Pretreatment liquid for inkjet ink, ink set, surface-treated substrate, image recording method, method for producing laminate, image-recorded matter, and laminate

Abstract

A pretreatment liquid for an inkjet ink, the pretreatment liquid containing resin particles, a surfactant, a coagulant, and water, the surfactant containing a compound represented by formula (1), and the coagulant containing at least one selected from the group consisting of polyvalent metal compounds and organic acids. Formula (1) is H (OCH2CH2) x (OCH (CH3) CH2) y (OCH2CH2) z-OH, in formula (1), x and z are each independently an integer of 1 or more, y is an integer of 1-500, and x + z is an integer of 2-1000.

Description

Technical Field

[0001] This invention relates to a pretreatment liquid for inkjet ink, an ink assembly, a surface-treated substrate, an image recording method, a method for manufacturing a laminate, an image recorder, and a laminate. Background Technology

[0002] In recent years, various studies have been conducted on pretreatment solutions used for image recording on non-permeable substrates.

[0003] For example, Japanese Patent Application Publication No. 2021-91765 discloses a pretreatment liquid for use with an aqueous inkjet ink containing pigment and water. The pretreatment liquid is characterized in that it contains a coagulant (A), a surfactant (B), a resin (C), and water. The coagulant (A) contains at least one selected from the group consisting of metal salts and cationic polymers, and the surfactant (B) contains a specific polyoxyalkylene amine.

[0004] Japanese Patent Application Publication No. 2002-79739 discloses the following: a surfactant having ethylene oxide chains and propylene oxide chains is used in a pretreatment solution of a colorless or light-colored material to be recorded, which contains 10 to 80% by weight of a compound that reduces the solubility or dispersibility of the recording solution and has a viscosity of 10 to 10,000 mPa·s at 25°C. Summary of the Invention

[0005] The technical problem to be solved by the invention Sometimes, after obtaining an image recorder by sequentially applying an inkjet ink pretreatment solution and inkjet ink to a non-permeable substrate to record an image, a laminating substrate is used to laminate the image-containing side of the obtained image recorder to manufacture a laminate. When inkjet ink is applied to the pretreatment layer formed by the pretreatment solution, the dot expansion (dot diameter) is insufficient, which sometimes results in stripes in the image. Therefore, it is sometimes required to further expand the dot diameter. Furthermore, in the manufacture of the laminate, it is sometimes required to increase the lamination strength between the laminating substrate and the image recorder.

[0006] The present invention was made in view of this situation. One embodiment of the present invention aims to solve the problem of providing an inkjet ink pretreatment solution, an ink group, and an image recording method that can further expand the dots of the inkjet ink and obtain a laminate with excellent lamination strength.

[0007] Another embodiment of the present invention aims to solve the problem of providing an image recorder, a surface-treated substrate, a laminate, and a method for manufacturing the laminate using the above-described inkjet ink pretreatment liquid.

[0008] means for solving technical problems The present invention includes the following methods.

[0009] <1> A pretreatment solution for inkjet ink comprises resin particles, surfactants, flocculants, and water. Surfactants comprise compounds represented by the following formula (1), The coagulant comprises at least one selected from the group consisting of polyvalent metal compounds and organic acids.

[0010] H(OCH2CH2) x (OCH(CH3)CH2) y (OCH2CH2) z -OH…(1) In equation (1), x and z are independent integers greater than or equal to 1, y is an integer from 1 to 500, and x+z is an integer from 2 to 1000.

[0011] <2> According to the pretreatment solution for inkjet ink described in <1>, wherein... The HLB value of the compound represented by formula (1) is less than 15.0.

[0012] <3> According to the pretreatment solution for inkjet inks described in <1> or <2>, wherein, The cloud point of the compound represented by formula (1) is above 50℃.

[0013] <4> The pretreatment solution for inkjet ink according to any one of <1> to <3>, wherein, Resin particles are particles containing urethane resin.

[0014] <5> According to the pretreatment solution for inkjet ink described in <4>, wherein... The particles containing urethane resin are particles that contain at least one selected from the group consisting of polyether-based urethane resins and polycarbonate-based urethane resins.

[0015] <6> According to the pretreatment solution for inkjet ink described in <4>, wherein... The urethane resin contained in the resin particles contains structural units derived from polycyclic aliphatic diols.

[0016] <7> The pretreatment solution for inkjet ink according to any one of <1> to <6>, wherein, (OCH2CH2) x and (OCH2CH2)z The total formula weight accounts for 15% to 50% of the molecular weight of the compound represented by formula (1).

[0017] <8> The pretreatment solution for inkjet ink according to any one of <1> to <7>, wherein, The content of the compound represented by formula (1) is 0.5% to 3% by mass relative to the total amount of pretreatment solution for inkjet ink.

[0018] <9> The pretreatment solution for inkjet ink according to any one of <1> to <8>, wherein, The mass ratio of the content of the compound represented by formula (1) to the content of resin particles is 0.05 to 0.50.

[0019] <10> The pretreatment solution for inkjet ink according to any one of <1> to <9>, wherein, The inkjet ink pretreatment solution is used for image recording on a non-permeable substrate.

[0020] <11> An ink assembly comprising: Pretreatment solution for inkjet inks as described in any one of <1> to <10>; and Inkjet ink contains water and pigment.

[0021] <12> A surface-treated substrate, comprising: Non-permeable substrates; and A pretreatment layer disposed on a non-permeable substrate and comprising the solid component of the inkjet ink pretreatment liquid as described in any one of <1> to <10>.

[0022] <13> An image recording method, comprising: The process of applying the pretreatment solution for inkjet ink as described in any one of <1> to <10> to a non-permeable substrate; and The process of recording images by applying inkjet ink containing water and pigment to a non-permeable substrate that has been pretreated with an inkjet ink pretreatment solution.

[0023] <14> A method for manufacturing a laminate, comprising: The process of obtaining an image recorder having a non-permeable substrate and an image disposed on the non-permeable substrate using the image recording method described in <13>; and The process of laminating a laminating substrate onto the side of an image recorder containing the image to obtain a laminate.

[0024] <15> An image recording medium comprising a non-permeable substrate and an image disposed on the non-permeable substrate, The images include: The pretreatment layer comprises the solid components of the inkjet ink pretreatment solution as described in any one of <1> to <10>; and An ink layer, disposed on a pretreatment layer, contains pigments.

[0025] <16> A laminate comprising: The image recording object described in <15>; and A laminating substrate is used to laminate the image-containing side of an image recorder.

[0026] Invention Effects According to one embodiment of the present invention, an inkjet ink pretreatment solution, an ink group, and an image recording method are provided that can further expand the dots of the inkjet ink and obtain a laminate with excellent lamination strength.

[0027] According to another embodiment of the present invention, an image recorder, a laminate, and a method for manufacturing the laminate using the above-described inkjet ink pretreatment solution are provided. Detailed Implementation

[0028] The following provides a detailed description of the pretreatment liquid for inkjet ink, the ink assembly, the surface-treated substrate, the image recording method, the manufacturing method of the laminate, the image recorder, and the laminate of the present invention.

[0029] In this specification, the numerical range indicated by “~” refers to the range encompassed by taking the values ​​before and after “~” as the minimum and maximum values, respectively.

[0030] In the numerical ranges described in this specification, the upper or lower limit of a certain numerical range can be replaced with the upper or lower limit of other numerical ranges described in different stages. Furthermore, the upper or lower limit of a certain numerical range described in this specification can also be replaced with the values ​​shown in the embodiments.

[0031] In this specification, the amount of each component in the composition refers to the total amount of the multiple substances present in the composition unless otherwise specified, in the case where multiple substances corresponding to each component are present in the composition.

[0032] In this specification, a combination of two or more preferred methods is a more preferred method.

[0033] In this specification, the term "process" includes not only independent processes, but also processes that can not be clearly distinguished from other processes, as long as the intended purpose of the process can be achieved.

[0034] In this specification, "image" refers to all membranes formed by sequentially applying a pretreatment solution and ink, and "image recording" refers to the formation of an image (i.e., a membrane).

[0035] Furthermore, the concept of "image" in this specification also includes solid images.

[0036] In this specification, "(meth)acrylate" is a concept that includes both acrylate and methacrylate. Furthermore, "(meth)acrylic acid" is a concept that includes both acrylic acid and methacrylic acid.

[0037] [Pretreatment solution for inkjet inks] The inkjet ink pretreatment solution (hereinafter also referred to as "pretreatment solution") of the present invention comprises resin particles, surfactant, coagulant and water, wherein the surfactant comprises a compound represented by the following formula (1) (hereinafter also referred to as "compound (1)"), and the coagulant comprises at least one selected from the group consisting of polyvalent metal compounds and organic acids.

[0038] H(OCH2CH2) x (OCH(CH3)CH2) y (OCH2CH2) z -OH…(1) In equation (1), x and z are independent integers greater than or equal to 1, y is an integer from 1 to 500, and x+z is an integer from 2 to 1000.

[0039] Using the pretreatment liquid of the present invention, an image recorder having a substrate and an image recorded on the substrate can be obtained. When a laminate is manufactured by laminating the surface of the image using a laminating substrate, the image recorder maintains the expansion of the points forming the image well and has excellent lamination strength.

[0040] Here, lamination strength refers to the peel strength when peeling the laminate and image recording material from the laminate formed by the above lamination [i.e., a laminate having a laminate structure of "laminated substrate / image recording material" (more specifically, a laminate structure of "laminated substrate / ink layer (image) / preprocessing layer / substrate").]

