Image recording method and laminate production method

Abstract

The present invention provides, for example, an image recording method comprising a step for recording an image by applying, by an inkjet recording method, an ink A and an ink B on a base material that is for recording an image and that contains a polymer containing vinyl chloride as a structural unit, wherein: the ink A contains a colorant and a polymerizable monomer A; the content of the polymerizable monomer A is not less than 80 mass% with respect to the total amount of the ink A; the ink B contains a polymerizable monomer B and either does not contain a colorant or has a colorant content of not more than 0.1 mass% with respect to the total amount of the ink B; the content of the polymerizable monomer B is not less than 80 mass% with respect to the total amount of the ink B; and the polymerizable monomers A and B are each a monofunctional polymerizable monomer having a solubility parameter of 17.0-21.3 MPa1 / 2.<sp / >

Description

Image recording method and method for manufacturing laminated body

[0001] This disclosure relates to an image recording method and a method for manufacturing a laminate.

[0002] Conventionally, technologies for recording images on resin substrates using inkjet inks have been proposed. As one example, a technology is known in which an image is recorded using inkjet ink, and then another substrate is laminated onto the image to produce a laminated body, and various studies have been conducted on this technology.

[0003] As a technique for recording an image on a substrate, for example, Japanese Patent Publication No. 2014-240153 describes an image forming method comprising, in this order, an image layer forming step of ejecting at least one colorant-containing active light-curable inkjet ink composition onto a recording medium to form an image layer, and a clear layer forming step of ejecting an active light-curable inkjet clear ink composition onto the image layer to form a clear layer, wherein the colorant-containing active light-curable inkjet ink composition contains 50% by mass or more of a monofunctional polymerizable compound in the polymerizable compound, and the active light-curable inkjet clear ink composition contains 50% by mass or more of a polyfunctional polymerizable compound in the polymerizable compound, and in the clear layer forming step, the active light-curable inkjet clear ink composition is scattered on the image layer to form a discontinuous clear layer. Furthermore, Japanese Patent Publication No. 2015-074204 describes a laminate label characterized by comprising: a printing medium; a first ink layer provided on the printed surface of a part of the printing medium; a second ink layer provided on the remaining area of ​​the printing medium excluding the part of the printing medium, which exhibits light-transmitting properties that allow the printed surface of the remaining area to be visible; and a laminate film affixed on the first ink layer and the second ink layer.

[0004] In lamination techniques such as those described in Japanese Patent Publication No. 2015-074204, a technique has been proposed in which an image recording substrate using a polymer containing polyvinyl chloride as a constituent unit is used as the base material, and an image is sandwiched between the substrates to obtain a laminate. When producing a laminate as in the above technique, it is practically required that the laminate strength of the resulting laminate (i.e., the peel strength between the image recording substrate and the image, and the peel strength between the laminating substrate and the image) be good. When a polymer containing polyvinyl chloride as a constituent unit is used in the manufacture of a laminate, improving its strength has been a challenge. In particular, when recording images with low color density, the laminate strength tends to decrease.

[0005] This disclosure has been made in view of these circumstances, and one embodiment of this disclosure aims to solve the problem of providing an image recording method and a method for manufacturing a laminate that provides excellent image adhesion (particularly the laminate strength when a laminate is manufactured) when using a substrate containing a polymer that includes vinyl chloride as a constituent unit, even when recording images with low color density.

[0006] This disclosure includes the following aspects: <1> A step of recording an image on an image recording substrate containing a polymer containing vinyl chloride as a constituent unit by applying ink A and ink B using an inkjet recording method, wherein ink A contains a colorant and polymerizable monomer A, and the content of polymerizable monomer A is 80% by mass or more of the total amount of ink A, ink B does not contain a colorant, or the content of a colorant relative to the total amount of ink B is 0.1% by mass or less, and contains polymerizable monomer B, and the content of polymerizable monomer B is 80% by mass or more of the total amount of ink B, and both polymerizable monomer A and polymerizable monomer B have a solubility parameter of 17.0 MPa １／２ ~21.3 MPa １／２Image recording method, wherein the image recording substrate comprises a first region and a second region, and the step of recording an image comprises the steps of applying ink A to the first region to record a first image and applying ink A and ink B to the second region to record a second image, as described in <1>. <3> Image recording method according to <2>, wherein the ratio of the amount of ink applied per unit area to the first region to the amount of ink applied per unit area to the second region is 0.8 to 1.25. <4> The amount of ink applied per unit area to the image recording substrate is 3 g / m². ２ ~15g / m ２ The image recording method described in any one of <1> to <3>. <5> The amount of ink A applied per unit area to the second region is 1 g / m ２ ~3g / m ２ The image recording method described in <2>. <6> The image recording method described in <2>, <3>, or <5>, wherein the step of recording a second image includes: applying ink A to a second region; irradiating the second region to which ink A has been applied with a first active energy ray to form an ink A film; applying ink B to the ink A film; and irradiating the second region to which ink B has been applied with a second active energy ray to record a second image. <7> The image recording method described in <6>, wherein the time from the time when ink A lands to the time when the first active energy ray is irradiated is 0.05 seconds to 0.5 seconds. <8> The exposure amount of the first active energy ray is 10 mJ / cm ２ ~100 mJ / cm ２The image recording method according to <6> or <7>. <9> The image recording method according to any one of <1> to <8>, wherein both polymerizable monomer A and polymerizable monomer B have one ethylenically unsaturated group and a molecular weight of 205 or less. <10> The image recording method according to any one of <1> to <9>, wherein the composition of 50% by mass or more of the polymerizable compound contained in ink A is the same as the composition of the polymerizable compound contained in ink B. <11> A method for producing a laminate, comprising the steps of: recording an image on an image recording substrate using the image recording method according to any one of <1> to <10>; and laminating a laminate substrate containing a polymer with vinyl chloride as a constituent unit onto the surface of the image.

[0007] According to one embodiment of the present disclosure, an image recording method and a method for manufacturing a laminate are provided that exhibit excellent image adhesion (particularly the laminate strength when a laminate is manufactured) when using a substrate containing a polymer that includes vinyl chloride as a constituent unit, even when recording images with low color density.

[0008] Figure 1 is a diagram illustrating the images recorded in the embodiment.

[0009] In this specification, numerical ranges indicated using "~" mean a range that includes the numbers before and after "~" as the minimum and maximum values, respectively. In numerical ranges described stepwise in this specification, the upper or lower limit stated in one numerical range may be replaced with the upper or lower limit of another numerical range described stepwise. Also, in numerical ranges described in this specification, the upper or lower limit stated in one numerical range may be replaced with the value shown in the example. In this specification, the amount of each component in a composition means the total amount of multiple substances present in the composition if there are multiple substances corresponding to each component in the composition, unless otherwise specified. In this specification, a combination of two or more preferred embodiments is a more preferred embodiment. In this specification, the term "process" is included not only in the sense of an independent process, but also in the sense of a process that cannot be clearly distinguished from other processes, as long as the intended purpose of that process is achieved.

[0010] In this specification, "image" means all films formed by applying ink, and "image recording" means forming an image (i.e., a film). Further, the concept of "image" in this specification also includes solid images. In this specification, the term "(meth)acryloyl group" is a concept encompassing both acryloyl group and methacryloyl group, the term "(meth)acrylate" is a concept encompassing both acrylate and methacrylate, and the term "(meth)acrylic" is a concept encompassing both acrylic and methacrylic.

[0011] [Image Recording Method] The image recording method of the present disclosure includes a step of recording an image by applying Ink A and Ink B by an inkjet recording method on an image recording substrate containing a polymer containing vinyl chloride as a constituent unit. Ink A contains a colorant and a polymerizable monomer A, and the content of the polymerizable monomer A is 80% by mass or more based on the total amount of Ink A. Ink B does not contain a colorant or the content of the colorant based on the total amount of Ink B is 0.1% by mass or less, and contains a polymerizable monomer B, and the content of the polymerizable monomer B is 80% by mass or more based on the total amount of Ink B. Both the polymerizable monomer A and the polymerizable monomer B are monofunctional polymerizable monomers having a solubility parameter of 17.0 MPa １／２ ~21.3 MPa １／２ thereof.

