Active energy ray-curable ink, ink set and method for producing laminate body

Abstract

To provide an active energy ray-curable ink which has excellent laminate adhesiveness with a base material for a laminate containing a polymer containing a vinyl chloride unit, can record an image having excellent light resistance and has excellent inkjet suitability and an application thereof.SOLUTION: There are provided: an active energy ray-curable ink which contains a resin-coated pigment in which a pigment is coated with a vinyl chloride-vinyl acetate copolymer resin and a polymerizable compound, wherein the pigment is a magenta pigment which is PR146 and / or PR254 or a yellow pigment which is at least one of PY110, PY155, PY185, PY138, PY150 and PY184, the content mass ratio of the vinyl chloride-vinyl acetate copolymer resin to the pigment is 0.25 to 4.00 and an Mp / D ratio, which is a ratio between the content Mp mass% of the pigment and the specific gravity D of the pigment based on the total amount of the ink, is 2.00 or less; and an application thereof.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present disclosure relates to an actinic energy ray-curable ink, an ink set, and a method for producing a laminate. [Background technology]

[0002] Various studies have been conducted on image recording using active energy ray-curable ink.

[0003] For example, Patent Document 1 describes an active energy ray-curable ink composition comprising (A) a polymerizable compound, (B) a photopolymerization initiator, and (C) an ultraviolet absorber and / or (D) a radical scavenger, wherein the polymerizable compound (A) comprises a monofunctional polymerizable compound and a polyfunctional polymerizable compound, and the monofunctional polymerizable compound comprises at least one monofunctional polymerizable compound (a) selected from the group consisting of a monofunctional polymerizable compound (a-1) having a molecular weight of 250 g / mol or less and a melting point of 25° C. or more, a monofunctional polymerizable compound (a-2) having a molecular weight of 250 g / mol or less, a melting point of less than 25° C. and a viscosity at 25° C. of 20 mPa·s or more, and a monofunctional polymerizable compound (a-3) other than the monofunctional polymerizable compound (a-1) and the monofunctional polymerizable compound (a-2) and having an amide group and a cyclic structure. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2021-161182 A Summary of the Invention [Problem to be solved by the invention]

[0005] In some cases, 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, and then 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 laminate. In this case, it is required to improve the adhesion between the image and the laminate substrate. Furthermore, there are cases where images require light resistance, and cases where active energy ray-curable inks require inkjet suitability (i.e., ejection properties from an inkjet head when used as inkjet ink).

[0006] 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 ink that has excellent lamination adhesion to a lamination substrate containing a polymer including vinyl chloride as a structural unit, is capable of recording an image that has excellent light fastness, and has excellent inkjet suitability. An object of another embodiment of the present disclosure is to provide an ink set and an image recording method that can record an image that has excellent light fastness and excellent adhesion to a lamination substrate that contains a polymer including vinyl chloride as a structural unit, using an active energy ray-curable ink that has excellent inkjet suitability. A problem to be solved by yet another embodiment of the present disclosure is to provide a method for producing a laminated body capable of producing a laminated body having excellent lamination adhesion between the lamination substrate and the image by laminating a lamination substrate containing a polymer containing vinyl chloride as a structural unit onto an image in an image recorded material that includes an image recording substrate and an image. [Means for solving the problem]

[0007] The present disclosure includes the following aspects. <1> The present invention comprises a resin-coated pigment in which a pigment is coated with a vinyl chloride-vinyl acetate copolymer resin, and a polymerizable compound, the pigment is a magenta pigment or a yellow pigment, the magenta pigment is at least one selected from the group consisting of Pigment Red 146 and Pigment Red 254; the yellow pigment is at least one selected from the group consisting of Pigment Yellow 110, Pigment Yellow 155, Pigment Yellow 185, Pigment Yellow 138, Pigment Yellow 150, and Pigment Yellow 184; The mass ratio of the vinyl chloride-vinyl acetate copolymer resin to the pigment is 0.25 to 4.00; When the content of the pigment in the total amount of the active energy ray-curable ink is defined as Mp% by mass and the specific gravity of the pigment is defined as D, the Mp / D ratio is 2.00 or less. Active energy ray curable ink. <2> In the vinyl chloride-vinyl acetate copolymer resin, the mass ratio of vinyl chloride units to vinyl acetate units is 7.0 or less. <1> 2. The active energy ray-curable ink according to claim 1 . <3> The polymerizable compound has a (meth)acryloyl group and a solubility parameter of 16.5 MPa. 1 / 2 ~21.3MPa 1 / 2 The polymerizable monomer A is <1> or <2> 2. The active energy ray curable ink according to claim 1 . <4> The composition further contains a resin T containing at least one group selected from the group consisting of a fluorohydrocarbon group, a polysiloxane group, and a hydrocarbon group having 12 or more carbon atoms, Resin T has a solubility parameter of 16.5MPa. 1 / 2 ~24.0MPa 1 / 2 The polymerizable monomer is a structural unit derived from <1> ~ <3> 10. The actinic ray-curable ink according to claim 9, <5> <1> ~ <4> 13. An ink set comprising the active energy ray-curable ink according to claim 12. <6> <1> ~ <4> The active energy ray-curable ink according to any one of the above items is used, An image recording method comprising the step of applying an active energy ray-curable ink by an inkjet recording method onto an image recording substrate containing a polymer containing vinyl chloride as a structural unit, thereby recording an image. <7> <6> obtaining an image recorded matter comprising an image recording substrate and an image by the image recording method according to the above item; a step of laminating a substrate for lamination containing a polymer containing vinyl chloride as a constituent unit onto an image in an image recording material to obtain a laminate; A method for producing a laminate comprising the steps of: Effect of the Invention

[0008] According to one embodiment of the present disclosure, there is provided an active energy ray-curable ink that has excellent lamination adhesion to a lamination substrate containing a polymer including vinyl chloride as a constituent unit, can record an image with excellent light resistance, and has excellent inkjet suitability. According to another embodiment of the present disclosure, there are provided an ink set and an image recording method that can record an image that has excellent light fastness and excellent lamination adhesion to a lamination substrate that contains a polymer including vinyl chloride as a constituent unit, using an active energy ray-curable ink that has excellent inkjet suitability. According to yet another embodiment of the present disclosure, there is provided a method for producing a laminated body, which can produce a laminated body having excellent lamination adhesion between the lamination substrate and the image by laminating a lamination substrate containing a polymer containing vinyl chloride as a constituent unit onto an image in an image recorded material that includes an image recording substrate and an image. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] 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.

[0010] In this specification, the amount of each component in a composition means the total amount of 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.

[0011] In this specification, the term "image" refers to a film formed by applying a pretreatment liquid and an ink in this order, 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.

[0012] 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.

[0013] [Active energy ray curable ink] The active energy ray-curable ink (hereinafter, simply referred to as "ink") of the present disclosure is The pigment contains a resin-coated pigment (hereinafter also referred to as a "vinyl chloride-vinyl acetate coated pigment") obtained by coating a pigment with a vinyl chloride-vinyl acetate copolymer resin (hereinafter also referred to as a "vinyl chloride-vinyl acetate resin"), and a polymerizable compound; the pigment is a magenta pigment or a yellow pigment, the magenta pigment is at least one selected from the group consisting of Pigment Red 146 and Pigment Red 254; the yellow pigment is at least one selected from the group consisting of Pigment Yellow 110, Pigment Yellow 155, Pigment Yellow 185, Pigment Yellow 138, Pigment Yellow 150, and Pigment Yellow 184; The mass ratio of the vinyl chloride acetate resin to the pigment is 0.25 to 4.00, When the content of the pigment in the total amount of the active energy ray-curable ink is defined as Mp% by mass and the specific gravity of the pigment is defined as D, the Mp / D ratio is 2.00 or less. This is an active energy ray curable ink. Hereinafter, pigment red and pigment yellow will also be referred to as PR and PY, respectively.

[0014] The ink of the present disclosure has excellent laminate adhesion (hereinafter also referred to as "PVC laminate adhesion") to a laminate substrate containing a polymer including vinyl chloride as a constituent unit (hereinafter also referred to as "PVC laminate substrate"), is capable of recording images with excellent light resistance, and has excellent inkjet suitability (i.e., ejection properties from an inkjet head when used as an inkjet ink). The reason why such an effect is obtained is considered to be as follows.

