Imaging method, imaging device and active energy ray curable composition combination

Abstract

The subject of the present invention is an imaging method, an imaging device and an active energy ray-curable composition combination. The present invention provides an imaging method, an imaging device and an active energy ray-curable composition combination that can form a cured product having excellent scratch resistance even after being exposed to very harsh conditions such as hot water. The imaging method includes: a composition A imparting step of imparting an active energy ray-curable composition A containing a polymerizable monomer having a phosphate group and a polyester resin to a substrate; a composition A curing step of curing the active energy ray-curable composition A; a composition B imparting step of imparting an active energy ray-curable composition B containing a multifunctional polymerizable compound having two or more polymerizable functional groups in the molecule to a cured product of the active energy ray-curable composition A; and a composition B curing step of curing the active energy ray-curable composition B.

Description

Technical Field

[0001] The present invention relates to a combination of an image forming method and an image forming apparatus, and an active energy ray-curable composition. Background Art

[0002] Inkjet printers have been used for printing large advertisements and wallpapers, and have been increasingly used for industrial applications such as packaging and beverage containers. Ink compositions used in inkjet printers include, for example, aqueous inkjet ink compositions, oily inkjet ink compositions, and active energy ray-curable inkjet ink compositions.

[0003] The active energy ray-curable composition is cured by irradiation with active energy rays and therefore has excellent drying properties even on a non-permeable substrate.

[0004] In particular, as the use of active energy ray-curable compositions has become more diverse, the types of base materials to which active energy ray-curable compositions are applied have also become more diverse. For example, plastics, metals, glass, etc. are used as base materials. In recent years, active energy ray-curable compositions having excellent adhesion and drying properties to these base materials have been required.

[0005] Furthermore, the cured product obtained by curing the printed active energy ray-curable composition is also required to have durability against treatment under very severe conditions.

[0006] For example, in food-related applications such as beverage containers, the containers are sometimes treated with hot water or alkaline solutions from the viewpoint of sterilization of the containers. Therefore, the cured product obtained by curing the printed active energy ray-curable composition is required to have durability against treatment with hot water or alkaline solutions.

[0007] In addition, when treated with hot water or an alkaline solution, the containers may rub against each other, and therefore, scratch resistance when immersed in hot water or an alkaline solution is also required.

[0008] With regard to these problems, for example, as an inkjet ink composition for obtaining a resin-coated metal plate having a resin film having sufficient adhesion to metal and excellent strength, there has been proposed an inkjet ink composition comprising a polymerizable monomer polymerizable by active energy rays and a photopolymerization initiator, wherein the polymerizable monomer contains 0.5 to 13% by mass of a polymerizable phosphate compound having a phosphate group and an ethylenic double bond group in the molecule, and 10 to 75% by mass of a monofunctional monomer having one ethylenic double bond group in the molecule and no phosphate group in all monomers, the photopolymerization initiator being composed of an acylphosphine oxide-based initiator and an α-hydroxyketone-based initiator having one or less phenyl groups in the skeleton, and having a viscosity of 3 to 50 MPa·s at 25° C. (for example, refer to Patent Document 1).

[0009] In addition, as energy-curable inks and coatings having improved adhesion to flexible base materials such as flexible film materials, energy-curable printing inks or coating compositions have been proposed, such as monomers containing acrylate groups, oligomers containing acrylate groups, or energy-curable printing inks or coating compositions containing a combination thereof, wherein the composition has a relative concentration of acrylate groups greater than 4.0 (see, for example, Patent Document 2).

[0010] Furthermore, as an active energy ray-curable composition that forms a high-hardness coating film with good adhesion to a substrate, an active energy ray-curable composition containing an N-substituted (meth)acrylamide (A) having a specific structure, a bifunctional (meth)acrylate (B) and (C), a trifunctional or tetrafunctional (meth)acrylate (D), a phosphoric acid (meth)acrylate (E) and an acylphosphine photopolymerization initiator (F) has been proposed (for example, see Patent Document 3).

[0011] As another example, an active energy ray-curable composition for forming a hard coating layer that can be cured by active energy rays as a laminate having excellent appearance, wear resistance, scratch resistance, substrate adhesion, heat resistance, moisture and heat resistance, and weather resistance and without cracking or peeling is proposed, which contains (A) a polyfunctional (meth)acrylate having a specific structure, (B) a urethane (meth)acrylate obtained by reacting a diol (b-1) having an alicyclic structure, a lactone (b-2), a polyisocyanate (b-3), and a hydroxyl-containing (meth)acrylate, and (C) an ultraviolet absorber (for example, refer to Patent Document 4).