[0041] Furthermore, using the pretreatment liquid of the present invention, it is possible to further expand the dots of ink applied to the pretreatment layer formed by the pretreatment liquid.

[0042] The reason why the pretreatment solution of the present invention achieves the above-mentioned effects is speculated as follows.

[0043] To improve the lamination strength in the laminate, it is necessary to improve the adhesion between the substrate and the pretreatment layer.

[0044] If the ink contains a highly hydrophilic surfactant, the diameter of the ink dots applied to the pretreatment layer increases. On the other hand, the adhesion between the substrate and the pretreatment layer decreases, and sometimes lamination strength cannot be obtained. Furthermore, if the ink contains a highly hydrophobic surfactant, although it does not affect the adhesion between the substrate and the pretreatment layer, the ink dots applied to the pretreatment layer are not easy to expand, and there is a tendency for stripes to be generated in the image.

[0045] In contrast, the pretreatment liquid of the present invention comprises compound (1), which simultaneously has an ethylene oxide chain as a hydrophilic group and an propylene oxide chain as a hydrophobic group. It is believed that the presence of the hydrophobic group in compound (1) maintains the adhesion between the substrate and the pretreatment layer. Furthermore, it is believed that when ink is applied to the pretreatment layer, the wettability of the ink is effectively improved due to the presence of hydrophilic groups at both ends of compound (1), and dot expansion is achieved. Thus, it is possible to simultaneously and effectively improve both dot expansion and adhesion in the image.

[0046] On the other hand, in the pretreatment solution described in Patent Document 1, the surfactant has propylene oxide chains at both ends. Furthermore, the pretreatment solution described in Patent Document 2 does not contain resin particles. Therefore, the pretreatment solutions described in Patent Documents 1 and 2 cannot achieve the effects of point expansion and lamination strength.

[0047] Next, the components contained in the pretreatment solution of the present invention will be described.

[0048] The pretreatment solution of the present invention comprises resin particles, surfactants, coagulants and water.

[0049] (surfactant) The pretreatment solution contains surfactants.

[0050] Surfactants contain compounds (1).

[0051] H(OCH2CH2) x (OCH(CH3)CH2) y (OCH2CH2) z -OH…(1) In equation (1), x and z are independent integers greater than or equal to 1, y is an integer from 1 to 500, and x+z is an integer from 2 to 1000.

[0052] Compound (1) simultaneously possesses an ethylene oxide chain as a hydrophilic group and an propylene oxide chain as a hydrophobic group. It is believed that the presence of the hydrophobic group in compound (1) maintains the adhesion between the substrate and the pretreatment layer. Furthermore, it is believed that when ink is applied to the pretreatment layer, the surface of the pretreatment layer becomes hydrophilic due to the presence of hydrophilic groups at both ends of compound (1), thus improving the wettability of the ink and promoting dot spread.

[0053] From the perspective of ease of synthesis, x and z in equation (1) are preferably the same.

[0054] Specifically, x+z is preferably an integer from 2 to 500, more preferably an integer from 4 to 100. Furthermore, y is preferably an integer from 1 to 100, more preferably an integer from 2 to 50.

[0055] From the perspective of expanding ink dots and increasing lamination strength, (OCH2CH2) x and (OCH2CH2) z The total formula weight of the compound (1) is preferably 15% to 50% of the molecular weight of the compound (1), more preferably 25% to 50%.

[0056] If the above ratio is 15% or higher, the surface of the pretreatment layer becomes hydrophilic, and the spots are easy to spread.

[0057] If the above ratio is below 50%, the lamination strength will increase.

[0058] The molecular weight of compound (1) is calculated based on the types and numbers of atoms constituting compound (1). Furthermore, (OCH2CH2) x and (OCH2CH2) z The total formula is the product of the formula of (OCH2CH2) and the sum of x and z.

[0059] The pretreatment solution may contain surfactants other than compound (1), but in order to further demonstrate the effect based on compound (1), the proportion of compound (1) in the surfactant is preferably 80% by mass or more, more preferably 90% by mass or more.

[0060] In particular, the surfactant is preferably composed of only compound (1).

[0061] The HLB value of compound (1) is preferably 15.0 or less, more preferably 13.0 or less. From the viewpoint of the liquid stability of the pretreatment solution, the lower limit of the HLB value is preferably 7.0.

[0062] If the HLB value is below 15.0, the balance between hydrophilic and hydrophobic groups is good, the lamination point is further extended, and the lamination strength is better.

[0063] HLB values ​​are determined using the Griffin method.

[0064] The HLB value, determined by the Griffin method, is a physical property value representing the degree of hydrophilicity and lipophilicity of a surfactant, ranging from 0 to 20. The smaller the HLB value, the higher the lipophilicity; the larger the HLB value, the higher the hydrophilicity.

[0065] HLB value = 20 × formula weight of the hydrophilic group (ethylene oxide) of the surfactant / molecular weight of the surfactant The cloud point of compound (1) is preferably 50°C or higher, more preferably 60°C or higher. The upper limit of the cloud point is not particularly limited, for example, it is 100°C.

[0066] If the cloud point is above 50℃, the pretreatment solution has excellent storage stability.

[0067] The cloud point is determined by the following method.

[0068] Dissolve 99g of ion-exchanged water and 1g of the sample uniformly. If it does not dissolve, cool until it does. Take about 5mL of the sample solution into a glass test tube, place a thermometer in the sample solution, and heat it while stirring until the sample solution becomes cloudy. Then, while stirring, slowly cool it, and read the temperature at which the sample solution becomes completely clear as the cloud point.

[0069] Compound (1) is commonly referred to as polypropylene glycol ethylene oxide adduct, polyoxyethylene polyoxypropylene glycol, polyoxyethylene polyoxypropylene block polymer or Pluronic (registered trademark) type nonionic surfactant.

[0070] Compound (1) may be a commercially available product.

[0071] As commercially available products, examples include: Sanyo Chemical Industries, Ltd. manufactures NEWPOL (registered trademark) PE series PE-61 [POE(5)POP(30)], PE-62 [POE(10)POP(30)], PE-71 [POE(5)POP(35)], PE-74 [POE(30)POP(35)], PE-75 [POE(48)POP(35)], and PE-78 [POE(150)POP(35)]; ADEKA CORPORATION manufactures the following Adeka Pluronic (registered trademark) L series products: L-31 [POE(3)POP(17)], L-34 [POE(16)POP(17)], L-44 [POE(20)POP(20)], L-61 [POE(5)POP(30)], L-62 [POE(10)POP(30)], L-64 [POE(25)POP(30)], L-101 [POE(8)POP(55)] and L-121 [POE(10)POP(65)]; Adeka Pluronic F series F-68 [POE(160)POP(30)], F-87 [POE(120)POP(40)], F-127 [POE(196)POP(67)]; Adeka Pluronic P-series P-85 [POE(54)POP(39)] and P-123 [POE(42)POP(67)]; BASF Japan Ltd. manufactures the Kolliphor series P188 [POE (160) POP (30)] and P407 [POE (196) POP (67)]; Lutrol series F68 [POE(160)POP(30)] and F127 [POE(196)POP(67)].

[0072] Furthermore, the number in parentheses after POE refers to the sum of x+z in equation (1). And the number in parentheses after POP refers to the value of y in equation (1).

[0073] For example, “POE(5)POP(30)” refers to a compound in formula (1) where x+z is 5 and y is 30.

[0074] The content of compound (1) is preferably 0.5% to 3% by mass relative to the total amount of the pretreatment liquid, more preferably 1% to 2.5% by mass.

[0075] If the content of compound (1) is 0.5% by mass or more, the ink dots are more likely to spread.

[0076] If the content of compound (1) is less than 3% by mass, the lamination strength is further improved.

[0077] (Resin particles) The pretreatment solution contains resin particles. By including resin particles in the pretreatment solution, the adhesion to the substrate is improved, and the lamination strength is increased.

[0078] The resin particles may contain only one type of resin or two or more types of resin.

[0079] The resin contained in the resin particles is preferably a water-insoluble resin.

[0080] In this invention, "water-insoluble" in water-insoluble resin refers to the property that the amount of water solubility in 100g of water at 25°C is less than 1.0g (more preferably less than 0.5g).

[0081] Examples of resins that constitute resin particles include acrylic resins and urethane resins.

[0082] From the viewpoint that the resin particles can exist stably in the pretreatment solution without agglomerating due to the coagulant, the resin particles are more preferably particles containing urethane resin.

[0083] In this invention, nonionic urethane resin refers to urethane resin that does not have ionic properties (i.e., anionic or cationic properties).

[0084] In this invention, urethane resin refers to a polymer containing urethane bonds.

[0085] Carbamate resins are synthesized, for example, by reacting diol compounds with diisocyanate compounds.

[0086] For details regarding diol compounds and diisocyanate compounds, please refer to paragraphs 0031 to 0036 of Japanese Patent Application Publication No. 2001-247787.

[0087] The urethane resin can be a polyester-based urethane resin with ester bonds in the main chain, a polycarbonate-based urethane resin with carbonate bonds in the main chain, or a polyether-based urethane resin with ether bonds in the main chain.

[0088] From the viewpoint of improving lamination strength, the resin particles are preferably particles comprising at least one selected from the group consisting of polyether-based urethane resins and polycarbonate-based urethane resins.

[0089] Furthermore, from the viewpoint of improving lamination strength, the resin particles are preferably urethane resin particles composed of urethane resin having structural units derived from polycyclic aliphatic diols.

[0090] Examples of polycyclic aliphatic diols include diols with bridged rings such as norbornene, bicyclic octane, bicyclic undecane, adamantane, tricyclic decane, and tetracyclic dodecane; and diols with spirocyclic rings.