[0015] The reason why the recorded image has excellent adhesion to the PVC laminate is believed to be because the ink used to record the image contains a vinyl chloride acetate-coated pigment. In other words, the pigment in the ink is coated with a vinyl chloride acetate resin that contains vinyl chloride units (i.e., structural units derived from vinyl chloride), which is believed to improve the affinity between the image and the PVC laminate substrate. It is believed that this effect can be obtained when the content mass ratio of the vinyl chloride acetate resin to the pigment (ie, the content mass ratio [vinyl chloride acetate resin / pigment]) is 0.25 or more.

[0016] The reason why the effect of the recorded image having excellent light resistance is obtained is believed to be because the pigment contained in the ink for recording the image is a magenta pigment (i.e., at least one selected from the group consisting of PR146 and PR254; hereinafter also referred to as a specific magenta pigment) or a yellow pigment (i.e., at least one selected from the group consisting of PY110, PY155, PY185, PY138, PY150, and PY184; hereinafter also referred to as a specific yellow pigment) which has excellent light resistance.

[0017] The reason why the ink has the effect of being excellent in inkjet suitability is believed to be because the above-mentioned specific magenta pigment has excellent color development among magenta pigments, and the above-mentioned specific yellow pigment has excellent color development among yellow pigments. In other words, because the pigment has excellent color development, the pigment content in the ink can be reduced (specifically, the Mp / D ratio can be set to 2.00 or less), and it is believed that the inkjet suitability is improved. The ink's excellent inkjet suitability is believed to be due in part to the content mass ratio (vinyl chloride / pigment) of 4.00 or less.

[0018] The inks of the present disclosure are described in more detail below.

[0019] <Vinyl chloride-coated pigment> The inks of the present disclosure contain at least one vinyl chloride-vinyl acetate coated pigment. As described above, the vinyl chloride-vinyl acetate-coated pigment is a resin-coated pigment in which a pigment is coated with a vinyl chloride-vinyl acetate resin (that is, a vinyl chloride-vinyl acetate copolymer resin). In other words, the vinyl chloride acetate coated pigment contains a pigment and a vinyl chloride acetate resin that coats the pigment. In the vinyl chloride acetate-coated pigment, the pigment may be directly coated with the vinyl chloride acetate resin, or may be coated via another component (for example, a pigment dispersing resin other than the vinyl chloride acetate resin).

[0020] (Pigments) The pigment in the vinyl chloride acetate coated pigment is the specific magenta pigment (i.e., at least one selected from the group consisting of PR146 and PR254) or the specific yellow pigment (i.e., at least one selected from the group consisting of PY110, PY155, PY185, PY138, PY150, and PY184) described above. As described above, the specific magenta pigment and the specific yellow pigment are both pigments that are excellent in light fastness and color development properties.

[0021] The specific magenta pigment and the specific yellow pigment are both pigments with excellent color development properties, so the content of the pigment in the ink can be reduced. Specifically, by using the specific magenta pigment or the specific yellow pigment as the pigment, the Mp / D ratio, where Mp is the pigment content relative to the total amount of the ink (mass %) and D is the specific gravity of the pigment, can be set to 2.00 or less. By having the Mp / D ratio of 2.00 or less, the inkjet suitability of the ink is ensured. There is no particular lower limit to the Mp / D ratio, but from the viewpoint of the optical density of the image, it is preferably 0.90 or more.

[0022] The content of the pigment (that is, the specific magenta pigment or specific yellow pigment) relative to the total amount of the ink (that is, the above Mp) is preferably 0.10% by mass to 8.00% by mass, and more preferably 0.50% by mass to 7.00% by mass.

[0023] When the ink contains a specific magenta pigment, the content of the specific magenta pigment relative to the total amount of the ink (that is, the above Mp) is more preferably 0.50% by mass to 3.50% by mass, and even more preferably 1.00% by mass to 3.00% by mass.

[0024] When the ink contains a specific magenta pigment, the content of the specific magenta pigment in the ink is 6 g / m 2 The optical density (OD) of a solid image recorded may be adjusted to a range of 0.8 or more.

[0025] When the ink contains a specific yellow pigment, the content of the specific yellow pigment relative to the total amount of the ink (i.e., the above Mp) is more preferably 0.50% by mass to 6.00% by mass, more preferably 1.00% by mass to 5.00% by mass, and even more preferably 1.00% by mass to 4.00% by mass.

[0026] When the ink contains a specific yellow pigment, the content of the specific yellow pigment in the ink is 6 g / m 2 The optical density (OD) of a solid image recorded may be adjusted to be 0.6 or more.

[0027] (vinyl chloride resin) The vinyl chloride acetate resin in the vinyl chloride-vinyl acetate coated pigment is a vinyl chloride-vinyl acetate copolymer resin. The vinyl chloride-vinyl acetate resin contains vinyl chloride units (ie, structural units derived from vinyl chloride) and vinyl acetate units (ie, structural units derived from vinyl acetate).

[0028] In terms of suitability for inkjet printing, the mass ratio of vinyl chloride units to vinyl acetate units in the vinyl chloride-vinyl acetate resin (hereinafter also referred to as "vinyl chloride / vinyl acetate ratio") is preferably 9.0 or less, and more preferably 7.0 or less. The lower limit of the vinyl chloride / vinyl acetate ratio is preferably 1.0, more preferably 1.5, from the viewpoint of PVC laminate adhesion.

[0029] The vinyl chloride-vinyl acetate resin may contain other structural units than vinyl chloride units and vinyl acetate units, but the combined proportion of vinyl chloride units and vinyl acetate units in the total amount of the vinyl chloride-vinyl acetate resin (or all structural units in the vinyl chloride-vinyl acetate resin) is preferably 80 mass% or more.

[0030] The weight average molecular weight (Mw) of the vinyl chloride-vinyl acetate resin is preferably 5,000 to 100,000, and more preferably 10,000 to 80,000.

[0031] 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.

[0032] The glass transition temperature (Tg) of the vinyl chloride-vinyl acetate resin is preferably 20°C to 150°C, more preferably 40°C to 100°C, and further preferably 50°C to 90°C.

[0033] 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.

[0034] In the vinyl chloride acetate coated pigment, the content mass ratio of the vinyl chloride acetate resin to the pigment (that is, the specific magenta pigment or the specific yellow pigment) (that is, the content mass ratio [vinyl chloride acetate resin / pigment]) is 0.25 to 4.00. By making the content mass ratio [vinyl chloride resin / pigment] 0.25 or more, the adhesion of the image to the PVC laminate is improved. By making the content mass ratio [vinyl chloride resin / pigment] 4.00 or less, the inkjet suitability of the ink is improved. The content mass ratio [vinyl chloride acetate resin / pigment] is preferably 0.30 to 3.50, more preferably 0.50 to 3.00, even more preferably 0.80 to 2.00, even more preferably 0.60 to 1.20, and even more preferably 0.80 to 1.00.

[0035] (Other pigment dispersion resins) The vinyl chloride acetate resin in the vinyl chloride acetate-coated pigment described above coats the pigment, and therefore functions as a pigment dispersing resin. The vinyl chloride acetate-coated pigment may contain a pigment dispersing resin other than the vinyl chloride acetate resin. One preferred embodiment of the vinyl chloride acetate-coated pigment is one in which the pigment is coated with the vinyl chloride acetate resin via another pigment dispersing resin (i.e., the pigment is coated with another pigment dispersing resin, which is then coated with the vinyl chloride acetate resin). The vinyl chloride-vinyl acetate-coated pigment of this embodiment can be produced by first dispersing the pigment with another pigment dispersing resin to prepare a pigment dispersion, and then adding the vinyl chloride-vinyl acetate resin to this pigment dispersion and carrying out a dispersion treatment.

[0036] Other examples of the pigment dispersing resin include (meth)acrylic resin, polyester resin, and polyurethane resin. As the other pigment dispersing resins, commercially available products may be used. Examples of commercially available products include the DISPERBYK series manufactured by BYK-Chemie and the Solsperse series manufactured by Lubrizol Japan. For other pigment dispersing resins, paragraphs 0113 and 0114 of Japanese Patent No. 5547018 may be referred to as appropriate.

[0037] When the vinyl chloride-vinyl acetate coated pigment contains another pigment dispersing resin, the content mass ratio of the other pigment dispersing resin to the pigment (i.e., the specific magenta pigment or the specific yellow pigment) (i.e., the content mass ratio [other pigment dispersing resin / pigment]) is preferably 0.01 to 1.00, and more preferably 0.03 to 0.50.