[0012] According to the image recording method of the present disclosure, when an image is recorded on an image recording substrate containing a polymer containing vinyl chloride as a constituent unit, the adhesion between the substrate and the image is excellent. And when a laminate substrate containing a polymer containing vinyl chloride as a constituent unit is laminated on the image recorded on the image recording substrate containing a polymer containing vinyl chloride as a constituent unit to obtain a laminate, the laminate strength of the obtained laminate (i.e., the peel strength between the image recording substrate and the image, and the peel strength between the laminate substrate and the image) is excellent. Particularly, even when recording an image with a low color density, a laminate having excellent adhesion between the substrate and the image and excellent laminate strength can be produced.

[0013] Typically, when recording images with high color density, a large amount of ink is applied to the image recording substrate, and when recording images with low color density, a small amount of ink is applied. When a large amount of ink is used, the polymerizable compounds contained in the ink penetrate the image recording substrate and remain largely in the ink film formed on the substrate. As the ink film hardens, polymerization of the polymerizable compounds progresses within the ink film, and the polymerized polymers become a binder. The colorants contained in the ink can exist in the image coated with the binder. Also, the binder tends to exist on the surface of the image. For example, when a laminate is obtained by laminating a laminating substrate onto the obtained image, the binder and the laminating substrate are heat-fused together, resulting in a laminate with excellent lamination strength. On the other hand, when a small amount of ink is used, the polymerizable compounds contained in the ink penetrate the image recording substrate and do not remain largely in the ink film formed on the substrate. As a result, the amount of binder present on the image surface decreases, and for example, when a laminating substrate is laminated onto the image, the thermal fusion with the laminating substrate may be insufficient, leading to a decrease in lamination strength.

[0014] In contrast, the image recording method of this disclosure uses two types of ink: ink A containing a coloring agent and ink B substantially free of a coloring agent. Therefore, even when a small amount of ink A containing a coloring agent is applied to record an image with low color density, the application of ink B substantially free of a coloring agent increases the overall amount of ink applied to the image recording substrate. Consequently, it is easier to ensure adhesion between the image recording substrate and the image, and even when a laminating substrate is laminated onto the obtained image, a laminate with excellent lamination strength can be produced.

[0015] Furthermore, both ink A and ink B have a solubility parameter of 17.0 MPa. １／２ ~21.3 MPa １／２Because it contains 80% by mass or more of monofunctional polymerizable monomers, it has high affinity for and easily penetrates image recording substrates containing polymers with vinyl chloride as a constituent unit. Therefore, it is possible to manufacture laminates with improved adhesion between the image recording substrate and the image, and with excellent lamination strength.

[0016] Japanese Patent Publication No. 2014-240153 and Japanese Patent Publication No. 2015-074204 do not contain any descriptions focusing on an image recording method using two types of ink containing specific components.

[0017] The image recording method described in this disclosure will be explained in more detail below.

[0018] <Image Recording Process> The image recording method of the present disclosure includes a step of applying ink A and ink B to an image recording substrate containing a polymer with vinyl chloride as a constituent unit using an inkjet recording method to record an image (hereinafter also referred to as the "image recording process").

[0019] (Image recording substrate) In the image recording process, ink is applied to the image recording substrate. This results in an image recording object that includes the image recording substrate and the image recorded on the image recording substrate.

[0020] The image recording substrate contains a polymer that includes vinyl chloride as a constituent unit.

[0021] A polymer containing vinyl chloride as a constituent unit may be a homopolymer of vinyl chloride (i.e., polyvinyl chloride), or it may be a copolymer containing vinyl chloride and other monomers other than vinyl chloride as constituent units.

[0022] Examples of copolymers containing vinyl chloride and other monomers other than vinyl chloride as constituent units 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.

[0023] In particular, the image recording substrate preferably contains polyvinyl chloride.

[0024] The image recording substrate may contain components other than polymers containing vinyl chloride as a constituent unit. Examples of other components include plasticizers, stabilizers, antioxidants, ultraviolet absorbers, binder resins, and colorants.

[0025] The image recording substrate may have a layer containing a polymer with 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 surface treatment layer is omitted. In other words, it is preferable that the surface of the image recording substrate to which the ink is applied contains a polymer with vinyl chloride as a constituent unit.

[0026] The thickness of the image recording substrate is not particularly limited, but is preferably 0.1 μm to 1000 μm, more preferably 0.1 μm to 800 μm, and even more preferably 1 μm to 500 μm.

[0027] In this disclosure, the thickness of the image recording substrate is measured using a micrometer (for example, a coolant-proof micrometer (manufactured by Mitutoyo Corporation)).

[0028] (Ink A) In the image recording process, an image is recorded using ink A. Ink A contains a coloring agent and polymerizable monomer A, and the content of polymerizable monomer A is 80% by mass or more of the total amount of ink A. Since ink A contains a coloring agent, it is a so-called colored ink.

[0029] Ink A may contain other polymerizable compounds besides polymerizable monomer A.

[0030] In this disclosure, "polymerizable compound" means a compound having a polymerizable group. Preferably, the polymerizable group is an ethylenically unsaturated group (i.e., a group containing an ethylenically double bond), and more preferably, a (meth)acryloyl group, an allyl group, a styryl group, or a vinyl group.

[0031] Polymerizable monomers are polymerizable compounds with a molecular weight of 1000 or less. Molecular weight is calculated based on the types and number of atoms that make up the compound.

[0032] A monofunctional polymerizable monomer refers to a polymerizable monomer that has only one polymerizable group, while a polyfunctional polymerizable monomer refers to a polymerizable monomer that has two or more polymerizable groups.

[0033] Examples of monofunctional polymerizable monomers include monofunctional (meth)acrylates, monofunctional (meth)acrylamides, monofunctional aromatic vinyl compounds, monofunctional vinyl ethers, and monofunctional N-vinyl compounds.

[0034] Examples of monofunctional (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, tert-octyl (meth)acrylate, isoamyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, and cyclohexyl (meth)acrylate. 4-n-butylcyclohexyl (meth)acrylate, 4-tert-butylcyclohexyl (meth)acrylate, bornyl (meth)acrylate, isobornyl (meth)acrylate, 2-ethylhexyl diglycol (meth)acrylate, butoxyethyl (meth)acrylate, 2-chloroethyl (meth)acrylate, 4-bromobutyl (meth)acrylate, cyanoethyl (meth)acrylate, benzyl (meth)acrylate, butoxymethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, 2-(2-methoxy Ethoxyethyl (meth)acrylate, 2-(2-butoxyethoxy)ethyl (meth)acrylate, 2,2,2-tetrafluoroethyl (meth)acrylate, 1H,1H,2H,2H-perfluorodecyl (meth)acrylate, 4-butylphenyl (meth)acrylate, phenyl (meth)acrylate, 2,4,5-tetramethylphenyl (meth)acrylate, 4-chlorophenyl (meth)acrylate, 2-phenoxymethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, glycidyl (meth)acrylate, Lysidyloxybutyl (meth)acrylate, glycidyloxyethyl (meth)acrylate, glycidyloxypropyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, cyclic trimethylolpropaneformal (meth)monoacrylate,Phenylglycidyl ether (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, diethylaminopropyl (meth)acrylate, trimethoxysilylpropyl (meth)acrylate, trimethylsilylpropyl (meth)acrylate, polyethylene oxide monomethyl ether (meth)acrylate, polyethylene oxide (meth)acrylate, polyethylene oxide monoalkyl ether (meth)acrylate, dipropylene glycol (meth)acrylate, polypropylene oxide monoalkyl ether (meth)acrylate, 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyhexahydrophthalic acid, 2-methacryloyloxyethyl-2-hydroxypropyl phthalate, ethoxydiethylene glycol (meth)acrylate, butoxydiethylene glycol (meth)acrylate, trifluoroethyl (meth)acrylate, perfluoro Cutyl ethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, ethylene oxide (EO) modified phenol (meth)acrylate, EO modified cresol (meth)acrylate, EO modified nonylphenol (meth)acrylate, propylene oxide (PO) modified nonylphenol (meth)acrylate, EO modified 2-ethylhexyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate Examples include dicyclopentanyl (meth)acrylate, (3-ethyl-3-oxetanylmethyl) (meth)acrylate, phenoxyethylene glycol (meth)acrylate, 2-carboxyethyl (meth)acrylate, 2-(meth)acryloyloxyethyl succinate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl acrylate, (3-ethyloxetan-3-yl)methyl acrylate, and 2-oxotetrahydrofuran-3-yl acrylate.