[0091] Specifically, examples of polycyclic aliphatic diols include 2,5-norbornanediol, bicyclic [2.2.2]octane-1,4-diethanol, 1,3-adamantanediol, and tricyclic decanediethanol (tricyclic [5.2.1.0 (2,6)]decanediethanol, etc.).

[0092] From the viewpoint of adhesion to the substrate, polycyclic aliphatic diols are preferably diols having a tricyclic decane ring, and more preferably tricyclic [5.2.1.0(2,6)]decanediethanol.

[0093] The weight-average molecular weight of the resin in the resin particles is preferably 1,000 to 300,000, more preferably 2,000 to 200,000, and even more preferably 5,000 to 100,000.

[0094] In this invention, the weight-average molecular weight (Mw) is determined by gel permeation chromatography (GPC). The GPC uses an HLC-8220 GPC (manufactured by Tosoh Corporation) as the column, with three TSKgeL SuperHZM-H, TSKgeL SuperHZ4000, and TSKgel SuperHZ2000 (all trade names manufactured by Tosoh Corporation) connected in series. THF (tetrahydrofuran) is used as the eluent.

[0095] Furthermore, as conditions, the sample concentration was set to 0.45% by mass, the flow rate to 0.35 ml / min, the sample injection volume to 10 μL, the measurement temperature to 40 °C, and a differential refractive index detector was used. The calibration curves were prepared using eight samples manufactured by Tosoh Corporation: "TSK standard, polystyrene": "F-40", "F-20", "F-4", "F-1", "A-5000", "A-2500", "A-1000", and "n-propylbenzene".

[0096] From the viewpoint of ejection stability, the average particle size of the resin particles is preferably 1 nm to 200 nm, more preferably 3 nm to 200 nm, and even more preferably 5 nm to 50 nm. Furthermore, the average particle size of the resin particles is determined by measuring the volume average particle size using a particle size distribution measuring device (e.g., Nikkiso Co., Ltd., product name "NANOTRAC UPA-EX150") via dynamic light scattering.

[0097] The content of resin particles relative to the total amount of pretreatment liquid is preferably 1% to 20% by mass, more preferably 5% to 15% by mass.

[0098] -Compound(1) / Resin Particles- In the pretreatment solution of the present invention, the mass ratio of the content of compound (1) to the content of resin particles is preferably 0.05 to 0.50, more preferably 0.07 to 0.30.

[0099] If the ratio is above 0.05, the point is prone to expansion.

[0100] If the ratio is below 0.5, the lamination strength increases.

[0101] (Flocculant) The pretreatment solution contains a coagulant. The coagulant contains at least one selected from the group consisting of polyvalent metal compounds and organic acids. From a processability point of view, the coagulant is preferably a polyvalent metal compound.

[0102] By including a coagulant in the pretreatment solution, the components contained in the subsequent ink can be coagulated, thereby improving image quality.

[0103] -Polyvalent metal compounds- Examples of polyvalent metal compounds include salts of alkaline earth metals (e.g., magnesium, calcium) from Group 2 of the periodic table, transition metals (e.g., lanthanum) from Group 3 of the periodic table, metals (e.g., aluminum) from Group 13 of the periodic table, and salts of lanthanides (e.g., neodymium).

[0104] Salts of these metals are preferably salts of organic acids, nitrates, chlorides, or thiocyanates, as described later.

[0105] The polyvalent metal compound is preferably a calcium or magnesium salt of an organic acid (e.g., formic acid, acetic acid, benzoic acid, etc.); a calcium or magnesium salt of nitric acid; or a calcium or magnesium salt of calcium chloride, magnesium chloride, or thiocyanate.

[0106] The polyvalent metal compound preferably dissociates into polyvalent metal ions and counter ions in the pretreatment solution.

[0107] -Organic acids- Organic acids can be exemplified by organic compounds that have acidic groups.

[0108] Examples of acidic groups include phosphate, phosphonic acid, hypophosphonic acid, sulfate, sulfonic acid, sulfinic acid, and carboxyl groups.

[0109] From the perspective of ink agglomeration speed, the acidic group is preferably a phosphate group or a carboxyl group, and more preferably a carboxyl group.

[0110] The acidic groups preferably dissociate in at least a portion of the pretreatment solution.

[0111] Examples of organic compounds containing a carboxyl group include (meth)acrylic acid, poly(meth)acrylic acid, acetic acid, formic acid, benzoic acid, ethylene glycol, 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, pyrrolidone carboxylic acid, pyranone carboxylic acid, pyrrolic carboxylic acid, furan carboxylic acid, pyridine carboxylic acid, coumaric acid, thiophene carboxylic acid, and nicotinic acid.

[0112] From the viewpoint of ink agglomeration speed, organic compounds with carboxyl groups are preferably carboxylic acids with a valence of 2 or higher (hereinafter also referred to as polycarboxylic acids), and more preferably dicarboxylic acids.

[0113] Specifically, the polycarboxylic 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.

[0114] The organic acid is preferably low in pKa (e.g., 1.0 to 5.0). Thus, by contacting with an organic acid with a lower pKa, the surface charge of particles such as pigments and resin particles in the ink, which are dispersed by weakly acidic functional groups such as carboxyl groups, can be reduced, thereby reducing dispersion stability.

[0115] The organic acid preferably has a low pKa, high solubility in water, and a valence of 2 or higher. Furthermore, the organic acid is more preferably characterized by a high buffering capacity in a pH region that is lower than the pKa of the functional groups (e.g., carboxyl groups) that stabilize the dispersion of particles in the ink.

[0116] The pretreatment solution may contain only one type of flocculant or two or more types.

[0117] The content of the coagulant relative to the total amount of the pretreatment liquid is preferably 0.1% to 40% by mass, more preferably 0.1% to 30% by mass, even more preferably 1% to 20% by mass, and especially preferably 1% to 10% by mass.

[0118] (water) The pretreatment solution contains water. The water content is not particularly limited, for example, it can be 50% to 90% by mass.

[0119] (Other ingredients) The pretreatment solution may contain other components besides resin particles, surfactants, coagulants, and water, as needed. Other components that may be contained in the pretreatment solution include organic solvents, defoamers, 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 polymers (e.g., the water-soluble polymers described in paragraphs 0026 to 0080 of Japanese Patent Application Publication No. 2013-001854).

[0120] (physical properties) From the viewpoint of ink agglomeration rate, the pH of the pretreatment solution is preferably 0.1 to 4.5, more preferably 0.2 to 4.0. The pH is measured using a pH meter at 25°C, for example using a pH meter (model "HM-31") manufactured by DKK-TOA CORPORATION.

[0121] From the viewpoint of ink agglomeration rate, the viscosity of the pretreatment solution is preferably 0.5 mPa·s to 10 mPa·s, more preferably 1 mPa·s to 5 mPa·s. The viscosity is a value measured using a viscometer at 25°C. Viscosity is measured using a viscometer at 25°C, for example, using a TV-22 type viscometer manufactured by Toki Sangyo Co., Ltd.

[0122] The surface tension of the pretreatment liquid is preferably below 60 mN / m, 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. The surface tension is measured using a surface tension meter at 25°C, for example, using an automatic surface tension meter (product name "CBVP-Z") manufactured by Kyowa Interface Science Co., Ltd., via the plate method.

[0123] (use) The pretreatment liquid of the present invention is used for inkjet inks. That is, the pretreatment liquid of the present invention is a liquid that is pre-applied to the substrate before inkjet ink is applied to the substrate.

[0124] In particular, the pretreatment solution of the present invention is preferably used for image recording on a non-permeable substrate. Images are recorded by sequentially applying the pretreatment solution and ink to the non-permeable substrate.

[0125] The pretreatment liquid of the present invention contains compound (1), thus exhibiting excellent adhesion to non-permeable substrates, and the ink dot expansion enables the recording of images with excellent image quality on non-permeable substrates.

[0126] -Non-permeable substrate- In this invention, the non-permeability of the non-permeable substrate refers to the property that its water absorption rate is less than 2.5% over 24 hours, as measured according to ASTM D570-98 (2018). Here, the "%" used as the unit of water absorption rate is a mass standard. The aforementioned water absorption rate is preferably less than 1.0%, and more preferably less than 0.5%.

[0127] Materials that can be used as non-permeable substrates include, for example, 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 alcohol acetal, nylon, acrylic resins, etc.).

[0128] The non-permeable substrate is preferably made of resin. That is, the non-permeable substrate is preferably a resin substrate.

[0129] From a general perspective, the preferred materials for non-permeable substrates are polypropylene, polyethylene, polyethylene terephthalate, nylon, acrylic resins, or polyvinyl chloride.

[0130] The shape of the non-permeable substrate is preferably sheet (film) or plate. Examples of non-permeable substrates with this shape include glass plates, metal plates, resin sheets (resin films), paper laminated with plastic, paper laminated or vapor-deposited with metal, and plastic sheets (plastic films) laminated or vapor-deposited with metal.

[0131] As a non-permeable substrate made of resin, examples include resin sheets (resin films), and more specifically, examples include flexible packaging materials for packaged food and floor guide panels in large retail stores.

[0132] In addition to sheet-like (film-like) or plate-like non-permeable substrates, textiles (fabricated fabrics) and non-woven fabrics formed from non-permeable fibers can also be cited as examples of non-permeable substrates.

[0133] The thickness of the non-permeable 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.

