Active energy ray-curable inkjet ink, image recording method and method for producing laminate body

Abstract

To provide an active energy ray-curable inkjet ink and the like capable of recording an image having excellent adhesiveness with a base material containing a polymer containing vinyl chloride as a constitutional unit.SOLUTION: There are provided: an active energy ray-curable inkjet ink which contains an acrylic resin containing a constitutional unit A derived from a polymerizable compound A containing at least one selected from the group consisting of a fluorinated hydrocarbon group, a polysiloxane group and a hydrocarbon group having 12 or more carbon atoms and a constitutional unit B derived from a polymerizable compound B having a polarity term of the HSP value of 4.8 MPa1 / 2 or more, wherein the content of constitutional unit A is 40 mass% or less based on the total amount of the acrylic resin and the content of the constitutional unit B is 15 mass% or more based on the total amount of the acrylic resin; and an application thereof.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present disclosure relates to an actinic radiation-curable inkjet ink, an image recording method, and a method for producing a laminate. [Background technology]

[0002] Conventionally, various studies have been made on image recording using ink.

[0003] For example, Patent Document 1 describes a photocurable ink composition that contains a resin including an amine structure having an α-hydrogen atom, at least one selected from the group consisting of an alkylthio group, an alkylenethioalkylene group, and a mercapto group, and at least one selected from the group consisting of a fluorohydrocarbon group, a polysiloxane group, and a hydrocarbon group having 12 or more carbon atoms, at least one of a monofunctional radically polymerizable monomer and a bifunctional radically polymerizable monomer, and a photopolymerization initiator, the resin including a structural unit (1) including an amine structure having an α-hydrogen atom, a structural unit (2) including at least one selected from the group consisting of an alkylthio group, an alkylenethioalkylene group, and a mercapto group, and a structural unit (3) including at least one selected from the group consisting of a fluorohydrocarbon group, a polysiloxane group, and a hydrocarbon group having 12 or more carbon atoms, and the weight average molecular weight of the resin is 5,000 to 30,000.

[0004] Patent Document 2 describes an ink composition that contains a polymer that contains a urethane bond or urea bond in its main chain structure and has a polymerizable group on its side chain, a polymerizable compound other than the above polymer, and a polymerization initiator, and the above polymer has one of a fluorine-substituted hydrocarbon group, a group containing a siloxane structure, and a long-chain alkyl group at at least one end of the main chain structure.

[0005] Patent Document 3 describes an actinic radiation-curable ink composition comprising a monofunctional radically polymerizable monomer, a polyfunctional oligomer having a glass transition temperature of 20°C or lower and an acrylate value of 300 g / value or higher, and a bifunctional radically polymerizable monomer having a viscosity at 25°C of 15 mPa·s or lower, wherein the monofunctional radically polymerizable monomer comprises an N-vinyl compound and a compound represented by formula (I), the content of the N-vinyl compound relative to the total amount of the ink composition is 10 to 50 mass%, and the content of the monofunctional radically polymerizable monomer relative to the total amount of the ink composition is 70 mass% or more.

[0006] Patent Document 4 describes an ink composition containing a polymer having a siloxane structure and a polymerizable group in the side chain, a polymerizable compound, and a photoinitiator. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Patent No. 6861811 [Patent Document 2] JP 2012-092330 A [Patent Document 3] JP 2013-237834 A [Patent Document 4] JP 2009-209353 A Summary of the Invention [Problem to be solved by the invention]

[0008] After an image is recorded on an image recording substrate containing a polymer (e.g., polyvinyl chloride) containing vinyl chloride as a structural unit to obtain an image recorded product, a laminate substrate containing a polymer containing vinyl chloride as a structural unit is laminated on the image in the image recorded product to produce a laminated product. In this case, it is required to improve the adhesion between the image recording substrate and the image, and between the image and the laminate substrate.

[0009] The present disclosure has been made in consideration of the above circumstances, and an object of one embodiment of the present disclosure is to provide an actinic ray-curable inkjet ink capable of recording an image having excellent adhesion to a substrate that contains a polymer including vinyl chloride as a structural unit. Another problem to be solved by another embodiment of the present disclosure is to provide an image recording method capable of recording an image having excellent adhesion to a substrate containing a polymer including vinyl chloride as a structural unit. Another problem to be solved by another embodiment of the present disclosure is to provide a method for producing a laminate having excellent adhesion between an image and a substrate that contains a polymer containing vinyl chloride as a structural unit. [Means for solving the problem]

[0010] The present disclosure includes the following aspects. <1> A structural unit A derived from a polymerizable compound A containing at least one selected from the group consisting of a fluorohydrocarbon group, a polysiloxane group, and a hydrocarbon group having 12 or more carbon atoms, and a polar term of the HSP value of 4.8 MPa 1 / 2 The present invention includes an acrylic resin including a structural unit B derived from the above polymerizable compound B, and a polymerizable monomer, The content of the structural unit A is 40% by mass or less based on the total amount of the acrylic resin, An active energy ray-curable inkjet ink, wherein the content of the structural unit B is 15 mass % or more based on the total amount of the acrylic resin. <2> The glass transition temperature of acrylic resin is below 150℃. <1> 13. The actinic ray-curable ink-jet ink according to claim 12. <3> The polymerizable compound A is a polymerizable compound containing at least one selected from the group consisting of a fluorohydrocarbon group and a polysiloxane group. <1> or <2> 13. The actinic ray-curable ink-jet ink according to claim 12. <4> The number average molecular weight of the polymerizable compound A is 5000 or less. <1> ~ <3> 10. The actinic ray-curable ink-jet ink according to claim 9, <5> The mass ratio of the structural unit A to the structural unit B is 0.01 to 0.65. <1> ~ <4> 10. The actinic ray-curable ink-jet ink according to claim 9, <6> Polymerizable compound B has a hydrogen bond term of HSP value of 11.0 MPa. 1 / 2 Below is the <1> ~ <5> 10. The actinic ray-curable ink-jet ink according to claim 9, <7> Polymerizable compound B has a hydrogen bond term of HSP value of 11.0 MPa. 1 / 2 Polymerizable compound B1 having a hydrogen bond term of HSP value of 11.0 MPa or less 1 / 2 and a polymerizable compound B2 having a molecular weight of more than <1> ~ <6> 10. The actinic ray-curable ink-jet ink according to claim 9, <8> a mass ratio of the content of the polymerizable compound B1 to the content of the polymerizable compound B2 is 1 to 20; <7> 13. The actinic ray-curable ink-jet ink according to claim 12. <9> The structural unit B is at least one structural unit selected from the group consisting of the following formulas (1) to (5): <1> ~ <8> 10. The actinic ray-curable ink-jet ink according to claim 9,

[0011] [ka]

[0012] In formula (1), R 11 represents a hydrogen atom or a hydrocarbon group, R 12 and R 13 R each independently represents a hydrocarbon group which may contain an oxygen atom or a hydrogen atom. 12 and R 13 may be bonded to each other to form a ring. In formula (2), R 21represents a hydrogen atom or a hydrocarbon group, R 22 and R 23 R each independently represents a hydrocarbon group which may contain an oxygen atom or a hydrogen atom. 22 and R 23 may be bonded to each other to form a ring. In formula (3), R 31 represents a hydrogen atom or a hydrocarbon group, L 11 represents a single bond or a divalent linking group, R 32 represents a hydrocarbon group containing at least one selected from the group consisting of -O-, -S-, -C(=O)-, -NH-, and -N<. In formula (4), R 41 represents a hydrogen atom or a hydrocarbon group, R 42 and R 43 R each independently represents a hydrogen atom, a cyano group, a hydrocarbon group having a carbonyl group, a phosphate ester group, or a heterocyclic group. 42 and R 43 may be bonded to each other to form a ring. In formula (5), R 51 represents a hydrogen atom or a hydrocarbon group. <10> The polymerizable monomer has a (meth)acryloyl group and a solubility parameter of 16.5 MPa. 1 / 2 ~21.3MPa 1 / 2 The polymerizable monomer C is <1> ~ <9> 10. The actinic ray-curable ink-jet ink according to claim 9, <11> The polymerizable monomer C has a molecular weight of 215 or less. <10> 13. The actinic ray-curable ink-jet ink according to claim 12. <12> The polymerizable monomers include N-vinyl compounds. <1> ~ <11> 10. The actinic ray-curable ink-jet ink according to claim 9, <13> The weighted average value of the glass transition temperature when all the polymerizable monomers contained in the active energy ray-curable inkjet ink are homopolymers is 0°C to 100°C. <1> ~ <12> 10. The actinic ray-curable ink-jet ink according to claim 9, <14> On an image recording substrate containing a polymer containing vinyl chloride as a structural unit, <1> ~ <13> 13. An image recording method comprising the step of applying the active energy ray-curable inkjet ink according to any one of claims 1 to 12 by an inkjet recording method to record an image. <15> On an image recording substrate containing a polymer containing vinyl chloride as a structural unit, <1> ~ <14> 1. A method for producing a laminate, comprising: a step of applying the active energy ray-curable inkjet ink according to any one of the above items by an inkjet recording method to record an image; and a step of placing a lamination substrate containing a polymer containing vinyl chloride as a constituent unit on the image, and laminating the image. Effect of the Invention

[0013] According to one embodiment of the present disclosure, there is provided an actinic ray-curable inkjet ink capable of recording an image having excellent adhesion to a substrate that contains a polymer including vinyl chloride as a structural unit. According to another embodiment of the present disclosure, there is provided an image recording method capable of recording an image having excellent adhesion to a substrate containing a polymer including vinyl chloride as a structural unit. According to another embodiment of the present disclosure, there is provided a method for producing a laminate having excellent adhesion between an image and a substrate containing a polymer including vinyl chloride as a structural unit. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] The active energy ray-curable inkjet ink, the image recording method, and the method for producing a laminate according to the present disclosure will be described in detail below.

[0015] In this specification, a numerical range indicated using "to" means a range that includes the numerical values ​​before and after "to" as the minimum and maximum values, respectively. In the numerical ranges described in this specification, the upper or lower limit value described in a certain numerical range may be replaced with the upper or lower limit value of another numerical range described in a certain numerical range. In addition, in the numerical ranges described in this specification, the upper or lower limit value described in a certain numerical range may be replaced with a value shown in the examples.

[0016] In this specification, the amount of each component in a composition means the total amount of the multiple substances present in the composition when multiple substances corresponding to each component are present in the composition, unless otherwise specified. As used herein, a combination of two or more preferred embodiments is a more preferred embodiment. In this specification, the term "process" includes not only an independent process but also a process that cannot be clearly distinguished from other processes, as long as the intended purpose of the process is achieved.

[0017] In this specification, the term "image" generally refers to a film formed by applying ink, and the term "image recording" refers to the formation of an image (that is, a film). Additionally, the concept of "image" in this specification also includes a solid image.

[0018] In this specification, the term "(meth)acrylate" is a concept that encompasses both acrylate and methacrylate, and the term "(meth)acrylic" is a concept that encompasses both acrylic and methacrylic.

[0019] The actinic ray-curable inkjet ink (hereinafter, simply referred to as "ink") of the present disclosure comprises a structural unit A derived from a polymerizable compound A containing at least one selected from the group consisting of a fluorohydrocarbon group, a polysiloxane group, and a hydrocarbon group having 12 or more carbon atoms, and a fluorine-containing polymerizable compound A having a polarity term of the HSP value of 4.8 MPa. 1 / 2The composition comprises an acrylic resin containing a structural unit B derived from a polymerizable compound B as described above, and a polymerizable monomer, wherein the content of the structural unit A is 40 mass% or less based on the total amount of the acrylic resin, and the content of the structural unit B is 15 mass% or more based on the total amount of the acrylic resin.

[0020] The ink of the present disclosure can record images that have excellent adhesion to a substrate that contains a polymer that includes vinyl chloride as a structural unit.

[0021] The reason why the above effect is achieved is presumed to be as follows.