[0035] Examples of monofunctional (meth)acrylamides include (meth)acrylamide, N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide, N-propyl(meth)acrylamide, N-n-butyl(meth)acrylamide, N-t-butyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N-methylol(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, and (meth)acryloylmorpholin.

[0036] Examples of monofunctional aromatic vinyl compounds include styrene, dimethylstyrene, trimethylstyrene, isopropylstyrene, chloromethylstyrene, methoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, methyl vinylbenzoate, 3-methylstyrene, 4-methylstyrene, 3-ethylstyrene, 4-ethylstyrene, 3-propylstyrene, 4-propylstyrene, 3-butylstyrene, 4-butylstyrene, 3-hexylstyrene, 4-hexylstyrene, 3-octylstyrene, 4-octylstyrene, 3-(2-ethylhexyl)styrene, 4-(2-ethylhexyl)styrene, 4-t-butoxycarbonylstyrene, and 4-t-butoxystyrene.

[0037] Examples of monofunctional vinyl ethers include methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, n-butyl vinyl ether, t-butyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl ether, lauryl vinyl ether, cyclohexyl vinyl ether, cyclohexylmethyl vinyl ether, 4-methylcyclohexylmethyl vinyl ether, benzyl vinyl ether, dicyclopentenyl vinyl ether, 2-dicyclopentenoxyethyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, butoxyethyl vinyl ether, methoxyethoxyethyl vinyl ether, ethoxyethoxyethyl vinyl ether, methoxypolyethylene glycol vinyl ether, tetrahydrofurfuryl vinyl ether, 2-hydroxyethyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxymethylcyclohexylmethyl vinyl ether, diethylene glycol monovinyl ether, polyethylene glycol vinyl ether, chloroethyl vinyl ether, chlorobutyl vinyl ether, chloroethoxyethyl vinyl ether, phenylethyl vinyl ether, and phenoxypolyethylene glycol vinyl ether.

[0038] Examples of monofunctional N-vinyl compounds include N-vinyl-ε-caprolactam and N-vinylpyrrolidone.

[0039] Examples of polyfunctional polymerizable monomers include polyfunctional (meth)acrylates and polyfunctional vinyl ethers.

[0040] Examples of polyfunctional (meth)acrylates include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, hexanediol di(meth)acrylate, heptanediol di(meth)acrylate, and EO-modified neopentyl glycol di(meth)acrylate. Crylate, PO-modified neopentyl glycol di(meth)acrylate, EO-modified hexanediol di(meth)acrylate, PO-modified hexanediol di(meth)acrylate, octanediol di(meth)acrylate, nonanediol di(meth)acrylate, decanediol di(meth)acrylate, dodecanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, glycerin di(meth)acrylate, pentaerythritol di(meth)acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, tricyclodecanedimethanol di(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, propoxylated bisphenol A di(meth)acrylate, 9,Examples include 9-bis[4-(2-hydroxyethoxy)phenyl]ful orange (meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane EO-added tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tri(meth)acryloyloxyethoxytrimethylolpropane, glycerin polyglycidyl ether poly(meth)acrylate, and tris(2-acryloyloxyethyl) isocyanurate.

[0041] Examples of polyfunctional vinyl ethers include 1,4-butanediol divinyl ether, ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether, bisphenol A alkylene oxide divinyl ether, bisphenol F alkylene oxide divinyl ether, trimethylolethane trivinyl ether, trimethylolpropane trivinyl ether, and ditrimethylolpropane. Examples include trivinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexanyl ether, EO-added trimethylolpropane trivinyl ether, PO-added trimethylolpropane trivinyl ether, EO-added ditrimethylolpropane tetravinyl ether, PO-added ditrimethylolpropane tetravinyl ether, EO-added pentaerythritol tetravinyl ether, PO-added pentaerythritol tetravinyl ether, EO-added dipentaerythritol hexanyl ether, and PO-added dipentaerythritol hexanyl ether.

[0042] -Polymerizable monomer A- The polymerizable monomer A contained in ink A may be one type or two or more types. Polymerizable monomer A has a solubility parameter (hereinafter also referred to as "SP value") of 17.0 MPa. １／２ ~21.3 MPa １／２ It is a monofunctional polymerizable monomer. As polymerizable monomer A, for example, among the above monofunctional polymerizable monomers, it has an SP value of 17.0 MPa １／２ ~21.3 MPa １／２ Examples of compounds include the following.

[0043] Because the solubility parameter of polymerizable monomer A is within the above range, ink A has high affinity for the image recording substrate and excellent solubility. Polymerization proceeds with a portion of ink A dissolved in the image recording substrate, improving the adhesion between the image recording substrate and the image, and consequently improving the laminate strength.

[0044] From the above perspective, the SP value of polymerizable monomer A is 18.0 MPa. １／２ ~19.5 MPa １／２ It is preferable that this be the case.

[0045] In this disclosure, the SP value of polymerizable monomer A refers to the Hansen solubility parameter. The Hansen solubility parameter is a representation in three dimensions of the solubility parameter introduced by Hildebrand, divided into three components: a dispersion term δd, a polarity term δp, and a hydrogen bonding term δh. The same applies to the SP value of polymerizable monomer B, which will be described later.

[0046] The SP value δ of polymerizable monomer A shall be the value calculated using the following formula A: SP value (δ) [MPa] １／２ ] = (δd ２ +δp ２ +δh ２ ) １／２ …(A)

[0047] The dispersion term δd, polarity term δp, and hydrogen bonding term δh are calculated using the HSPiP (version 4.1.07) software.

[0048] Examples of polymerizable monomer A include the following compounds: N-vinyl-ε-caprolactam (SP value: 19.2 MPa) １／２ ) Cyclohexyl acrylate (SP value: 17.9 MPa) １／２ ) Ethoxydiethylene glycol acrylate (SP value: 18.2 MPa) １／２ ) Tetrahydrofurfurylacrylate (SP value: 18.8 MPa) １／２ ) Cyclic trimethylolpropaneform monoacrylate (SP value: 19.0 MPa) １／２ (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl acrylate (SP value: 18.2 MPa) １／２ (3-ethyloxetan-3-yl)methyl acrylate (SP value: 18.6 MPa) １／２ ) 2-oxotetrahydrofuran-3-yl acrylate (SP value: 21.2 MPa) １／２ )

[0049] Polymerizable monomer A preferably has one ethylenically unsaturated group and a molecular weight of 205 or less.

[0050] A molecular weight of 205 or less for polymerizable monomer A indicates a relatively low molecular weight. A molecular weight of 205 or less for polymerizable monomer A makes ink A more easily soluble in the image recording substrate. As a result, the adhesion between the image recording substrate and the ink film improves, and the lamination strength is enhanced. Furthermore, a molecular weight of 205 or less for polymerizable monomer A shortens the distance between crosslinking points, increasing the density of the ink film and thus improving the lamination strength.

[0051] The lower limit of the molecular weight of polymerizable monomer A, which has a molecular weight of 205 or less, is not particularly limited, but for example, it is 100.

[0052] The content of polymerizable monomer A is 80% by mass or more, preferably 80% to 90% by mass, relative to the total amount of ink A. When the content of polymerizable monomer A is 80% by mass or more, high lamination strength can be obtained.