[0134] Hydrophilic treatment can be applied to non-permeable substrates. Examples of hydrophilic treatments include corona treatment, plasma treatment, heat treatment, abrasion treatment, light irradiation treatment (e.g., UV treatment), and flame treatment, but are not limited to these. Corona treatment can be performed, for example, using the Corona Master (product name "PS-10S", manufactured by Shinko Electric & Instrumentation Co., Ltd.). The conditions for corona treatment should be appropriately selected based on the type of non-permeable substrate.

[0135] Non-permeable substrates can be transparent non-permeable substrates.

[0136] Here, transparency means that the transmittance of visible light with wavelengths of 400nm to 700nm is 80% or more (preferably 90% or more).

[0137] When the non-permeable substrate is a transparent non-permeable substrate, the image can be easily visually identified through the non-recording side of the non-permeable substrate.

[0138] For example, when the non-permeable substrate is a transparent non-permeable substrate, and a pretreatment liquid, coloring ink and white ink are sequentially applied to the non-permeable substrate to record an image, the colored image (e.g., a patterned image such as characters, graphics, etc.) against a white image (e.g., a solid image) can be easily visually identified from the non-recording side of the non-permeable substrate through the non-permeable substrate.

[0139] [Surface-treated substrate] The surface treatment substrate of the present invention preferably includes a non-permeable substrate and a pretreatment layer disposed on the non-permeable substrate and containing the solid components of the pretreatment liquid described above.

[0140] Details of the non-permeable substrate are as described above.

[0141] The solid components of a pretreatment solution refer to the components contained in the pretreatment solution other than volatile components (e.g., water and organic solvents). Specifically, the solid components of a pretreatment solution are resin particles, coagulants, surfactants (including compounds (1)), etc.

[0142] The surface-treated substrate of the present invention is obtained, for example, by applying a pretreatment liquid to a non-permeable substrate and then drying it using a known method to remove the volatile components contained in the pretreatment liquid.

[0143] Since the pretreatment layer in the surface-treated substrate of the present invention contains the aforementioned compound (1), the dots can be easily expanded by applying ink, thereby enabling the recording of images with excellent image quality on the surface-treated substrate. Furthermore, since the surface-treated substrate of the present invention contains the aforementioned compound (1), the adhesion between the non-permeable substrate and the pretreatment layer is excellent. Therefore, when an image is recorded on the pretreatment layer and a laminating substrate is laminated, the resulting laminate exhibits excellent lamination strength.

[0144] [Ink Set] The ink kit of the present invention comprises the above-mentioned pretreatment liquid and an inkjet ink (hereinafter also referred to as "ink") containing water and pigment.

[0145] The ink kit of the present invention may contain only one type of ink or two or more types of ink.

[0146] From a design perspective, the ink set preferably includes white ink and colored inks other than white ink. Examples of colored inks other than white ink include magenta ink, turquoise ink, yellow ink, and black ink.

[0147] The following describes the preferred method for selecting inks in the ink group.

[0148] (pigment) The ink contained in the ink group of the present invention contains pigments. The pigments contained in the ink may be one type or two or more types.

[0149] Pigments can be either commercially available organic or inorganic pigments. Examples of pigments include those described in Seishiro Itō's "Encyclopedia of Pigments" (2000), W. Herbst and K. Hunger's "Industrial Organic Pigments", Japanese Patent Application Publication No. 2002-12607, Japanese Patent Application Publication No. 2002-188025, Japanese Patent Application Publication No. 2003-26978, and Japanese Patent Application Publication No. 2003-342503.

[0150] Furthermore, the pigment can be a water-insoluble pigment that can be dispersed in water with the aid of a dispersant, or it can be a self-dispersible pigment. A self-dispersible pigment is a pigment that can be dispersed in water even without the use of a dispersant. For example, a self-dispersible pigment is a compound formed by direct chemical bonding to the surface of the pigment or through chemical bonding to the surface of the pigment via other groups, consisting of at least one hydrophilic group selected from the group consisting of carbonyl, hydroxyl, carboxyl, sulfonyl, phosphate, etc., and their salts.

[0151] Examples of organic pigments include azo pigments, polycyclic pigments, dye chelates, nitro pigments, nitroso pigments, and aniline black. Examples of azo pigments include azo lakes, insoluble azo pigments, condensed azo pigments, and chelated azo pigments. Examples of polycyclic pigments include phthalocyanine pigments, perylene pigments, perylene ketone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, indigo pigments, thioindolinone pigments, isoindolineone pigments, and quinophthalone pigments. Examples of dye chelates include basic dye-type chelates and acidic dye-type chelates.

[0152] Examples of inorganic pigments include titanium dioxide, iron oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, cadmium red, chrome yellow, and carbon black.

[0153] From the viewpoint of image density and ink ejectibility, the pigment content in the ink is preferably 1% to 20% by mass relative to the total amount of ink, more preferably 1% to 15% by mass, and even more preferably 1% to 10% by mass.

[0154] (water) The ink in the ink group of the present invention contains water. The water content is not particularly limited, for example, it is 40% to 70% by mass.

[0155] (additive) Ink can contain additives such as organic solvents, resin particles, surfactants, co-sensitizers, UV absorbers, antioxidants, anti-fading agents, conductive salts, and alkaline compounds, as needed.

[0156] (physical properties) From the viewpoint of improving ejection stability, the pH of the ink is preferably 7 to 10, and more preferably 7.5 to 9.5. The pH is measured using a pH meter at 25°C, for example, using a pH meter (model "HM-31") manufactured by DKK-TOA CORPORATION.

[0157] The viscosity of the ink is preferably 0.5 mPa·s to 30 mPa·s, more preferably 2 mPa·s to 20 mPa·s, even more preferably 2 mPa·s to 15 mPa·s, and even more preferably 3 mPa·s to 10 mPa·s. The viscosity is measured using a viscometer at 25°C, for example, using a TV-22 type viscometer manufactured by Toki Sangyo Co., Ltd.

[0158] The surface tension of the ink is preferably below 60 mN / m, more preferably 20 mN / m to 50 mN / m, and even more preferably 30 mN / m to 45 mN / m. The surface tension is measured using a surface tension meter at 25°C, for example, by the plate method using an automatic surface tension meter (product name "CBVP-Z") manufactured by Kyowa Interface Science Co., Ltd.

[0159] [Image recording method] The image recording method of the present invention includes: a step of applying the pretreatment liquid to a non-permeable substrate (hereinafter referred to as the "pretreatment liquid application step"); and a step of applying an ink containing water and pigment to a non-permeable substrate to which the pretreatment liquid has been applied to record an image using an inkjet recording method (hereinafter referred to as the "image recording step").

[0160] (Pretreatment solution application process) In the pretreatment liquid application process, the pretreatment liquid is applied to a non-permeable substrate.

[0161] Details of the non-permeable substrate are as described above.

[0162] The method of applying the pretreatment solution is not particularly limited, and well-known methods such as coating, immersion, and inkjet recording can be cited.

[0163] As a coating method, known coating methods include those using rod coaters, extrusion die coaters, air knife coaters, scraper coaters, bar coaters, doctor blade coaters, extrusion coaters, and reverse roller coaters.

[0164] There are no particular restrictions on the way ink is ejected in inkjet recording. It can be any of the known methods, such as charge control methods that use electrostatic induction to eject ink, on-demand inkjet methods (pressure pulse methods) that use the vibration pressure of piezoelectric elements, acoustic inkjet methods that convert electrical signals into sound beams that irradiate the ink and eject the ink using radiation pressure, and thermal inkjet methods (Bubble Jet (registered trademark)) that heat the ink to form bubbles and use the resulting pressure.

[0165] When the pretreatment liquid is applied via inkjet recording, it can be filled into the ink tank of the inkjet recording device instead of ink.

[0166] As an inkjet recording method, the inkjet recording method described in Japanese Patent Application Publication No. 54-59936 is particularly effective, in which ink undergoes a rapid volume change under the influence of heat energy, and the ink is ejected from the nozzle by the force generated by this change in state. The method described in paragraphs 0093 to 0105 of Japanese Patent Application Publication No. 2003-306623 is also applicable as an inkjet recording method.

[0167] When using inkjet recording, a pretreatment solution is applied to a non-permeable substrate by ejecting the pretreatment solution from the nozzle of the inkjet head.

[0168] As inkjet head types, there are reciprocating methods that use a short, strip-shaped serial head to scan and record simultaneously across the width of the medium being recorded, and traveling methods that use a line head that arranges recording elements corresponding to the entire area of ​​one side of the medium being recorded.

[0169] In the traveling mode, by scanning the recording medium along a direction intersecting the arrangement direction of the recording elements, image recording can be performed on the entire surface of the recording medium. In the traveling mode, the transport system, such as a carriage that scans with short strip-shaped nozzles as in the reciprocating mode, is unnecessary. Furthermore, compared to the reciprocating mode, the traveling mode eliminates the need for complex scanning control between the carriage and the recording medium; only the recording medium moves. Therefore, the traveling mode enables higher speed image recording compared to the reciprocating mode.

[0170] The pretreatment solution is preferably applied using an inkjet head with a resolution of 300 dpi or higher (more preferably 600 dpi or higher, and even more preferably 800 dpi or higher). Here, dpi is an abbreviation for dots per inch, where 1 inch is 2.54 cm.

[0171] From the viewpoint of obtaining high-definition images, the amount of pretreatment liquid droplets ejected from the nozzle of the inkjet head is preferably 1 pL (picoliter) to 10 pL, more preferably 1.5 pL to 6 pL.

[0172] (Image recording process) In the image recording process, an inkjet recording method is used to apply ink to a non-permeable substrate that has been pretreated with a pretreatment solution to record an image. Details regarding the inkjet recording method are the same as those for the inkjet recording method in the pretreatment solution application method.

