize 500 g of an aqueous dispersion of Resin 1 (solids content: 20.1% by mass). The synthesized Resin 1 had a glass transition temperature of 70°C. Furthermore, the weight-average molecular weight of Resin 1 was 110,000.

[0457] <Synthesis of Resins Used in Pretreatment Liquids of Examples 2 to 28 and Comparative Examples 1 to 5>

[0458] The resins used in the pretreatment solutions of Examples 2 to 28 and Comparative Examples 1 to 5 were synthesized by the same method as that for synthesizing Resin 1, except that the types and amounts of monomers used as raw materials were changed to those shown in Table 1.

[0459] The monomers used in the synthesis of the resin and the ClogP values ​​of the monomers are as follows.

[0460] (Monomer containing a hydrophobic group)

[0461] [Chemical Formula 26]

[0462]

[0463] (Hydrogen-bonding group-containing monomer)

[0464] [Chemical Formula 27]

[0465]

[0466] (Anionic group-containing monomer)

[0467] [Chemical Formula 28]

[0468]

[0469] (Other monomers)

[0470] [Chemical Formula 29]

[0471]

[0472] [Example 1]

[0473] <Preparation of Pretreatment Liquid>

[0474] The components described in the following "Composition of Pretreatment Liquid" were mixed to prepare a pretreatment liquid.

[0475] - Composition of pretreatment solution -

[0476] ·Aqueous dispersion of resin 1···The amount of resin 1 is 10.0% by mass

[0477] · Water-soluble organic solvent: Propylene glycol···5.0 mass%

[0478] · Coagulant: Malonic acid···5.0 mass%

[0479] Defoaming agent (product name "TSA-739", manufactured by Momentive Performance Materials Japan LLC., solid content concentration 15% by mass; emulsion-type silicone defoaming agent) The amount of the defoaming agent is 0.01% by mass

[0480] Ion exchange water The remainder to 100% by mass

[0481] <Preparation of ink>

[0482] The components described in the following "Composition of Ink" were mixed to prepare a cyan ink.

[0483] -Ink composition-

[0484] Cyan pigment dispersion (product name "Projet Cyan APD1000", manufactured by FUJIFILM Imaging Colorants, pigment concentration 12% by mass) ···20% by mass

[0485] ·The following polymer particle aqueous dispersion···8% by mass

[0486] · Water-soluble organic solvent: Propylene glycol···20.0 mass%

[0487] Surfactant (product name "OLFINE E1010", manufactured by Nissin Chemical Industry Co., Ltd.) 1.0 mass%

[0488] Ion exchange water The remainder to 100% by mass

[0489] -Preparation of polymer particle aqueous dispersion-

[0490] A polymer particle aqueous dispersion was prepared as follows.

[0491] A 2-liter three-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet tube was charged with 560.0 g of methyl ethyl ketone and heated to 87°C. Subsequently, while maintaining the reflux state in the reaction vessel (hereinafter, the reflux state was maintained until the reaction was completed), a mixed solution containing 220.4 g of methyl methacrylate, 301.6 g of isobornyl methacrylate, 58.0 g of methacrylic acid, 108 g of methyl ethyl ketone, and 2.32 g of dimethyl 2,2'-azobis(2-methylpropionate) (product name "V-601", manufactured by FUJIFILM WakoPure Chemical Corporation) as a polymerization initiator was added dropwise at a constant rate over 2 hours to the methyl ethyl ketone in the reaction vessel. After the dropwise addition was completed, the mixture was stirred for 1 hour. The stirred solution was subjected to the following step (1).

[0492] Step (1) A solution containing 1.16 g of "V-601" and 6.4 g of methyl ethyl ketone was added, and the mixture was stirred for 2 hours.

[0493] Next, the operation of step (1) was repeated four times, and a solution containing 1.16 g of "V-601" and 6.4 g of methyl ethyl ketone was further added, and stirring was continued for 3 hours.

[0494] After the reaction, the solution was cooled to 65°C, 163.0 g of isopropyl alcohol was added, and the mixture was cooled naturally to obtain a polymerization solution (solids concentration 41.0% by mass) containing a copolymer of methyl methacrylate / isobornyl methacrylate / methacrylic acid (mass ratio = 38 / 52 / 10). The weight average molecular weight (Mw) of the copolymer was 63,000, and the acid value was 65.1 mgKOH / g.