[0038] <Polymerizable compound> The ink of the present disclosure contains at least one polymerizable compound. The polymerizable compound may be any compound containing a polymerizable group, and is preferably a compound containing an ethylenically unsaturated group as the polymerizable group. The ethylenically unsaturated group is preferably a vinyl group, an allyl group, or a (meth)acryloyl group.

[0039] The molecular weight of the polymerizable compound is preferably 1,000 or less, more preferably 500 or less, and further preferably 300 or less. Hereinafter, a polymerizable compound having a molecular weight of 1000 or less may be referred to as a polymerizable monomer.

[0040] The proportion of the polymerizable compound (preferably the polymerizable monomer) in the total amount of the ink is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, and still more preferably 80% by mass or more.

[0041] (Polymerizable monomer A) The polymerizable compound in the ink of the present disclosure preferably has a (meth)acryloyl group and a solubility parameter of 16.5 MPa. 1 / 2 ~21.3MPa 1 / 2 The polymerizable monomer A is

[0042] The SP value of polymerizable monomer A is 16.5MPa. 1 / 2 ~21.3MPa 1 / 2 It is. This allows the polymerization of polymerizable monomer A to proceed 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, achieving excellent laminate peel strength. The SP value of polymerizable monomer A is 18MPa. 1 / 2 ~19.5MPa 1 / 2 It is preferable that:

[0043] In the present disclosure, the SP value (ie, the solubility parameter) of the polymerizable monomer A means the Hansen solubility parameter. The Hansen solubility parameter is a solubility parameter introduced by Hildebrand, which is divided into three components, a dispersion term δd, a polar term δp, and a hydrogen bonding term δh, and expressed in a three-dimensional space.

[0044] The SP value δ of the polymerizable monomer A is a value calculated using the following formula (A). SP value (δ) [MPa 1 / 2 ]=(δd 2 +δp 2 +δh 2 ) 1 / 2 …(A)

[0045] The dispersion term δd, the polar term δp, and the hydrogen bond term δh are calculated using HSPiP (version 4.1.07) software.

[0046] The polymerizable monomer A has a (meth)acryloyl group (preferably an acryloyl group). This provides excellent polymerization properties to the polymerizable monomer A. As a result, the ink provides excellent curing properties. From the viewpoint of further improving the curability of the ink (that is, the polymerizability of polymerizable monomer A), polymerizable monomer A preferably has a (meth)acryloyloxy group (preferably an acryloyloxy group).

[0047] The number of (meth)acryloyl groups contained in the polymerizable monomer A may be only one, or may be two or more, but is preferably only one.

[0048] The molecular weight of the polymerizable monomer A is preferably 215 or less. This allows the ink to penetrate more easily into the image recording substrate, improving the adhesion of the image to the image recording substrate. Furthermore, the distance between crosslinking points is shortened, improving the density of the ink film. As a result, the laminate peel strength is improved. The molecular weight of the polymerizable monomer A is more preferably 205 or less, and further preferably 200 or less.

[0049] Examples of the polymerizable monomer A 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: 19.0MPa 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: 16.7MPa 1 / 2 )

[0050] Among these, from the viewpoint of improving adhesion to the image recording substrate and adhesion to the laminating substrate, the polymerizable monomer A 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.

[0051] The content of polymerizable monomer A is preferably 30% by mass to 75% by mass, more preferably 40% by mass to 70% by mass, and even more preferably 44% by mass to 63% by mass, based on the total amount of the ink.

[0052] (N-vinyl compounds) The polymerizable compound in the ink of the present disclosure preferably contains at least one N-vinyl compound. This further improves the adhesion between the image and the image recording substrate, resulting in further improvement in the laminate peel strength. N-vinyl compounds are compounds in which a vinyl group is bonded to a nitrogen atom, and are classified as polymerizable monomers. The N-vinyl compound has an SP value of 16.5 MPa, similar to polymerizable monomer A. 1 / 2 ~21.3MPa 1 / 2 Therefore, it contributes to the adhesion between the image recording substrate and the image.

[0053] 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.

[0054] 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.

[0055] 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.

[0056] The mass ratio of the content of the N-vinyl compound to the content of the polymerizable monomer A is preferably 0.30 or more, more preferably 0.35 or more, and even more preferably 0.50 or more. When the mass ratio is 0.30 or more, the curability of the ink is improved, and the adhesion between the image and the substrate for lamination is further improved.

[0057] N-vinyl compounds tend to have a high glass transition temperature when made into homopolymers, and therefore, the upper limit of the mass ratio is not particularly limited, but from the viewpoint of obtaining thermal softening properties in the ink film, the mass ratio of the content of the N-vinyl compound to the content of the polymerizable monomer A is preferably 0.30 to 0.80, more preferably 0.35 to 0.75, and even more preferably 0.5 to 0.70.

[0058] The total proportion of the polymerizable monomer A and the N-vinyl compound in all the polymerizable compounds 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 compounds contained in the ink may be the polymerizable monomer A and the N-vinyl compound.

[0059] The total proportion of the polymerizable monomer A and the N-vinyl compound to the total amount of the ink is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, and still more preferably 80% by mass or more.

[0060] (Other polymerizable monomers) The ink of the present disclosure may contain, as the other polymerizable monomer (hereinafter also referred to as "other monomer"), a polymerizable monomer other than the polymerizable monomer A and the N-vinyl compound.

[0061] The polymerizable group of the other polymerizable monomer is preferably a radical polymerizable group, more preferably a photoradical polymerizable group, and even more preferably an ethylenically unsaturated group. Examples of the other polymerizable monomer include (meth)acrylate compounds, (meth)acrylamide compounds, vinyl ether compounds, allyl compounds, and unsaturated carboxylic acids.

[0062] (Proportion of polymerizable monomers with molecular weight of 205 or less) The proportion of polymerizable monomers having a molecular weight of 205 or less among all polymerizable compounds contained in the ink of the present disclosure is preferably 80% by mass or more, more preferably 90% by mass or more. When the proportion is 80% by mass or more, the solubility of the ink in the image recording substrate is increased, and the adhesion between the image recording substrate and the image is improved. The upper limit of the proportion is not particularly limited, and the proportion may be 100% by mass. In other words, all polymerizable compounds contained in the ink may be polymerizable monomers having a molecular weight of 205 or less.

[0063] The proportion of polymerizable monomers having a molecular weight of 205 or less relative to the total amount of the ink is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, and still more preferably 80% by mass or more.

[0064] (Ratio of monofunctional polymerizable monomer) The proportion of monofunctional polymerizable monomers (i.e., polymerizable monomers having one polymerizable group; the same applies below) in all polymerizable compounds contained in the ink is preferably 90% by mass or more, and more preferably 92% by mass or more. When the above proportion is 90% by mass or more, cure shrinkage due to residual stress is suppressed, and adhesion between the image recording substrate and the image is improved. The upper limit of the above proportion is not particularly limited, and the above proportion may be 100% by mass. In other words, all polymerizable compounds contained in the ink may be monofunctional polymerizable monomers.

[0065] The proportion of the monofunctional polymerizable monomer in the total amount of the ink is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, and still more preferably 80% by mass or more.

[0066] (Weighted average value of glass transition temperature when made into homopolymer) 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 temperature is from 0° C. to 100° C., the ink film (ie, image) obtained by curing the ink has excellent thermal softening properties, and therefore the adhesion between the image and the substrate for lamination is further improved.

[0067] The glass transition temperature of the polymerizable monomer as a homopolymer is measured by the following method. Note that the term "polymerizable monomer" used herein refers to a compound having a polymerizable group and a molecular weight of 1000 or less.

[0068] 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.

[0069] 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.

[0070] The weighted average glass transition temperature is calculated using the following formula: In the formula, T 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.

[0071] Weighted average value of glass transition temperature = ΣT i C i / ΣC i

[0072] (Polymerization initiator) The ink of the present disclosure 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.

[0073] Examples of the polymerization initiator include an alkylphenone compound, an acylphosphine compound, an aromatic Examples of the compound include 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.

[0074] 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.

[0075] The acylphosphine oxide compound includes a monoacylphosphine oxide compound and a bisacylphosphine oxide compound, and a bisacylphosphine oxide compound is preferred.

[0076] 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.

[0077] 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, 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-trimethylphenylphosphine oxide), and bis(2,4,6-trimethylphenylphosphine 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 Sphing 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.

[0078] 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).

[0079] 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.

[0080] 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.).