[0053] Ink A may contain other polymerizable compounds besides polymerizable monomer A.

[0054] Other polymerizable compounds may be monofunctional polymerizable compounds or polyfunctional polymerizable compounds.

[0055] -Coloring Agent- Ink A contains at least one coloring agent. There are no particular restrictions on the coloring agent, and any known coloring material such as pigments, water-soluble dyes, and disperse dyes can be arbitrarily selected and used. Among these, pigments are preferred as the coloring agent because they have excellent weather resistance and rich color reproduction.

[0056] The type of pigment is not particularly limited and may be either an organic pigment or an inorganic pigment. Examples of pigments include those described in "Dictionary of Pigments" edited by Seijiro Ito (published in 2000), "Industrial Organic Pigments" by W. Herbst and K. Hunger, Japanese Patent Publication No. 2002-12607, Japanese Patent Publication No. 2002-188025, Japanese Patent Publication No. 2003-26978, and Japanese Patent Publication No. 2003-342503.

[0057] If ink A contains a pigment as a coloring agent, it may also contain a pigment dispersant as needed.

[0058] Regarding colorants such as pigments and pigment dispersants, prior art documents such as paragraphs 0152 to 0158 of Japanese Patent Publication No. 2011-225848 and paragraphs 0132 to 0149 of Japanese Patent Publication No. 2009-209352 can be appropriately referred to.

[0059] If ink A contains a coloring agent, the amount of coloring agent is preferably 0.1% to 20% by mass, and more preferably 0.5% to 10% by mass, relative to the total amount of ink A.

[0060] -Other Components- Ink A may contain other components not listed above. Examples of other components include photopolymerization initiators, polymerization inhibitors, sensitizers, resins, ultraviolet absorbers, antioxidants, fade inhibitors, conductive salts, etc. For other components, publicly available documents such as Japanese Patent Publication No. 2011-225848 and Japanese Patent Publication No. 2009-209352 can be appropriately referred to.

[0061] - Physical properties of ink A - From the viewpoint of dispensing performance, the viscosity of ink A is preferably 4 mPa·s to 50 mPa·s, more preferably 4 mPa·s to 30 mPa·s, and even more preferably 4 mPa·s to 15 mPa·s.

[0062] Viscosity refers to the value measured at 25°C. Viscosity is measured using a viscometer, for example, a VISCOMETER RE-85L (manufactured by Toki Sangyo Co., Ltd.).

[0063] From the viewpoint of ejection performance, the surface tension of ink A 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.

[0064] Surface tension refers to the value measured at 25°C. Surface tension is measured using a surface tension meter, for example, the "Automatic Surface Tensionometer CBVP-Z (manufactured by Kyowa Interface Science Co., Ltd.)".

[0065] (Ink B) In the image recording process, an image is recorded using ink B. Ink B does not contain a colorant, or the colorant content relative to the total amount of ink B is 0.1% by mass or less, and it contains polymerizable monomer B, with the polymerizable monomer B content being 80% by mass or more relative to the total amount of ink B. The polymerizable monomer B has an SP value of 17.0 MPa. １／２ ~21.3 MPa １／２ It is a monofunctional polymerizable monomer.

[0066] If ink B does not contain a colorant, or if the colorant content relative to the total amount of ink B is 0.1% by mass or less, it means that ink B is substantially colorant-free. Ink B is a so-called clear ink. If ink B contains a colorant, it is preferable that the colorant content is 0.05% by mass or less.

[0067] Ink B differs from Ink A in that it substantially does not contain colorants. With respect to components other than colorants, the preferred embodiments of each component of Ink A are the same as the preferred embodiments of each component of Ink B.

[0068] The polymerizable monomer B contained in ink B may be one type or two or more types. The preferred embodiment of polymerizable monomer B contained in ink B is the same as the preferred embodiment of polymerizable monomer A contained in ink A. Specifically, the SP value of polymerizable monomer B is 18.0 MPa. １／２ ~19.5 MPa １／２ Preferably, the polymerizable monomer B has one ethylenically unsaturated group and a molecular weight of 205 or less.

[0069] The content of polymerizable monomer B is 80% by mass or more, and preferably 85% to 95% by mass, relative to the total amount of ink B. When the content of polymerizable monomer B is 80% by mass or more, high lamination strength can be obtained.

[0070] Furthermore, from the viewpoint of affinity between ink A and ink B, it is preferable that the composition of 50% by mass or more of the polymerizable compounds contained in ink A is the same as the composition of the polymerizable compounds contained in ink B. Whether or not the composition of the polymerizable compounds contained in ink A and the polymerizable compounds contained in ink B is the same at 50% by mass or more can be determined by analysis using high-performance liquid chromatography.

[0071] The proportion of matching compositions is preferably 50% by mass or more, and more preferably 80% by mass or more. The proportion of matching compositions may also be 100% by mass.

[0072] (Ink Application) In the image recording process, ink A and ink B are applied using an inkjet recording method. Hereafter, matters common to ink A and ink B will simply be described as "ink".

[0073] There are no particular restrictions on the ink ejection method in an inkjet recording system, and any known method may be used, such as a charge control method that ejects ink using electrostatic attraction, a drop-on-demand method (pressure pulse method) that utilizes the vibration pressure of a piezoelectric element, an acoustic inkjet method that converts an electrical signal into an acoustic beam and irradiates the ink to eject ink using the radiation pressure, and a thermal inkjet (bubble jet®) method that heats the ink to form bubbles and utilizes the resulting pressure.

[0074] As an inkjet recording method, the method described in Japanese Patent Publication No. 54-59936 is particularly effective, as it involves the ink undergoing a rapid volume change due to the action of thermal energy, and the force resulting from this state change ejects the ink from the nozzle. As an inkjet recording method, the method described in paragraphs 0093 to 0105 of Japanese Patent Publication No. 2003-306623 can also be applied.

[0075] Ink is applied to the image recording substrate using an inkjet recording method by ejecting ink from the nozzles of the inkjet head.

[0076] Inkjet head systems include the shuttle system, which uses a short serial head to scan the recording medium in the width direction while recording, and the line system, which uses a line head in which recording elements are arranged to cover the entire width of one side of the recording medium.

[0077] In the line method, image recording can be performed across the entire surface of the recording medium by scanning it in a direction intersecting the arrangement direction of the recording elements. The line method eliminates the need for a transport system such as a carriage that scans the short head, which is required in the shuttle method. Furthermore, compared to the shuttle method, the line method eliminates the need for complex scanning control of the carriage movement and the recording medium, as only the recording medium moves. For this reason, the line method enables faster image recording compared to the shuttle method.

[0078] Ink application is preferably carried out using an inkjet head having a resolution of 300 dpi or higher (more preferably 600 dpi or higher, and even more preferably 800 dpi or higher). Here, dpi is an abbreviation for dots per inch, and 1 inch is equal to 2.54 cm.

[0079] From the viewpoint of obtaining a high-definition image, the amount of ink droplets ejected from the nozzle of the inkjet head is preferably 1 pL (picoliters) to 10 pL, and more preferably 1.5 pL to 6 pL.

[0080] From the viewpoint of recording images with varying shades, it is preferable that the image recording substrate includes a region for recording images with high color density (first region) and a region for recording images with low color density (second region). The image recording process preferably includes a step of applying ink A to the first region to record a first image, and a step of applying ink A and ink B to the second region to record a second image.

[0081] Using ink A (i.e., colored ink), a first image (i.e., an image with high color density) can be recorded. By using ink A (i.e., colored ink) and ink B (i.e., clear ink) in combination, a second image (i.e., an image with low color density) can be recorded. Because it exhibits excellent lamination strength in images with low color density, it exhibits excellent lamination strength throughout the entire image with varying shades.

[0082] The ratio of the amount of ink applied per unit area to the first region to the amount of ink applied per unit area to the second region is preferably 0.8 to 1.25, and more preferably 0.9 to 1.1.