[0022] The ink of the present disclosure is applied to a substrate containing a polymer containing vinyl chloride as a structural unit, and then an active energy ray is irradiated to obtain an image recording material in which an ink film is formed as an image on the substrate. When the ink film is formed, the colorant (e.g., pigment) that may be contained in the ink tends to be unevenly distributed on the surface of the ink film. The present inventors have found that when a substrate for lamination containing a polymer containing vinyl chloride as a structural unit is further laminated on the ink film, the colorant unevenly distributed on the surface of the ink film tends to inhibit the adhesion between the ink film and the substrate for lamination. In contrast, the ink of the present disclosure contains an acrylic resin that includes a structural unit A and a structural unit B, the content of the structural unit A being 40% by mass or less relative to the total amount of the acrylic resin, and the content of the structural unit B being 15% by mass or more relative to the total amount of the acrylic resin. The structural unit A is a structural unit derived from a polymerizable compound A that includes at least one selected from the group consisting of a fluorohydrocarbon group, a polysiloxane group, and a hydrocarbon group having 12 or more carbon atoms. When the structural unit A is included, the acrylic resin is likely to be unevenly distributed at the gas-liquid interface of the ink. As a result, when the ink is cured to form an ink film, the acrylic resin can be present on the surface of the ink film rather than the colorant, and the adhesion between the ink film (i.e., the image) and the lamination substrate can be improved.

[0023] Since the structural unit A does not have a very high affinity with polymers that contain vinyl chloride as a structural unit, the content of the structural unit A is set to 40 mass % or less. Vinyl chloride has a large polarity term in the HSP value. Therefore, the polarity term of the HSP value for acrylic resin is 4.8 MPa. 1 / 2 When the structural unit B derived from the polymerizable compound B described above is contained in an amount of 15% by mass or more, the adhesion between the image and the substrate for lamination is improved.

[0024] In other words, structural unit A allows the acrylic resin to be unevenly distributed on the surface of the ink film, and structural unit B, which has a high affinity with the polymer containing vinyl chloride as a structural unit, improves adhesion between the image and the substrate for lamination.

[0025] Patent Documents 1 to 4 do not disclose an ink containing an acrylic resin in which the content of structural unit A is 40% by mass or less and the content of structural unit B is 15% by mass or more.

[0026] Hereinafter, each component contained in the ink according to an embodiment of the present disclosure will be described.

[0027] [Active energy beam curable inkjet ink] The ink according to an embodiment of the present disclosure is an active energy ray-curable inkjet ink. That is, the ink according to an embodiment of the present disclosure is cured by irradiation with active energy rays. Examples of active energy rays include gamma rays, beta rays, electron beams, ultraviolet rays, and visible light rays. Of these, the active energy rays are preferably ultraviolet rays. The ink according to an embodiment of the present disclosure is preferably an ultraviolet ray-curable inkjet ink.

[0028] <Acrylic resin> The inks of the present disclosure include at least one acrylic resin. In the present disclosure, acrylic resin refers to a resin containing structural units derived from a compound having a (meth)acryloyl group (for example, a (meth)acrylic acid ester).

[0029] The acrylic resin is a polymerizable compound A having a polarity term of HSP value of 4.8 MPa, and a structural unit A derived from the polymerizable compound A containing at least one selected from the group consisting of a fluorohydrocarbon group, a polysiloxane group, and a hydrocarbon group having 12 or more carbon atoms. 1 / 2 and a structural unit B derived from the polymerizable compound B described above.

[0030] (Structural unit A) The acrylic resin contains a structural unit A derived from a polymerizable compound A containing at least one selected from the group consisting of a fluorohydrocarbon group, a polysiloxane group, and a hydrocarbon group having 12 or more carbon atoms. The structural unit A contained in the acrylic resin may be of only one type, or of two or more types.

[0031] The content of the structural unit A is 40 mass % or less based on the total amount of the acrylic resin. Since the acrylic resin contains the structural unit A, the content of the structural unit A exceeds 0 mass % with respect to the total amount of the acrylic resin.

[0032] Since fluorohydrocarbon groups, polysiloxane groups, and hydrocarbon groups having 12 or more carbon atoms have low cohesive energy, acrylic resins containing these groups tend to be unevenly distributed at the gas-liquid interface of the ink. As a result, when the ink is cured to form an ink film, the acrylic resin can be present on the surface of the ink film rather than on the colorant (e.g., pigment) that may be contained in the ink, and the adhesion between the ink film (i.e., the image) and the lamination substrate can be improved.

[0033] From the viewpoint of distributing the acrylic resin unevenly on the surface of the ink film and improving blocking resistance, the content of structural unit A is preferably 1% by mass or more, more preferably 3% by mass or more, and preferably 5% by mass or more. On the other hand, from the viewpoint of increasing the affinity with the laminate substrate and improving the blocking resistance, the content of structural unit A is preferably 37% by mass or less, more preferably 32% by mass or less, and even more preferably 25% by mass or less.

[0034] A fluorohydrocarbon group means a hydrocarbon group substituted with at least one fluorine atom. Examples of the fluorinated hydrocarbon group include a fluorinated alkyl group, a fluorinated alkenyl group, and a fluorinated aryl group. As the fluorinated hydrocarbon group, a fluorinated alkyl group is preferred, and a perfluoroalkyl group is particularly preferred. The number of fluorine atoms in the fluorohydrocarbon group is preferably 6 or more, and more preferably 8 or more. The upper limit of the number of fluorines in the fluorohydrocarbon group is not particularly limited, but an upper limit of 40, for example, is given. The number of carbon atoms in the fluorohydrocarbon group is preferably 3 or more, and more preferably 4 or more. The upper limit of the number of carbon atoms in the fluorohydrocarbon group is not particularly limited, but an example of the upper limit is 20.

[0035] Examples of the hydrocarbon group having 12 or more carbon atoms include an alkyl group, an alkenyl group, an aryl group, an alkylaryl group, an aralkyl group, etc. As the hydrocarbon group having 12 or more carbon atoms, an alkyl group is particularly preferable. The number of carbon atoms in the hydrocarbon group having 12 or more carbon atoms is preferably 14 or more, and more preferably 16 or more. There is no particular upper limit to the number of carbon atoms in a hydrocarbon group having 12 or more carbon atoms, but the upper limit is, for example, 30.

[0036] A polysiloxane group means a divalent group containing repeating Si-O bonds. It is more preferable that the structural unit A contains a monovalent group containing a polysiloxane group. An example of the monovalent group containing a polysiloxane group is the following group (P).

[0037] [ka]

[0038] In the group (P), R P1 and R P2each independently represents a hydrocarbon group having 1 to 6 carbon atoms or the following group (Z), R P3 ~R P5 each independently represents a hydrocarbon group having 1 to 6 carbon atoms, x represents an integer of 1 to 100, and * represents a bonding position. If x is an integer equal to or greater than 2, there are multiple R P1 may be the same or different, and there may be multiple R P2 may be the same or different. In the group (P), the number of Si—O bonds (ie, siloxane bonds) is 2 or more.

[0039] [ka]

[0040] In group (Z), R Z1 ~R Z5 each independently represents a hydrocarbon group having 1 to 6 carbon atoms, z represents an integer of 0 to 100, and * represents a bonding position. When z is an integer of 2 or more, there are multiple R Z1 may be the same or different, and there may be multiple R Z2 may be the same or different.

[0041] As x in the group (P), an integer of 1 to 50 is preferable, an integer of 1 to 20 is more preferable, and an integer of 1 to 10 is particularly preferable. In the group (P), R P1 ~R P5 The hydrocarbon groups having 1 to 6 carbon atoms in each of the above are each independently preferably a methyl group, an ethyl group, an n-butyl group, or a phenyl group, more preferably a methyl group, an n-butyl group, or a phenyl group, and particularly preferably a methyl group or an n-butyl group.

[0042] As z in the group (Z), an integer of 0 to 50 is preferable, an integer of 0 to 20 is more preferable, and an integer of 0 to 10 is particularly preferable. In group (Z), R Z1 ~R Z5The hydrocarbon groups having 1 to 6 carbon atoms in each of the above are each independently preferably a methyl group, an ethyl group or a phenyl group, more preferably a methyl group or a phenyl group, and particularly preferably a methyl group.

[0043] Examples of the structural unit A include structural units derived from vinyl monomers (for example, (meth)acrylic acid esters, (meth)acrylamides, etc.).

[0044] As the structural unit A, a structural unit derived from a (meth)acrylic acid ester is preferable, and a structural unit represented by the following formula (A1) is more preferable. [ka]

[0045] In the structural unit (A1), R 61 represents a hydrogen atom or a methyl group, L 2 represents a single bond or a linking group; X 11 represents a fluorohydrocarbon group, a monovalent group including a polysiloxane group, or a hydrocarbon group having 12 or more carbon atoms.

[0046] X 11 In the above, preferred embodiments of the fluorohydrocarbon group, the monovalent group containing a polysiloxane group, and the hydrocarbon group having 12 or more carbon atoms are as described above.

[0047] R 61 represents a hydrogen atom or a methyl group, and a methyl group is preferable.

[0048] L 2 The linking group represented by the following formula is preferably a divalent hydrocarbon group having 1 to 11 carbon atoms (more preferably 2 to 11 carbon atoms, and even more preferably 2 to 8 carbon atoms). The divalent hydrocarbon group may have a substituent such as a hydroxy group or an alkoxy group. Examples of the divalent hydrocarbon group include an alkylene group, an alkenylene group, an arylene group, an alkylenearylene group, an alkylenearylenealkylene group, an alkylenecarbonyloxyalkylene group, and an arylenecarbonyloxyalkylene group. As the divalent hydrocarbon group, an alkylene group having 1 to 11 carbon atoms (more preferably 1 to 6 carbon atoms) is particularly preferred.

[0049] Specific examples of the constitutional unit represented by formula (A1) are as follows.

[0050] [ka]

[0051] [ka]

[0052] [ka]

[0053] The structural unit A is a structural unit derived from a polymerizable compound A, and can be introduced into the acrylic resin by using the polymerizable compound A as a raw material.

[0054] The polymerizable compound A may be a commercially available product. Examples of commercially available products include X-22-174ASX, X-22-174BX, KF-2012, X-22-2426, and X-22-2404 (manufactured by Shin-Etsu Chemical Co., Ltd.); FM00711, FM-0721, FM-0725, and TM-0701T (manufactured by JNC Corporation); Viscoat 3F and Viscoat 13F (manufactured by Osaka Organic Chemical Industry Co., Ltd.).

[0055] In particular, from the viewpoint of further improving the adhesion to the substrate for lamination, the polymerizable compound A is preferably a polymerizable compound containing at least one selected from the group consisting of a fluorohydrocarbon group and a polysiloxane group.

[0056] When the number average molecular weight (Mn) of the polymerizable compound A is large, the effect of distributing the acrylic resin unevenly on the surface is enhanced, and the peelability is also improved. From the viewpoint of further improving the adhesion to the lamination substrate, the number average molecular weight of the polymerizable compound A is preferably 5000 or less, and more preferably 3000 or less. On the other hand, from the viewpoint of blocking resistance, the number average molecular weight of the polymerizable compound A is preferably 400 or more, and more preferably 700 or more.

[0057] In the present disclosure, the number average molecular weight is measured using a gel permeation chromatograph (GPC). For example, HLC-8220GPC (manufactured by Tosoh Corporation) is used as the GPC, three TSKgel Super Multipore HZ-H (manufactured by Tosoh Corporation, 4.6 mm ID x 15 cm) are used as the columns, and THF (tetrahydrofuran) is used as the eluent. The conditions are a sample concentration of 0.45 mass%, a flow rate of 0.35 ml / min, a sample injection amount of 10 μl, a measurement temperature of 40° C., and detection is performed using a differential refractive index (RI) detector. The calibration curve is prepared using eight samples of "TSK Standard Polystyrene" manufactured by Tosoh Corporation under the product names "F-40", "F-20", "F-4", "F-1", "A-5000", "A-2500", "A-1000", and "n-propylbenzene" as standard samples.

[0058] When the molecular weight of the polymerizable compound A is 1000 or less, the molecular weight is calculated from the type and number of atoms constituting the polymerizable compound A.

[0059] (Structural unit B) The polarity term of the HSP value of acrylic resin is 4.8MPa. 1 / 2 The acrylic resin contains a structural unit B derived from the above polymerizable compound B. The structural unit B contained in the acrylic resin may be of only one type, or may be of two or more types.