[0495] Next, 317.3 g of the obtained polymerization solution (solid content concentration 41.0% by mass) was weighed, and 46.4 g of isopropyl alcohol, 1.65 g of a 20% by mass maleic anhydride aqueous solution (equivalent to 0.3% by mass as maleic acid relative to the copolymer), and 40.77 g of a 2 mol / L sodium hydroxide aqueous solution were added thereto, and the temperature of the liquid in the reaction vessel was raised to 70°C.

[0496] Next, 380 g of distilled water was added dropwise to the solution heated to 70° C. at a rate of 10 mL / min to disperse the solution in water.

[0497] Then, under reduced pressure, the temperature of the liquid in the reaction vessel was maintained at 70°C for 1.5 hours to distill off a total of 287.0 g of isopropyl alcohol, methyl ethyl ketone, and distilled water. To the resulting liquid, 0.278 g of PROXEL GXL(S) (manufactured by Arch Chemical Japan, Inc.) (equivalent to 440 ppm of benzisothiazoline-3-one relative to the polymer solids content) was added.

[0498] The obtained liquid was filtered through a 1 μm filter, and the filtrate was recovered to obtain an aqueous dispersion of polymer particles having a solid content concentration of 26.5% by mass.

[0499] [Examples 2 to 28, Comparative Examples 1 to 5]

[0500] For Examples other than Example 7 and Comparative Examples 1 to 5, pretreatment liquids were prepared in the same manner as in Example 1, except that the resin used in the pretreatment liquid was changed. For Example 7, a pretreatment liquid was prepared in the same manner as in Example 1, except that the malonic acid used as the coagulant in Example 1 was replaced with calcium acetate, and the resin used in the pretreatment liquid was changed.

[0501] Furthermore, regarding Examples 2 to 28 and Comparative Examples 1 to 5, inks were prepared by the same method as in Example 1.

[0502] Table 2 shows the physical properties of the resin contained in the pretreatment liquid, the physical properties of each structural unit constituting the resin, and the type of coagulant for each Example and each Comparative Example.

[0503] Specifically, the type of anionic group possessed by the resin contained in the pretreatment liquid, the ClogP value, and the glass transition temperature of the resin contained in the pretreatment liquid are described. If the resin contained in the pretreatment liquid does not have an anionic group, the column for the type of anionic group is marked as "-".

[0504] The content of the structural unit derived from the (meth)acrylate having a chain alkyl group having 2 or more carbon atoms (described as “C2 unit” in the table) is described for the resin.

[0505] Regarding the structural unit derived from the monomer containing a hydrogen-bonding group constituting the resin, the ClogP value of the monomer containing a hydrogen-bonding group and whether the structural unit derived from the monomer containing a hydrogen-bonding group corresponds to the structural unit represented by formula (1) or formula (2) (described as "unit (1) or unit (2)" in the table) are described. If it corresponds, the structural unit is described; if it does not correspond, it is described as "-".

[0506] Regarding the structural unit derived from the anionic group-containing monomer constituting the resin, the ClogP value of the anionic group-containing monomer and whether the structural unit derived from the anionic group-containing monomer corresponds to the structural unit represented by formula (3) or formula (4) (described as "unit (3) or unit (4)" in the table) are described. If it corresponds, the structural unit is described; if it does not correspond, it is described as "-".

[0507] Regarding the structural units derived from the hydrophobic group-containing monomer constituting the resin, whether the resin has structural units represented by formulae (A) to (F) (described as "units (A) to (F)" in the table) is described.

[0508] Next, image recording was performed using the pre-treatment liquid and ink prepared in each of the Examples and Comparative Examples.

[0509] <Image Record>

[0510] An inkjet recording apparatus was prepared. The apparatus consisted of a conveyor system for continuously conveying a long, non-permeable substrate; a wire bar coater for applying a pretreatment liquid to the non-permeable substrate; and an inkjet head for applying ink to the surface of the non-permeable substrate coated with the pretreatment liquid. A polyethylene terephthalate (PET) substrate (product name "FE2001," manufactured by Futamura Chemical Co., Ltd., with a thickness of 25 μm, a width of 500 mm, and a length of 2000 m) was prepared as the non-permeable substrate.