[0083] By adjusting the above ratio to the above range, the lamination strength becomes uniform between images with high and low color density, resulting in superior lamination strength across the entire image with varying shades.

[0084] The amount of ink applied per unit area to the second region is calculated based on the sum of the amounts of ink A and ink B applied to the second region.

[0085] The amount of ink applied is calculated, for example, using one of the following methods 1 to 3. Method 1 involves applying a desired halftone density (the percentage of the total area where the image is recorded) to the image recording substrate, 1 m² ２ The image is recorded over a certain area. The mass of the substrate before image recording and the mass of the substrate after image recording are measured, and the amount of ink applied is calculated from the mass difference. The amount of ink applied can be arbitrarily changed by setting the halftone density and adjusting the ink ejection amount of the device. Alternatively, as method 2, the image recorded on the image recording substrate is cut in the thickness direction. The thickness of the image is measured from the resulting cross-section. The amount of ink applied is calculated based on the thickness of the image and the specific gravity of the ink. Furthermore, as method 3, the amount of ink applied is calculated based on the setting values ​​related to image recording of the inkjet recording device when performing image recording using an inkjet recording device.

[0086] The amount of ink applied per unit area to the image recording substrate is 3 g / m². ２ ~15g / m ２ Preferably, the amount of ink applied per unit area to the first region is 3 g / m². ２ ~15g / m ２ It is preferable that the amount of ink applied per unit area to the second region be 3 g / m². ２ ~15g / m ２ It is preferable that this be the case.

[0087] The amount of ink applied per unit area to the image recording substrate is 3 g / m². ２ As a result, the ink penetrates the image recording substrate, and uneven distribution of the colorant on the image surface is suppressed. Consequently, the lamination strength is improved. The amount of ink applied per unit area to the image recording substrate is 15 g / m². ２ The following factors allow the ink to harden more easily and improve the lamination strength.

[0088] From the above perspective, the amount of ink applied per unit area to the image recording substrate is 5 g / m². ２ ~8g / m ２ It is preferable that it be so.

[0089] The amount of ink A applied per unit area to the second region is 1 g / m². ２ ~3g / m ２ This may also be the case. Conventionally, 1 g / m² is applied to the image recording substrate. ２ ~3g / m ２ When ink A was applied at a certain amount, the lamination strength tended to decrease significantly. However, by applying ink B together with ink A, the application amount of ink A was reduced to 1 g / m². ２ ~3g / m ２ Even so, it exhibits excellent lamination strength. In other words, a laminate with excellent lamination strength can be obtained regardless of the amount of ink A applied. The density, color tone, etc., of the resulting image can be controlled by the amount of ink A (i.e., colored ink) applied. From the standpoint of ensuring lamination strength, the amount of ink A applied can be arbitrarily adjusted, and a laminate containing an image with excellent gradation can be obtained.

[0090] The amount of ink B applied per unit area to the second region is 1 g / m². ２ ~8g / m ２ Preferably, it is 2 g / m ２ ~6g / m ２ It is preferable that it be so.

[0091] The image recording step preferably further includes a step of irradiating the applied ink with active energy rays.

[0092] By irradiating ink applied to an image recording substrate with active energy rays, polymerization reactions of polymerizable compounds contained in the ink proceed. This allows for image fixation and improvement of image hardness and other properties.

[0093] Examples of active energy rays include gamma rays, beta rays, electron beams, ultraviolet rays, and visible light.

[0094] The irradiation conditions and basic irradiation method for the active energy rays can be those disclosed in Japanese Patent Publication No. 60-132767. Specifically, the irradiation method is preferably one in which light sources are provided on both sides of the head unit including the ink ejection device, and the head unit and light sources are scanned in a so-called shuttle manner, or one in which irradiation is performed by a separate light source that does not involve driving.

[0095] Discharge lamps and laser light sources (gas lasers and solid-state lasers, etc.) are the main light sources used. Examples of widely known discharge lamps include mercury lamps, metal halide lamps, and ultraviolet fluorescent lamps. Semiconductor light sources such as UV-LEDs (light-emitting diodes) and UV-LDs (laser diodes) are also promising as light sources for ultraviolet irradiation due to their small size, long lifespan, high efficiency, and low cost. Among these, metal halide lamps, high-pressure mercury lamps, medium-pressure mercury lamps, low-pressure mercury lamps, or UV-LEDs are preferred as light sources for ultraviolet irradiation.

[0096] When recording a first image and a second image, the first image is recorded using ink A, and the second image is recorded using ink A and ink B. In the process of recording the second image, the order in which ink A and ink B are applied is not particularly limited. Ink B may be applied after ink A, or ink A may be applied after ink B. From the viewpoint of further improving the lamination strength, it is preferable to apply ink B after ink A.

[0097] In the image recording process, a preferred embodiment of the process for recording a second image is as follows:

[0098] The process of recording a second image preferably includes the steps of: applying ink A to a second region; irradiating the second region to which ink A has been applied with a first active energy ray to form an ink A film; applying ink B to the ink A film; and irradiating the second region to which ink B has been applied with a second active energy ray to record a second image.

[0099] By applying ink B after applying ink A, it is possible to suppress the uneven distribution of the colorant contained in ink A on the image surface. In particular, the binder (polymerized polymer of polymerizable compound) is more likely to be present on the image surface, and the colorant contained in ink A can exist in the image coated with the binder. Therefore, when a laminate substrate is laminated onto the obtained image to obtain a laminate, the binder and the laminate substrate are heat-fused together, improving the lamination strength.

[0100] The time from the moment ink A hits the surface until the first active energy ray is irradiated is preferably 0.05 seconds to 0.5 seconds, and more preferably 0.08 seconds to 0.3 seconds. When the above time is 0.05 seconds or more, ink A penetrates the image recording substrate appropriately, and then the polymerizable monomer A contained in ink A polymerizes, improving the adhesion between the image recording substrate and the image. When the above time is 0.5 seconds or less, ink A does not penetrate the image recording substrate too much, and the uneven distribution of the colorant contained in ink A on the image surface can be suppressed. As a result, the lamination strength is improved.

[0101] The exposure dose of the first active energy ray irradiated onto the second region coated with ink A is 10 mJ / cm². ２ ~100 mJ / cm ２ Preferably, it is 20 mJ / cm ２ ~80 mJ / cm ２ It is more preferable that the exposure dose of the first active energy ray be 10 mJ / cm². ２ As a result, the uneven distribution of colorants on the image surface caused by excessive ink penetration into the image recording substrate can be suppressed. Consequently, excellent laminate strength is achieved. The exposure dose of the first active energy ray was 100 mJ / cm². ２ As a result of the following, the ink penetrates the image recording substrate appropriately, resulting in good adhesion between the image recording substrate and the image, and excellent lamination strength.

[0102] The exposure dose of the second active energy ray irradiated onto the second region coated with ink B is 10 mJ / cm². ２~100 mJ / cm ２ Preferably, it is 20 mJ / cm ２ ~80 mJ / cm ２ It is preferable that it be so.

[0103] The second region to which ink B is applied may be irradiated with a second active energy ray in two stages. The first stage of exposure is also called pinning exposure, and the second stage of exposure is also called main exposure.

[0104] The exposure dose for the first stage of the second active energy ray is 10 mJ / cm². ２ ~100 mJ / cm ２ Preferably, it is 20 mJ / cm ２ ~60 mJ / cm ２ It is preferable that it be so.

[0105] The exposure dose for the second stage of the second active energy ray is 50 mJ / cm², from the perspective of completely curing the ink. ２ ~1000mJ / cm ２ Preferably, it is 200 mJ / cm ２ ~800 mJ / cm ２ It is preferable that it be so.

[0106] [Method for manufacturing a laminated body] The method for manufacturing a laminated body according to the present disclosure includes the steps of recording an image on an image recording substrate using the image recording method described above, and directly laminating a laminate substrate containing a polymer with vinyl chloride as a constituent unit onto the image (hereinafter also referred to as the "laminating step").

[0107] The details of the process for recording an image on an image recording substrate using an image recording method are as described above.