[0060] The content of the structural unit B is 15 mass % or more based on the total amount of the acrylic resin. Since the acrylic resin contains the structural unit A in addition to the structural unit B, the content of the structural unit B is less than 100 mass % based on the total amount of the acrylic resin.

[0061] Since vinyl chloride has a large polarity term in the HSP value, the polarity term in the HSP value for acrylic resin is 4.8 MPa. 1 / 2 When the structural unit B derived from the polymerizable compound B described above is contained in an amount of 15% by mass or more, the adhesion between the image and the substrate for lamination is improved. From the above viewpoints, the content of the structural unit B is preferably 25% by mass or more, more preferably 40% by mass or more, even more preferably 55% by mass or more, and particularly preferably 70% by mass or more.

[0062] The SP value (Hildebrand solubility parameter: δ) is a physical property defined as the square root of the cohesive energy density, and is a numerical value that indicates the solubility behavior of a substance. The HSP value (Hansen solubility parameter) is a parameter that takes into account the polarity of a substance by dividing the SP value into three components: the dispersion term (δD), the polarity term (δP), and the hydrogen bond term (δH). δ 2 = δD 2 +δP 2 +δH 2 It is expressed as:

[0063] In this disclosure, the dispersion term, polarity term, and hydrogen bond term of the HSP value are calculated using the Hansen Solubility Parameter software (product name "HSPiP 5 th The molecular weight is calculated based on the structure of the compound using the "Radiation Molecular Weights" ("Radiation Molecular Weights"), which is a numerical calculation method for determining the molecular weight of a compound.

[0064] In order to enhance the affinity with the substrate for lamination and to further improve the adhesion with the substrate for lamination, the polarity term of the HSP value of the polymerizable compound B is 5.0 MPa. 1 / 2 It is preferable that the pressure is 5.3MPa or more. 1 / 2 More preferably, it is 5.6 MPa or more. 1 / 2 More preferably, it is equal to or greater than this.

[0065] The upper limit of the polarity term of the HSP value is not particularly limited, but is, for example, 21.5 MPa. 1 / 2 It is.

[0066] In order to enhance the affinity with the substrate for lamination and to further improve the adhesion with the substrate for lamination, the hydrogen bond term of the HSP value of the polymerizable compound B is set to 11.0 MPa. 1 / 2 It is preferable that the temperature is 10.0 MPa or less. 1 / 2 More preferably, it is 8.6 MPa or less. 1 / 2 More preferably, it is 8.0 MPa or less. 1 / 2 It is particularly preferable that the value is 7.5 MPa or less. 1 / 2 Most preferably, it is:

[0067] The lower limit of the hydrogen bond term of the HSP value is not particularly limited, but is, for example, 3.0 MPa. 1 / 2 It is.

[0068] As described above, the acrylic resin may contain two or more types of structural unit B. When the acrylic resin contains two or more types of structural unit B, the acrylic resin is synthesized using two or more types of polymerizable compounds. When there are two or more polymerizable compounds, it is preferred that at least one polymerizable compound B among the two or more polymerizable compounds satisfies the preferred ranges of the polarity term and hydrogen bond term of the HSP value described above. Specifically, "in polymerizable compound B, the hydrogen bond term of the HSP value is 11.0 MPa 1 / 2 The term "is equal to or less than 11.0 MPa" means that the hydrogen bond term of the HSP value of at least one polymerizable compound B among two or more polymerizable compounds is 11.0 MPa 1 / 2 This means that:

[0069] From the viewpoint of further improving blocking resistance, it is preferable that the structural unit B contained in the acrylic resin contains two or more types. Specifically, the polymerizable compound B has a hydrogen bond term of HSP value of 11.0 MPa. 1 / 2 Polymerizable compound B1 having a hydrogen bond term of HSP value of 11.0 MPa or less 1 / 2and a polymerizable compound B2 which is greater than When the acrylic resin contains a structural unit B1 derived from a polymerizable compound B1 and a structural unit B2 derived from a polymerizable compound B2, the long-term blocking resistance is improved while maintaining adhesion to the laminate substrate.

[0070] From the viewpoint of further improving adhesion to the laminate substrate and blocking resistance, the mass ratio of the content of the polymerizable compound B1 to the content of the polymerizable compound B2 is preferably 1 to 20, and more preferably 2 to 17.

[0071] The structural unit B is preferably at least one type of structural unit selected from the group consisting of the following formulas (1) to (5).

[0072] [ka]

[0073] In formula (1), R 11 represents a hydrogen atom or a hydrocarbon group, R 12 and R 13 R each independently represents a hydrocarbon group which may contain an oxygen atom or a hydrogen atom. 12 and R 13 may be bonded to each other to form a ring. In formula (2), R 21 represents a hydrogen atom or a hydrocarbon group, R 22 and R 23 R each independently represents a hydrocarbon group which may contain an oxygen atom or a hydrogen atom. 22 and R 23 may be bonded to each other to form a ring. In formula (3), R 31 represents a hydrogen atom or a hydrocarbon group, L 11 represents a single bond or a divalent linking group, R 32 represents a hydrocarbon group containing at least one selected from the group consisting of -O-, -S-, -C(=O)-, -NH-, and -N<. In formula (4), R41 represents a hydrogen atom or a hydrocarbon group, R 42 and R 43 R each independently represents a hydrogen atom, a cyano group, a hydrocarbon group having a carbonyl group, a phosphate ester group, or a heterocyclic group. 42 and R 43 may be bonded to each other to form a ring. In formula (5), R 51 represents a hydrogen atom or a hydrocarbon group.

[0074] -Formula (1)- In formula (1), R 11 is preferably a hydrogen atom or a methyl group. In formula (1), R 12 and R 13 The hydrocarbon group represented by the formula (I) may be a linear hydrocarbon group, a branched hydrocarbon group, or a cyclic hydrocarbon group, but is preferably a linear hydrocarbon group.

[0075] R 12 and R 13 The hydrocarbon group represented by the formula (I) may be a saturated hydrocarbon group or an unsaturated hydrocarbon group, but is preferably a saturated hydrocarbon group. That is, R 12 and R 13 The hydrocarbon group represented by the formula (I) is more preferably a linear alkyl group.

[0076] R 12 and R 13 The hydrocarbon group represented by the following formula preferably has 1 to 10 carbon atoms.

[0077] Examples of hydrocarbon groups which may contain an oxygen atom include an -O-monovalent hydrocarbon group, a -divalent hydrocarbon group -OH, a -divalent hydrocarbon group -O-monovalent hydrocarbon group, and a -divalent hydrocarbon group -C=(O)O-monovalent hydrocarbon group.

[0078] R 12 and R 13from the viewpoints of reducing the hydrogen bonding property of the acrylic resin, increasing the affinity with the polymer containing vinyl chloride as a structural unit, and reducing the viscosity of the ink, it is preferable that each of them independently be a hydrocarbon group that may contain an oxygen atom.

[0079] Also, R 12 and R 13 R are preferably bonded to each other to form a ring. 12 and R 13 The ring formed by bonding together is preferably a 5- to 8-membered ring.

[0080] Examples of the constitutional unit represented by formula (1) include the following constitutional units.

[0081] [ka]

[0082] -Formula (2)- In formula (2), R 21 is preferably a hydrogen atom or a methyl group. In formula (2), R 22 and R 23 The hydrocarbon group represented by the formula (I) may be a linear hydrocarbon group, a branched hydrocarbon group, or a cyclic hydrocarbon group, but is preferably a linear hydrocarbon group.

[0083] R 22 and R 23 The hydrocarbon group represented by the formula (I) may be a saturated hydrocarbon group or an unsaturated hydrocarbon group, but is preferably a saturated hydrocarbon group. That is, R 22 and R 23 The hydrocarbon group represented by the formula (I) is more preferably a linear alkyl group.

[0084] R 22 and R 23 The hydrocarbon group represented by the following formula (1) preferably has 1 to 10 carbon atoms, and more preferably has 2 to 8 carbon atoms.

[0085] Examples of hydrocarbon groups which may contain an oxygen atom include the -divalent hydrocarbon group -OH, the -divalent hydrocarbon group -O-monovalent hydrocarbon group, the -divalent hydrocarbon group -C=(O)-monovalent hydrocarbon group, and the -divalent hydrocarbon group -C=(O)O-monovalent hydrocarbon group.

[0086] In formula (2), R 22 and R 23 from the viewpoints of reducing the hydrogen bonding property of the acrylic resin, increasing the affinity with the polymer containing vinyl chloride as a structural unit, and reducing the viscosity of the ink, it is preferable that each of them independently be a hydrocarbon group that may contain an oxygen atom.

[0087] Also, R 22 and R 23 R are preferably bonded to each other to form a ring. 22 and R 23 The ring formed by bonding together is preferably a 5- to 8-membered ring.

[0088] Examples of the constitutional unit represented by formula (2) include the following constitutional units.

[0089] [ka]

[0090] -Formula (3)- In formula (3), R 31 is preferably a hydrogen atom or a methyl group. In formula (3), L 11 The divalent linking group represented by the formula (L13) is preferably an alkylene group having 1 to 3 carbon atoms or a group represented by any one of the following formulas (L11) to (L14), more preferably an alkylene group having 1 to 3 carbon atoms or a group represented by any one of the following formulas (L11) to (13), and even more preferably an alkylene group having 1 to 3 carbon atoms or a group represented by the following formula (L11).

[0091] [ka]

[0092] In formula (L11), L represents an alkylene group having 1 to 3 carbon atoms, n represents an integer of 1 to 4, *1 represents the bonding position to the oxygen atom, *2 represents R 32 represents the bonding position with In formula (L12), L represents an alkylene group having 1 to 3 carbon atoms, *1 represents the bonding position with the oxygen atom, *2 represents R 32 represents the bonding position with In formula (L13), L 1 and L 2 each independently represents an alkylene group having 1 to 3 carbon atoms, *1 represents the bonding position with an oxygen atom, *2 represents R 32 represents the bonding position with In formula (L14), *1 represents the bonding position with the oxygen atom, and *2 represents R 32 represents the bonding position with

[0093] In formula (L11), n ​​is preferably an integer of 1 to 3, more preferably 1 or 2, and particularly preferably 1.

[0094] In formula (3), R 32 The hydrocarbon group represented by the formula (I) may be a linear hydrocarbon group, a branched hydrocarbon group, or a cyclic hydrocarbon group, but is preferably a hydrocarbon group containing a ring structure.

[0095] R 32 The hydrocarbon group represented by the formula (I) may be a saturated hydrocarbon group or an unsaturated hydrocarbon group, but is preferably a saturated hydrocarbon group.

[0096] R 32 The hydrocarbon group represented by the following formula (1) preferably has 3 to 20 carbon atoms, more preferably 3 to 15 carbon atoms, further preferably 3 to 12 carbon atoms, and particularly preferably 3 to 10 carbon atoms.

[0097] In a hydrocarbon group containing at least one selected from the group consisting of -O-, -S-, -C(=O)-, -NH-, and -N<, examples of a combination of two or more of -O-, -S-, -C(=O)-, -NH-, and -N< include -C(=O)O-, -OC(=O)O-, -C(=O)-NH-, and a pyrrolidone ring.

[0098] R 32 is preferably a hydrocarbon group containing -C(=O)-NH-, a hydrocarbon group containing -C(=O)O-, a hydrocarbon group containing -OCO-, or a hydrocarbon group containing a hydroxyl group.

[0099] Examples of the constitutional unit represented by formula (3) include the following constitutional units.

[0100] [ka]

[0101] -Formula (4)- In formula (4), R 41 is preferably a hydrogen atom or a methyl group. In formula (4), R 42 and R 43 The monovalent heterocyclic group represented by the following formula (I) refers to a group in which one hydrogen atom has been removed from a heterocyclic compound. The heterocycle in the monovalent heterocyclic group is preferably a 5- or 6-membered ring. The heterocycle may form a condensed ring with an aliphatic ring, an aromatic ring, or another heterocycle.

[0102] Examples of the heteroatom in the hetero ring include a N atom, an O atom, and a S atom, with a N atom being preferred.