[0511] Using an inkjet recording apparatus, a cyan solid image was recorded as follows while continuously conveying the non-permeable substrate at 830 mm / sec. The pretreatment liquid was applied to the substrate by a wire bar coater at a pressure of approximately 1.7 g / m2 The ink was applied to a non-permeable substrate in the following manner and then dried at 60°C for 5 seconds. Next, the ink was applied as a solid image to the surface of the non-permeable substrate coated with the pre-treatment liquid under the following application conditions. The applied ink was dried at 90°C for 20 seconds to record a cyan solid image. Both the pre-treatment liquid and the ink were dried using warm air drying.

[0512] -Ink application conditions-

[0513] Inkjet head: 1200dpi / 20-inch wide piezoelectric full-line head (dpi is the abbreviation of dots per inch (dots per inch), 1 inch is 2.54 cm)

[0514] The amount of ink ejected from the inkjet head: 4.0pL

[0515] After image recording, dot diameter, streak unevenness, and adhesion were evaluated. Furthermore, blocking resistance and storage stability were evaluated using the pretreatment solutions prepared in each Example and Comparative Example. The evaluation methods are as follows. The evaluation results are shown in Table 2.

[0516] <point diameter>

[0517] A cyan dot image was recorded using the same method as described above, but with the ink applied as a dot pattern (dot ratio 3%) rather than a solid image. The dot diameter was measured using a dot analyzer (product name "DA-6000," manufactured by Oji Scientific Instruments). Twenty dots were selected, and the average of the circle-equivalent diameters of the selected dots was used as the dot diameter. The dot diameter was evaluated according to the following evaluation criteria. The best dot expansion was rated "AA" in this evaluation criteria.

[0518] AA: 50μm or more

[0519] A: 45 μm or more and less than 50 μm

[0520] B: 40 μm or more and less than 45 μm

[0521] C: 35 μm or more and less than 40 μm

[0522] D: 30 μm or more and less than 35 μm

[0523] E: less than 30μm

[0524] <Uneven streaks>

[0525] In the solid image, an area measuring 50 mm (in the direction of transport of the impermeable substrate) x 20 mm (in a direction perpendicular to the transport direction of the impermeable substrate) was designated as the "striation evaluation area." The striation evaluation area within the solid image was visually observed to determine the presence and extent of striations parallel to the transport direction of the impermeable substrate. The image's striations were evaluated according to the following evaluation criteria. The image with the most suppressed striations was rated "AA."

[0526] In the following evaluation criteria, easily visually recognizable streaking unevenness means streaking unevenness that can be visually recognizable when observed from a distance of 50 cm.

[0527] AA: No occurrence of streaking unevenness is visually recognized in the solid image.

[0528] A: One very fine streak of unevenness is visually recognized in the solid image.

[0529] B: Several very fine streaks of unevenness are visually recognized in the solid image.

[0530] C: The number of easily visible streaks in the solid image is 2 or less.

[0531] D: There are three easily visible streaks in the solid image.

[0532] E: There are 4 or more streaks that are easily visible in the solid image.

[0533] <Adhesion>

[0534] Five minutes after the solid image was recorded (i.e., dried at 90°C for 20 seconds), a piece of transparent tape (registered trademark No. 405, manufactured by Nichiban Co., Ltd., 12 mm wide, hereinafter referred to as "tape") was attached to the solid image. The tape was then peeled off from the solid image to evaluate the image adhesion. Specifically, the tape was attached and peeled off using the following method.

[0535] Take out the tape at a constant speed and cut it into a length of about 75mm to obtain a tape piece. Overlay the obtained tape piece on the solid image, stick the 12mm wide and 25mm long area in the center of the tape piece with your fingers, and rub it hard with your fingertips. Among them, the 12mm wide and 25mm long area of ​​the solid image where the tape piece is stuck is set as the "evaluation area" below. Within 5 minutes after sticking the tape piece, grab the end of the tape piece and peel it off at an angle as close to 60° as possible for 0.5 seconds to 1.0 seconds. Then, calculate the area ratio (%) of the image remaining on the non-permeable substrate relative to the entire evaluation area of ​​the solid image, and evaluate the adhesion of the image according to the following evaluation criteria. In the following evaluation criteria, the most excellent grade of image adhesion is "AA".

[0536] AA: The area ratio (%) of the image remaining on the non-permeable substrate is 95% or more and 100% or less.

[0537] A: The area ratio (%) of the image remaining on the non-permeable substrate is 90% or more and less than 95%.

[0538] B: The area ratio (%) of the image remaining on the non-permeable substrate is 70% or more and less than 90%.