[0108] (Laminating Substrate) The laminating substrate contains a polymer that includes vinyl chloride as a constituent unit. The preferred embodiment of the laminating substrate is the same as the preferred embodiment of the image recording substrate.

[0109] (Laminating Method) In the laminating process, the laminating substrate is directly laminated (i.e., heat-pressed) onto the image recorded on the image recording substrate in the image recording method. That is, in the laminating process, the image recording object, which includes the image recording substrate and the image, and the laminating substrate are laminated together with the image and the laminating substrate in contact. This results in a laminated body having a layered structure of laminating substrate / image / image recording substrate.

[0110] From the viewpoint of suppressing thermal decomposition, the upper limit of the lamination temperature (i.e., the heat-sealing temperature) is preferably 200°C, more preferably 160°C, and even more preferably 140°C.

[0111] Note that the heat-pressing temperature refers to the surface temperature of the substrate used for lamination.

[0112] The lamination pressure (i.e., the heat-sealing pressure) is preferably 0.1 MPa to 20 MPa, and more preferably 0.5 MPa to 15 MPa.

[0113] The lamination time (i.e., the heat-pressing time) is, for example, between 10 and 500 seconds.

[0114] The laminate obtained by the manufacturing method of the laminate according to this disclosure can be used, for example, as flooring or walling material for transportation equipment (railways, buses, etc.) or as flooring or walling material for buildings.

[0115] The present disclosure will be further described below with reference to examples, but the present disclosure is not limited to the following examples unless it exceeds the spirit of the disclosure.

[0116] <Preparation of Cyanide Pigment Dispersion> Mix the following components and stir for 20 minutes at 5000 rpm at 25°C using a mixer (Silverson L4R) to obtain a preliminary dispersion. Place the obtained preliminary dispersion into a disperser motor mill M50 (Eiger), and disperse using zirconia beads with a diameter of 0.65 mm at a peripheral speed of 9 m / s for 4 hours to obtain a cyanide pigment dispersion.

[0117] • Cyan pigment: Pigment blue 15:4 (product name "HELIOGEN BLUE D 7110 F", manufactured by DIC Corporation) ... 30 parts by mass • Dispersant 1: Product name "Solsperse 32000", manufactured by Lubrizol Corporation ... 10 parts by mass • PEA: Phenoxyethyl acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd. ... 59 parts by mass • Polymerization inhibitor: Product name "FLORSTAB UV12", manufactured by Kromachem Corporation (a mixture of the active ingredient N-nitroso-N-phenylhydroxylamine aluminum salt and PEA, with a mixing ratio of 1:9) ... 1 part by mass

[0118] <Preparation of Inks A1-A7 and B1-B9> The above cyan pigment dispersion was mixed with other components to prepare each ink so that the content (mass%) of each component listed in Tables 1 and 2 was as indicated in Tables 1 and 2.

[0119] Details of each component in Tables 1 and 2 are as follows: Both polymerizable monomer A and polymerizable monomer B have an SP value of 17.0 MPa. １／２ ~21.3 MPa １／２ It is a monofunctional polymerizable monomer. Other polymerizable compounds have an SP value of 17.0 MPa. １／２ ~21.3 MPa １／２ It is a polymerizable compound that does not fall under the category of monofunctional polymerizable monomers.

[0120] (Polymerizable monomer A, polymerizable monomer B) ・NVC: N-vinyl-ε-caprolactam ・CHA: Cyclohexyl acrylate (Product name "Viscote #155", manufactured by Osaka Organic Chemical Industry Co., Ltd.) ・EOEOEA: Ethoxydiethylene glycol acrylate (Product name "Viscote #190", manufactured by Osaka Organic Chemical Industry Co., Ltd.) ・PEA: Phenoxyethyl acrylate (Product name "Viscote #192", manufactured by Osaka Organic Chemical Industry Co., Ltd.) ・CTFA: Cyclic trimethylolpropane formal monoacrylate (Product name "Viscote #200", manufactured by Osaka Organic Chemical Industry Co., Ltd.) ・THFA: Tetrahydrofurfuryl acrylate (Product name "Viscote #150", manufactured by Osaka Organic Chemical Industry Co., Ltd.) ・FA512-AS: Dicyclopentenyloxyethyl acrylate (Product name "FA512-AS", manufactured by Resonaq) • Medol-10: (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl acrylate (product name "Medol-10", manufactured by Osaka Organic Chemical Industry Co., Ltd.)

[0121] (Other polymerizable compounds) ・ACMO: Acryloylmorpholine (KJ Chemicals) ・TMCHA: 3,3,5-trimethylcyclohexyl acrylate (product name "Viscote #196", manufactured by Osaka Organic Chemical Industry Co., Ltd.) ・Oligomer B: product name "Shiko UV3300", manufactured by Mitsubishi Chemical Corporation ・Urethane acrylate: product name "Ebecryl 4101", manufactured by Daicel Ornex Co., Ltd.

[0122] (Polymerization inhibitors) ・TEMPOL: 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, manufactured by Tokyo Chemical Industry Co., Ltd. ・UV-12: Product name "FLORSTAB UV12", manufactured by Kromachem

[0123] (Sensitizer) DETX: 2,4-diethylthioxanthone

[0124] (Photopolymerization initiator) ・Omni. 819: Bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (product name "Omnirad 819", manufactured by IGM Resins B.V.)

[0125] (Resin) ・Polymer A: A polymer manufactured by the following manufacturing method.

[0126] (Coloring agent) Cyan pigment: Pigment Blue 15:4 (Product name "HELIOGEN BLUE D 7110 F", manufactured by DIC Corporation)

[0127] (Dispersant) • Dispersant 1: Product name "Solsperse 32000", manufactured by Lubrizol.

[0128] -Method for producing Polymer A- 1-propanol (203.7 g) and N-vinyl-ε-caprolactam (NVC) (127.5 g) are weighed into a 1 L three-necked flask equipped with a condenser, and heated and stirred at 75°C under a nitrogen stream. Separately, a mixed solution prepared by mixing 1-propanol (135.8 g), hydroxyethyl methacrylate (HEMA) (7.5 g), X-22-174ASX (methacrylate-modified silicone) (manufactured by Shin-Etsu Chemical Co., Ltd.) (15.0 g), and V-601 (2,2'-azobis(isobutyrate)dimethyl; polymerization initiator manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) (10.5 g) is added dropwise to the flask over 3 hours. After the dropwise addition is complete, the mixture is stirred for a further 1 hour at 75°C, then the temperature is raised to 90°C and the reaction is continued for a further 3 hours. The mixture is allowed to cool to room temperature (25°C; the same applies hereafter). Then, phenoxyethyl acrylate (PEA) (350.0 g) and 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPOL) (3.5 g) are added, and 1-propanol is removed by distillation under reduced pressure conditions of 80°C / 50 hPa to obtain a 30% by mass phenoxyethyl acrylate (PEA) solution of polymer A (a copolymer of NVC / HEMA / one-terminated methacrylic-modified silicone = 85 / 5 / 10 (mass ratio)). The weight-average molecular weight of polymer A is 5000.

[0129] [Examples 1 to 19, Comparative Examples 1 to 10] <Image Recording> Using ink A shown in Table 1 and ink B shown in Table 2, image recording is performed as follows. An inkjet recording device is used as the image recording device, which is equipped with an inkjet head (product name "Samba G3L", manufactured by Fujifilm Corporation), a pinning LED light source (UV-LED irradiator with a peak wavelength of 385 nm (product name "G5AP", manufactured by Kyocera Corporation)), and a final exposure LED light source (UV-LED irradiator with a peak wavelength of 385 nm (product name "G5A", manufactured by Kyocera Corporation)). A polyvinyl chloride substrate (product name "PVC35phr", manufactured by Okamoto Corporation) is used as the image recording substrate.