[0081] 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.

[0082] (Surfactant) The ink may contain at least one surfactant. 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.

[0083] (Polymerization inhibitor) The ink of the present disclosure preferably contains at least one polymerization inhibitor.

[0084] 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).

[0085] 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.

[0086] 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.

[0087] (resin) The inks of the present disclosure may contain at least one resin. The resin referred to here means a resin other than the resin in the resin-coated pigment (that is, the vinyl chloride-vinyl acetate-coated pigment) (that is, a resin contained outside the resin-coated pigment).

[0088] Examples of the resin include epoxy resins, vinyl chloride resins, polyester resins, (meth)acrylic resins, urethane resins, chlorinated polyolefins, and polyketones.

[0089] The vinyl chloride resin means a polymer containing vinyl chloride as a structural unit. The vinyl chloride resin 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 a structural unit.

[0090] An example of the (meth)acrylic resin is a copolymer of methyl methacrylate and n-butyl methacrylate.

[0091] The urethane resin means a polymer having a urethane bond in the main chain. The urethane resin is produced, for example, by reacting a polyisocyanate compound with a polyol compound.

[0092] The ink of the present disclosure preferably contains a resin T that contains at least one group selected from the group consisting of a fluorohydrocarbon group, a polysiloxane group, and a hydrocarbon group having 12 or more carbon atoms. When the resin contains at least one group selected from the group consisting of a fluorohydrocarbon group, a polysiloxane group, and a hydrocarbon group having 12 or more carbon atoms, the solubility of the ink in the image-recording substrate is increased, and the adhesion between the image-recording substrate and the image is improved.

[0093] A fluorohydrocarbon group is a hydrocarbon group substituted with at least one fluorine atom. means. 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.

[0094] 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.

[0095] A polysiloxane group means a divalent group containing repeating Si-O bonds. The specific resin more preferably contains a monovalent group containing a polysiloxane group. An example of the monovalent group containing a polysiloxane group is the following group (P).

[0096] [ka]

[0097] In the group (P), R P1 and R P2 each 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.

[0098] [ka]

[0099] 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.

[0100] 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 or a phenyl group, more preferably a methyl group or a phenyl group, and particularly preferably a methyl group.

[0101] 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 Z5 The 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.

[0102] -Structural unit (1) 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- Resin T preferably contains at least one type of structural unit (1) containing at least one type selected from the group consisting of a fluorohydrocarbon group, a polysiloxane group, and a hydrocarbon group having 12 or more carbon atoms.

[0103] Examples of the structural unit (1) include structural units derived from vinyl monomers (for example, (meth)acrylic acid esters, (meth)acrylamides, etc.), structural units derived from diol compounds, and structural units derived from diisocyanate compounds.

[0104] As the structural unit (1), a structural unit derived from a (meth)acrylic acid ester is preferable, and the following structural unit (1A) is more preferable.

[0105] [ka]

[0106] In the structural unit (1A), R 31 represents a hydrogen atom or a methyl group, L 31 represents a single bond or a linking group; X 31 represents a fluorohydrocarbon group, a monovalent group including a polysiloxane group, or a hydrocarbon group having 12 or more carbon atoms, and two *s each represent a bonding position.

[0107] X 31 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.

[0108] R 31 represents a hydrogen atom or a methyl group, and a methyl group is preferable.

[0109] L 31 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.

[0110] Specific examples of the structural unit (1A) that contains at least one type selected from the group consisting of a fluorohydrocarbon group, a polysiloxane group, and a hydrocarbon group having 12 or more carbon atoms are as follows.

[0111] [ka]

[0112] [ka]

[0113] Specific examples of the structural unit (1) include the following structural units.

[0114] [ka]

[0115] In addition to the above structural unit (1), resin T preferably contains at least one structural unit (2) containing at least one selected from the group consisting of an alkylthio group, an alkylenethioalkylene group, and a mercapto group.

[0116] Examples of the structural unit (2) include an alkylthio group, an alkylenethioalkylene group, an oxyalkylenethioalkyleneoxy group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 10 carbon atoms), a mercapto group, a mercaptoalkyl group (preferably having 1 to 10 carbon atoms), and a mercaptoalkylamino group (preferably having 1 to 10 carbon atoms).

[0117] The alkylthio group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, further preferably 6 to 20 carbon atoms, and particularly preferably 10 to 20 carbon atoms, from the viewpoint of further suppressing yellowing of an image. The alkylenethioalkylene group preferably has 2 to 20 carbon atoms, and more preferably 2 to 10 carbon atoms, from the viewpoint of further suppressing yellowing of the image.

[0118] Examples of the structural unit (2) also include structural units derived from vinyl monomers containing at least one selected from the group consisting of an alkylthio group, an alkylenethioalkylene group, and a mercapto group (e.g., (meth)acrylic acid ester, (meth)acrylamide, etc.).

[0119] As the structural unit (2) containing at least one selected from the group consisting of an alkylthio group, an alkylenethioalkylene group, and a mercapto group, from the viewpoint of further suppressing yellowing of the image, an alkylthio group is preferred, and an alkylthio group as a terminal group of the main chain of the resin T is particularly preferred.

[0120] Specific examples of the structural unit (2) are as follows:

[0121] [ka]

[0122] [ka]

[0123] In addition to the above structural unit (1), resin T preferably contains at least one structural unit (3) that contains an amine structure having an α-hydrogen atom. Examples of the structural unit (3) include a structural unit derived from a vinyl monomer (for example, a (meth)acrylic acid ester, a (meth)acrylamide, etc.), a structural unit derived from a diol compound, a structural unit derived from a diamine compound, and a structural unit derived from a diisocyanate compound. Here, the (meth)acrylic acid ester is a raw material for the (meth)acrylic resin, the diisocyanate compound is a raw material for the urethane resin or urea resin, the diol compound is a raw material for the urethane resin, and the diamine compound is a raw material for the urea resin.

[0124] As the structural unit (3), a structural unit derived from a (meth)acrylic acid ester is preferable, and the following structural unit (3A) is more preferable.

[0125] [ka]

[0126] In the structural unit (3A), R 11represents a hydrogen atom or a methyl group, R 12 , R 13 and R 14 each independently represents a hydrogen atom or a hydrocarbon group; L 11 represents a linking group, and the two *'s each represent a bonding position. 12 and L 11 may be linked to each other to form a ring, R 12 and R 13 may be linked to each other to form a ring.

[0127] In the structural unit (3A), R 11 represents a hydrogen atom or a methyl group, and is preferably a methyl group.

[0128] In the structural unit (3A), R 12 , R 13 and R 14 The number of carbon atoms in the hydrocarbon groups in each of the above is preferably 1 to 11, more preferably 1 to 6, and particularly preferably 1 to 3.

[0129] R 12 , R 13 and R 14 Examples of the hydrocarbon group in include an alkyl group, an alkenyl group, an aryl group, an alkylaryl group, and an aralkyl group. An alkyl group or an aryl group is preferable, and an alkyl group is more preferable.

[0130] R 12 , R 13 and R 14 The hydrocarbon group in the formula (I) may be substituted, in which case examples of the substituent include a hydroxy group and an alkoxy group.

[0131] R 13 and R 14 From the viewpoint of further suppressing stickiness of an image, each independently is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and even more preferably a hydrogen atom or a methyl group.

[0132] R13 and R 14 From the viewpoint of further suppressing stickiness of the image, it is particularly preferable that R is a hydrogen atom. 13 and R 14 The hydrogen atoms in R are all α-hydrogen atoms. 13 and R 14 In the case where all of the α-hydrogen atoms are hydrogen atoms, the amine structure has a large number of α-hydrogen atoms, and therefore the function of the amine structure (i.e., the function of suppressing the inhibition of radical polymerization by oxygen) is more effectively exhibited, and therefore, in this case, stickiness of the image is significantly suppressed.

[0133] R 12 From the viewpoint of further suppressing stickiness of an image, a hydrocarbon group is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, an alkyl group having 1 to 3 carbon atoms is even more preferable, a methyl group or an ethyl group is even more preferable, and a methyl group is particularly preferable. R 12 When is a hydrocarbon group (more preferred embodiments are as described above), R 12 The stickiness of the image is suppressed compared to when R is a hydrogen atom. 12 is a hydrocarbon group (as described above in a more preferred embodiment), the formation of NO radicals is suppressed, and as a result, the function of the amine structure (i.e., the function of suppressing the inhibition of radical polymerization by oxygen) is more effectively exhibited.