[0012] An object of the present invention is to provide an image forming method capable of forming a cured product having excellent scratch resistance even after exposure to extremely severe conditions such as hot water.

[0013] [Patent Literature]

[0014] [Patent Document 1]: Japanese Patent Publication No. 2012-162615

[0015] [Patent Document 2]: Japanese Patent Publication No. 2015-513601

[0016] [Patent Document 3]: Japanese Patent Publication No. 2020-186372

[0017] [Patent Document 4]: Japanese Patent Publication No. 2010-215843 Summary of the invention

[0018] The imaging method of the present invention as a means for solving the above-mentioned problems includes: a composition A imparting step of imparting an active energy ray-curable composition A containing a polymerizable monomer having a phosphate group and a polyester resin to a base material; a composition A curing step of curing the active energy ray-curable composition A; a composition B imparting step of imparting an active energy ray-curable composition B containing a multifunctional polymerizable compound having two or more polymerizable functional groups in the molecule to a cured product of the active energy ray-curable composition A; and a composition B curing step of curing the active energy ray-curable composition B.

[0019] According to the present invention, it is possible to provide an image forming method capable of forming a cured product having excellent scratch resistance even after exposure to extremely severe conditions such as hot water. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 Shown is a schematic diagram of an example of a two-dimensional or three-dimensional imaging device according to the present invention.

[0021] Figure 2 FIG. 1 is a schematic diagram showing an example of another two-dimensional or three-dimensional imaging device according to the present invention.

[0022] The symbols in the figure are explained as follows:

[0023] 1 Storage tank

[0024] 21 Supply roller

[0025] 22Recorded medium

[0026] 23a, 23b, 23c, 23d printing units

[0027] 24a, 24b, 24c, 24d light sources

[0028] 25 processing units

[0029] 26 printed material take-up roller

[0030] 3 movable platforms

[0031] 30 Modeling head unit

[0032] 31, 32 support nozzle unit

[0033] 33, 34 Ultraviolet irradiation mechanism

[0034] 35 Three-dimensional objects

[0035] 36 Support body lamination part

[0036] 37 Modeling object support base

[0037] 38 movable platforms

[0038] 39 Imaging device

[0039] 4Active energy rays

[0040] 5Active energy ray curable composition

[0041] 6 Curing layer DETAILED DESCRIPTION

[0042] (Imaging method and imaging device)

[0043] The imaging method of the present invention comprises: a composition A imparting step of imparting an active energy ray-curable composition A containing a polymerizable monomer having a phosphate group and a polyester resin to a substrate; a composition A curing step of curing the active energy ray-curable composition A; a composition B imparting step of imparting an active energy ray-curable composition B containing a multifunctional polymerizable compound having two or more polymerizable functional groups in the molecule to a cured product of the active energy ray-curable composition A; and a composition B curing step of curing the active energy ray-curable composition B, and further comprises other steps as required.

[0044] The imaging device of the present invention includes: a composition A imparting mechanism for imparting an active energy ray-curable composition A containing a polymerizable monomer having a phosphate group and a polyester resin to a base material; a composition A curing mechanism for curing the active energy ray-curable composition A; a composition B imparting mechanism for imparting an active energy ray-curable composition B containing a multifunctional polymerizable compound having two or more polymerizable functional groups in the molecule to a cured product of the active energy ray-curable composition A, and a composition B curing mechanism for curing the active energy ray-curable composition B, and further includes other mechanisms as required.

[0045] The imaging method of the present invention can be preferably implemented using the imaging device of the present invention, the composition A imparting step can be preferably implemented by the composition A imparting mechanism, the composition A curing step can be preferably implemented by the composition A curing mechanism, the composition B imparting step can be preferably implemented by the composition B imparting mechanism, and the other steps can be preferably implemented by the other mechanisms.

[0046] First, in order to have excellent scratch resistance even after treatment under very severe conditions such as hot water, the cured product must have high strength and not be easily peeled off from the base material.

[0047] The workers of the present invention have conducted an in-depth study of the prior art and found the following problems.

[0048] In the inkjet ink composition described in Patent Document 1, the adhesion was investigated, but the adhesion was sometimes poor after being immersed in hot water or an alkaline solution.