[0103] Examples of the heterocycle include a pyridine ring, a piperidine ring, a furan ring, a furfuran ring, a thiophene ring, a pyrrole ring, a quinoline ring, a morpholine ring, an indole ring, an imidazole ring, a pyrazole ring, a carbazole ring, a phenothiazine ring, a phenoxazine ring, an indoline ring, a pyrrolidone ring, a thiazole ring, a pyrazine ring, a thiadiazine ring, a benzoquinoline ring, and a thiadiazole ring.

[0104] In formula (4), R 42 and R 43 From the viewpoint of increasing the affinity with the polymer containing vinyl chloride as a structural unit, it is preferable that each of them independently be a cyano group or a monovalent heterocyclic group.

[0105] Examples of the constitutional unit represented by formula (4) include the following constitutional units.

[0106] [ka]

[0107] -Formula (5)- In formula (5), R 51 The hydrocarbon group represented by the formula (I) may be a straight-chain hydrocarbon group, a branched-chain hydrocarbon group, or a cyclic hydrocarbon group.

[0108] R 51 The hydrocarbon group represented by the formula (I) may be a saturated hydrocarbon group or an unsaturated hydrocarbon group, but is preferably a saturated hydrocarbon group.

[0109] R 51 The hydrocarbon group represented by the following formula preferably has 1 to 10 carbon atoms.

[0110] Examples of the constitutional unit represented by formula (5) include the following constitutional units.

[0111] [ka]

[0112] The structural unit B is a structural unit derived from a polymerizable compound B, and can be introduced into the acrylic resin by using the polymerizable compound B as a raw material.

[0113] The polar term (δP) and hydrogen bond term (δH) of the HSP value for each polymerizable compound are shown below. The unit is MPa. 1 / 2 It is. The polymerizable compound shown in Table 1 has a polarity term of HSP value of 4.8 MPa. 1 / 2 and does not fall under polymerizable compound B. The polymerizable compounds shown in Tables 2 to 6 have a polarity term of HSP value of 4.8 MPa. 1 / 2 This is a polymerizable compound having the above structure, and corresponds to polymerizable compound B. In the case of a polymerizable compound derived from a structural unit represented by any one of the above formulae (1) to (5), the corresponding formula is described.

[0114] [Table 1]

[0115] [Table 2]

[0116] [Table 3]

[0117] [Table 4]

[0118] [Table 5]

[0119] [Table 6]

[0120] The acrylic resin preferably contains two or more types of the structural unit B. When the acrylic resin contains two or more types of structural units B, it is preferable that the structural unit B contains a structural unit represented by formula (1) and a structural unit represented by formula (2), or a structural unit represented by formula (1) and a structural unit represented by formula (3).

[0121] From the viewpoint of unevenly distributing the acrylic resin on the surface of the ink film and improving blocking resistance, the mass ratio of structural unit A to structural unit B is preferably 0.01 or more, more preferably 0.03 or more, and even more preferably 0.05 or more. From the viewpoint of increasing the affinity with the laminate substrate and improving the blocking resistance, the mass ratio of structural unit A to structural unit B is preferably 0.65 or less, more preferably 0.55 or less, even more preferably 0.45 or less, and particularly preferably 0.35 or less. From the above viewpoints, the mass ratio of the structural unit A to the structural unit B is preferably from 0.01 to 0.65, more preferably from 0.03 to 0.55, even more preferably from 0.05 to 0.45, and particularly preferably from 0.05 to 0.35.

[0122] The acrylic resin may contain other structural units in addition to the structural unit A and the structural unit B.

[0123] From the viewpoint of improving adhesion to the laminate substrate, the total content of the structural unit A and the structural unit B is preferably 30% by mass or more, more preferably 45% by mass or more, and even more preferably 60% by mass or more, based on the total amount of the acrylic resin. The total content of the structural unit A and the structural unit B may be 100% by mass. That is, the acrylic resin may be composed of only the structural unit A and the structural unit B.

[0124] When the acrylic resin contains other structural units, the other structural units are not particularly limited, and examples thereof include structural units derived from monofunctional polymerizable monomers described below.

[0125] (Physical Properties) The glass transition temperature of the acrylic resin is preferably 150° C. or lower, more preferably 130° C. or lower, and even more preferably 100° C. or lower. There are no particular limitations on the lower limit of the glass transition temperature, but from the viewpoint of blocking resistance, it is preferably −20° C.

[0126] In the present disclosure, the glass transition temperature is measured using a differential scanning calorimeter, for example, a product named "DSC-60" manufactured by Shimadzu Corporation.

[0127] When the glass transition temperature of the acrylic resin is 150° C. or lower, the mobility of the acrylic resin is improved when the laminate substrate is thermocompression bonded to the image, and the adhesion to the laminate substrate is improved.

[0128] The solubility parameter (SP value) of acrylic resin is 7.5MPa. 1 / 2 ~14.0MPa 1 / 2 Preferably, the pressure is 8.5 MPa. 1 / 2 ~13.0MPa 1 / 2 More preferably, it is 9.5 MPa. 1 / 2 ~12.0MPa 1 / 2 It is even more preferable that:

[0129] In this disclosure, the SP value means the Hansen solubility parameter.

[0130] The SP value of an acrylic resin is calculated as follows. Completely dissolve 100 mg of a sample in 2 mL of THF, and add deionized water or n-hexane dropwise to the solution. The SP value of the sample is calculated from the volume fraction at which the solution becomes cloudy using the following formula. SP value of THF = δ T Water SP value = δ W SP value of n-hexane = δ H Volume fraction (water): deionized water / (deionized water + THF) = V W Volume fraction (hexane): Hexane / (Hexane+THF)=V H SP value of deionized water / THF mixed solution = δ WT = δ T ×(1-V W )+δ W ×V W SP value of n-hexane / THF mixed solution = δ HT = δT × (1-V H )+δ H ×V H SP value of sample = δ P =(δ WT ×(V W ) 0.5 +δ HT ×(VH) 0.5 ) / ((VW) 0.5 +(VH) 0.5 )

[0131] When the SP value of the acrylic resin is within the above range, the adhesion to the laminate substrate is improved.

[0132] From the viewpoint of improving adhesion to the substrate for lamination, the weight average molecular weight of the acrylic resin is preferably at least 1000, more preferably at least 3000, and even more preferably at least 5000. On the other hand, from the viewpoint of the ejection property and storage stability of the ink, the weight average molecular weight of the acrylic resin is preferably at most 80000, more preferably at most 60000, and even more preferably at most 40000.

[0133] In the present disclosure, the weight average molecular weight is measured by a method similar to the method for measuring the number average molecular weight described above.

[0134] From the viewpoint of improving adhesion to the lamination substrate, the content of the acrylic resin is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and even more preferably 0.5% by mass or more, based on the total amount of the ink, while from the viewpoint of the ejection property and storage stability of the ink, the content of the acrylic resin is preferably 10% by mass or less, more preferably 8% by mass or less, and even more preferably 6% by mass or less, based on the total amount of the ink.

[0135] <Polymerizable monomer> The inks of the present disclosure include at least one polymerizable monomer. In this disclosure, "monomer" refers to a compound having a molecular weight of 1000 or less. In the present disclosure, the polymerizable monomer refers to a monomer having at least one polymerizable group in one molecule. The polymerizable group may be a cationic polymerizable group or a radical polymerizable group, and from the viewpoint of curability, it is preferable that the radical polymerizable group is a radical polymerizable group. In addition, from the viewpoint of curability, it is preferable that the radical polymerizable group is an ethylenically unsaturated group.

[0136] The polymerizable monomer may be a monofunctional polymerizable monomer having one polymerizable group, or a polyfunctional polymerizable monomer having two or more polymerizable groups.

[0137] -Monofunctional polymerizable monomer- The monofunctional polymerizable monomer is not particularly limited as long as it is a monomer having one polymerizable group. From the viewpoint of curability, the monofunctional polymerizable monomer is preferably a monofunctional radical polymerizable monomer, and more preferably a monofunctional ethylenically unsaturated monomer.

[0138] Examples of the monofunctional ethylenically unsaturated monomer include monofunctional (meth)acrylates, monofunctional (meth)acrylamides, monofunctional aromatic vinyl compounds, monofunctional vinyl ethers, and monofunctional N-vinyl compounds.

[0139] Examples of monofunctional (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, tert-octyl (meth)acrylate, isoamyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, and cyclohexyl (meth)acrylate. acrylate, 4-n-butylcyclohexyl (meth)acrylate, 4-tert-butylcyclohexyl (meth)acrylate, bornyl (meth)acrylate, isobornyl (meth)acrylate, 2-ethylhexyl diglycol (meth)acrylate, butoxyethyl (meth)acrylate, 2-chloroethyl (meth)acrylate, 4-bromobutyl (meth)acrylate, cyanoethyl (meth)acrylate, benzyl (meth)acrylate, butoxymethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, 2-(2-methoxy (2-ethoxy)ethyl (meth)acrylate, 2-(2-butoxyethoxy)ethyl (meth)acrylate, 2,2,2-tetrafluoroethyl (meth)acrylate, 1H,1H,2H,2H-perfluorodecyl (meth)acrylate, 4-butylphenyl (meth)acrylate, phenyl (meth)acrylate, 2,4,5-tetramethylphenyl (meth)acrylate, 4-chlorophenyl (meth)acrylate, 2-phenoxymethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, glycidyl (meth)acrylate , glycidyloxybutyl (meth)acrylate, glycidyloxyethyl (meth)acrylate, glycidyloxypropyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, cyclic trimethylolpropane formal (meth)acrylate,Phenyl glycidyl ether (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, diethylaminopropyl (meth)acrylate, trimethoxysilylpropyl (meth)acrylate, trimethylsilylpropyl (meth)acrylate, polyethylene oxide monomethyl ether (meth)acrylate, polyethylene oxide (meth)acrylate, polyethylene oxide monoalkyl ether (meth)acrylate, dipropylene glycol (meth)acrylate, polypropylene oxide monoalkyl ether (meth)acrylate, 2-methacryloyloxyethyl succinate, 2-methacryloyloxyhexahydrophthalic acid, 2-methacryloyloxyethyl-2-hydroxypropyl phthalate, ethoxydiethylene glycol (meth)acrylate, butoxydi Ethylene glycol (meth)acrylate, trifluoroethyl (meth)acrylate, perfluorooctylethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, ethylene oxide (EO) modified phenol (meth)acrylate, EO modified cresol (meth)acrylate, EO modified nonylphenol (meth)acrylate, propylene oxide (PO) modified nonylphenol (meth)acrylate, EO modified 2-ethylhexyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentanyl (meth)acrylate, (3-ethyl-3-oxetanylmethyl) (meth)acrylate, phenoxyethylene glycol (meth)acrylate, 2-carboxyethyl (meth)acrylate and 2-(meth)acryloyloxyethyl succinate.

[0140] Examples of monofunctional (meth)acrylamides include (meth)acrylamide, N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide, N-propyl(meth)acrylamide, Nn-butyl(meth)acrylamide, Nt-butyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N-methylol(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, and (meth)acryloylmorpholine.

[0141] Examples of monofunctional aromatic vinyl compounds include styrene, dimethylstyrene, trimethylstyrene, isopropylstyrene, chloromethylstyrene, methoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, vinyl benzoic acid methyl ester, 3-methylstyrene, 4-methylstyrene, 3-ethylstyrene, 4-ethylstyrene, 3-propylstyrene, 4-propylstyrene, 3-butylstyrene, 4-butylstyrene, 3-hexylstyrene, 4-hexylstyrene, 3-octylstyrene, 4-octylstyrene, 3-(2-ethylhexyl)styrene, 4-(2-ethylhexyl)styrene, allylstyrene, isopropenylstyrene, butenylstyrene, octenylstyrene, 4-t-butoxycarbonylstyrene, and 4-t-butoxystyrene.

[0142] Examples of monofunctional vinyl ethers include methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, n-butyl vinyl ether, t-butyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl ether, lauryl vinyl ether, cyclohexyl vinyl ether, cyclohexylmethyl vinyl ether, 4-methylcyclohexylmethyl vinyl ether, benzyl vinyl ether, dicyclopentenyl vinyl ether, 2-dicyclopentenoxyethyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, butoxyethyl vinyl ether, methoxyethoxyethyl vinyl ether, ethoxyethoxyethyl vinyl ether, methoxypolyethylene glycol vinyl ether, tetrahydrofurfuryl vinyl ether, 2-hydroxyethyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxymethylcyclohexylmethyl vinyl ether, diethylene glycol monovinyl ether, polyethylene glycol vinyl ether, chloroethyl vinyl ether, chlorobutyl vinyl ether, chloroethoxyethyl vinyl ether, phenylethyl vinyl ether, and phenoxypolyethylene glycol vinyl ether.