[0539] C: The area ratio (%) of the image remaining on the non-permeable substrate is 50% or more and less than 70%.

[0540] D: The area ratio (%) of the image remaining on the non-permeable substrate is 30% or more and less than 50%.

[0541] E: The area ratio (%) of the image remaining on the non-permeable substrate is less than 30%.

[0542] <Evaluation of Blocking Resistance>

[0543] The pretreatment liquid was applied to a coating layer of about 1.7 g / m 2, and then dried at 60°C for 5 seconds. The non-permeable substrate A coated with the pretreatment liquid was cut into 3 cm squares. The non-permeable substrate A coated with the pretreatment liquid and a non-permeable substrate B different from the non-permeable substrate A were overlapped in such a way that the surface coated with the pretreatment liquid became the inner side, and then placed at room temperature. A 2.5 cm × 2.5 cm × 0.3 cm flat rubber plate was placed on the non-permeable substrate B. In addition, a 2.5 cm × 2.5 cm × 0.3 cm flat plastic plate was placed on the rubber plate so that the 2.5 cm × 2.5 cm surface overlapped. A 500 g weight was placed on the plastic plate and left to stand for 1 day. After 1 day, the contact surface of the non-permeable substrate B with the non-permeable substrate A coated with the pretreatment liquid was visually observed. Blocking resistance was evaluated according to the following evaluation criteria based on the degree of transfer of the pretreatment liquid components to the non-permeable substrate B and the visibility of the non-permeable substrate B. In the following evaluation criteria, the most excellent blocking resistance was rated "A."

[0544] A: Transfer of the components of the pretreatment liquid could not be confirmed on the entire back surface of the non-permeable substrate B, and the visibility of the transparent portion of the non-permeable substrate B was not impaired.

[0545] B: Transfer of the pretreatment liquid components was observed in a range greater than 0% and less than 30% of the total area of ​​the back surface of the non-permeable substrate B. Although the transparency of the non-permeable substrate B was slightly impaired, it was within a practically acceptable range.

[0546] C: Transfer of the components of the pretreatment liquid was observed in a range of 30% or more and less than 70% of the total area of ​​the back surface of the non-permeable substrate, and the transparency of the non-permeable substrate was significantly impaired.

[0547] D: Transfer of the components of the pretreatment liquid was observed over 70% or more of the total area of ​​the back surface of the non-permeable substrate, and the transparency of the non-permeable substrate was significantly impaired.

[0548] <Storage Stability>

[0549] Place 25 g of the pretreatment solution in a 30 mL polyethylene bottle. Place the bottle containing the pretreatment solution in a thermostat set at 50°C and store for 2 weeks. Measure the viscosity of the pretreatment solution before and after storage, and calculate the Δ viscosity (mPa·s) using the following formula.

[0550] Δ viscosity = (viscosity of the pretreatment solution after storage at 50°C for 2 weeks) - (viscosity of the pretreatment solution before storage)

[0551] The viscosity of the pretreatment liquid was measured using a VISCOMETER TV-22 viscometer (manufactured by Toki Sangyo Co., Ltd.) while the temperature was adjusted to 25°C. The storage stability of the pretreatment liquid was evaluated based on the Δ viscosity obtained in this manner according to the following evaluation criteria. In the following evaluation criteria, the pretreatment liquid with the most excellent storage stability was rated "A."

[0552] A: Δ viscosity is 0.1 mPa·s or less.

[0553] B: Δ viscosity is greater than 0.1 mPa·s and not more than 0.4 mPa·s.

[0554] C: Δ viscosity is greater than 0.4 mPa·s and less than 1.0 mPa·s.

[0555] D: Δ viscosity is greater than 1.0 mPa·s and not more than 2.0 mPa·s.

[0556] E: Δ viscosity is greater than 2.0 mPa·s.

[0557]

[0558]

[0559] As shown in Tables 1 and 2, it can be seen that in Examples 1 to 25, the pretreatment liquid contains an anionic resin and an aqueous medium, the ClogP value of the anionic resin is 1.40 or greater, and the content of the structural unit derived from the (meth)acrylic acid alkyl ester having a chain alkyl group with 2 or more carbon atoms in the anionic resin is less than 5% by mass relative to the total mass of the anionic resin, so the dot diameter is large.