[0049] In the energy-curable printing ink or coating composition described in the above-mentioned Patent Document 2, acidic acrylate oligomers, acrylic acid, β-carboxyethyl acrylate, etc. are exemplified as acid-modified adhesion promoters. Although the adhesion is studied, the adhesion after treatment under harsh conditions such as hot water or alkaline solution is not studied.

[0050] Patent Document 3 describes an active energy ray-curable composition containing a multifunctional (meth)acrylate such as a bifunctional (meth)acrylate, a trifunctional or a tetrafunctional (meth)acrylate, and a phosphoric acid (meth)acrylate, but the scratch resistance of the composition when treated with hot water is sometimes poor.

[0051] Patent Document 4 describes a laminate having at least a primer layer composed of an acrylic resin and a hard coat layer composed of an active energy ray-curable composition in this order, but the abrasion resistance when treated with water is sometimes poor.

[0052] When a multifunctional polymerizable compound is contained in an active energy ray-curable composition in order to improve the strength of the cured product, the greater the content of the multifunctional polymerizable compound, the greater the strength of the cured product. However, due to the influence of the multifunctional polymerizable compound, curing shrinkage sometimes occurs during curing, significantly reducing the adhesion to the substrate.

[0053] In addition, due to a significant decrease in adhesion, the scratch resistance may be significantly reduced, or the cured product may be easily peeled off from the base material when exposed to harsh conditions such as hot water.

[0054] The present inventors have conducted intensive studies and have found that, by applying a predetermined combination of active energy ray-curable composition A (hereinafter sometimes referred to as "composition A") to a substrate to form a layer consisting of its cured product, the cured product of composition A can exhibit excellent adhesion even after being exposed to extremely harsh conditions such as hot water.

[0055] In addition, the workers of the present invention have found that by applying an active energy ray-curable composition B of a specified combination (hereinafter sometimes simply referred to as "composition B") to the cured product of the above-mentioned composition A to form a layer composed of the cured product, a cured product having excellent scratch resistance can be formed even after exposure to extremely harsh conditions such as hot water.

[0056] That is, the workers of the present invention have discovered that by using an active energy ray-curable composition A containing a polymerizable monomer having a phosphate group and a polyester resin, and an active energy ray-curable composition B containing a multifunctional polymerizable compound having two or more polymerizable functional groups in the molecule in combination to form a cured product in a layered manner, a cured product having excellent scratch resistance can be obtained.

[0057] Although the reason is not yet certain, it is speculated as follows.

[0058] For example, when an active energy ray-curable composition is applied to an impermeable substrate such as glass, the composition does not penetrate into the substrate, and the adhesion between the cured product and the substrate tends to decrease.

[0059] However, it is considered that by using a polymerizable monomer having a phosphate group, the phosphate group partially dissolves the matrix material to exhibit interaction between the matrix material and the composition, and that a cured product of the composition can exhibit very high adhesion to the matrix material.

[0060] Regarding the reduction in the adhesion between the substrate and the cured product, for example, when the cured product formed on the substrate is immersed in hot water or an alkaline solution, it is believed that the hot water or alkaline solution penetrates into the interface between the substrate and the cured product and the interior of the cured product, resulting in a significant reduction in adhesion.

[0061] In contrast, by including a polymerizable monomer having a phosphate group and a polyester resin in the composition, the interaction between the composition and the base material or the strength of the cured product can be very excellent, and it is believed that hot water and alkaline solutions can be inhibited from entering the interface between the base material and the cured product or the interior of the cured product, and even after being immersed in hot water or an alkaline solution, very excellent adhesion can be exhibited.

[0062] In order to improve the strength of the cured product, it is also being considered to include a multifunctional polymerizable compound.

[0063] When a composition contains a polymerizable monomer having a phosphate group and a multifunctional polymerizable compound, the strength of the cured product can be improved because a cross-linked structure is formed by the multifunctional polymerizable compound. On the other hand, it is believed that in the composition, the polymerizable monomer having a phosphate group enters the interior of the cross-linked structure, the interaction between the phosphate group and the matrix material is reduced, and the scratch resistance is reduced.