[0143] Examples of monofunctional N-vinyl compounds include N-vinyl-ε-caprolactam and N-vinylpyrrolidone.

[0144] -Polyfunctional polymerizable monomer- The polyfunctional polymerizable monomer is not particularly limited as long as it is a compound having two or more polymerizable groups. From the viewpoint of curability, the polyfunctional polymerizable compound is preferably a polyfunctional radical polymerizable monomer, and more preferably a polyfunctional ethylenically unsaturated monomer.

[0145] Examples of polyfunctional ethylenically unsaturated monomers include polyfunctional (meth)acrylates and polyfunctional vinyl ethers.

[0146] Examples of polyfunctional (meth)acrylates include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, and tetraethylene glycol di(meth). ) acrylate, neopentyl glycol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, hexanediol di(meth)acrylate, heptanediol di(meth)acrylate, EO modified neopentyl glycol di(meth)acrylate, PO modified neopentyl glycol di(meth)acrylate, EO modified hexanediol di(meth)acrylate, PO modified hexanediol di(meth)acrylate, octanediol di(meth)acrylate, nonanediol di(meth)acrylate, Decanediol di(meth)acrylate, dodecanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, glycerin di(meth)acrylate, pentaerythritol di(meth)acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, Examples of the acryloyloxyethyl isocyanurate include ethyl acrylate, ...

[0147] The polyfunctional (meth)acrylate may be a urethane (meth)acrylate which is a reaction product of a bifunctional isocyanate compound and a hydroxyl group-containing polyfunctional (meth)acrylate. Examples of the bifunctional isocyanate compound include the compounds described below.

[0148] The polyfunctional (meth)acrylate may be an epoxy (meth)acrylate which is a reaction product of (meth)acrylic acid and an epoxy resin, such as bisphenol A type epoxy resin and cresol novolac type epoxy resin.

[0149] Examples of polyfunctional vinyl ethers include 1,4-butanediol divinyl ether, ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether, bisphenol A alkylene oxide divinyl ether, bisphenol F alkylene oxide divinyl ether, trimethylolethane trivinyl ether, trimethylolpropane trivinyl ether, and ditrimethylolpropane trivinyl ether. Examples of the vinyl ethers include ethylenediaminetetravinyl ether, ...

[0150] Among them, the polymerizable monomer has a (meth)acryloyl group and a solubility parameter (SP value) of 16.5 MPa. 1 / 2 ~21.3MPa 1 / 2 It is preferable that the polymerizable monomer C is

[0151] When the ink contains polymerizable monomer C, polymerization of polymerizable monomer C proceeds while the ink is adequately soaked into the image-recording substrate, resulting in an image with excellent adhesion to the image-recording substrate, and as a result, excellent laminate peel strength is achieved. The SP value of polymerizable monomer C is 18MPa. 1 / 2 ~19.5MPa 1 / 2 It is preferable that:

[0152] From the viewpoint of further improving the curability of the ink (that is, the polymerizability of the polymerizable monomer C), it is preferable that the polymerizable monomer C has a (meth)acryloyloxy group (preferably an acryloyloxy group).

[0153] The number of (meth)acryloyl groups contained in the polymerizable monomer C may be only one, or may be two or more, but is preferably only one.

[0154] The molecular weight of the polymerizable monomer C is preferably 215 or less. Since the ink is more easily absorbed into the image recording substrate, the adhesion of the image to the image recording substrate is improved. Furthermore, the distance between crosslinking points is shortened, so the density of the ink film is improved. As a result, the laminate peel strength is improved.

[0155] The molecular weight of the polymerizable monomer C is more preferably 205 or less, and further preferably 200 or less.

[0156] Examples of the polymerizable monomer C include the following compounds. Tetrahydrofurfuryl acrylate (SP value: 18.8 MPa 1 / 2 ) Cyclic trimethylolpropane formal acrylate (SP value: 19.0 MPa 1 / 2 ) Ethoxydiethylene glycol acrylate (SP value: 18.2 MPa 1 / 2 ) Cyclohexyl acrylate (SP value: 17.9 MPa 1 / 2 ) Isobornyl acrylate (SP value: 17.1 MPa 1 / 2 ) Phenoxyethyl acrylate (SP value: 19.44 MPa 1 / 2 ) N,N-Dimethylacrylamide (SP value: 21.4MPa 1 / 2 ) 4-tert-Butylcyclohexyl acrylate (SP value: 16.7MPa 1 / 2 ) 3,3,5-trimethylcyclohexyl acrylate (SP value: 16.7MPa 1 / 2 ) 4-Hydroxybutyl acrylate (SP value: 21.0 MPa 1 / 2 ) 2-Methyl-2-ethyl-1,3-dioxolan-4-yl) methyl acrylate (SP value: 18.2 MPa) 1 / 2 ) Benzyl acrylate (SP value: 19.0 MPa 1 / 2 ) (3-Ethyloxetan-3-yl)methyl acrylate (SP value: 18.6 MPa 1 / 2 ) 2-Oxotetrahydrofuran-3-yl acrylate (SP value: 21.2 MPa 1 / 2 ) Lauryl acrylate (SP value: 16.7 MPa 1 / 2 )

[0157] In particular, from the viewpoint of improving adhesion to the image recording substrate and adhesion to the laminating substrate, the polymerizable monomer C preferably contains at least one selected from the group consisting of tetrahydrofurfuryl acrylate, cyclic trimethylolpropane formal acrylate, cyclohexyl acrylate, and ethoxydiethylene glycol acrylate, more preferably contains at least one selected from the group consisting of cyclic trimethylolpropane formal acrylate, cyclohexyl acrylate, and ethoxydiethylene glycol acrylate, and even more preferably contains at least one selected from the group consisting of cyclohexyl acrylate and ethoxydiethylene glycol acrylate.

[0158] The content of polymerizable monomer C is preferably 30% by mass to 75% by mass, more preferably 40% by mass to 70% by mass, and further preferably 44% by mass to 63% by mass, based on the total amount of the ink.

[0159] The polymerizable monomer preferably contains at least one N-vinyl compound. When the ink contains an N-vinyl compound, the adhesion between the image and the image-recording substrate is improved, and as a result, the laminate peel strength is improved.

[0160] The N-vinyl compound has an SP value of 16.5 MPa, similar to polymerizable monomer C. 1 / 2 ~21.3MPa 1 / 2 Many of the compounds fall into this category. Therefore, they contribute to the adhesion between the image-recording substrate and the image.

[0161] Examples of N-vinyl compounds include N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylcarbazole, N-vinylimidazole, N-vinylphthalimide, N-vinylacetamide, N-vinylformamide, and 5-methyl-3-vinyl-2-oxazolidinone.

[0162] Among these, from the viewpoint of high solubility in the image recording substrate and improving adhesion between the image recording substrate and the image, the N-vinyl compound is preferably at least one selected from the group consisting of N-vinylcaprolactam and 5-methyl-3-vinyl-2-oxazolidinone.

[0163] The content of the N-vinyl compound is preferably 10% by mass to 50% by mass, more preferably 15% by mass to 40% by mass, and even more preferably 20% by mass to 30% by mass, based on the total amount of the ink.

[0164] The total proportion of the polymerizable monomer C and the N-vinyl compound in all the polymerizable monomers contained in the ink is preferably 80% by mass or more, more preferably 90% by mass or more. The upper limit of the proportion is not particularly limited, and the proportion may be 100% by mass. In other words, all the polymerizable monomers contained in the ink may be the polymerizable monomer C and the N-vinyl compound.

[0165] The weighted average of the glass transition temperatures when all the polymerizable monomers contained in the ink are homopolymers is preferably 0° C. to 100° C., more preferably 5° C. to 50° C., and even more preferably 10° C. to 30° C. When the weighted average is 0° C. to 100° C., the ink film (i.e., image) obtained by curing the ink has excellent thermal softening properties, and therefore the image has excellent adhesion to the substrate for lamination.

[0166] The glass transition temperature in the case where the polymerizable monomer is made into a homopolymer is measured by the following method.

[0167] First, a homopolymer having a weight average molecular weight of 10,000 to 20,000 is produced using a polymerizable monomer. The glass transition temperature of the produced homopolymer is measured according to the method described in JIS K7121:2012.

[0168] In the present disclosure, the glass transition temperature is measured using a differential scanning calorimeter, for example, a product named "DSC-60" manufactured by Shimadzu Corporation. In the present disclosure, the weight average molecular weight is measured using a gel permeation chromatograph (GPC). For example, HLC-8220GPC (manufactured by Tosoh Corporation) is used as the GPC, three TSKgel Super Multipore HZ-H (manufactured by Tosoh Corporation, 4.6 mm ID x 15 cm) are used as the columns, and THF (tetrahydrofuran) is used as the eluent. The conditions are a sample concentration of 0.45 mass%, a flow rate of 0.35 ml / min, a sample injection amount of 10 μL, a measurement temperature of 40° C., and detection is performed using a differential refractive index (RI) detector. The calibration curve is prepared using eight samples of "TSK Standard Polystyrene" manufactured by Tosoh Corporation under the product names "F-40", "F-20", "F-4", "F-1", "A-5000", "A-2500", "A-1000", and "n-propylbenzene" as standard samples.

[0169] The glass transition temperature of a homopolymer varies depending on the weight average molecular weight of the homopolymer. However, when the weight average molecular weight is in the range of 10,000 to 20,000, the variation is negligibly small.

[0170] The weighted average glass transition temperature is calculated using the following formula: i represents the glass transition temperature of the i-th polymerizable monomer contained in the ink when it is treated as a homopolymer, and C i represents the content (mass %) of the i-th polymerizable monomer relative to the total amount of ink.

[0171] Weighted average value of glass transition temperature = ΣT i C i / ΣC i

[0172] From the viewpoint of improving the curability of the ink, the content of the polymerizable monomer is preferably 40% by mass to 95% by mass, and more preferably 60% by mass to 90% by mass, based on the total amount of the ink.

[0173] (Polymerization initiator) The ink preferably contains at least one polymerization initiator. The polymerization initiator is preferably a photoradical polymerization initiator that absorbs light to generate radicals that are polymerization initiating species.

[0174] Examples of the polymerization initiator include alkylphenone compounds, acylphosphine compounds, aromatic onium salt compounds, organic peroxides, thio compounds, hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, compounds having a carbon-halogen bond, and alkylamine compounds.

[0175] Among these, the polymerization initiator is preferably at least one selected from the group consisting of an acylphosphine compound and a thio compound, more preferably at least one selected from the group consisting of an acylphosphine oxide compound and a thioxanthone compound, and further preferably a combination of an acylphosphine oxide compound and a thioxanthone compound.

[0176] The acylphosphine oxide compound includes a monoacylphosphine oxide compound and a bisacylphosphine oxide compound, and a bisacylphosphine oxide compound is preferred.

[0177] Examples of the monoacylphosphine oxide compound include isobutyryldiphenylphosphine oxide, 2-ethylhexanoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, (2,4,6-trimethylbenzoyl)ethoxyphenylphosphine oxide, o-toluyldiphenylphosphine oxide, pt-butylbenzoyldiphenylphosphine oxide, 3-pyridylcarbonyldiphenylphosphine oxide, acryloyldiphenylphosphine oxide, benzoyldiphenylphosphine oxide, pivaloylphenylphosphinic acid vinyl ester, acryloyldiphenylphosphine oxide, benzoyldiphenylphosphine oxide ... Examples of the diphenylphosphine oxide include dipoylbisdiphenylphosphine oxide, pivaloyldiphenylphosphine oxide, p-toluyldiphenylphosphine oxide, 4-(t-butyl)benzoyldiphenylphosphine oxide, terephthaloylbisdiphenylphosphine oxide, 2-methylbenzoyldiphenylphosphine oxide, versatoyldiphenylphosphine oxide, 2-methyl-2-ethylhexanoyldiphenylphosphine oxide, 1-methyl-cyclohexanoyldiphenylphosphine oxide, pivaloylphenylphosphine acid methyl ester, and pivaloylphenylphosphine acid isopropyl ester.