[0130] An image of a 2 mm x 2 mm square grid pattern, as shown in Figure 1, is recorded on the image recording substrate. P1 corresponds to the first region of the image recording substrate, and P2 corresponds to the second region of the image recording substrate. First, the ink described in "Type" of "First Ink" in Tables 3 to 6 is dispensed onto the first and second regions of the image recording substrate according to the "Amount of Ink in the First Region" and "Amount of Ink in the Second Region" described in Tables 3 to 6. In Tables 3 to 6, "Amount of Ink in the First Region" in "First Ink" means the amount of first ink applied per unit area to the first region. "Amount of Ink in the Second Region" in "First Ink" means the amount of first ink applied per unit area to the second region. After applying the first ink, ultraviolet light is irradiated using a pinning LED light source at the "Exposure Amount of First Active Energy Ray" described in Tables 3 to 6. The time between applying the first ink and irradiating with ultraviolet light is the "Time until Irradiation of First Active Energy Ray" described in Tables 3 to 6.

[0131] Next, the inks listed in the "Type" column of "Second Ink" in Tables 3 to 6 are dispensed onto the first and second regions of the image recording substrate according to the "Amount of Ink in the First Region" and "Amount of Ink in the Second Region" listed in Tables 3 to 6. In Tables 3 to 6, "Amount of Ink in the First Region" for "Second Ink" refers to the amount of second ink applied per unit area to the first region. "Amount of Ink in the Second Region" for "Second Ink" refers to the amount of second ink applied per unit area to the second region. After applying the second ink, ultraviolet light is irradiated using a pinning LED light source at the "First Stage Exposure Amount of Second Active Energy Ray" listed in Tables 3 to 6. Furthermore, ultraviolet light is irradiated using a final exposure LED light source at the "Second Stage Exposure Amount of Second Active Energy Ray" listed in Tables 3 to 6. By completing the above steps, an image recording material including the image recording substrate and an image is obtained. In Tables 3 to 6, "Ink Application Ratio" refers to the ratio of the amount of ink applied per unit area to the first region to the amount of ink applied per unit area to the second region.

[0132] The amount of ink applied to the first and second regions is calculated based on the image recording settings of the inkjet recording device.

[0133] <Manufacturing of Laminated Body> A polyvinyl chloride substrate (product name "SG800", manufactured by KN Trading Co., Ltd., 75 μm thick) is used as the laminating substrate. The laminating substrate is placed on the image in the image recording material obtained above (i.e., on the image recorded on the image recording substrate). In this state, the image recording material and the laminating substrate are heat-pressed together using a desktop automatic transfer press (product name "AF-54TEN", Asahi Textile Machinery Co., Ltd.). This obtains a laminated body having a layered structure of image recording substrate / image / laminating substrate. The lamination temperature (i.e., heat-pressure temperature) is set to 145°C. The lamination pressure (i.e., heat-pressure pressure) is set to 2.2 MPa, and the lamination time (i.e., heat-fusion time) is set to 310 seconds for lamination. Furthermore, the lamination is performed at a lamination pressure of 9.5 MPa and a lamination time of 65 seconds.

[0134] The following is an evaluation of the laminate strength.

[0135] <Laminate Strength> A sample for evaluating laminate strength is prepared using the following method. A 3.2 cm × 3.2 cm image recording sample is cut from the image recording obtained from the image recording described above. Also, a 3.2 cm × 3.2 cm laminate substrate sample is cut from the laminate substrate described above. A 12 μm thick PET (polyethylene terephthalate) sheet is placed on the image recording surface of the image recording sample, in a 1.0 cm × 3.2 cm area including one side of the image recording sample. Next, a 3.2 cm × 3.2 cm laminate substrate sample is placed over the entire area on the image recording surface of the image recording sample, including the area where the PET sheet is placed (1.0 cm × 3.2 cm area) and the area where the PET sheet is not placed (2.2 cm × 3.2 cm area). In this state, the image recording sample and the laminate substrate sample are laminated under the same conditions as the lamination process described above. By removing the PET sheet from the resulting laminate, an evaluation sample is obtained.

[0136] In the evaluation sample, the area where the PET sheet was not placed before the lamination process adheres to the image recording sample and the lamination substrate sample. On the other hand, in the evaluation sample, the area where the PET sheet was placed before the lamination process does not adhere to the image recording sample and the lamination substrate sample. Next, in the area where the image recording sample and the lamination substrate sample do not adhere, a tensile test is performed by pulling the image recording sample and the lamination substrate sample in opposite directions to measure the peel strength. The tensile test is performed using a tensile testing machine (product name "Autograph AGS-X 5KN", manufactured by Shimadzu Corporation). Two evaluation samples are prepared, and the tensile test is performed twice. The average value of the peel strength from the two tests is calculated as the "lamination strength," and the lamination strength of the laminate is evaluated based on the evaluation criteria below. In the evaluation criteria below, the rank that is best for lamination strength is "A." A: Lamination strength is 7.5 N / cm or higher. B: Lamination strength is 3.5 N / cm or higher but less than 7.5 N / cm. C: Lamination strength is 2.5 N / cm or higher but less than 3.5 N / cm. D: Lamination strength is 1.5 N / cm or higher but less than 2.5 N / cm. E: Lamination strength is less than 1.5 N / cm.

[0137]

[0138]

[0139]

[0140]

[0141]

[0142]

[0143] As shown in Tables 3 to 6, Examples 1 to 19 include a step of recording an image by applying ink A and ink B to an image recording substrate containing a polymer with vinyl chloride as a constituent unit using an inkjet recording method, wherein ink A contains a colorant and polymerizable monomer A, with the polymerizable monomer A content being 80% by mass or more of the total amount of ink A, ink B does not contain a colorant, or the colorant content relative to the total amount of ink B is 0.1% by mass or less, and also contains polymerizable monomer B, with the polymerizable monomer B content being 80% by mass or more of the total amount of ink B, and both polymerizable monomer A and polymerizable monomer B have a solubility parameter of 17.0 MPa. １／２ ~21.3 MPa １／２ Because it is a monofunctional polymerizable monomer, the resulting laminate exhibits excellent lamination strength.

[0144] On the other hand, in Comparative Example 1, ink B was not used, resulting in inferior lamination strength. In Comparative Examples 2 and 5, the content of polymerizable monomer A was less than 80% by mass of the total amount of ink A, resulting in inferior lamination strength. In Comparative Examples 3 and 6, the content of polymerizable monomer B was less than 80% by mass of the total amount of ink B, resulting in inferior lamination strength. In Comparative Examples 4 and 7, the content of polymerizable monomer A was less than 80% by mass of the total amount of ink A, and the content of polymerizable monomer B was less than 80% by mass of the total amount of ink B, resulting in inferior lamination strength.

[0145] In Example 1, the ratio of the amount of ink applied per unit area to the first region to the amount of ink applied per unit area to the second region was 0.8 to 1.25, and the laminate strength was superior compared to Examples 2 and 3.

[0146] In Example 1, the amount of ink applied per unit area to the image recording substrate was 3 g / m². ２ ~15g / m ２ Therefore, it exhibits superior laminate strength compared to Examples 4 and 5.

[0147] In Example 1, ink A was applied first, followed by ink B, resulting in superior lamination strength compared to Example 10.

[0148] In Example 1, the time from the moment ink A hit the surface until the first active energy ray was irradiated was 0.05 seconds to 0.5 seconds, which is superior to Examples 6 and 7 in terms of laminate strength.

[0149] In Example 1, the exposure dose of the first active energy ray was 10 mJ / cm². ２ ~100 mJ / cm ２ Therefore, it exhibits superior lamination strength compared to Examples 8 and 9.

[0150] In Example 1, both polymerizable monomer A and polymerizable monomer B have one ethylenically unsaturated group and a molecular weight of 205 or less, resulting in superior lamination strength compared to Example 11.

[0151] In Example 12, the composition of 50% or more by mass of the polymerizable compounds contained in ink A is the same as the composition of the polymerizable compounds contained in ink B, and the laminate strength is superior compared to Example 13.