[0134] In the structural unit (3A), L 11 represents a linking group. L 11 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.

[0135] Specific examples of the structural unit (3) are as follows:

[0136] [ka]

[0137] [ka]

[0138] Resin T has an SP value of 16.5MPa 1 / 2 ~24.0MPa 1 / 2 It is preferable that the resin T contains a structural unit derived from a polymerizable monomer having an SP value of 16.5 MPa. 1 / 2 ~24.0MPa 1 / 2 When the ink contains a structural unit derived from a polymerizable monomer having the formula (I), at least one group selected from the group consisting of a fluorohydrocarbon group, a polysiloxane group, and a hydrocarbon group having 12 or more carbon atoms is oriented on the surface of the ink film, thereby improving the affinity with the laminate substrate.

[0139] The SP value of the polymerizable monomer contained in the resin T is measured in the same manner as the SP value of the polymerizable monomer A described above.

[0140] The weight average molecular weight (Mw) of the resin is preferably from 1000 to 70,000, and more preferably from 5000 to 50,000.

[0141] When the ink contains a resin, the content of the resin is preferably 0.1% to 10% by mass, more preferably 0.1% to 5.0% by mass, and even more preferably 0.1% to 2.0% by mass, relative to the total amount of the ink.

[0142] (solvent) The ink of the present disclosure does not contain a solvent, or if it does contain a solvent, the content of the solvent relative to the total amount of the ink is preferably 5% by mass or less (preferably 3% by mass or less, more preferably 2% by mass or less, and even more preferably 1% by mass or less). As used herein, the term "solvent" includes both organic and inorganic solvents (eg, water).

[0143] (Other Ingredients) The ink of the present disclosure 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.

[0144] (Ink properties) From the viewpoint of suitability for inkjet printing, the viscosity of the ink of the present disclosure 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.

[0145] 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.).

[0146] From the viewpoint of inkjet suitability, the surface tension of the ink of the present disclosure 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.

[0147] 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.).

[0148] [Ink set] The ink set of the present disclosure includes the ink of the present disclosure described above (i.e., active energy ray-curable ink). The ink set of the present disclosure may be a set consisting of two or more of the above-mentioned inks of the present disclosure, or may be a set including two or more of the above-mentioned inks of the present disclosure and one or more inks other than the inks of the present disclosure.

[0149] Since the ink set of the present disclosure contains the ink of the present disclosure, the ink set of the present disclosure provides effects similar to those provided by the ink of the present disclosure. The ink set of the present disclosure can record multi-color images.

[0150] Inks other than the inks of the present disclosure (hereinafter also referred to as "other inks") that may be included in the ink set of the present disclosure are not particularly limited, except that they are inks that do not satisfy at least one of the conditions for the inks of the present disclosure. The other inks may be inks that do not satisfy some of the conditions for inks in the present disclosure (for example, pigment type, Mp / D ratio, etc.) but satisfy the remaining conditions. In this case, for other ink components, reference can be made to the description of the ink in this disclosure as appropriate.

[0151] For example, the other ink may be an ink in which the vinyl chloride acetate-coated pigment in the ink of the present disclosure (i.e., a vinyl chloride acetate-coated pigment in which a specific magenta pigment or a specific yellow pigment is coated with a vinyl chloride acetate resin) is changed to another vinyl chloride acetate-coated pigment. The other vinyl chloride acetate-coated pigments referred to here are pigments other than the specific magenta pigment and the specific yellow pigment (hereinafter also referred to as "other pigments") that are coated with vinyl chloride acetate resin. In yet another embodiment of the other ink, the other pigment may be contained in the ink in an embodiment other than the embodiment in which it is contained in the other vinyl chloride acetate coated pigment.

[0152] As other pigments that can be contained in other inks, for example, pigments described in publicly known documents such as Japanese Patent No. 5901335 can be used without any particular restrictions.

[0153] Examples of the other pigments include known organic pigments and inorganic pigments, as well as resin particles dyed with a dye, commercially available pigment dispersions, and surface-treated pigments (for example, pigments dispersed in water, liquid organic compounds, insoluble resins, or the like as a dispersion medium, and pigments whose surfaces have been treated with resins, pigment derivatives, or the like). Other pigments include those described in, for example, "Dictionary of Pigments" edited by Seijiro Ito (published by Asakura Publishing Co., Ltd. in 2000), "Organic Pigments Handbook" written by Isao Hashimoto (published by Color Office Co., Ltd. in 2006), "Industrial Organic Pigments" edited by W. Herbst and K. Hunger (published by Wiley-VHC in 1992), JP-A Nos. 2002-12607, 2002-188025, 2003-26978, 2003-342503, and 2009-235370. Examples of organic pigments include yellow pigments, magenta pigments, cyan pigments, green pigments, orange pigments, brown pigments, violet pigments, black pigments, and white pigments.

[0154] Examples of yellow pigments as other pigments include monoazo pigments, disazo pigments, non-benzidine azo pigments, azo lake pigments, condensed azo pigments, acid dye lake pigments, basic dye lake pigments, anthraquinone pigments, quinophthalone pigments, pyrazolone pigments, acetolone pigments, metal complex pigments, nitroso pigments, metal complex azomethine pigments, benzimidazolone pigments, and isoindoline pigments (excluding specific yellow pigments). Of these, examples of pigments that can be preferably used include CI Pigment Yellow (hereinafter, abbreviated as PY) 1, PY3, PY12, PY13, PY14, PY16, PY17, PY18, PY24, PY60, PY74, PY83, PY93, PY94, PY95, PY97, PY100, PY109, PY115, PY117, PY120, PY128, PY133, PY139, PY151, PY153, PY154, PY166, PY167, PY173, PY175, PY180, PY181, PY194, PY213, PY214, and PY219. Among these, monoazo pigments, disazo pigments, benzimidazolone pigments such as acetolone pigments, and isoindoline pigments are preferred, with isoindoline pigments being most preferred.

[0155] Other magenta pigments include, for example, monoazo pigments, β-naphthol pigments, disazo pigments, azo lake pigments, condensed azo pigments, acid dye lake pigments, basic dye lake pigments, anthraquinone pigments, thioindigo pigments, perinone pigments, perylene pigments, quinacridone pigments, isoindolinone pigments, alizarin lake pigments, naphthrone pigments, naphthol AS lake pigments, naphthol AS pigments, and diketopyrrolopyrrole pigments (excluding specific magenta pigments). Among these, examples of pigments that can be preferably used include CI Pigment Red (hereinafter abbreviated as PR) 1, PR2, PR3, PR4, PR5, PR6, PR21, PR38, PR42, PR46, PR53:1, PR57:1, PR52:1, PR46, PR48, PR81, PR83, PR88, PR144, PR149, PR166, PR179, PR178, PR190, PR224, PR123, PR224, PR19, PR1 22, PR202, PR207, PR209, PR180, PR83, PR170, PR171, PR172, PR174, PR175, PR176, PR177, PR179, PR185, PR194, PR208, PR214, PR220, PR221, PR242, PR247, PR255, PR256, PR262, PR268, PR264, PR269, PR272, PR282, CI Pigment Violet 19, and the like. Among these, quinacridone pigments are preferred, and unsubstituted quinacridone, dimethylquinacridone, dichloroquinacridone, and mixed crystals thereof, such as PR42, PR122, PR202, PR209, PR282, and CI Pigment Violet (hereinafter abbreviated as PV) 19, are preferred.

[0156] Examples of other cyan pigments include disazo pigments, phthalocyanine pigments, acid dye lake pigments, basic dye lake pigments, anthraquinone pigments, and alkali blue pigments. Examples of pigments that can be preferably used include CI Pigment Blue (hereinafter abbreviated as PB) 1, PB15, PB15:1, PB15:2, PB15:3, PB15:4, PB15:6, PB16, PB18, PB24, PB25, PB60, PB79, etc. Among these, copper phthalocyanine pigments are preferred, with PB15, PB15:1, PB15:2, PB15:3, PB15:4, and PB15:6 being preferred.