[0178] Examples of the bisacylphosphine oxide compound include bis(2,6-dichlorobenzoyl)phenylphosphine oxide, bis(2,6-dichlorobenzoyl)-2,5-dimethylphenylphosphine oxide, bis(2,6-dichlorobenzoyl)-4-ethoxyphenylphosphine oxide, bis(2,6-dichlorobenzoyl)-4-propylphenylphosphine oxide, bis(2,6-dichlorobenzoyl)-2-naphthylphosphine oxide, and bis(2,6-dichlorobenzoyl). Bis(2,6-dichlorobenzoyl)-1-naphthylphosphine oxide, bis(2,6-dichlorobenzoyl)-4-chlorophenylphosphine oxide, bis(2,6-dichlorobenzoyl)-2,4-dimethoxyphenylphosphine oxide, bis(2,6-dichlorobenzoyl)decylphosphine oxide, bis(2,6-dichlorobenzoyl)-4-octylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2, 5-Dimethylphenylphosphine oxide, bis(2,6-dichloro-3,4,5-trimethoxybenzoyl)-2,5-dimethylphenylphosphine oxide, bis(2,6-dichloro-3,4,5-trimethoxybenzoyl)-4-ethoxyphenylphosphine oxide, bis(2-methyl-1-naphthoyl)-2,5-dimethylphenylphosphine oxide, bis(2-methyl-1-naphthoyl)-4-ethoxyphenylphosphine oxide, bis(2-methyl-1-naphthoyl)-2- naphthylphosphine oxide, bis(2-methyl-1-naphthoyl)-4-propylphenylphosphine oxide, bis(2-methyl-1-naphthoyl)-2,5-dimethylphenylphosphine oxide, bis(2-methoxy-1-naphthoyl)-4-ethoxyphenylphosphine oxide, bis(2-chloro-1-naphthoyl)-2,5-dimethylphenylphosphine oxide and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide.

[0179] Among them, the acylphosphine oxide compound preferably contains at least one selected from the group consisting of bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (product name "Omnirad 819", manufactured by IGM Resins BV) and 2,4,6-trimethylbenzoyldiphenylphosphine oxide (product name "Omnirad TPO-H", manufactured by IGM Resins BV).

[0180] Thioxanthone compounds include thioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-dodecylthioxanthone, 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, 1-methoxycarbonylthioxanthone, 2-ethoxycarbonylthioxanthone, 3-(2-methoxyethoxycarbonyl)thioxanthone, 4-butoxycarbonylthioxanthone, and 5-methylthioxanthone. 1-Butoxycarbonyl-7-methylthioxanthone, 1-Cyano-3-chlorothioxanthone, 1-Ethoxycarbonyl-3-chlorothioxanthone, 1-Ethoxycarbonyl-3-ethoxythioxanthone, 1-Ethoxycarbonyl-3-aminothioxanthone, 1-Ethoxycarbonyl-3-phenylsulfurylthioxanthone, 3,4-Di[2-(2-methoxyethoxy)ethoxycarbonyl]thioxanthone, 1-Ethoxycarbonyl-3-phenylsulfurylthioxanthone, 3,4-Di[2-(2-methoxyethoxy)ethoxycarbonyl]thioxanthone, 2-Methyl-6-(1,1-dimethoxybenzyl)thioxanthone, 2-Methyl-6-(1,1-dimethoxybenzyl)thioxanthone, 2-Methyl-6-morpholinomethylthioxanthone, 2-Methyl-6-morpholinomethylthioxanthone, n-Allylthioxanthone-3,4-dicarboximide, n-Octylthioxanthone-3,4-dicarboximide, N-(1,1,3,3-tetramethylthioxanthone ... methylbutyl)thioxanthone-3,4-dicarboximide, 1-phenoxythioxanthone, 6-ethoxycarbonyl-2-methoxythioxanthone, 6-ethoxycarbonyl-2-methylthioxanthone, thioxanthone-2-polyethylene glycol ester, and 2-hydroxy-3-(3,4-dimethyl-9-oxo-9H-thioxanthone-2-yloxy)-N,N,N-trimethyl-1-propanaminium chloride.

[0181] The thioxanthone compound may be a commercially available product, such as the SPEEDCURE series manufactured by Lambson (e.g., SPEEDCURE 7010, SPEEDCURE CPTX, SPEEDCURE ITX, etc.).

[0182] When the ink contains a polymerization initiator, the content of the polymerization initiator is preferably 2% by mass or more, and more preferably 5% by mass or more, based on the total amount of the ink, from the viewpoint of improving the curability of the ink. The upper limit of the content of the polymerization initiator is not particularly limited, but is, for example, 10% by mass.

[0183] (Surfactant) The ink may include at least one surfactant.

[0184] However, from the viewpoint of increasing the affinity between the image recording substrate and the ink, it is preferable that the ink does not contain a surfactant, or that the content of the surfactant relative to the total amount of the ink is less than 0.1 mass %. When the ink contains a surfactant, a commonly known surfactant can be used as the surfactant.

[0185] (Polymerization inhibitor) The inks of the present disclosure preferably include at least one polymerization inhibitor.

[0186] Examples of the polymerization inhibitor include p-methoxyphenol, quinones (e.g., hydroquinone, benzoquinone, methoxybenzoquinone, etc.), phenothiazine, catechols, alkylphenols (e.g., dibutylhydroxytoluene (BHT)), alkylbisphenols, zinc dimethyldithiocarbamate, copper dimethyldithiocarbamate, copper dibutyldithiocarbamate, copper salicylate, thiodipropionic acid esters, mercaptobenzimidazole, phosphites, 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO), 2,2,6,6-tetramethyl-4-hydroxypiperidine-1-oxyl (TEMPOL), and tris(N-nitroso-N-phenylhydroxylamine) aluminum salt (also known as Cupferron Al).

[0187] Among them, the polymerization inhibitor preferably contains at least one selected from the group consisting of p-methoxyphenol, catechols, quinones, alkylphenols, TEMPO, TEMPOL, and tris(N-nitroso-N-phenylhydroxylamine)aluminum salts, and more preferably contains at least one selected from the group consisting of p-methoxyphenol, hydroquinone, benzoquinone, BHT, TEMPO, TEMPOL, and tris(N-nitroso-N-phenylhydroxylamine)aluminum salts.

[0188] When the ink contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01% by mass to 2.0% by mass, more preferably 0.02% by mass to 1.0% by mass, and even more preferably 0.03% by mass to 0.5% by mass, relative to the total amount of the ink.

[0189] (water) The ink may contain a small amount of water. Specifically, the content of water relative to the total amount of the ink is preferably 3 mass % or less, more preferably 2 mass % or less, and even more preferably 1 mass % or less. The ink is preferably a non-aqueous ink that is substantially free of water.

[0190] (Coloring agent) The ink preferably contains at least one colorant. The colorant is not particularly limited, and may be arbitrarily selected from known colorants such as pigments, water-soluble dyes, disperse dyes, etc. Among them, the colorant is preferably a pigment from the viewpoints of excellent weather resistance and excellent color reproducibility.

[0191] The type of pigment is not particularly limited, and may be either an organic pigment or an inorganic pigment. Examples of the pigments include those described in "Encyclopedia of Pigments" edited by Seijiro Ito (published in 2000), "Industrial Organic Pigments" by W. Herbst and K. Hunger, and JP-A Nos. 2002-12607, 2002-188025, 2003-26978, and 2003-342503.

[0192] When the ink uses a pigment as the colorant, it may contain a dispersant as necessary.

[0193] For colorants such as pigments and pigment dispersants, known documents such as paragraphs 0152 to 0158 of JP-A No. 2011-225848 and paragraphs 0132 to 0149 of JP-A No. 2009-209352 can be appropriately referred to.

[0194] When the ink contains a colorant, the content of the colorant is preferably 0.1% by mass to 20% by mass, and more preferably 0.5% by mass to 10% by mass, relative to the total amount of the ink.

[0195] (Other Ingredients) The ink may contain other components in addition to those described above. Examples of other components include ultraviolet absorbers, co-sensitizers, antioxidants, anti-fading agents, and conductive salts. For other components, reference may be made to publicly known documents such as JP-A-2011-225848 and JP-A-2009-209352, as appropriate.

[0196] (Ink properties) From the viewpoint of ejection properties, the viscosity of the ink is preferably from 5 mPa·s to 50 mPa·s, more preferably from 10 mPa·s to 30 mPa·s, and even more preferably from 10 mPa·s to 25 mPa·s.

[0197] Viscosity refers to the value measured at 25°C. The viscosity is a value measured using a viscometer, and can be measured using, for example, a VISCOMETER RE-85L (manufactured by Toki Sangyo Co., Ltd.).

[0198] From the viewpoint of ejection properties, the surface tension of the ink is preferably 60 mN / m or less, more preferably 20 mN / m to 50 mN / m, and even more preferably 25 mN / m to 45 mN / m.

[0199] The surface tension refers to the value measured at 25°C. The surface tension is a value measured using a surface tensiometer, and can be measured, for example, using an Automatic Surface Tentiometer CBVP-Z (manufactured by Kyowa Interface Science Co., Ltd.).

[0200] [Image recording method] The image recording method of the present disclosure includes a step of applying the ink of the present disclosure by an inkjet recording method onto an image recording substrate containing a polymer including vinyl chloride as a constituent unit to record an image (hereinafter also referred to as the "image recording step").

[0201] <Image recording substrate> The image recording substrate contains a polymer containing vinyl chloride as a structural unit.

[0202] A polymer containing vinyl chloride as a structural unit may be a homopolymer of vinyl chloride (i.e., polyvinyl chloride), or a copolymer containing vinyl chloride and a monomer other than vinyl chloride as structural units.

[0203] Examples of copolymers containing vinyl chloride and a monomer other than vinyl chloride as a constituent unit include vinyl chloride-urethane copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic acid copolymer, vinyl chloride-vinyl acetate-vinyl alcohol copolymer, and vinyl chloride-ethylene-vinyl acetate copolymer.

[0204] In particular, it is preferable that the image recording substrate contains polyvinyl chloride.

[0205] The image recording substrate may contain components other than the polymer containing vinyl chloride as a structural unit, such as a plasticizer, a stabilizer, an antioxidant, an ultraviolet absorber, a binder resin, and a white pigment.

[0206] The image recording substrate may have a layer containing a polymer containing vinyl chloride as a constituent unit and a surface treatment layer, but from the viewpoint of obtaining adhesion between the image recording substrate and the image by dissolving the ink in the image recording substrate, it is preferable that the image recording substrate does not have a surface treatment layer. In other words, the surface of the image recording substrate to which the ink is applied preferably contains a polymer containing vinyl chloride as a constituent unit.

[0207] The thickness of the image recording substrate is not particularly limited, but is, for example, preferably from 0.1 μm to 1,000 μm, more preferably from 0.1 μm to 800 μm, and even more preferably from 1 μm to 500 μm.

[0208] <How to apply ink> The ink is applied by an ink jet recording method.

[0209] The ink ejection method in the inkjet recording method is not particularly limited, and may be any of the well-known methods, such as a charge control method that uses electrostatic attraction to eject ink, a drop-on-demand method (pressure pulse method) that uses the vibration pressure of a piezoelectric element, an acoustic inkjet method in which an electric signal is converted into an acoustic beam and irradiated onto the ink to eject ink using radiation pressure, and a thermal inkjet (Bubble Jet (registered trademark)) method in which ink is heated to form bubbles and the resulting pressure is utilized.

[0210] As the inkjet recording method, in particular, the method described in JP-A-54-59936 can be effectively used, in which ink subjected to the action of thermal energy undergoes a sudden volume change, and the ink is ejected from the nozzle by the action force caused by this state change. As the inkjet recording method, the method described in paragraphs 0093 to 0105 of JP-A-2003-306623 can also be applied.

[0211] Application of ink to an image recording substrate by ink jet recording is carried out by ejecting the ink from the nozzles of an ink jet head.

[0212] Inkjet head methods include the shuttle method, in which a short serial head is scanned across the width of the recording medium to perform recording, and the line method, which uses a line head in which recording elements are arranged to cover the entire area of ​​one side of the recording medium.