[0064] However, the workers of the present invention have conducted research and found that simply using a composition containing a polymerizable monomer having a phosphate group and a multifunctional polymerizable compound separately and separately sometimes fails to show excellent scratch resistance. For example, using (1) a composition containing a polymerizable monomer having a phosphate group and (2) a composition containing a multifunctional polymerizable compound, a cured product (layer) of (2) is formed on a cured product (layer) of (1) formed on a glass substrate. When the printed material is subjected to a pencil hardness test according to JIS K5600-5-4 (scratch hardness: pencil method), it is known that although the cured product (layer) of (1) remains on the glass substrate, the cured product (layer) of (2) is easily scraped off.

[0065] Regarding this point, it is speculated that a large difference in internal stress occurs between the cured product (layer) of (1) and the cured product (layer) of (2), and the interaction between the layers is reduced, so that only the cured product (layer) of (2) is scraped off and cannot exhibit excellent scratch resistance.

[0066] After intensive research, the workers of the present invention have found that after separating the polymerizable monomer having a phosphate group and the multifunctional polymerizable compound into their respective compositions, by further making (1) contain a polyester resin, it is possible to exhibit high adhesion and excellent scratch resistance. This is believed to be because the polymerizable monomer having a phosphate group has a high affinity with the ester structure having a polyester structure similar to the polyester resin, and the cured product (layer) formed on the base material itself becomes strong, and a cured product (layer) with moderate stress can be formed. In addition, by making (1) contain a polyester resin, the reduction of the interaction between the layers can be suppressed, so it is believed that excellent scratch resistance can be exhibited.

[0067] In this specification, "hot water" refers to water heated to 80° C. or higher under normal pressure, that is, water having a temperature of 80° C. or higher and 100° C. or lower under normal pressure.

[0068] <Composition A applying step and composition A applying mechanism>

[0069] The composition A application step is a step of applying the active energy ray-curable composition A containing a polymerizable monomer having a phosphate ester group and a polyester resin to a substrate.

[0070] The composition A applying mechanism is a mechanism for applying the active energy ray-curable composition A containing a polymerizable monomer having a phosphate group and a polyester resin to a base material.

[0071] -Active energy ray-curable composition A-

[0072] The active energy ray-curable composition contains a polyester resin and a polymerizable monomer having a phosphate group, and further contains other components and the like as necessary.

[0073] - Polymerizable monomer having a phosphate group - The above-mentioned active energy ray-curable composition contains a polymerizable monomer having a phosphate group. In the present invention, by containing a polymerizable monomer having a phosphate group, for example, when the above-mentioned substrate material is glass, the phosphate group partially dissolves the substrate material, thereby improving the interaction between the substrate material and the composition, and making the cured product of the composition have very high adhesion to the substrate material.

[0074] The polymerizable functional group in the polymerizable monomer having a phosphate group is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a (meth)acryloyl group and the like.

[0075] The polymerizable monomer having a phosphate group is preferably a polyfunctional monomer having two or more polymerizable functional groups in the molecule, and more preferably a polyfunctional monomer having three polymerizable functional groups in the molecule.

[0076] When the polymerizable monomer having a phosphate group is a multifunctional monomer having two or more polymerizable functional groups in the molecule, the cured product of the composition A after being immersed in hot water can exhibit very excellent scratch resistance. In addition, the cured product of the composition A after being immersed in an alkaline solution can have better adhesion to the substrate.

[0077] Examples of the polymerizable monomer having a phosphate group include 2-acryloyloxyethyl acid phosphate (polymerizable functional group number: 1), 2-(meth)acryloyloxyethyl dihydrogen phosphate (polymerizable functional group number: 1), dipentaerythritol penta(meth)acryloyloxy dihydrogen phosphate (polymerizable functional group number: 5), etc. These may be used alone or in combination of two or more.

[0078] As the polymerizable monomer having an acidic group, a commercially available product can be used.

[0079] Examples of the commercially available products include SR9050NS (manufactured by Sartomer, number of polymerizable functional groups: 1), SR9051NS (manufactured by Sartomer, number of polymerizable functional groups: 3), and Light-Acrylate P-1A(N) (manufactured by Kyoeisha Chemical Co., Ltd., number of polymerizable functional groups: 1).

[0080] The content of the polymerizable monomer having a phosphate group is preferably 3% by mass or more and 10% by mass or less based on the total amount of the composition A.

[0081] When the content of the polymerizable monomer having a phosphate group is 3% by mass or more and 10% by mass or less relative to the total amount of the composition A, the cured product can exhibit excellent scratch resistance even after being immersed in hot water. In addition, the cured product can exhibit excellent adhesion even after being immersed in an alkaline solution. Furthermore, when the content of the polymerizable monomer having a phosphate group is 3% by mass or more and 10% by mass or less relative to the total amount of the composition A, an active energy ray-curable composition having excellent resistance to degradation due to contact with liquid and excellent ejection stability can be obtained.