[0157] Examples of other green pigments include phthalocyanine pigments, metal complex pigments, etc. Examples of pigments that can be preferably used include CI Pigment Green (hereinafter abbreviated as PG) 7, PG8, PG10, PG36, etc. The orange pigment as the other pigment is a pigment that exhibits an orange color, and examples thereof include isoindoline pigment, anthraquinone pigment, β-naphthol pigment, naphthol AS pigment, isoindolinone pigment, perinone pigment, disazo pigment, quinacridone pigment, acetolone pigment, pyrazolone pigment, etc. Examples of pigments that can be preferably used include CI Pigment Orange (hereinafter abbreviated as PO) 2, PO3, PO4, PO5, PO13, PO15, PO16, PO22, PO24, PO34, PO36, PO38, PO43, PO48, PO49, PO51, PO55, PO60, PO61, PO62, PO64, PO66, PO72, PO74, etc. Among them, isoindoline pigment is preferable. Other examples of brown pigments include naphthrone pigments such as PBr25 and PBr32. Examples of violet pigments as other pigments include naphthrone pigments, perylene pigments, naphthol AS pigments, dioxazine pigments, etc. Examples of pigments that can be preferably used include CI Pigment Violet (hereinafter abbreviated as PV) 13, PV17, PV23, PV29, PV32, PV37, PV50, etc. Examples of other black pigments include carbon black, indazine pigments, and perylene pigments, and more specifically, CI Pigment Black (hereinafter abbreviated as PBk) 1, PBk7, PBk31, and PBk32. Among these, quinacridone pigments such as PB15:3, 15:4, 15:6, PR122, PV19, and solid solutions containing these, PY74, 139, 120, 151, 154, 180, PBk7, and the like are preferred from the viewpoint of color development and light resistance. Other white pigments include, for example, zinc oxide (CI Pigment White) 4, titanium oxide (6), zinc sulfide (7), zirconium oxide (zirconium white) (12), calcium carbonate (18), aluminum oxide-silicon oxide (kaolin clay) (19), barium sulfate (21 or 22), aluminum hydroxide (alumina white) (23), silicon oxide (27), and calcium silicate (28). The inorganic particles used for the white pigment may be a single particle, or may be a composite particle with an oxide of silicon, aluminum, zirconium, titanium, or the like, an organometallic compound, or an organic compound. Among these, titanium oxide is preferably used. In addition to titanium oxide, other white pigments (which may be ones other than the above-mentioned white pigments) may be used in combination.

[0158] [Image Recording Method] The image recording method of the present disclosure is an image recording method in which the ink of the present disclosure or the ink set of the present disclosure is used. The image recording method of the present disclosure includes a step of applying an active energy ray-curable ink to an image recording substrate containing a polymer including vinyl chloride as a structural unit, by an inkjet recording method, to record an image. The image recording method of the present disclosure may include other steps as necessary.

[0159] The image recording method of the present disclosure uses the ink of the present disclosure, and therefore the image recording method of the present disclosure provides effects similar to those provided by the ink of the present disclosure.

[0160] <Image recording substrate> In the image recording method of the present disclosure, an image recording substrate containing a polymer containing vinyl chloride as a structural unit is used.

[0161] 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.

[0162] 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.

[0163] In particular, it is preferable that the image recording substrate contains polyvinyl chloride.

[0164] 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.

[0165] 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.

[0166] 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.

[0167] <Image recording process> The step of recording an image in the image recording method of the present disclosure (hereinafter also referred to as the "image recording step") is a step of applying the ink of the present disclosure to the above-mentioned image recording substrate by an inkjet recording method to record an image.

[0168] <Ink application> There are no particular limitations on the method of applying ink (i.e., ejection method) in the inkjet recording method, and any of the well-known methods may be used, 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.

[0169] 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.

[0170] 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.

[0171] 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.

[0172] 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.

[0173] 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.

[0174] 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.

[0175] <Drying> The image recording step preferably includes a step of drying the applied ink after the ink has been applied onto the image recording substrate.

[0176] The ink may be dried naturally, but is preferably dried by heating.

[0177] The heating temperature in the heat drying is preferably 30°C to 90°C, and more preferably 50°C to 80°C.

[0178] 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.).

[0179] 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.

[0180] <Active energy ray irradiation> 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.

[0181] 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.

[0182] Examples of the active energy ray include ultraviolet light, visible light, and electron beams. Among them, the active energy ray is preferably ultraviolet light.

[0183] 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.

[0184] 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.

[0185] 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.

[0186] [Method for producing laminate] The method for producing a laminate according to the present disclosure includes the steps of: obtaining an image recorded product including an image recording substrate and an image by the image recording method according to the present disclosure described above; a step of laminating a substrate for lamination containing a polymer containing vinyl chloride as a constituent unit onto an image in an image recording material to obtain a laminate; Includes. The method for producing a laminate according to the present disclosure may include other steps as necessary.

[0187] In the method for producing a laminated body of the present disclosure, the ink of the present disclosure is used in the process of obtaining an image recorded matter, and therefore the method for producing a laminated body of the present disclosure achieves effects similar to those achieved by the ink of the present disclosure.

[0188] <Step of Obtaining Image Recorded Material> The method for producing a laminate according to the present disclosure includes a step of obtaining an image recorded article comprising an image recording substrate and an image by the image recording method according to the present disclosure described above. For details of the process for obtaining an image recording material, the above-mentioned image recording method of the present disclosure can be appropriately referred to.

[0189] <Process for obtaining laminate> The method for producing a laminated body of the present disclosure includes a step of obtaining a laminated body by laminating a lamination substrate containing a polymer containing vinyl chloride as a constituent unit onto an image in an image recorded matter.

[0190] <Lamination substrate> The laminate substrate contains a polymer containing vinyl chloride as a structural unit. 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.

[0191] <Lamination> In this step, a laminate is obtained by laminating a substrate onto the image in the image recorded product. During lamination, the lamination substrate may be placed directly on the image, or may be placed via another layer such as an adhesive layer. However, in the method for producing a laminated body of the present disclosure, since the ink film (i.e., image) obtained by curing the ink has excellent thermal softening properties, it is preferable not to use other layers. 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 makes it possible to obtain a laminated body having a layered structure of substrate for image recording / image / substrate for lamination.

[0192] The lamination is preferably carried out by thermocompression bonding the image and the substrate for lamination at a temperature of 100° C. or higher. When the weighted average of the glass transition temperatures when all the polymerizable monomers contained in the ink are homopolymers is 0°C to 100°C, the image and the substrate for lamination are thermally fused by thermocompression bonding at a temperature of 100°C or higher, and the adhesion between the image and the substrate for lamination is further improved.

[0193] 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.

[0194] The temperature during thermocompression bonding refers to the surface temperature of the substrate to be laminated.

[0195] The pressure during thermocompression bonding is preferably 0.1 MPa to 20 MPa, and more preferably 0.5 MPa to 15 MPa.

[0196] The time for thermocompression bonding is, for example, 10 seconds to 500 seconds.

[0197] 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.

[0198] 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

[0199] 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.

[0200] [Examples 1 to 10 and 101 to 106, Comparative Examples 1 to 5 and 101 to 102] <Preparation of vinyl chloride-vinyl acetate-coated pigment> Methyl ethyl ketone (300 g) was placed in a 500 mL beaker, and then a pigment (50 g) and a pigment dispersing resin (Solsperse 39000, manufactured by Lubrizol Japan) (5 g) were added thereto, and the mixture was stirred at 2,500 rpm for 120 minutes using a mixer (Silverson L4R) to obtain pigment dispersion 1. To the obtained pigment dispersion 1, a vinyl chloride-vinyl acetate resin (i.e., a vinyl chloride-vinyl acetate copolymer resin) shown in Table 1 or Table 2 was added, and the mixture was stirred at 2500 rpm for 10 minutes using a mixer (Silverson L4R) to obtain pigment dispersion 2. The amount of the vinyl chloride-vinyl acetate resin used was adjusted so that the mass ratio of the vinyl chloride-vinyl acetate resin to the pigment was the value shown in Table 1 or Table 2. In the obtained pigment dispersion 2, the pigment is coated with the vinyl chloride acetate resin via the pigment dispersant 1 to form a vinyl chloride acetate-coated pigment. Next, the pigment dispersion 2 was heated to evaporate the methyl ethyl ketone, thereby obtaining a vinyl chloride acetate-coated pigment in a solid state.

[0201] In Comparative Example 3, a vinyl acetate-coated pigment (that is, a polyvinyl acetate-coated pigment) was obtained in the same manner as in the preparation of the vinyl chloride-vinyl acetate-coated pigment, except that vinyl acetate resin was used instead of vinyl chloride-vinyl acetate resin.