[0213] In the line method, an image can be recorded on the entire surface of a recording medium by scanning the recording medium in a direction intersecting the arrangement direction of the recording elements. The line method does not require a transport system such as a carriage that scans a short head in the shuttle method. Furthermore, compared to the shuttle method, the line method does not require complex scanning control of the carriage movement and the recording medium, and only the recording medium moves. Therefore, the line method achieves faster image recording speeds than the shuttle method.

[0214] The ink is preferably applied using an inkjet head having a resolution of 300 dpi or more (more preferably 600 dpi or more, and even more preferably 800 dpi or more), where dpi is an abbreviation for dots per inch, and 1 inch is 2.54 cm.

[0215] From the viewpoint of obtaining a high-definition image, the amount of ink droplets 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.

[0216] <Drying process> The image recording step preferably includes a step of drying the applied ink after the ink is applied onto the image recording substrate (hereinafter also referred to as a "drying step").

[0217] The ink may be dried naturally, but is preferably dried by heating.

[0218] The heating temperature in the heat drying is preferably 30°C to 90°C, and more preferably 50°C to 80°C.

[0219] Examples of the heat drying method include infrared (IR) drying, hot air drying, and methods using a heating device (eg, a heater, a hot plate, a heating furnace, etc.).

[0220] The heat drying can be carried out by heating the ink from at least one of the image recording surface side and the non-image recording surface side of the image recording substrate.

[0221] <Active energy ray irradiation process> The image recording step preferably includes a step of applying an ink onto an image recording substrate and then irradiating the applied ink with active energy rays (hereinafter also referred to as an "active energy ray irradiation step").

[0222] By irradiating the ink applied onto the image recording substrate with active energy rays, a polymerization reaction of the polymerizable compound contained in the ink proceeds, thereby fixing the image and improving the hardness, etc., of the image.

[0223] Examples of the active energy ray include ultraviolet light, visible light, and electron beams. Among them, the active energy ray is preferably ultraviolet light.

[0224] The peak wavelength of the ultraviolet light is preferably from 200 nm to 405 nm, more preferably from 220 nm to 390 nm, and even more preferably from 220 nm to 380 nm.

[0225] The UV exposure was 20 mJ / cm 2 ~5J / cm 2 and preferably 100 mJ / cm 2 ~1,500mJ / cm 2 It is more preferable that the irradiation conditions and basic irradiation method are those disclosed in JP-A-60-132767. Specifically, the irradiation method is preferably a method in which light sources are provided on both sides of a head unit including an ink ejection device and the head unit and light sources are scanned by a so-called shuttle method, or a method in which irradiation is performed by a separate light source that does not involve driving.

[0226] Discharge lamps and laser light sources (gas lasers, solid-state lasers, etc.) are mainly used as light sources for ultraviolet irradiation, and as discharge lamps, for example, mercury lamps, metal halide lamps, and ultraviolet fluorescent lamps are widely known. In addition, semiconductor light sources such as UV-LEDs (light-emitting diodes) and UV-LDs (laser diodes) are small, have a long life, are highly efficient, and are low cost, and are expected to be light sources for ultraviolet irradiation. Among them, the light source for ultraviolet irradiation is preferably a metal halide lamp, a high-pressure mercury lamp, a medium-pressure mercury lamp, a low-pressure mercury lamp, or a UV-LED.

[0227] [Manufacturing method of laminated body] The method for producing a laminate according to the present disclosure includes a step of applying the ink according to the present disclosure by an inkjet recording method onto an image-recording substrate containing a polymer containing vinyl chloride as a constituent unit to record an image (i.e., an image-recording step), and a step of placing a laminating substrate containing a polymer containing vinyl chloride as a constituent unit on the image and laminating them (hereinafter also referred to as a "laminating step").

[0228] The image recording step in the method for producing a laminate according to the present disclosure is similar to the image recording step in the above-described image recording method, and therefore a description thereof will be omitted.

[0229] <Lamination substrate> The preferred embodiments of the substrate for lamination are the same as those of the substrate for image recording, and therefore the description thereof will be omitted.

[0230] <Lamination method> In the lamination process, the substrate for lamination is placed on the image. At this time, another layer such as an adhesive layer may be provided on the image, and the substrate for lamination may be placed via the other layer. However, in the method for producing a laminated body of the present disclosure, since the ink film (i.e., the image) obtained by curing the ink has excellent thermal softening properties, it is preferable not to provide another layer. In other words, it is preferable to laminate the image and the substrate for lamination by overlapping them so that they are in contact with each other. This results in a laminated body having a layered structure of the substrate for image recording / image / substrate for lamination.

[0231] The upper limit of the temperature during thermocompression bonding is preferably 200°C, more preferably 160°C, and even more preferably 140°C, from the viewpoint of suppressing thermal decomposition.

[0232] The temperature during thermocompression bonding refers to the surface temperature of the substrate to be laminated.

[0233] The pressure during thermocompression bonding is preferably 0.1 MPa to 20 MPa, and more preferably 0.5 MPa to 15 MPa.

[0234] The time for thermocompression bonding is, for example, 10 seconds to 500 seconds.

[0235] Thermocompression bonding may be performed in two stages. For example, the pressure in the first stage may be 0.5 MPa to 5 MPa, and the pressure in the second stage may be higher than the pressure in the first stage, 6 MPa to 15 MPa.

[0236] The laminate obtained by the method for producing a laminate according to the present disclosure can be used, for example, as a flooring or wall material for transportation equipment (trains, buses, etc.) or a flooring or wall material for buildings. EXAMPLES

[0237] Hereinafter, the present disclosure will be described more specifically with reference to examples. However, the present disclosure is not limited to the following examples as long as it does not depart from the gist of the disclosure.

[0238] [Examples 1 to 15, Comparative Examples 1 and 2] <Synthesis of acrylic resin> n-Butanol (137.6 g) and N-vinyl-ε-caprolactam (50.0 g) were weighed into a 500 ml three-neck flask equipped with a cooling tube, and heated and stirred at 75° C. under a nitrogen stream. Separately, a mixed solution prepared by mixing n-butanol (91.7 g), tetrahydrofurfuryl acrylate (30.0 g), X-22-174ASX (manufactured by Shin-Etsu Chemical Co., Ltd.) (20.0 g), and V-601 (2,2'-azobis(isobutyric acid) dimethyl; polymerization initiator manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) (4.0 g) was added dropwise to the above flask over 3 hours. After the dropwise addition was completed, the mixture was stirred at 85° C. for another 3 hours to react. The mixture was allowed to cool to room temperature (25°C; the same applies below), then methanol (170.6 g) was added and stirred to obtain a mixed solution, which was then added dropwise to a mixed solution of methanol (300.0 g) and water (3000 g), and the separated component was dried to obtain a white solid of acrylic resin P1. The weight average molecular weight (Mw) of the acrylic resin P1 was 20,000.

[0239] Acrylic resin P1 was used in Example 1. In Examples 2 to 15 and Comparative Examples 1 to 3, acrylic resins were synthesized in the same manner as in Example 1, except that polymerizable compound A, polymerizable compound B, and other polymerizable compounds shown in Table 7 were used, the amounts of raw materials were adjusted to achieve the composition ratios shown in Table 7, and the amount of polymerization initiator was changed to adjust the molecular weight.

[0240] Details of the polymerizable compound A, the polymerizable compound B, and the other polymerizable compounds are as follows.

[0241] (Polymerizable compound A) Silicone 1: Methacrylate containing a polysiloxane group (product name "X-22-174ASX", manufactured by Shin-Etsu Chemical Co., Ltd.) Silicone 2: Methacrylate containing a polysiloxane group (product name "X-22-2404", manufactured by Shin-Etsu Chemical Co., Ltd.) Silicone 3: Methacrylate containing a polysiloxane group (product name "KF-2012", manufactured by Shin-Etsu Chemical Co., Ltd.) Silicone 4: Methacrylate containing a polysiloxane group (product name "X-22-2426", manufactured by Shin-Etsu Chemical Co., Ltd.) Fluorine 1: 1H,1H,2H,2H-tridecafluorooctyl acrylate (product name: Viscoat 13F, manufactured by Osaka Organic Chemical Industry Co., Ltd.) ·C18MA: Stearyl methacrylate

[0242] (Polymerizable compound B) NVC: N-vinyl-ε-caprolactam ·THFA: Tetrahydrofurfuryl acrylate ACMO: 4-Acryloylmorpholine MMA: Methyl methacrylate HPMAA: N-(2-hydroxypropyl) methacrylamide HEMA: 2-hydroxyethyl methacrylate

[0243] (Other polymerizable compounds) ·BA: Butyl acrylate IBOMA: Isobornyl methacrylate

[0244] <Preparation of Cyan Pigment Dispersion> The following components were mixed and stirred for 10 minutes at 2,500 rpm using a mixer (Silverson L4R) to obtain a mixture. The mixture was then placed in a bead mill disperser DISPERMAT LS (VMA) and dispersed for 6 hours at 2,500 rpm using 0.65 mm diameter YTZ balls (Nikkato Corporation) to obtain a cyan pigment dispersion.

[0245] Cyan pigment: Product name "IRGALITE BLUE GLVO", manufactured by BASF... 30% by mass BYK-168: Product name "DISPERSE BYK-168", manufactured by BYK... 20% by mass DVE-3: Triethylene glycol divinyl ether, manufactured by BASF...50% by weight

[0246] <Ink Preparation> The above cyan pigment dispersion (6% by mass) was mixed with the following components to prepare an ink. CHA: Cyclohexyl acrylate, manufactured by Tokyo Chemical Industry Co., Ltd.... 42.6% by mass EOEOEA: Ethoxydiethylene glycol acrylate, manufactured by Tokyo Chemical Industry Co., Ltd.... 17.0% by mass NVC: N-vinylcaprolactam, manufactured by Tokyo Chemical Industry Co., Ltd.... 25.5% by mass ITX: 2-isopropylthioxanthone, Fujifilm Wako Pure Chemical Industries, Ltd.... 2% by mass Omni.819: Bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (product name "Omnirad 819", manufactured by IGM Resins BV)… 2.8% by mass Omni.TPO-H: 2,4,6-trimethylbenzoyldiphenylphosphine oxide (product name "Omnirad TPO-H", manufactured by IGM Resins BV)... 2.8% by mass TEMPOL: 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, manufactured by Tokyo Chemical Industry Co., Ltd.... 0.3% by mass Acrylic resin listed in Table 7: 1% by mass

[0247] <Manufacturing of laminated bodies> -Image recording process- As an image recording substrate, a polyvinyl chloride substrate (product name "PVC35phr", manufactured by Okamoto Corporation) was prepared. A rubber heater (SR100, manufactured by Three High Co., Ltd.) and an ultraviolet (UV) irradiation device (Vzero, manufactured by Integration Technology Co., Ltd.) were attached to an Affit inkjet printer (KEGON) to prepare a modified inkjet printer. The output of the rubber heater was set so that the image recording substrate to which the ink was applied could be heated to about 60°C. The ink drying time when UV irradiation was performed (i.e., the time from when the ink discharged from the inkjet head landed on the image recording substrate to when it was irradiated with UV) was adjusted to be 10 seconds. Specifically, the ink drying time was adjusted by adjusting the transport speed (5 m / min to 25 m / min) and the timing of opening and closing the UV shutter. The ink was discharged from the inkjet head of a modified inkjet printer to record a solid image on an image recording substrate, thereby obtaining an image recording material. The resolution was 1200 dpi (dots per inch) x 600 dpi.

[0248] -Lamination process- A polyvinyl chloride base material (product name "SG800", manufactured by KN Trading Co., Ltd., thickness 75 μm) was used as the lamination base material. A substrate for lamination was placed on the image recorded on the substrate for image recording. The image and the substrate for lamination were thermally and pressure-bonded using a tabletop automatic transfer press (product name "AF-54TEN", Asahi Textile Machinery Co., Ltd.). This resulted in a laminate having a layered structure of substrate for image recording / image / substrate for lamination. The temperature in the thermocompression bonding was 130° C. The thermocompression bonding was performed at a pressure of 2 MPa for 300 seconds.

[0249] <Peel strength measurement> The peel strength of the laminated sample was measured by the following method.