[0082] The contact with liquid refers to, for example, contact between a member such as a jig for applying the active energy ray-curable composition such as an inkjet head and the active energy ray-curable composition in the case of inkjet printing.

[0083] When the content of the polymerizable monomer having a phosphate group exceeds 10% by mass relative to the total amount of the composition A, the metal parts may sometimes deteriorate, especially when in contact with metal parts. Therefore, from the viewpoint of resistance to degradation caused by contact with liquid, the content of the polymerizable monomer having a phosphate group is preferably 10% by mass or less relative to the total amount of the composition A.

[0084] --Polyester resin--

[0085] The polyester resin is not particularly limited and may be appropriately selected according to the intended purpose.

[0086] Since the polyester resin has a chemical structure similar to the phosphate group in the phosphate group, the affinity of each molecule is high. Therefore, by using the polyester resin and the monomer having the phosphate group in combination, the hardness of the obtained cured product can be further increased, and the effect of inhibiting the cohesive failure of the cured product can be improved.

[0087] As the polyester resin, from the viewpoint of compatibility with monomers (for example, monomers, organic solvents, etc.), polyester resins that are soluble in monomers or organic solvents, etc. These may be used alone or in combination of two or more.

[0088] As the polyester resin, a commercially available product can be used.

[0089] Examples of the commercially available products include UVAD-081 (manufactured by Osaka Soda Co., Ltd., with a number average molecular weight of 1400), UVAD-085 (manufactured by Osaka Soda Co., Ltd., with a number average molecular weight of 2000), Vylon GK-810 (manufactured by Toyobo Co., Ltd., with a number average molecular weight of 6000), Vylon 200 (manufactured by Toyobo Co., Ltd., with a number average molecular weight of 17000), Vylon GK-360 (manufactured by Toyobo Co., Ltd., with a number average molecular weight of 16000), and Vylon 600 (manufactured by Toyobo Co., Ltd., with a number average molecular weight of 16000).

[0090] In addition, the polyester resin is preferably a polyester resin having an unsaturated bond. When the polyester resin is a polyester resin having an unsaturated bond, the adhesion between the cured product after immersion in hot water or an alkaline solution and the base material can be further improved.

[0091] Examples of the polyester resin having an unsaturated bond include UVAD-081 (manufactured by Osaka Soda Co., Ltd., number average molecular weight 1400) and UVAD-085 (manufactured by Osaka Soda Co., Ltd., number average molecular weight 2000).

[0092] The number average molecular weight of the polyester resin is preferably 3000 or less, more preferably 2000 or less, and further preferably 500 or more and 2000 or less. When the number average molecular weight of the polyester resin is 3000 or less, the adhesion between the cured product of the composition A and the substrate can be improved. Furthermore, when the number average molecular weight of the polyester resin is 3000 or less, the spraying stability of the composition A can be improved.

[0093] The content of the polyester resin is preferably 3% by mass or more and 15% by mass or less, more preferably 3% by mass or more and 10% by mass or less, and further preferably 5% by mass or more and 10% by mass or less, relative to the total amount of the composition A. When the content of the polyester resin is 3% by mass or more and 15% by mass or less relative to the total amount of the composition A, the cured product of the composition A after being immersed in hot water can exhibit very excellent scratch resistance. In addition, the cured product of the composition A after being immersed in an alkaline solution can have better adhesion to the substrate. Furthermore, when the content of the polyester resin is 3% by mass or more and 15% by mass or less relative to the composition A, the spraying stability of the composition A can be improved.

[0094] --Other ingredients--

[0095] Examples of the other components include polymerizable compounds other than the polymerizable monomer having a phosphate group, surfactants, polymerization initiators, polymerization accelerators, colorants, organic solvents, and other components.

[0096] - Polymerizable compounds other than polymerizable monomers having a phosphate group -

[0097] The polymerizable compound other than the polymerizable monomer having a phosphate group is not particularly limited, and conventionally known polymerizable compounds can be used.

[0098] Examples of polymerizable compounds other than the polymerizable monomer having a phosphate group include polymerizable monomers and polymerizable oligomers.