[0202] The components shown in Table 1 or Table 2 are as follows. -Pigment (magenta pigment)- ·PR254 … Pigment Red 254 ·PR146 … Pigment Red 146 ·PR150 (comparison) … Pigment Red 150 ·PR202 (Comparison ... Pigment Red 202 -Pigment (yellow pigment)- ·PY110 … Pigment Yellow 110 PY155: Pigment Yellow 155 PY138: Pigment Yellow 138 ·PY150 … Pigment Yellow 150 PY184: Pigment Yellow 184 PY185: Pigment Yellow 185 PY109 (comparison) ... Pigment Yellow 109 PY180 (comparison) ... Pigment Yellow 180 - Vinyl chloride-vinyl acetate copolymer resin (i.e., vinyl chloride-vinyl acetate copolymer resin) - · Vinyl chloride acetate resin 1: Vinnol H40 / 43 manufactured by Wacker Chemie AG. The vinyl chloride / vinyl acetate ratio (i.e., the mass ratio of vinyl chloride units to vinyl acetate units) is shown in Table 1. Mw 40,000-50,000. Tg 58°C. Vinyl chloride-vinyl acetate resin 2: Vinnol H40 / 50 manufactured by Wacker Chemie AG. The vinyl chloride / vinyl acetate ratio is shown in Table 1. Vinyl chloride-vinyl acetate resin 3: Solvin C manufactured by Nissin Chemical Industry Co., Ltd. The vinyl chloride / vinyl acetate ratio is shown in Table 1. Mw 75,000. Tg 70℃. Vinyl chloride-vinyl acetate resin 4: Solvine CNL manufactured by Nissin Chemical Industry Co., Ltd. The vinyl chloride / vinyl acetate ratio is shown in Table 1. Mw 35,000. Tg 69°C. - Vinyl acetate resin (i.e., polyvinyl acetate resin) (comparison resin) - · Vinyl acetate resin (for comparison) ... Polyvinyl acetate resin manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. Mw 90000.

[0203] The numerical value of each component in Table 1 indicates the content (mass %) of each component relative to the total amount of the finally obtained ink. A blank cell in Table 1 means that the corresponding ingredient is not contained.

[0204] <Ink Preparation> The vinyl chloride-vinyl acetate coated pigment or vinyl acetate coated resin shown in Table 1 or Table 2 was mixed with components other than the vinyl chloride-vinyl acetate coated pigment and vinyl acetate coating resin in the amounts (mass%) shown in Table 1 or Table 2 to prepare inks. Here, the pigment content (mass%) shown in Table 1 or Table 2 is the ink application amount of 6 g / m 2 The optical density (OD) of a solid image recorded in the above manner was adjusted to 0.8 for magenta and 0.6 for yellow.

[0205] Details of the components in Table 1 or Table 2 other than the vinyl acetate-coated pigment and the vinyl acetate-coated resin are as follows:

[0206] (Polymerizable monomer A) ·EOEOEA... Ethoxydiethylene glycol acrylate. Molecular weight 188. SP value 18.2MPa 1 / 2 The homopolymer Tg is -54℃. ·CHA...Cyclohexyl acrylate. Molecular weight 154. SP value 17.9MPa 1 / 2 The homopolymer Tg is 15℃.

[0207] (N-vinyl compounds) ·NVC: N-vinylcaprolactam. Molecular weight: 139. SP value: 19.2MPa 1 / 2 The homopolymer Tg is 90℃.

[0208] (Polymerization initiator) ITX: 2-isopropylthioxanthone Omni.819: Bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (product name: Omnirad 819, manufactured by IGM Resins BV) Omni.TPO-H: 2,4,6-trimethylbenzoyldiphenylphosphine oxide (product name: Omnirad TPO-H, manufactured by IGM Resins BV)

[0209] (Polymerization inhibitor) ·TEMPOL … 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl

[0210] (resin) Resin T1: The following resin T1 (weight average molecular weight 10,000) was synthesized with reference to the synthesis method in Example 8 of Japanese Patent No. 6,861,811.

[0211] [ka]

[0212] <Image recording> 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 10 seconds. The ink drying time in this case was adjusted by adjusting the conveying 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 the image recording substrate, thereby obtaining an image recording material having a laminated structure of the image recording substrate / image. The resolution in the image recording was 1200 dpi (dots per inch) x 600 dpi.

[0213] <Manufacturing of laminated bodies> A polyvinyl chloride base material (product name "SG800", manufactured by KN Trading Co., Ltd., thickness 75 μm) was prepared as a base material for lamination. This substrate for lamination was laminated onto the image in the image recorded above, to obtain a laminate having a layered structure of image recording substrate / image / substrate for lamination. The lamination was performed using a tabletop automatic transfer press (product name "AF-54TEN", Asahi Textile Machinery Co., Ltd.) by performing thermocompression bonding at a thermocompression temperature of 130°C, a pressure of 2 MPa for 300 seconds, and then at a pressure of 10 MPa for 60 seconds.

[0214] <Evaluation> The ink and the recorded image were evaluated as follows. The results are shown in Table 1 or Table 2.

[0215] (PVC laminate adhesion in the image) A 3.2 cm x 3.2 cm image recording sample was cut from the image recorded area of ​​the image recording. Also, a polyvinyl chloride (PVC) substrate (product name "SG800", manufactured by KN Trading Co., Ltd., thickness 75 μm) was prepared as a substrate for lamination, and a substrate sample for lamination measuring 3.2 cm×3.2 cm was cut out from this substrate for lamination. A 12 μm thick PET (polyethylene terephthalate) sheet was placed on the image 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 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 production of the laminated body described above.The PET sheet was removed from the resulting laminate to obtain a sample for evaluation. In the evaluation sample, in the area where the PET sheet was not placed before lamination, the image recording sample and the lamination substrate sample were bonded to each other, whereas in the evaluation sample, in the area where the PET sheet was placed before lamination, the image recording sample and the lamination substrate sample were not bonded to each other. 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).

[0216] Two evaluation samples were prepared as described above, and the tensile test was carried out on each of the two evaluation samples. The average peel strength for each of the two evaluation samples was calculated, and the PVC laminate adhesion was evaluated based on the obtained average peel strength and in accordance with the following evaluation criteria. In the following evaluation criteria, the most excellent rank for PVC laminate adhesion is "6".

[0217] -Evaluation criteria for PVC laminate adhesion- 6: The average peel strength was 9 N / cm or more. 5: The average peel strength was 7 N / cm or more and less than 9 N / cm. 4: The average peel strength was 3 N / cm or more and less than 7 N / cm. 3: The average peel strength was 2 N / cm or more and less than 3 N / cm. 2: The average peel strength was 1 N / cm or more and less than 2 N / cm. 1: The average peel strength was 0.1 N / cm or more and less than 1 N / cm. 0: The peel strength was less than 0.1 N / cm.

[0218] (Inkjet suitability) The inkjet suitability of each ink was evaluated as follows. Images were continuously recorded on 40 sheets of the recording paper under the same conditions as the above image recording, except that the polyvinyl chloride substrate as the image recording substrate was changed to an inkjet recording paper (Gasai, manufactured by Fujifilm Corporation). Hereinafter, the recording paper on which the image was recorded is referred to as the "inkjet suitability evaluation sample." The 40 sheets of the inkjet suitability evaluation samples were visually observed, and the number of sheets of the inkjet suitability evaluation samples on which nozzle clogs (i.e., image defects caused by poor nozzle ejection) were confirmed was counted. Based on these results, the inkjet suitability of the ink was evaluated according to the following evaluation criteria. In the following evaluation criteria, the most excellent rank for inkjet suitability is "5".

[0219] -Evaluation criteria for inkjet suitability- 5: Of the 40 samples, 0 samples showed nozzle dropout. 4: Of the 40 samples, one or two samples showed nozzle dropout. 3: Of the 40 samples, 3 or 4 samples showed nozzle dropout. 2: Of the 40 samples, 5 to 8 samples showed nozzle missing. 1: Of 40 samples, more than 9 samples had nozzle missing.

[0220] (Lightfastness of image) The image in the image recording was measured using a xenon weather meter XL75 manufactured by Suga Test Instruments Co., Ltd., with an irradiance of 40 W / m 2 An accelerated light fastness test was carried out under conditions of a black panel temperature of 35° C. and a humidity of 55% RH. Before the accelerated light fastness test and 350 hours after the start of the accelerated light fastness test, the CIE LAB values ​​(L*, a*, b*) of the image were measured using an X-rite eXact colorimeter manufactured by X-Rite under light source conditions of D50 and status-T, and the color difference ΔE was calculated based on the results. Based on the obtained color difference ΔE, the light fastness of the image was evaluated according to the following evaluation criteria. In the following evaluation criteria, the most excellent light fastness of the image is ranked as "5".