[0560] On the other hand, in Comparative Example 1, the pretreatment liquid contained a cationic resin instead of an anionic resin, so the dot diameter was small, streaks were observed in the image, and the adhesion of the image to the non-permeable substrate was poor.

[0561] In Comparative Example 2, the pretreatment liquid contained a cationic resin instead of an anionic resin, and the cationic resin contained 5% by mass or more of a structural unit derived from an alkyl (meth)acrylate having a chain alkyl group having 2 or more carbon atoms, relative to the total mass of the cationic resin. Consequently, the dot diameter was small, significant streaking was observed in the image, and the image exhibited poor adhesion to the non-permeable substrate.

[0562] In Comparative Example 3, the pretreatment liquid contained a nonionic resin instead of an anionic resin, so the dot diameter was very small and significant streak unevenness was observed in the image.

[0563] In Comparative Example 4, the anionic resin contained in the pretreatment liquid contained 5% by mass or more of a structural unit derived from an alkyl (meth)acrylate having a chain alkyl group having 2 or more carbon atoms, relative to the total mass of the anionic resin. Therefore, the dot diameter was very small and significant streaking was observed in the image.

[0564] In Comparative Example 5, the ClogP value of the anionic resin contained in the pretreatment liquid was less than 1.40, so the dot diameter was very small and significant streak unevenness was observed in the image.

[0565] In Example 22, since the ClogP value of the anionic group-containing monomer is not less than -4.00, it can be seen that the dot diameter is larger than that of Examples 15 and 16, and streaking unevenness of the image is further suppressed.

[0566] In Example 22, since the anionic resin has a salt of a sulfonic group, it is found that the dot diameter is larger than in Examples 13 and 14, streaking unevenness in the image is further suppressed, and the storage stability of the pretreatment liquid is excellent.

[0567] In Example 22, since the anionic resin contains the structural unit represented by formula (2), it is found that the dot diameter is larger than that in Example 15 and the streak unevenness of the image is further suppressed.

[0568] In Examples 21 to 25, the anionic resin contains a structural unit derived from a monomer containing a hydrogen-bonding group, and the ClogP value of the monomer containing a hydrogen-bonding group is greater than 0.20. Therefore, it can be seen that compared with Examples 2 to 5 and Examples 8 to 9, the dot diameter is large and the streak unevenness of the image is further suppressed.

[0569] In Examples 21 to 25, since the structural unit represented by formula (4) is contained, it is found that the adhesion to the non-permeable substrate is more excellent than that of Example 27.

[0570] In Examples 21 to 25, the structural unit represented by formula (4) is contained, and Y in formula (4) 3 Since it is -OH, it can be seen that the adhesion to the non-permeable substrate is excellent compared with Examples 6 and 20.

[0571] In Examples 21 to 25, the content of the structural unit derived from the hydrogen-bonding group-containing monomer was 5% by mass or more relative to the total mass of the anionic resin, indicating that the adhesion to the non-permeable substrate was superior to that of Example 19. Furthermore, in Examples 21 to 25, the content of the structural unit derived from the hydrogen-bonding group-containing monomer was 50% by mass or less relative to the total mass of the anionic resin, indicating that the dot diameter was larger and image streaking was further suppressed compared to Example 17.

[0572] In Examples 21 to 25, the anionic resin contains at least one selected from the group consisting of structural units represented by Formula (A) to Formula (F). Therefore, it is found that the adhesion to the non-permeable substrate is better than that of Example 12.

[0573] In Examples 21 to 25, the glass transition temperature of the anionic resin was -30°C or higher, demonstrating superior adhesion to non-permeable substrates, blocking resistance, and storage stability in the pre-treatment solution compared to Example 10. Furthermore, the dot diameters were large, and image streaking was suppressed. Furthermore, in Examples 21 to 25, the glass transition temperature of the anionic resin was below -100°C, demonstrating even better adhesion to non-permeable substrates compared to Example 11.

[0574] The above describes an embodiment group using cyan ink as the ink, but in these embodiment groups, even when the cyan ink is changed to an ink other than cyan ink (for example, magenta ink, yellow ink, black ink, etc.) or when at least one of the inks other than cyan ink is used to record a multi-color image in addition to the cyan ink, the same effect as the above-mentioned embodiment group can of course be obtained.