[0173] (Other processes) The image recording method of the present invention may include other steps besides the pretreatment liquid application step and the image recording step.

[0174] After the pretreatment liquid is applied, the pretreatment liquid applied to the non-permeable substrate can be heated and dried. Examples of mechanisms for heating and drying the pretreatment liquid include known heating mechanisms such as heaters, known air supply mechanisms such as dryers, and mechanisms combining these.

[0175] Examples of methods for heating and drying pretreatment liquids include heating the non-permeable substrate from the side opposite to the surface to which the pretreatment liquid was applied using a heater, blowing warm air or hot air onto the surface of the non-permeable substrate to which the pretreatment liquid was applied, heating the non-permeable substrate from the surface to which the pretreatment liquid was applied or from the side opposite to the surface to which the pretreatment liquid was applied using an infrared heater, and combining these methods.

[0176] The heating temperature for heating and drying the pretreatment liquid is preferably 35°C or higher, more preferably 40°C or higher. There is no particular upper limit to the heating temperature, but 100°C is preferred, 90°C is more preferred, and 70°C is even more preferred.

[0177] The heating and drying time is not particularly limited, but it is preferably 0.5 seconds to 60 seconds, more preferably 0.5 seconds to 20 seconds, and even more preferably 0.5 seconds to 10 seconds.

[0178] [Manufacturing method of laminate] The method for manufacturing a laminate of the present invention includes: a step of obtaining an image recording object having a non-permeable substrate and an image disposed on the non-permeable substrate by the image recording method of the present invention; and a step of laminating a laminating substrate onto the side of the image recording object on which the image is disposed to obtain a laminate.

[0179] According to the image recording method of the present invention, it is possible to manufacture an image recorder having an impermeable substrate and an image recorded on the impermeable substrate, and having excellent lamination strength when a laminating substrate is laminated onto the image.

[0180] Therefore, the image recording method of the present invention is preferably used in the manufacture of a laminate comprising the above-described image recording material and a laminating substrate laminated on the side of the image recording material on which the image is recorded.

[0181] According to the method for manufacturing a laminate of the present invention, it is possible to manufacture a laminate with excellent lamination strength between an image recorder and a substrate for lamination.

[0182] For the process of obtaining image recordings, please refer to the image recording method of the present invention described above.

[0183] The process of obtaining a laminate is to laminate a laminating substrate onto the image-containing side of an image recording medium. Lamination can be performed, for example, by attaching the laminating substrate to the image-containing side of the image recording medium via another layer (e.g., an adhesive layer), or by attaching the laminating substrate to the image-containing side of the image recording medium using a laminating machine. In the latter case, a commercially available laminating machine can be used.

[0184] The lamination temperature during lamination is not particularly limited. For example, when attaching image recording material and laminating substrate via other layers (e.g., adhesive layers), a temperature of 20°C or higher is acceptable. Furthermore, when using a laminator, the temperature of the lamination rollers can be set within the range of 20°C to 80°C. The pressing force of the lamination roller pair can be selected appropriately as needed.

[0185] The substrate for lamination is preferably a resin substrate. The resin substrate is not particularly limited; for example, a substrate made of thermoplastic resin can be cited.

[0186] Examples of resin substrates include those formed by molding thermoplastic resin into sheets. The resin substrate preferably comprises polypropylene, polyethylene terephthalate, nylon, polyethylene, or polyimide.

[0187] The shape of the resin substrate is not particularly limited, but a sheet-like resin substrate is preferred. The thickness of the resin substrate is preferably 10 μm to 200 μm, more preferably 10 μm to 100 μm.

[0188] In the process of obtaining the laminate, the laminating substrate can be directly laminated to the side of the image recorder where the image is located, or it can be laminated to the side of the image recorder where the image is located via other layers (e.g., adhesive layers).

[0189] Lamination, in which a laminating substrate is directly laminated onto the side of an image recorder containing an image, can be performed using known methods such as hot pressing or hot welding.

[0190] Furthermore, the lamination of the laminating substrate to the side of the image recorder where the image is disposed via an adhesive layer can be carried out, for example, by applying an adhesive to the side of the image recorder where the image is disposed, placing the laminating substrate, and then bonding the image recorder and the laminating substrate together.

[0191] Furthermore, lamination when the image is laminated onto the side of the image recorder containing the image via an adhesive layer can also be implemented by methods such as compression lamination (i.e., sandwich lamination).

[0192] The adhesive layer preferably contains an isocyanate compound. When the adhesive layer contains an isocyanate compound, the lamination strength can be further improved because the adhesion between the adhesive layer and the image is further enhanced.

[0193] [Image Records] The image recording of the present invention comprises a non-permeable substrate and an image disposed on the non-permeable substrate, the image including a pretreatment layer containing solid components of the pretreatment liquid and an ink layer disposed on the pretreatment layer and containing pigment.

[0194] The laminate obtained by laminating a laminating substrate onto the image recording material of the present invention has excellent lamination strength.

[0195] The preferred configurations of the components in the image recording are as described above.

[0196] [Laminate] The laminate of the present invention comprises the above-described image recording material and a laminating substrate for laminating the side of the image recording material having the above-described image.

[0197] The laminate of the present invention has excellent lamination strength.

[0198] In the laminate, the laminating substrate can be directly laminated to the side of the image recorder where the image is disposed, or it can be laminated to the side of the image recorder where the image is disposed via other layers (adhesive layers).

[0199] The laminate of the present invention is preferably manufactured by the manufacturing method of the laminate of the present invention.

[0200] The preferred methods for the substrate and adhesive layer used in lamination are the same as those described in the section on the method of manufacturing the laminate.

[0201] Example The present invention will be further described in detail below through embodiments, but the present invention is not limited to the following embodiments as long as it does not depart from its spirit.

[0202] In Examples 1-18, a pretreatment solution was prepared by mixing the resin particles, coagulant, and surfactant listed in Table 1 with an organic solvent, a defoamer, and water.

[0203] • Resin particles…content as recorded in Table 1 • Flocculant…contents listed in Table 1 Surfactants…contents listed in Table 1 • Organic solvent: 1,2-propanediol (manufactured by FUJIFILM Wako Pure Chemical Corporation) …1% by mass • Defoamer (product name "TSA-739", manufactured by Momentive Performance Materials Japan LLC.)... The solid component as a defoamer is 0.01% by mass. Water… makes the pretreatment solution a total of 100% by mass. In Examples 21-38, a pretreatment solution was prepared by mixing the following resin particles, the coagulant listed in Table 2, the surfactant and organic solvent, the defoamer and water.

[0204] • Resin particles (polyether urethane resin particles 2: product name "HYDRAN WLI-602", manufactured by DICCOporation)...10% by mass • Flocculant…contents listed in Table 2 Surfactants…contents listed in Table 2 • Organic solvents…contents listed in Table 2 • Defoamer (product name "TSA-739", manufactured by Momentive Performance Materials Japan LLC.)... The solid component as a defoamer is 0.01% by mass. Water… makes the pretreatment solution a total of 100% by mass. The detailed composition of the pretreatment solution is as follows.

[0205] (Resin particles) • Polyether-based urethane resin particles: Product name "HYDRAN WLI-630AR", manufactured by DIC CORPORATION • Acrylic resin particles: Product name "Sunacryl FB-810 ECO", manufactured by Muraya Chemical Laboratory Co., Ltd. • Polyester-based urethane resin particles: Product name "SUPERFLEX 500M", manufactured by DKS Co. Ltd. • Polycarbonate-based urethane resin particles: Product name "HYDRAN WLI-620AR", manufactured by DICCORPORATION • Particles of urethane resin A (urethane resin having structural units derived from polycyclic aliphatic diols): The following method was used to synthesize the urethane resin A (urethane resin having structural units derived from polycyclic aliphatic diols) according to Example 1 of Japanese Patent Application Publication No. 2022-146167.

[0206] • Polyether-based urethane resin particles 2: Product name "HYDRAN WLI-602", manufactured by DIC CORPORATION Preparation of an aqueous dispersion of urethane resin A- A simple pressurized reaction apparatus equipped with a stirrer and a heating device was loaded with 35.9 parts by mass of tricyclo[5.2.1.0(2,6)]decanediethanol as a polycyclic aliphatic diol, 4.5 parts by mass of 2,2-dimethylolpropionic acid as a polyol with carboxyl groups, 37.4 parts by mass of 4,4-diphenylmethane diisocyanate as an aromatic polyisocyanate, 22.1 parts by mass of isophorone diisocyanate as an aliphatic isocyanate, and 54 parts by mass of methyl ethyl ketone as an organic solvent for the reaction. The apparatus was stirred at 70°C for 12 hours to carry out a urethane esterification reaction, thereby producing a methyl ethyl ketone solution of urethane prepolymer (P1) with isocyanate groups.

[0207] Next, 2.9 parts by mass of triethylamine as a neutralizing agent were added to the methyl ethyl ketone solution of the obtained urethane prepolymer (P1) and homogenized. Then, 176 parts by mass of deionized water as an aqueous medium were added while stirring at 200 rpm to disperse the polyurethane prepolymer in water. The resulting dispersion was heated to 50°C and stirred for 4 hours to carry out a chain growth reaction based on the amino groups formed by the reaction of water with isocyanate groups. The methyl ethyl ketone was removed by distillation at 60°C under reduced pressure. Then, water was added to adjust the solids concentration to 30% by weight, thereby obtaining an aqueous dispersion of urethane resin A. Uramate resin A exists as resin particles in the aqueous dispersion.