[0221] -Evaluation criteria for light resistance- 5: ΔE≦3 4:3<ΔE≦5 3:5<ΔE≦7 2:7<ΔE≦9 1:9<ΔE

[0222] [Table 1]

[0223] [Table 2]

[0224] As shown in Tables 1 and 2, the inks of each example were The pigment contains a resin-coated pigment (i.e., a vinyl chloride-vinyl acetate-coated pigment) in which the pigment is coated with a vinyl chloride-vinyl acetate resin (i.e., a vinyl chloride-vinyl acetate copolymer resin), and a polymerizable compound; the pigment is a magenta pigment or a yellow pigment, the magenta pigment is at least one selected from the group consisting of PR146 and PR254; the yellow pigment is at least one selected from the group consisting of PY110, PY155, PY185, PY138, PY150, and PY184; The mass ratio of the vinyl chloride acetate resin to the pigment is 0.25 to 4.00, The Mp / D ratio, which is the ratio of the pigment content Mp (mass %) relative to the total amount of ink to the specific gravity D of the pigment, is 2.00 or less. As shown in Tables 1 and 2, in each Example, the PVC laminate adhesion of the image, the inkjet suitability of the ink, and the light resistance of the image were excellent.

[0225] The results of the comparative examples compared to the respective examples were as follows. In Comparative Example 1, in which the content mass ratio of vinyl chloride acetate resin to pigment was less than 0.25, the adhesion of the image to the PVC laminate was reduced. In Comparative Example 2, in which the content mass ratio of vinyl chloride acetate resin to pigment was more than 4.00, the inkjet suitability of the ink was reduced. In Comparative Example 3, in which an ink containing vinyl acetate resin instead of vinyl chloride-vinyl acetate resin was used, the suitability of the image for PVC lamination decreased. In Comparative Example 4, in which the comparative magenta pigment PR150 was used, the lightfastness of the image was reduced. This is believed to be because the comparative magenta pigment PR150 has lower lightfastness (i.e., the pigment itself has lower lightfastness) than the examples PR146 and PR254. In Comparative Example 5, which used the comparative magenta pigment PR202 and had an Mp / D ratio of more than 2.00, the PVC laminate adhesion of the image and the inkjet suitability of the ink were reduced. The reason for this is thought to be that the comparative magenta pigment PR202 has poor color development compared to the examples PR146 and PR254, so in order to obtain the same image OD (0.8) as the examples, it became necessary to increase the pigment content (specifically, to make the Mp / D ratio greater than 2.00). In Comparative Example 101, in which the comparative yellow pigment PY109 was used, and Comparative Example 102, in which the comparative yellow pigment PY180 was used, the PVC laminate adhesion of the image and the inkjet suitability of the ink were reduced for the same reasons as in Comparative Example 5.

[0226] The results of Examples 1 and 3 to 5 show that when the PVC / Vinyl Acetate ratio (i.e., the mass ratio of vinyl chloride units to vinyl acetate units in the vinyl chloride-vinyl acetate copolymer resin) is 7.0 or less (Examples 1, 3, and 4), the inkjet suitability of the ink is further improved.

[0227] The results of Examples 1 and 6 show that when Resin T1 is contained (Example 6), the PVC lamination resistance is further improved. Here, resin T1 has a solubility parameter of 16.5 MPa. 1 / 2 ~24.0MPa 1 / 2and at least one group selected from the group consisting of a fluorohydrocarbon group, a polysiloxane group, and a hydrocarbon group having 12 or more carbon atoms.

[0228] Example 201 In the image recording, the magenta ink in Example 1, the yellow ink in Example 103, the cyan ink C1 described below, and the black ink Bk1 described below were applied in layered order to record a 4C solid image, and an image recorded material including an image recording substrate and a 4C solid image was obtained in the same manner as in Example 1, except that the magenta ink in Example 1, the yellow ink in Example 103, the cyan ink C1 described below, and the black ink Bk1 described below were applied in layered order to record a 4C solid image. Using the obtained image recorded matter, the PVC laminate adhesion of the image and the light resistance of the image were evaluated in the same manner as in Example 1. As a result, similarly to Example 1, the PVC laminate adhesion of the image was rated "5", and the light resistance of the image was rated "5".

[0229] <Cyan ink C1> Cyan ink C1 was prepared in the same manner as in the preparation of the magenta ink of Example 1, except that the vinyl chloride acetate-coated pigment (i.e., the vinyl chloride acetate-coated magenta pigment) used in the preparation of the magenta ink of Example 1 was changed to the vinyl chloride acetate-coated cyan pigment described below. With respect to the total amount of the cyan ink C1, the content of the cyan pigment (specifically, pigment blue 15:3) was 1.80 mass %, and the content of the vinyl chloride-vinyl acetate resin 1 was 1.62 mass %.

[0230] (vinyl chloride coated cyan pigment) A vinyl chloride-acetate-coated cyan pigment was obtained in the same manner as in the preparation of the vinyl chloride-acetate-coated pigment in Example 1 (i.e., the vinyl chloride-acetate-coated magenta pigment), except that the magenta pigment PR254 was changed to the cyan pigment Pigment Blue 15:3.

[0231] <Black ink Bk1> Black ink Bk1 was prepared in the same manner as in the preparation of the magenta ink of Example 1, except that the vinyl chloride acetate-coated pigment (i.e., the vinyl chloride acetate-coated magenta pigment) used in the preparation of the magenta ink of Example 1 was changed to the vinyl chloride acetate-coated black pigment described below. With respect to the total amount of the black ink Bk1, the content of the black pigment (that is, Pigment Black 7) was 2.80 mass %, and the content of the vinyl chloride-vinyl acetate resin 1 was 2.52 mass %.

[0232] (vinyl chloride coated black pigment) A vinyl chloride-acetate-coated black pigment was obtained in the same manner as in the preparation of the vinyl chloride-acetate-coated pigment in Example 1 (i.e., the vinyl chloride-acetate-coated magenta pigment), except that the magenta pigment PR254 was changed to the black pigment Pigment Black 7.

Claims

1. The present invention comprises a resin-coated pigment in which a pigment is coated with a vinyl chloride-vinyl acetate copolymer resin, and a polymerizable compound, the pigment is a magenta pigment or a yellow pigment, the magenta pigment is at least one selected from the group consisting of Pigment Red 146 and Pigment Red 254, the yellow pigment is at least one selected from the group consisting of Pigment Yellow 110, Pigment Yellow 155, Pigment Yellow 185, Pigment Yellow 138, Pigment Yellow 150, and Pigment Yellow 184; a content mass ratio of the vinyl chloride-vinyl acetate copolymer resin to the pigment is 0.25 to 4.00; where Mp is the content of the pigment relative to the total amount of the active energy ray-curable ink and D is the specific gravity of the pigment, the Mp / D ratio is 2.00 or less. Active energy ray curable ink.

2. 2. The active energy ray-curable ink according to claim 1, wherein the mass ratio of vinyl chloride units to vinyl acetate units in the vinyl chloride-vinyl acetate copolymer resin is 7.0 or less.

3. The polymerizable compound 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 according to claim 1 , comprising a polymerizable monomer A represented by the formula:

4. The composition further contains a resin T containing at least one group selected from the group consisting of a fluorohydrocarbon group, a polysiloxane group, and a hydrocarbon group having 12 or more carbon atoms, The resin T has a solubility parameter of 16.5 MPa. １／２ ~24.0MPa １／２ The polymerizable monomer is a structural unit derived from The actinic ray curable ink according to claim 1 .

5. An ink set comprising the active energy ray-curable ink according to any one of claims 1 to 4.

6. The active energy ray-curable ink according to any one of claims 1 to 4 is used, An image recording method comprising the step of applying the active energy ray-curable ink to an image recording substrate containing a polymer containing vinyl chloride as a structural unit, by an inkjet recording method, to record an image.

7. obtaining an image recorded matter comprising the image recording substrate and the image by the image recording method according to claim 6; a step of laminating a substrate for lamination containing a polymer containing vinyl chloride as a constituent unit onto the image in the image recorded product to obtain a laminate; A method for producing a laminate comprising the steps of:

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