[0250] The evaluation samples were prepared in the following manner. A 3.2 cm×3.2 cm image recording sample was cut out from the image recorded product obtained in the image recording step. Also, a 3.2 cm×3.2 cm lamination substrate sample was cut out from the lamination substrate. A 12 μm thick PET (polyethylene terephthalate) sheet was placed on the image recording surface of the image recording sample in a 1.0 cm×3.2 cm area including one side of the image recording sample. Next, a 3.2 cm×3.2 cm lamination substrate sample was placed over the entire area on the image recording surface of the image recording sample where the PET sheet was placed (1.0 cm×3.2 cm area) and the area where the PET sheet was not placed (2.2 cm×3.2 cm area). In this state, the image recording sample and the lamination substrate sample were laminated under the same conditions as in the lamination step described above.The PET sheet was removed from the resulting laminate to obtain a sample for evaluation.

[0251] In the evaluation sample, the image recording sample and the laminate substrate sample were bonded in the area where the PET sheet was not placed before the lamination process, whereas in the evaluation sample, the image recording sample and the laminate substrate sample were not bonded in the area where the PET sheet was placed before the lamination process. Next, in the area where the image recording sample and the laminate substrate sample were not bonded, a tensile test was performed in which the image recording sample and the laminate substrate sample were pulled in opposite directions to measure the peel strength. The tensile test was performed using a tensile tester (product name "Autograph AGS-X 5KN", manufactured by Shimadzu Corporation). Two evaluation samples were prepared and the tensile test was performed twice. The average value of the two peel strengths was used. The evaluation criteria are as follows: 5: The peel strength was 4 N / cm or more. 4: The peel strength was 3 N / cm or more and less than 4 N / cm. 3: The peel strength was 2 N / cm or more and less than 3 N / cm. 2: The peel strength was 1 N / cm or more and less than 2 N / cm. 1: The peel strength was 0.1 N / cm or more and less than 1 N / cm.

[0252] <Evaluation of blocking resistance> A 2.2cm x 2.2cm image recording sample was cut out from the image recording product obtained in the image recording process, sandwiched between 2.2cm x 2.2cm polyvinyl chloride substrates on both sides, and further sandwiched between aluminum and acrylic plates on both sides. A 2kg weight was placed on top of the resulting laminate, and it was left to stand at 70°C for 24 hours. The transfer area ratio of the ink image transferred to the polyvinyl chloride substrate was calculated. The evaluation criteria are as follows: 5: Ink transfer rate is less than 5%. 4: The ink transfer rate is 5% or more and less than 10%. 3: The ink transfer rate is 10% or more but less than 20%. 2: The ink transfer rate is 20% or more but less than 40%. 1: Ink transfer rate is 40% or more.

[0253] The evaluation results are shown in Table 7.

[0254] [Table 7]

[0255] As shown in Table 7, in Examples 1 to 15, the polarity term of the HSP value is 4.8 MPa, and the polarity term of the HSP value is 4.8 MPa. 1 / 2 The composition contains an acrylic resin containing a structural unit B derived from the polymerizable compound B described above, and a polymerizable monomer, and the content of structural unit A is 40 mass% or less based on the total amount of the acrylic resin, and the content of structural unit B is 15 mass% or more based on the total amount of the acrylic resin. Therefore, it was found that the composition has excellent adhesion to the laminate substrate. On the other hand, in Comparative Example 1, the content of the structural unit B was less than 15 mass %, and it was found that the adhesion to the laminate substrate was poor. In Comparative Example 2, the content of the structural unit A was more than 40 mass %, and it was found that the adhesion to the laminate substrate was poor.

[0256] In Example 6, the glass transition temperature of the acrylic resin was 150° C. or lower, and it was found that, compared with Example 7, the adhesion to the laminate substrate was excellent.

[0257] In Example 8, since the polymerizable compound A is a polymerizable compound containing at least one selected from the group consisting of a fluorohydrocarbon group and a polysiloxane group, it was found that the adhesion to the laminate substrate and the blocking resistance were excellent compared to Example 9.

[0258] In Example 11, since the number average molecular weight of the polymerizable compound A was 5,000 or less, it was found that the adhesion to the laminate substrate was superior compared to Example 12.

[0259] In Example 2, the mass ratio of the structural unit A to the structural unit B was 0.01 or more, and therefore it was found that the adhesion to the laminate substrate was superior to that of Example 1. In Example 4, the mass ratio of the structural unit A to the structural unit B was 0.65 or less, and therefore it was found that the adhesion to the laminate substrate was superior to that of Example 5.

[0260] In Example 14, the hydrogen bond term of the HSP value in the polymerizable compound B is 11.0 MPa. 1 / 2 Since the results are shown below, it was found that the adhesion to the laminate substrate was superior to that of Example 15.

[0261] In Example 14, since the structural unit B is at least one structural unit selected from the group consisting of the following formulas (1) to (5), it was found that the adhesion to the laminate substrate was superior to that of Example 13.

[0262] [Examples 16 to 29] Acrylic resins were synthesized in the same manner as in Example 1, except that the polymerizable compound A, the polymerizable compound B, and other polymerizable compounds shown in Table 8 were used, the amounts of the raw materials were adjusted so as to obtain the composition ratios shown in Table 8, and the amount of the polymerization initiator was changed to adjust the molecular weight.

[0263] The details of the polymerizable compound B that was not used in Examples 1 to 15 are as follows.

[0264] (Polymerizable compound B) NVP: N-vinylpyrrolidone ·THFM: Tetrahydrofurfuryl methacrylate ACMO: 4-Acryloylmorpholine VMOX: 5-methyl-3-vinyloxazolidin-2-one

[0265] An ink was prepared in the same manner as in Example 1, and a laminate was produced.

[0266] The peel strength of the obtained laminate was measured in the same manner as in Example 1. The blocking resistance was evaluated by the following method, which is stricter than the blocking resistance evaluation method.

[0267] <Evaluation of blocking resistance 2> A 2.2cm x 2.2cm image recording sample was cut out from the image recording product obtained in the image recording process, sandwiched between 2.2cm x 2.2cm polyvinyl chloride substrates on both sides, and further sandwiched between aluminum and acrylic plates on both sides. A 2kg weight was placed on top of the resulting laminate, and it was left to stand at 70°C for 72 hours. The transfer area ratio of the ink image transferred to the polyvinyl chloride substrate was calculated. The evaluation criteria are as follows: 5: Ink transfer rate is less than 5%. 4: The ink transfer rate is 5% or more and less than 10%. 3: The ink transfer rate is 10% or more but less than 20%. 2: The ink transfer rate is 20% or more but less than 40%. 1: Ink transfer rate is 40% or more.

[0268] The evaluation results are shown in Table 8.

[0269] [Table 8]

[0270] As shown in Table 8, in Examples 16 to 29, the polar term of the HSP value is 4.8 MPa, and the polarity term of the HSP value is 4.8 MPa. 1 / 2 The composition contains an acrylic resin containing a structural unit B derived from the polymerizable compound B described above, and a polymerizable monomer, and the content of structural unit A is 40 mass% or less based on the total amount of the acrylic resin, and the content of structural unit B is 15 mass% or more based on the total amount of the acrylic resin. Therefore, it was found that the composition has excellent adhesion to the laminate substrate.

[0271] In particular, in Examples 16 to 18, the polymerizable compound B has a hydrogen bond term of the HSP value of 11.0 MPa. 1 / 2 Polymerizable compound B1 having a hydrogen bond term of HSP value of 11.0 MPa or less 1 / 2 It was found that the blocking resistance was remarkably improved compared to Example 3 because the polymerizable compound B2 having a molecular weight exceeding 1000 mg / kg was contained.

Claims

1. A structural unit A derived from a polymerizable compound A containing at least one selected from the group consisting of a fluorohydrocarbon group, a polysiloxane group, and a hydrocarbon group having 12 or more carbon atoms, and a polar term of the HSP value of 4.8 MPa １／２ The present invention includes an acrylic resin containing a structural unit B derived from the above polymerizable compound B, and a polymerizable monomer, The content of the structural unit A is 40 mass% or less based on the total amount of the acrylic resin, the content of the structural unit B is 15% by mass or more based on the total amount of the acrylic resin.

2. The active energy ray-curable ink-jet ink according to claim 1 , wherein the acrylic resin has a glass transition temperature of 150° C. or lower.

3. 3. The active energy ray-curable ink-jet ink according to claim 1, wherein the polymerizable compound A is a polymerizable compound containing at least one selected from the group consisting of the fluorohydrocarbon group and the polysiloxane group.

4. 3. The active energy ray-curable ink-jet ink according to claim 1, wherein the polymerizable compound A has a number average molecular weight of 5,000 or less.

5. 3. The active energy ray-curable ink-jet ink according to claim 1, wherein a mass ratio of the structural unit A to the structural unit B is from 0.01 to 0.

65.

6. The polymerizable compound B has a hydrogen bond term of the HSP value of 11.0 MPa. １／２ 3. The actinic ray-curable ink-jet ink according to claim 1, wherein the active energy ray-curable ink-jet ink is:

7. The polymerizable compound B has a hydrogen bond term of the HSP value of 11.0 MPa. １／２ and a polymerizable compound B1 having a hydrogen bond term of the HSP value of 11.0 MPa or less. １／２ and a polymerizable compound B2, which is greater than or equal to 1.

8. 8. The active energy ray-curable ink-jet ink according to claim 7, wherein a mass ratio of a content of the polymerizable compound B1 to a content of the polymerizable compound B2 is 1 to 20.

9. 3. The active energy ray-curable ink-jet ink according to claim 1, wherein the structural unit B is at least one structural unit selected from the group consisting of the following formulas (1) to (5): 【Chemistry 1】 In formula (1), R １１ represents a hydrogen atom or a hydrocarbon group; R １２ and R １３ R each independently represents a hydrocarbon group which may contain an oxygen atom or a hydrogen atom. １２ and R １３ may be bonded to each other to form a ring. In formula (2), R ２１ represents a hydrogen atom or a hydrocarbon group; R ２２ and R ２３ R each independently represents a hydrocarbon group which may contain an oxygen atom or a hydrogen atom. ２２ and R ２３ may be bonded to each other to form a ring. In formula (3), R ３１ represents a hydrogen atom or a hydrocarbon group; L １１ represents a single bond or a divalent linking group; R ３２ represents a hydrocarbon group containing at least one selected from the group consisting of -O-, -S-, -C(=O)-, -NH-, and -N<. In formula (4), R ４１ represents a hydrogen atom or a hydrocarbon group; R ４２ and R ４３ R each independently represents a hydrogen atom, a cyano group, a hydrocarbon group having a carbonyl group, a phosphate group, or a monovalent heterocyclic group. ４２ and R ４３ may be bonded to each other to form a ring. In formula (5), R ５１ represents a hydrogen atom or a hydrocarbon group.

10. The polymerizable monomer has a (meth)acryloyl group and a solubility parameter of 16.5 MPa. １／２ ~21.3MPa １／２ The active energy ray-curable ink-jet ink according to claim 1 or 2, further comprising a polymerizable monomer C represented by the formula:

11. The active energy ray-curable ink-jet ink according to claim 10, wherein the polymerizable monomer C has a molecular weight of 215 or less.

12. 3. The active energy ray-curable ink-jet ink according to claim 1, wherein the polymerizable monomer comprises an N-vinyl compound.

13. 3. The active energy ray-curable ink-jet ink according to claim 1, wherein a weighted average value of glass transition temperatures of all polymerizable monomers contained in the active energy ray-curable ink-jet ink is 0° C. to 100° C. when each of the polymerizable monomers is a homopolymer.

14. 3. An image recording method comprising a step of applying the active energy ray-curable ink-jet ink according to claim 1 or 2 to an image recording substrate containing a polymer containing vinyl chloride as a structural unit, by an ink-jet recording method, to record an image.

15. 3. A method for producing a laminate, comprising: a step of applying the active energy ray-curable inkjet ink according to claim 1 or 2 to an image-recording substrate containing a polymer containing vinyl chloride as a structural unit, by an inkjet recording method, to record an image; and a step of placing a laminating substrate containing a polymer containing vinyl chloride as a structural unit on the image, and laminating the image.

Images