[0099] Examples of polymerizable compounds other than the polymerizable monomer having a phosphate group include tetrahydrofurfuryl acrylate, phenoxyethyl acrylate, 2-hydroxyethyl acrylate, ethyl acrylate, 2-hydroxypropyl acrylate, isobutyl acrylate, tert-butyl acrylate, cyclic trimethylolpropane formal monoacrylate, imide acrylate, 2,2,2-trifluoroethyl acrylate, N-vinylformamide, cyclohexyl acrylate, benzyl acrylate, 4-tert-butylcyclohexyl acrylate, caprolactone-modified tetrahydrofurfuryl acrylate, ethoxylated tribromophenyl acrylate, phenoxydiglycol acrylate, vinyl pyrrolidone, acrylic acid. 2-hydroxy-3-phenoxypropyl ester, 1,4-cyclohexanedimethanol monoacrylate, stearyl acrylate, lauryl acrylate, 3,3,5-trimethylcyclohexyl acrylate, ethoxylated nonylphenyl acrylate, alkoxylated 2-phenoxyethyl acrylate, phenoxy polyethylene glycol acrylate, dimethyl acrylamide, hydroxyethyl acrylamide, isopropyl acrylamide, diethyl acrylamide, dimethylaminopropyl acrylamide and other monofunctional polymerizable compounds, and pentaerythritol tri(meth)acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetra(meth)acrylate 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, hydroxypivalic acid neopentyl glycol di(meth)acrylate, Polyfunctional polymerizable compounds such as tetramethylolmethane tri(meth)acrylate, dimethyloltricyclodecane di(meth)acrylate, modified glycerol tri(meth)acrylate, bisphenol A diglycidyl ether (meth)acrylate adduct, modified bisphenol A di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, hydroxypivalic acid neopentyl glycol (meth)acrylate adduct, 2-hydroxy-3-acryloxypropyl methacrylate, urethane acrylate oligomer, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate hexamethylene diisocyanate urethane prepolymer, etc.

[0100] These may be used alone or in combination of two or more.

[0101] In addition, a (meth)acrylic acid adduct means an acrylic acid adduct or a methacrylic acid adduct, and a (meth)acrylate means an acrylate or a methacrylate.

[0102] As the polymerizable compound other than the polymerizable monomer having a phosphate group, a polyfunctional monomer having two or more polymerizable functional groups in the molecule is preferred.

[0103] The content of the polyfunctional monomer having two or more polymerizable functional groups in the molecule is preferably 25% by mass or less, more preferably 15% by mass or less, and further preferably 10% by mass or less relative to the total amount of composition A. If the content of the polyfunctional monomer having two or more polymerizable functional groups in the molecule is 25% by mass or less relative to the total amount of composition A, the cured product of the composition A after being immersed in hot water can exhibit very excellent scratch resistance. In addition, the cured product of the composition A after being immersed in an alkaline solution can have better adhesion to the substrate material.

[0104] From the viewpoint of improving the wettability of the active energy ray-curable composition A to a substrate, the active energy ray-curable composition A more preferably contains a surfactant.

[0105] The surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include TEGO (registered trademark) WET270 (manufactured by EVONIK).

[0106] ---Polymerization initiator---

[0107] The active energy ray-curable composition A of the present invention may also contain a polymerization initiator. As a polymerization initiator, it is sufficient that the active species such as free radicals or cations can be generated by the energy of the active energy rays and the polymerization of the polymerizable compound (monomer or oligomer) can be initiated. As such a polymerization initiator, a known free radical polymerization initiator or cationic polymerization initiator, base generator, etc. can be used alone or in combination of two or more, wherein a free radical polymerization initiator is preferably used. In addition, in order to obtain a sufficient curing speed, the polymerization initiator preferably contains 5 to 20% by mass relative to the total mass (100% by mass) of the composition.

[0108] Examples of free radical polymerization initiators include aromatic ketones, acylphosphine oxide compounds, aromatic onium salt compounds, organic peroxides, thio compounds (thioxanthone compounds, phenylthio-containing compounds, etc.), hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, compounds having a carbon-halogen bond, and alkylamine compounds.

[0109] In addition, in addition to the above-mentioned polymerization initiator, a polymerization accelerator (sensitizer) can also be used. As the polymerization accelerator, there is no particular limitation, for example, preferably trimethylamine, methyl dimethanolamine, triethanolamine, p-diethylaminoacetophenone, ethyl p-dimethylaminobenzoate, p-dimethylaminobenzoic acid-2-ethylhexyl ester, N,N-dimethylbenzylamine and 4,4'-bis(diethylamino)benzophenone and other amine compounds, and its content can be appropriately set according to the polymerization initiator used and its amount.