[0208] (Flocculant) • Acetic acid (Ca) monohydrate: Calcium acetate monohydrate (manufactured by FUJIFILM Wako Pure Chemical Corporation) • Magnesium acetate tetrahydrate: Magnesium acetate tetrahydrate (manufactured by FUJIFILM Wako Pure Chemical Corporation) • Calcium lactate pentahydrate: Calcium lactate pentahydrate (manufactured by FUJIFILM Wako Pure Chemical Corporation) • Magnesium lactate trihydrate: Magnesium lactate trihydrate (manufactured by FUJIFILM Wako Pure Chemical Corporation) • Formic acid (Ca): Calcium formate (manufactured by FUJIFILM Wako Pure Chemical Corporation) • Magnesium formate dihydrate: Magnesium formate dihydrate (manufactured by Sigma-Aldrich Co. LLC.) • Malonic acid (manufactured by FUJIFILM Wako Pure Chemical Corporation) (surfactant) -Compound(1)- ·PE-62: Product name "NEWPOL PE-62", manufactured by Sanyo Chemical Industries, Ltd., [POE (10) POP (30)] ·PE-74: Product name "NEWPOL PE-74", manufactured by Sanyo Chemical Industries, Ltd., [POE (30) POP (35)] ·PE-75: Product name "NEWPOL PE-75", manufactured by Sanyo Chemical Industries, Ltd., [POE (48) POP (35)] ·PE-78: Product name "NEWPOL PE-78", manufactured by Sanyo Chemical Industries, Ltd., [POE (150) POP (35)] • L-31: Product name "Adeka Pluronic L-31", manufactured by ADEKA CORPORATION, [POE (3) POP (17)] • L-64: Product name "Adeka Pluronic L-64", manufactured by ADEKA CORPORATION, [POE (25) POP (30)] • L-44: Product name "Adeka Pluronic L-44", manufactured by ADEKA CORPORATION, [POE (20) POP (20)] The number in parentheses after POE refers to the sum of x+z in equation (1). Furthermore, the number in parentheses after POP refers to the value of y in equation (1).

[0209] -A surfactant that is not equivalent to compound (1)- • EMULGEN 103: Product name "EMULGEN 103", manufactured by Kao Corporation, polyoxyethylene lauryl ether • E1010: Product name "OLFINE E1010", manufactured by Nissin Chemical Industry Co., Ltd., is an ethylene oxide adduct of ethynylene glycol. ·25R-2: Product name "Adeka Pluronic 25R-2", manufactured by ADEKA CORPORATION, H (OCH(CH3)CH2) a (OCH2CH2) b (OCH(CH3)CH2) c -OH (Organic solvent) PD: 1,2-Propanediol (manufactured by FUJIFILM Wako Pure Chemical Corporation) 2P: 2-Propanol (manufactured by FUJIFILM Wako Pure Chemical Corporation) <Ink Preparation> In preparing the ink, the pigment dispersion is prepared first.

[0210] The following pigment dispersions were prepared as blue-green, magenta, yellow, and black pigment dispersions. These pigment dispersions are all dispersions of pigments of various colors dispersed by cross-linking polymers.

[0211] • Blue-green pigment dispersion…Product name “APD4000Cyan (pigment concentration 20.0% by mass)”, manufactured by FUJIFILMImaging Colorants, Inc. • Magenta Pigment Dispersion 1…Product name: “APD4000 Magenta (pigment concentration 18.5% by mass)”, manufactured by FUJIFILM Imaging Colorants, Inc. • Magenta Pigment Dispersion 2…Product name “APD1000RED (pigment concentration 14.3% by mass)”, manufactured by FUJIFILMImaging Colorants, Inc. • Yellow pigment dispersion…Product name “APD4000 Yellow (pigment concentration 19.9% ​​by mass)”, manufactured by FUJIFILMImaging Colorants, Inc. • Black pigment dispersion… (Product name “APD4000Black (pigment concentration 15.0% by mass)”, manufactured by FUJIFILMImaging Colorants, Inc.) (Preparation of blue-green ink 1) Blue-green ink 1 was prepared by mixing the following components.

[0212] • APD4000 Cyan Pigment Dispersion (CI Pigment Blue 15:3) … 3.0% by mass (as pigment solids content) • Propylene glycol (PG) (water-soluble organic solvent) …25% by mass • Propylene glycol monomethyl ether (PM) (water-soluble organic solvent) …1% by mass Neocryl A1091 (styrene-acrylic polymer resin particulate dispersion)...5.0% by mass as solids content. • OLFINE E1010 (acetylene glycol surfactant manufactured by Nissin Chemical Co., Ltd.) …0.5% by mass • Silicone-based surfactant (Byk3450) …0.5% by mass Colloidal silica (SNOWTEX XS manufactured by Nissan Chemical Corporation)...is present in a solid content of 0.05% by mass. Water... makes the total a surplus of 100% by mass. (Preparation of blue-green ink 2) The propylene glycol monomethyl ether contained in blue-green ink 1 was changed to diethylene glycol monobutyl ether, and the resin particles were changed to the following resin particles. Otherwise, blue-green ink 2 was prepared by the same method as blue-green ink 1.

[0213] ·EVAFANOL HA-55 (Polycarbonate-based urethane polymer resin particulate dispersion, manufactured by Nicca Chemical Co., Ltd.) (Preparation of blue-green ink 3) The content of OLFINE E1010 in blue-green ink 2 was changed to 2.0% by mass, and the resin particles were changed to the following resin particles. Otherwise, blue-green ink 3 was prepared by the same method as blue-green ink 1.

[0214] ·EVAFANOL HA-55 (polycarbonate-based urethane polymer resin particulate dispersion, manufactured by Nicca Chemical Co., Ltd.)...4.0% by weight as solids content Neocryl A1091 (styrene-acrylic polymer resin particulate dispersion)... is 1.0% by mass as a solid component. (Preparation of magenta ink 1) The blue-green pigment dispersion contained in blue-green ink 1 was changed to magenta pigment dispersion 1, propylene glycol monomethyl ether was changed to diethylene glycol monobutyl ether, and the resin particles were changed to the following resin particles. Otherwise, magenta ink 1 was prepared by the same method as blue-green ink 1.

[0215] ·EVAFANOL HA-55 (Polycarbonate-based urethane polymer resin particulate dispersion, manufactured by Nicca Chemical Co., Ltd.) (Preparation of magenta ink 2) The content of magenta pigment dispersion 1 in magenta ink 1 was changed from 3.0% by mass (as the amount of solid pigment component) to 4.0% by mass of magenta pigment dispersion 1 and 1.5% by mass of magenta pigment dispersion 2, and the content of OLFINEE1010 was changed to 2.0% by mass. Otherwise, magenta ink 2 was prepared by the same method as magenta ink 1.

[0216] (Preparation of magenta ink 3) Magenta ink 3 was prepared by changing the resin particles contained in magenta ink 2 to the following resin particles, except that magenta ink 3 was prepared by the same method as magenta ink 2.

[0217] • Styrene-acrylic polymer resin particulate dispersion (product name "Joncryl PDX-7615", manufactured by BASF) (Preparation of Yellow Ink 1) The blue-green pigment dispersion contained in blue-green ink 1 was changed to a yellow pigment dispersion, the propylene glycol monomethyl ether was changed to diethylene glycol monobutyl ether, and the resin particles were changed to the following resin particles. Except for these, yellow ink 1 was prepared by the same method as blue-green ink 1.

[0218] ·EVAFANOL HA-55 (Polycarbonate-based urethane polymer resin particulate dispersion, manufactured by Nicca Chemical Co., Ltd.) (Preparation of Yellow Ink 2) Yellow ink 2 was prepared by changing the content of OLFINE E1010 in yellow ink 1 to 2.0% by mass, except that yellow ink 2 was prepared by the same method as yellow ink 1.

[0219] (Preparation of black ink 1) The blue-green pigment dispersion contained in blue-green ink 1 was changed to a black pigment dispersion, the propylene glycol monomethyl ether was changed to diethylene glycol monobutyl ether, and the resin particles were changed to the following resin particles. Except for these, black ink 1 was prepared by the same method as blue-green ink 1.

[0220] ·EVAFANOL HA-55 (Polycarbonate-based urethane polymer resin particulate dispersion, manufactured by Nicca Chemical Co., Ltd.) (Preparation of Black Ink 2) The black pigment dispersion contained in black ink 1 was changed to 4.0% by mass of black pigment dispersion, 1.0% by mass of blue-green pigment dispersion, and 1.0% by mass of magenta pigment dispersion 1, and the content of OLFINE E1010 was changed to 2.0% by mass. Otherwise, black ink 2 was prepared by the same method as black ink 1.

[0221] <Preparation of White Ink 1> In preparing white ink, a white pigment dispersion was prepared in advance.

[0222] (Preparation of block polymers) 266 parts by mass of diethylene glycol dimethyl ether, 6.2 parts by mass of 2-iodo-2-cyanopropane, 120 parts by mass of methyl methacrylate (MMA), 28.8 parts by mass of acrylic acid (AA), 67.2 parts by mass of cyclohexyl methacrylate (CHMA), 7.9 parts by mass of azodimethylisovalerate, and 0.7 parts by mass of 2-tert-butyl-4,6-dimethylphenol were added to a reaction apparatus equipped with a stirrer, countercurrent condenser, thermometer, and nitrogen inlet tube. Nitrogen gas was introduced while stirring was performed.

[0223] Next, the temperature of the mixture in the reaction apparatus was raised to 70°C and allowed to polymerize for 3 hours to obtain a polymerization solution A containing the MMA / AA / CHMA copolymer.