Claims

1. A pretreatment solution for a non-permeable substrate, comprising an anionic resin and an aqueous medium. The ClogP value of the anionic resin is greater than 1.40, The content of the structural unit derived from the (meth)acrylate having a chain alkyl group having 2 or more carbon atoms in the anionic resin is less than 5% by mass relative to the total mass of the anionic resin. The anionic resin contains a structural unit derived from a monomer containing an anionic group, The ClogP value of the anionic group-containing monomer is greater than -4.00, The anionic resin contains at least one structural unit selected from the group consisting of a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2) as the structural unit derived from the anionic group-containing monomer. The content of the structural unit derived from the anionic group-containing monomer is 1% by mass to 15% by mass relative to the total mass of the anionic resin. The anionic resin contains a structural unit derived from a monomer containing a hydrogen bonding group, The ClogP value of the hydrogen-bonding group-containing monomer is greater than 0.20, The structural unit derived from the monomer containing a hydrogen-bonding group is at least one selected from the group consisting of a structural unit represented by the following formula (3) and a structural unit represented by the following formula (4), The content of the structural unit derived from the hydrogen-bonding group-containing monomer is 5% by mass to 50% by mass relative to the total mass of the anionic resin. In formula (1) and formula (2), R 1 Each independently represents a hydrogen atom or a methyl group, L 1 Each independently represents an alkylene group having 1 to 10 carbon atoms or a single bond, each independently represents a hydrogen atom or a cation, In formula (3) and formula (4), R 2 Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, In formula (3), A 2 represents -NH-, L 2 represents an alkylene group having 1 to 6 carbon atoms or a single bond, Y 2 represents an alkyl group having 1 to 6 carbon atoms, -OH, -OR 3 、-NH2、-NR 3 H, -NR 3 R 4 or -C(=O)R 3 , In formula (4), L 3 represents one divalent group selected from the second group consisting of an alkylene group having 1 to 6 carbon atoms, -O-, and -C(=O)-, or a divalent group consisting of a combination of two or more selected from the second group, Y 3 Represents a halogen atom, -OH, -NH2, -NR 3 H or -C(=O)R 3 , R 3 and R 4 Each independently represents an alkyl group having 1 to 6 carbon atoms.

2. The non-permeable substrate pretreatment liquid according to claim 1, wherein The anionic resin has at least one group selected from the group consisting of a sulfonic group and a salt of a sulfonic group.

3. The non-permeable substrate pretreatment liquid according to claim 1, wherein Y in the formula (3) 2 And Y in the formula (4) 3 -OH, -NH2 or -NR 3 H.

4. The non-permeable substrate pretreatment liquid according to claim 1 or 2, wherein The anionic resin contains at least one selected from the group consisting of structural units represented by the following formulae (A) to (F). In formula (A) to formula (F), R 5 Each independently represents a hydrogen atom or a methyl group, R 6 Each independently represents an alkyl group, an alkenyl group or an alkynyl group, m is an integer from 0 to 5, n is an integer from 0 to 11, L 5 It represents one divalent group selected from the fourth group consisting of an alkylene group having 1 to 18 carbon atoms, an arylene group having 6 to 18 carbon atoms, -O-, -NH-, -S-, and -C(=O)-; a divalent group consisting of a combination of two or more selected from the fourth group; or a single bond.

5. The non-permeable substrate pretreatment liquid according to claim 1 or 2, wherein The anionic resin has a glass transition temperature of -30°C or higher and lower than 100°C.

6. An ink set comprising: The non-permeable substrate pretreatment liquid according to any one of claims 1 to 5; and Ink, containing colorant and water.

7. An image recording substrate comprising: non-permeable substrates; and The pretreatment layer is provided on at least one surface of the impermeable substrate and contains the solid content of the impermeable substrate pretreatment liquid according to any one of claims 1 to 5.

8. An image record comprising: non-permeable substrates; and The image is provided on at least one surface of the non-permeable substrate and comprises the solid component of the non-permeable substrate pretreatment liquid according to any one of claims 1 to 5 and a colorant. 9 . A method for producing an image recording substrate, comprising applying the non-permeable substrate pretreatment liquid according to claim 1 to a non-permeable substrate.

10. An image recording method, comprising: a step of applying the non-permeable substrate pretreatment liquid according to any one of claims 1 to 5 to the non-permeable substrate; and A step of recording an image by applying ink containing a colorant and water to the surface of the non-permeable substrate to which the non-permeable substrate pretreatment liquid has been applied using an inkjet recording method.

Images