[0110] ---Color---

[0111] The active energy ray-curable composition A of the present invention may also contain a color material. As the color material, various pigments or dyes may be used to impart a glossy color such as black, white, magenta, cyan, yellow, green, orange, gold or silver, depending on the purpose or required characteristics of the composition of the present invention. The amount of the color material can be appropriately determined by considering the desired color concentration or dispersibility in the composition, and although there is no particular regulation, it is preferably 0.1 to 20% by mass relative to the total mass (100% by mass) of the composition. In addition, the active energy ray-curable composition of the present invention may also be colorless and transparent without containing a color material. In this case, for example, it is preferable to use a protective layer for protecting an image.

[0112] As the pigment, an inorganic pigment or an organic pigment may be used, and one kind may be used alone or two or more kinds may be used in combination.

[0113] As the inorganic pigment, for example, carbon black (CI Pigment Black 7) such as furnace black, lamp black, acetylene black, channel black, etc., iron oxide, and titanium oxide can be used.

[0114] Examples of organic pigments include azo pigments such as insoluble azo pigments, condensed azo pigments, azo lakes, and chelated azo pigments; polycyclic pigments such as phthalocyanine pigments, perylene and perylene pigments, anthraquinone pigments, quinacridone pigments, dioxane pigments, thioindigo pigments, isoindolinone pigments, and quinophthalone pigments; dye chelates (e.g., basic dye type chelates, acid dye type chelates, etc.); lake pigments (e.g., basic dye type lakes, acid dye type lakes, etc.); nitro pigments, nitroso pigments, aniline black, and daylight fluorescent pigments.

[0115] In addition, in order to improve the dispersibility of the pigment, a dispersant may be further included.

[0116] The dispersant is not particularly limited, and examples thereof include dispersants commonly used for preparing pigment dispersions such as polymer dispersants.

[0117] As the dye, for example, acid dyes, direct dyes, reactive dyes, and basic dyes can be used, and one of them may be used alone or two or more of them may be used in combination.

[0118] ---Organic solvents---

[0119] Although the active energy ray-curable composition A of the present invention may contain an organic solvent, it is better not to contain it if possible. If it is a composition that does not contain an organic solvent, especially a volatile organic solvent (VOCfree: does not contain volatile organic compounds), the place where the composition is stored is safer and environmental pollution can be prevented. In addition, "organic solvent" can refer to general non-reactive organic solvents such as ether, ketone, xylene, ethyl acetate, cyclohexanone, toluene, etc., and should be distinguished from reactive monomers. In addition, "free" of organic solvent means that it is substantially not contained, preferably less than 0.1% by mass.

[0120] ---Other ingredients---

[0121] The active energy ray-curable composition A of the present invention may contain other known components as required. There are no particular restrictions on other components, and examples thereof include conventionally known inhibitors, leveling agents, defoamers, fluorescent whitening agents, penetration enhancers, wetting agents (humectants), fixers, viscosity stabilizers, mildew inhibitors, preservatives, antioxidants, ultraviolet absorbers, chelating agents, pH adjusters, and thickeners.

[0122] [Preparation of Active Energy Ray-Curable Composition A]

[0123] The active energy ray-curable composition A of the present invention can be prepared using the above-mentioned various components, and its adjustment means or conditions are not particularly limited. For example, the polymerization monomer, pigment, dispersant, etc. can be put into a disperser such as a ball mill, kitty mill, disk mill, pin mill, DYNO-MILL, etc., and the pigment dispersion can be prepared after dispersion, and the pigment dispersion can be further adjusted by mixing the polymerization monomer, initiator, inhibitor, surfactant, etc. into the pigment dispersion.

[0124] [Viscosity]

[0125] The viscosity of the active energy ray-curable composition A of the present invention can be appropriately adjusted according to the application or means of use. Although there is no particular limitation, from the viewpoint of further improving the interaction between the substrate and the active energy ray-curable composition and showing better adhesion, it is preferably 40 MPa·s or less at 25°C, and more preferably 30 MPa·s or less.

[0126] The viscosity can be measured, for example, by a cone-plate rotational viscometer VISCOMETER TVE-25L manufactured by Toki Sangyo Co., Ltd., using a cone rotor (1°34'×R24) at a rotation speed of 50 rpm and constant temperature circulating water set at 25° C. The temperature of the circulating water can be adjusted using VISCOMATEV-150III.