[0224] Three hours later, a portion of the above-mentioned polymerization solution A was sampled, and the result of solid composition determination was 42.0% by mass, confirming that most of the monomers had polymerized.

[0225] Furthermore, the weight-average molecular weight (Mw) of the MMA / AA / CHMA copolymer was determined using GPC to be 7,500.

[0226] The acid value of the MMA / AA / CHMA copolymer is 101.0 mg KOH / g.

[0227] Next, a mixture of 35.2 parts by mass of benzyl methacrylate (BzMA) and 0.3 parts by mass of 2,2'-azobis(2,4-dimethylpentanonitrile) (product name "V-65", manufactured by FUJIFILM Wako Pure Chemical Corporation) was added to the above polymerization solution A, and polymerized at 70°C for 3 hours to obtain polymerization solution B containing block polymer 1.

[0228] Block polymer 1 is a block polymer comprising an A block as an MMA / AA / CHMA copolymer and a B block as a BzMA homopolymer.

[0229] The solid content of the obtained polymerization solution B was determined to be 43.2% by mass, confirming that most of the monomers had polymerized.

[0230] Furthermore, block polymer 1 has a Mw of 8,500 and an acid value of 89.3 mg KOH / g. Block polymer 1 was used as a pigment dispersant.

[0231] (Preparation of white pigment dispersion) A polymerization solution B containing block polymer 1 (136.4 parts by mass), butyl carbitol (163.6 parts by mass), and CI pigment white 6 (trade name "JR-405", titanium dioxide particles, manufactured by TAYCA CORPORATION) as a white pigment (450 parts by mass) were mixed and stirred using a disperser. Then, the white pigment was thoroughly dispersed using a horizontal media disperser to obtain an oily pigment dispersion. The average particle size of the white pigment dispersed in the oily pigment dispersion was 290 nm. The viscosity of the oily pigment dispersion (25°C) was 86.3 mPa·s.

[0232] Next, while stirring 700 parts by weight of the above-mentioned oily pigment dispersion using a disperser, a mixture consisting of 4.0 parts by weight of potassium hydroxide and 341 parts by weight of water was slowly added to neutralize it. Then, the white pigment was fully dispersed using a horizontal media disperser to obtain a pigment dispersion.

[0233] Next, the obtained pigment dispersion was subjected to ultrafiltration using a cross-flow ultrafiltration (UF) device (manufactured by Sartorius) with 600 mL of deionized water per minute. The liquid temperature was maintained at 25°C, and each ultrafiltration cycle was performed 10 times, with each cycle consisting of one times the volume of the liquid. After adding deionized water, a white pigment dispersion with a pigment concentration of 45% by mass and a pigment dispersant concentration of 3.7% by mass was obtained.

[0234] A white ink 1 with a pigment concentration of 14% by mass was prepared by mixing the components shown below.

[0235] • Aqueous white pigment dispersion… to achieve a pigment concentration of 14% by mass. Propylene glycol…25% by mass ·Propylene glycol monomethyl ether…1% by mass ·Propylene glycol monopropyl ether…1% by mass Neocryl A1091…3% mass • OLFINE E1010…0.5% of mass Byk3450…0.5% of mass Colloidal silica...is present in a solid component amount of 0.05% by mass. Water…makes the total amount of white ink 100% by mass. (Preparation of white ink 2) White ink 2 was prepared by changing the propylene glycol monomethyl ether contained in white ink 1 to diethylene glycol monobutyl ether and changing the resin particles to the following resin particles. Otherwise, white ink 2 was prepared by the same method as white ink 1.

[0236] ·EVAFANOL HA-55 (Polycarbonate-based urethane polymer resin particulate dispersion, manufactured by Nicca Chemical Co., Ltd.) (Preparation of white ink 3) White ink 3 was prepared by changing the propylene glycol monomethyl ether contained in white ink 1 to diethylene glycol monobutyl ether and changing the resin particles to the following resin particles. Otherwise, white ink 3 was prepared by the same method as white ink 1.

[0237] • Styrene-acrylic polymer resin particulate dispersion (product name "Joncryl PDX-7615", manufactured by BASF) [Image Recording] As a non-permeable substrate (hereinafter also referred to as "substrate"), a biaxially stretched polypropylene film (OPP) (product name "FOR", manufactured by FUTAMURA CHEMICAL CO.,LTD., thickness 20μm, width 100mm, length 240mm) was prepared.

[0238] An image recording device is prepared, which has a conveying mechanism for conveying a substrate, and is provided in sequence upstream of the substrate conveying direction as a wire rod coating machine for applying pretreatment liquid, a first inkjet head for applying blue-green ink, and a second inkjet head for applying white ink.

[0239] Both the first and second inkjet heads are piezoelectric full-line printheads with a width of 1200 dpi / 20 inch. Here, dpi is an abbreviation for dots per inch.

[0240] Both the first and second inkjet heads are configured as linear printheads, with the printheads arranged in a direction orthogonal to the transport direction of the substrate (i.e., the width direction of the substrate).

[0241] The inkjet heads mentioned above were Samba (registered trademark) G3L (manufactured by FUJIFILM Dimatix, Inc.).

[0242] The aforementioned image recording device includes a substrate, a pretreatment liquid, blue-green ink, and white ink.

[0243] An image recorder was obtained by sequentially applying a pretreatment solution, blue-green ink 1, and white ink 1 to a substrate. The specific method is as follows.

[0244] While the substrate is moved at a constant speed of 50 mm / s, a pretreatment solution is applied to the substrate using a wire-wound bar coater. The application mass of the pretreatment solution is set to 2.0 g / m³. 2 .

[0245] One second after the application of the pretreatment liquid ends, the pretreatment liquid is dried by blowing warm air at 60°C at a wind speed of 22 m / s for 3 seconds using a dryer, thereby forming a pretreatment liquid layer on the substrate.

[0246] While the substrate with the pretreatment liquid layer is moved at a constant speed of 50 m / min, blue-green ink is applied in a solid image pattern to the surface of the pretreatment liquid layer, thus forming a blue-green ink layer. White ink is then applied in a solid image pattern to the surface of the blue-green ink layer to form a white ink layer. The ejection conditions for both the blue-green and white inks are set to a resolution of 1200 dpi × 1200 dpi and an ejection frequency of 39.37 kHz.

[0247] The obtained image recordings were used to create laminates, and the lamination strength was evaluated. Furthermore, the dot diameter of the blue-green ink was evaluated. Additionally, the storage stability of the pretreatment solution was evaluated. The evaluation methods are as follows.

[0248] [evaluate] <Lamination strength> A region with a length of 200 mm and a width of 100 mm, in which a solid image is set on the entire surface (hereinafter also referred to as the lamination strength evaluation region) is cut out from the above image record and used as the lamination strength evaluation sample.

[0249] On the solid image of the lamination strength evaluation sample, a dry lamination adhesive (main agent TM-320 (isocyanate compound) / curing agent CAT-13B (alcohol compound), manufactured by Toyo-Morton, Ltd.) was applied using a rod coater and dried at 70°C for 10 seconds. Furthermore, an unstretched polypropylene film (CPP) (trade name: PYLEN P1128, manufactured by TOYOBO CO.,LTD., 25 μm thick) was stacked as the lamination substrate. In this state, the lamination substrate and the lamination strength evaluation sample were bonded together to obtain a laminate. The obtained laminate was then aged at 40°C for 48 hours.

[0250] Sample pieces measuring 100 mm in length and 15 mm in width were cut from the cured laminate.

[0251] Next, the laminating substrate and the lamination strength evaluation sample were peeled off from one end of the sample sheet along its length up to 30 mm. The remaining 70 mm length was left in place with the laminating substrate and the lamination strength evaluation sample bonded together.

[0252] Next, a tensile test was performed on the laminate substrate and the laminate strength evaluation sample of the peeled portion in opposite directions. The tensile direction was set perpendicular to the remaining 70mm length region (the region in which the laminate substrate and the laminate strength evaluation sample are bonded together).

[0253] The tensile test is used to determine the peel strength of the substrate and the laminate strength evaluation sample used to peel the remaining 70mm length of the above-mentioned area. The obtained peel strength is taken as the laminate strength.

[0254] In addition, the above tensile tests were conducted at 25°C using a tensile testing machine (product name "TENSILON RTM-25", manufactured by ORIENTECCO.,LTD.).

[0255] The evaluation criteria are as follows.

[0256] AA: Lamination strength is 2.0N / 15mm or higher.

[0257] A: The lamination strength is above 1.5N / 15mm and less than 2.0N / 15mm.

[0258] B: The lamination strength is above 1.0N / 15mm and less than 1.5N / 15mm.

[0259] C: The lamination strength is ≥0.5N / 15mm and <1.0N / 15mm.

[0260] D: Lamination strength is less than 0.5 N / 15 mm.

[0261] <Diameter of Point> Using the method described in the image recording section above, a 2cm square image of the Duty 10% was recorded, allowing for confirmation of the point shape. The Duty 10% image portion was then magnified for observation. The point diameters of the obtained images from 30 points were measured, and the average value was calculated. This average value was used as the point diameter. The point diameter was measured using a point analyzer DA-6000 manufactured by Oji Scientific Instruments Co., Ltd.

[0262] The evaluation criteria are as follows.

[0263] A: The point diameter is 35μm or more.

[0264] B: The point diameter is greater than 33μm and less than 35μm.

[0265] C: The point diameter is greater than 30μm and less than 33μm.

[0266] D: The point diameter is less than 30μm.