[0152] Comparative Examples 1, 8 to 10 show that when ink B is not used, the amount of ink A applied per unit area to the second region is 1 g / m². ２ ~3g / m ２ In this case, the lamination strength is greatly reduced. In contrast, as shown in Examples 17 to 19, when ink B is used, the amount of ink A applied per unit area to the second region is 1 g / m². ２ ~3g / m ２ Even so, it has excellent lamination strength.

[0153] [Example 100] <Preparation of Magenta Pigment Dispersion> A magenta pigment dispersion is obtained in the same manner as the preparation of the cyanide pigment dispersion, except that the following components are mixed.

[0154] • Magenta pigment: Pigment Red 254 (product name "Irgazin Red L 3670 HD", manufactured by DIC Corporation) ... 30 parts by mass • Dispersant 2: Product name "EFKA PX 4701", manufactured by BASF Corporation ... 10 parts by mass • PEA: Phenoxyethyl acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd. ... 59 parts by mass • Polymerization inhibitor: Product name "FLORSTAB UV12", manufactured by Kromachem (a mixture of the active ingredient N-nitroso-N-phenylhydroxylamine aluminum salt and PEA, with a mixing ratio of 1:9) ... 1 part by mass

[0155] <Preparation of Yellow Pigment Dispersion> A yellow pigment dispersion is obtained in the same manner as the preparation of the cyanide pigment dispersion, except that the following components are mixed.

[0156] • Yellow pigment: Pigment Yellow 155 (product name "INKJET YELLOW 4GC", manufactured by Heubach) ... 30 parts by mass • Dispersant 1: product name "Solsperse 32000", manufactured by Lubrizol ... 10 parts by mass • PEA: Phenoxyethyl acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd. ... 59 parts by mass • Polymerization inhibitor: product name "FLORSTAB UV12", manufactured by Kromachem (a mixture of the active ingredient N-nitroso-N-phenylhydroxylamine aluminum salt and PEA, with a mixing ratio of 1:9) ... 1 part by mass

[0157] <Preparation of Black Pigment Dispersion> A black pigment dispersion is obtained in the same manner as the preparation of the cyanide pigment dispersion, except that the following components are mixed.

[0158] • Black pigment: Carbon black (product name "Special Black 250", manufactured by Orion Co., Ltd.) ... 30 parts by mass • Dispersant 1: Product name "Solsperse 32000", manufactured by Lubrizol Co., Ltd. ... 10 parts by mass • PEA: Phenoxyethyl acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd. ... 59 parts by mass • Polymerization inhibitor: Product name "FLORSTAB UV12", manufactured by Kromachem Co., Ltd. (A mixture of the active ingredient N-nitroso-N-phenylhydroxylamine aluminum salt and PEA, with a mixing ratio of 1:9) ... 1 part by mass

[0159] Ink A1M, Ink A1Y, and Ink A1Bk are prepared in the same manner as Ink A1, except that the cyan pigment dispersion is changed to a magenta pigment dispersion, a yellow pigment dispersion, and a black pigment dispersion.

[0160] <Image Recording> Image recording is performed in the same manner as in Example 1 using Ink A1, Ink A1M, Ink A1Y, Ink A1Bk, and Ink B1.

[0161] Ink A1Y is ejected onto the image recording substrate under the following conditions. Application amount of Ink A1Y per unit area to the first region: 2 g / m ２ Application amount of Ink A1Y per unit area to the second region: 0.3 g / m ２

[0162] After applying Ink A1Y, ultraviolet light is irradiated at an exposure amount of 50 mJ / cm ２ 0.1 second later.

[0163] Next, Ink A1 is ejected under the following conditions. Application amount of Ink A1 per unit area to the first region: 0.3 g / m ２ Application amount of Ink A1 per unit area to the second region: 0.06 g / m ２

[0164] After applying Ink A1, ultraviolet light is irradiated at an exposure amount of 50 mJ / cm ２ 0.1 second later.

[0165] Next, Ink A1M is ejected under the following conditions. Application amount of Ink A1M per unit area to the first region: 3.5 g / m ２ Application amount of Ink A1M per unit area to the second region: 0.6 g / m ２

[0166] After applying Ink A1M, ultraviolet light is irradiated at an exposure amount of 50 mJ / cm ２ 0.1 second later.

[0167] Next, Ink A1Bk is ejected under the following conditions. Application amount of Ink A1Bk per unit area to the first region: 0.2 g / m ２ Application amount of Ink A1Bk per unit area to the second region: 0.04 g / m２

[0168] After applying ink A1Bk, the exposure dose was set to 50 mJ / cm after 0.1 seconds. ２ Ultraviolet light is then applied.

[0169] Next, ink B1 is ejected under the following conditions: Amount of ink B1 applied per unit area to the first region: 0 g / m² ２ Amount of ink B1 applied per unit area to the second region: 5 g / m² ２

[0170] After applying ink B1, the exposure dose was set to 50 mJ / cm after 0.1 seconds. ２ Ultraviolet light is irradiated. Furthermore, the exposure dose is 800 mJ / cm². ２ Ultraviolet light is then applied.

[0171] Based on the above, an image recording material containing an image recording substrate and an image is obtained. A laminate is also manufactured in the same manner as in Example 1, and the laminate strength is evaluated. The evaluation result is "A".

[0172] Furthermore, the disclosure of Japanese Patent Application No. 2025-027160, filed on 21 February 2025, is incorporated herein by reference in its entirety. In addition, all documents, patent applications, and technical standards described herein are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard were specifically and individually indicated as being incorporated by reference.

Claims

1. The process includes a step of recording an image on an image recording substrate containing a polymer containing vinyl chloride as a constituent unit by applying ink A and ink B using an inkjet recording method, wherein ink A contains a colorant and polymerizable monomer A, and the content of polymerizable monomer A is 80% by mass or more of the total amount of ink A; ink B does not contain a colorant, or the content of a colorant relative to the total amount of ink B is 0.1% by mass or less, and contains polymerizable monomer B, and the content of polymerizable monomer B is 80% by mass or more of the total amount of ink B; and both polymerizable monomer A and polymerizable monomer B have a solubility parameter of 17.0 MPa. １／２ ~21.3 MPa １／２ A monofunctional polymerizable monomer, and an image recording method.

2. The image recording method according to claim 1, wherein the image recording substrate includes a first region and a second region, and the step of recording the image includes the steps of applying ink A to the first region to record a first image and applying ink A and ink B to the second region to record a second image.

3. The image recording method according to claim 2, wherein the ratio of the amount of ink applied per unit area to the first region to the amount of ink applied per unit area to the second region is 0.8 to 1.

25.

4. The amount of ink applied per unit area to the image recording substrate is 3 g / m². ２ ~15g / m ２ The image recording method according to claim 1.

5. The amount of ink A applied per unit area to the second region is 1 g / m². ２ ~3g / m ２ The image recording method according to claim 2.

6. The image recording method according to claim 2, wherein the step of recording the second image includes: applying the ink A onto the second region; irradiating the second region to which the ink A has been applied with a first active energy ray to form an ink A film; applying the ink B onto the ink A film; and irradiating the second region to which the ink B has been applied with a second active energy ray to record the second image.

7. The image recording method according to claim 6, wherein the time from the moment the ink A lands to the moment the first active energy ray is irradiated is 0.05 seconds to 0.5 seconds.

8. The exposure dose of the first active energy ray is 10 mJ / cm². ２ ~100 mJ / cm ２ The image recording method according to claim 6.

9. The image recording method according to claim 1, wherein both polymerizable monomer A and polymerizable monomer B have one ethylenically unsaturated group and a molecular weight of 205 or less.

10. The image recording method according to claim 1, wherein the composition of 50% by mass or more of the polymerizable compounds contained in ink A is the same as the composition of the polymerizable compounds contained in ink B.

11. A method for producing a laminate, comprising the steps of: recording an image on an image recording substrate using the image recording method described in any one of claims 1 to 10; and laminating a laminate substrate containing a polymer with vinyl chloride as a constituent unit onto the surface of the image.

Images