[0267] <Preservation Stability> The pretreatment solution was placed in a 9 mL vial (trade name: LABORANSCREW TUBE, manufactured by AS ONE Corporation) and sealed. The vial was stored in a constant temperature bath at 60°C for one week. The viscosity before and after storage was measured. The viscosity before storage was denoted as A, and the viscosity after storage was denoted as B. The viscosity change rate was calculated according to the following formula.

[0268] Viscosities were measured at 25°C using a TV-22 viscometer manufactured by Toki Sangyo Co., Ltd.

[0269] Viscosity change rate (%) = [(BA) / A] × 100 The evaluation criteria are as follows.

[0270] A: The viscosity change rate is within ±5%.

[0271] B: Viscosity change rate greater than ±5% and within ±10% C: Viscosity change rate greater than ±10%. Alternatively, the pretreatment solution has gelled and cannot be evaluated.

[0272] The evaluation results are shown in Table 1.

[0273] In Table 1, the values ​​recorded in the coagulant column refer to the content of each coagulant.

[0274] In the “Compound (1)” column, if the surfactant is equivalent to compound (1), it is recorded as “Y”, and if it is not equivalent to compound (1), it is recorded as “N”.

[0275] "EO chain ratio" refers to the proportion of the total molecular weight of ethylene oxide chains in the total molecular weight of the surfactant.

[0276] "Compound (1) / Resin Particles" refers to the mass ratio of the content of compound (1) to the content of resin particles.

[0277] As shown in Table 1, in Examples 1 to 18, it can be seen that the pretreatment liquid contains resin particles, surfactant, coagulant and water. The surfactant contains compound (1), and the coagulant contains at least one selected from the group consisting of polyvalent metal compounds and organic acids. Therefore, the ink imparted has a large dot diameter and excellent lamination strength when the laminate is manufactured.

[0278] On the other hand, in Comparative Example 1, it is known that no surfactant is contained, so the expansion of the dots is insufficient.

[0279] In Comparative Examples 2 to 4, it can be seen that the compound (1) is not contained and a surfactant that is not equivalent to the compound (1) is contained, so the expansion of the point and the lamination strength cannot be taken into account.

[0280] In Example 5, it was found that the HLB value of compound (1) was below 15.0, and therefore the point spread and lamination strength were excellent compared with Example 3.

[0281] In Example 1, it is known that the cloud point of compound (1) is above 50°C, and therefore, compared with Example 13, the cloud point expansion and lamination strength are excellent.

[0282] In Example 1, it is known that the resin particles are particles containing urethane resin, and therefore the lamination strength is excellent compared to Example 14.

[0283] In Examples 1 and 16, it is known that the resin particles are particles comprising at least one selected from the group consisting of polyether-based urethane resins and polycarbonate-based urethane resins, and therefore the lamination strength is superior compared to Example 15.

[0284] In Example 17, it is known that the resin particles contain structural units derived from polycyclic aliphatic diols, and therefore exhibit superior lamination strength compared to Example 15.

[0285] In Example 12, it is known that the total molecular weight of the ethylene oxide chain accounts for more than 15% of the molecular weight of compound (1), and therefore the dot diameter is larger than that in Example 13.

[0286] In Example 2, it is known that the total molecular weight of the ethylene oxide chain accounts for less than 50% of the molecular weight of compound (1). Therefore, compared with Example 3, the point spreadability and lamination strength are excellent.

[0287] In Example 6, it is known that the content of compound (1) is 0.5% by mass or more, and therefore the point spread and lamination strength are excellent compared with Example 9.

[0288] In Example 7, it is known that the content of compound (1) is less than 3% by mass, and therefore the point spread and lamination strength are excellent compared with Example 8.

[0289] In Example 6, it is known that the mass ratio of the content of compound (1) to the content of resin particles is 0.05 or more, and therefore the point spread and lamination strength are excellent compared with Example 9.

[0290] In Example 8, it was found that the mass ratio of the content of compound (1) to the content of resin particles was less than 0.50, and therefore the lamination strength was excellent compared with Example 11.

[0291] Next, a pretreatment liquid, blue-green ink 2, and white ink 1 were sequentially applied to a substrate to obtain an image recorder. The image recording method was the same as in Example 1, etc. The obtained image recorder was evaluated using the same method as in Example 1, etc.

[0292] The evaluation results are shown in Table 2.

[0293] As shown in Table 2, in Examples 21 to 38, it can be seen that the ink applied has a large dot diameter and excellent lamination strength when the laminate is manufactured.

[0294] Next, image recordings were obtained using ink sets 1 to 3.

[0295] In ink group 1, blue-green ink 2, magenta ink 1, yellow ink 1 and black ink 1 are used to sequentially apply pretreatment liquid, blue-green ink 2, magenta ink 1, yellow ink 1, black ink 1 and white ink 2 to the substrate.

[0296] In ink group 2, blue-green ink 3, magenta ink 2, yellow ink 2 and black ink 2 are used to sequentially apply pretreatment liquid, blue-green ink 3, magenta ink 2, yellow ink 2, black ink 2 and white ink 3 to the substrate.

[0297] In ink group 3, blue-green ink 2, magenta ink 2, yellow ink 2 and black ink 2 are used to sequentially apply pretreatment liquid, blue-green ink 2, magenta ink 2, yellow ink 2, black ink 2 and white ink 2 to the substrate.

[0298] In addition, in ink groups 1 to 3, pretreatment solutions of 21 to 38 were used as pretreatment solutions respectively.

[0299] Except for the following changes, the obtained image recordings were evaluated using the same method as in Example 1.

[0300] In the evaluation of lamination strength, when only cyan ink was used, it was applied with a duty of 100% and in a solid image, as described above. In contrast, when using a combination of inks, cyan ink, magenta ink, yellow ink, and black ink were applied with a duty of 25% and in a solid image, respectively.

[0301] In evaluating dot diameter, using only cyan ink, as described above, an image with a duty of 10% was recorded. In contrast, when using a combination of inks, images with cyan, magenta, yellow, and black inks were superimposed and recorded with a duty of 2.5%.

[0302] In any of the ink groups 1 to 3, the evaluation result for lamination strength is AA, and the evaluation result for dot diameter is A.

[0303] Furthermore, the entire disclosure of Japanese Patent Application No. 2023-166468, filed on September 27, 2023, is incorporated herein by reference. Moreover, all documents, patent applications, and technical standards described in this specification are incorporated herein by reference to the same extent as those specifically described and incorporated herein by reference.

Claims

1. A pretreatment solution for inkjet ink, comprising resin particles, surfactant, flocculant, and water. The surfactant comprises a compound represented by the following formula (1), The coagulant comprises at least one selected from the group consisting of polyvalent metal compounds and organic acids. H(OCH2CH2) x (OCH(CH3)CH2) y (OCH2CH2) z -OH…(1) In equation (1), x and z are independent integers greater than or equal to 1, y is an integer from 1 to 500, and x+z is an integer from 2 to 1000.

2. The pretreatment solution for inkjet ink according to claim 1, wherein, The HLB value of the compound represented by the formula (1) is less than 15.

0.

3. The pretreatment solution for inkjet ink according to claim 1, wherein, The cloud point of the compound represented by the formula (1) is above 50°C.

4. The pretreatment solution for inkjet ink according to claim 1, wherein, The resin particles are particles containing urethane resin.

5. The pretreatment solution for inkjet ink according to claim 4, wherein, The particles containing urethane resin are particles comprising at least one selected from the group consisting of polyether-based urethane resins and polycarbonate-based urethane resins.

6. The pretreatment solution for inkjet ink according to claim 4, wherein, The urethane resin contained in the resin particles comprises structural units derived from polycyclic aliphatic diols.

7. The pretreatment solution for inkjet ink according to claim 1, wherein, (OCH2CH2) x and (OCH2CH2) z The total amount of the compound represented by formula (1) accounts for 15% to 50% of the molecular weight of the compound.

8. The pretreatment solution for inkjet ink according to claim 1, wherein, The content of the compound represented by the formula (1) is 0.5% to 3% by mass relative to the total amount of the pretreatment solution for inkjet ink.

9. The pretreatment solution for inkjet ink according to claim 1, wherein, The mass ratio of the content of the compound represented by the formula (1) to the content of the resin particles is 0.05 to 0.

50.

10. The pretreatment solution for inkjet ink according to claim 1, wherein, The inkjet ink pretreatment solution is used for image recording on a non-permeable substrate.

11. An ink assembly comprising: Pretreatment solution for inkjet inks according to any one of claims 1 to 10; and Inkjet inks that contain water and pigments.

12. A surface-treated substrate, comprising: Non-permeable substrate; and A pretreatment layer disposed on the non-permeable substrate and comprising the solid components of the inkjet ink pretreatment liquid according to any one of claims 1 to 10.

13. An image recording method, comprising: A process of applying the pretreatment solution for inkjet ink as described in any one of claims 1 to 10 to a non-permeable substrate; and The process of recording an image by applying inkjet ink containing water and pigment to a non-permeable substrate that has been treated with an inkjet ink pretreatment solution.

14. A method for manufacturing a laminate, comprising: The process of obtaining an image record having the non-permeable substrate and an image disposed on the non-permeable substrate by the image recording method of claim 13; and The process of laminating a laminating substrate onto the side of the image recorder where the image is disposed to obtain a laminate.

15. An image recording medium comprising: Non-permeable substrates; and An image positioned on the non-permeable substrate. The image includes: A pretreatment layer comprising the solid components of the pretreatment liquid for inkjet ink as described in any one of claims 1 to 10; and An ink layer, disposed on the pretreatment layer, contains pigment.

16. A laminate comprising: The image recording object of claim 15; and A laminating substrate for laminating the side of the image recorder having the image.

Images