[0127] The method for applying the active energy ray-curable composition A to the substrate is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include coating with a bar coater, coating with a coating roller, and an inkjet method.

[0128] There is no particular limitation on the above-mentioned substrate material, and it can be appropriately selected according to the purpose. For example, paper, silk, fiber, cloth, leather, metal, plastic, glass, wood, ceramic or their composite materials can be cited. The active energy ray-curable composition of the present invention can form a good solidified product in non-permeable substrate materials such as metal, plastic, glass, ceramic, etc. Among them, it is particularly suitable to use a glass substrate material. As the above-mentioned glass substrate material, for example, transparent glass, surface-treated glass, etc. can be cited. As the surface-treated glass, for example, the surface is processed into opaque frosted glass, and the glass coated with tin, etc. can be cited.

[0129] In addition, as the shape of the base material, for example, a base material having a planar shape may be mentioned, and a base material having a non-planar shape such as a bottle may be used.

[0130] <Composition A Curing Step and Composition A Curing Mechanism>

[0131] The composition A curing step is a step of curing the active energy ray-curable composition A.

[0132] The composition A curing mechanism is a mechanism for curing the active energy ray-curable composition A.

[0133] [Active energy rays]

[0134] The active energy ray used in the present invention to cure the active energy ray-curable composition is not particularly limited as long as it is an electron beam, α-ray, β-ray, γ-ray, X-ray, etc., other than ultraviolet rays, and can provide the required energy to promote the polymerization reaction of the polymerizable components in the composition. In particular, when a high-energy light source is used, the polymerization reaction can be carried out even without using a polymerization initiator.

[0135] The curing mechanism of the composition A is not particularly limited and may be appropriately selected depending on the intended purpose. Examples of the curing mechanism include an active energy ray irradiation mechanism.

[0136] Examples of the active energy ray irradiation mechanism include GaN-based semiconductor ultraviolet light emitting devices, ultraviolet light emitting diodes (UV-LEDs), ultraviolet laser diodes (UV-LDs), and metal halide lamps.

[0137] [Curing method of active energy ray-curable composition A]

[0138] As a method for curing the above-mentioned active energy ray-curable composition A by irradiating the above-mentioned active energy ray, for example, there can be listed: (1) a method of curing the above-mentioned active energy ray-curable composition A by irradiating the above-mentioned active energy ray immediately after the above-mentioned active energy ray-curable composition A is applied to a base material, and (2) a method of curing the above-mentioned active energy ray-curable composition A by irradiating the above-mentioned active energy ray after a certain period of time has passed after the above-mentioned active energy ray-curable composition A is applied to a base material, and the like.

[0139] From the viewpoint of improving the scratch resistance after hot water immersion or the adhesion after alkaline solution immersion, preferred is the method of (2) applying the above-mentioned active energy ray-curable composition A to the substrate and then irradiating the above-mentioned active energy ray after a certain period of time to cure the above-mentioned active energy ray-curable composition A.

[0140] This can be inferred that by leaving the above-mentioned active energy ray-curable composition A to stand for a certain period of time after it is imparted to the base material until it is irradiated with the above-mentioned active energy ray, the above-mentioned active energy ray-curable composition A imparted to the base material can act on the base material for a longer time, thereby making the interaction between the base material and the above-mentioned active energy ray-curable composition A stronger.

[0141] The time from application of the active energy ray-curable composition A to irradiation of the substrate with active energy rays (elapsed time after application) is preferably 5 seconds to 30 seconds, more preferably 5 seconds to 20 seconds.

[0142] <Composition B applying step and composition B applying mechanism>

[0143] The composition B imparting step is a step of imparting an active energy ray-curable composition B containing a polyfunctional polymerizable compound having two or more polymerizable functional groups in a molecule to the cured product of the active energy ray-curable composition A.

[0144] The composition B imparting mechanism is a mechanism for imparting the active energy ray-curable composition B containing a multifunctional polymerizable compound having two or more polymerizable functional groups in the molecule to the cured product of the active energy ray-curable composition A.

[0145] -Active energy ray-curable composition B-

[0146] The active energy ray-curable composition B contains a polyfunctional polymerizable compound having two or more polymerizable functional groups in the molecule, and further contains other components as necessary.

[0147] - Polyfunctional polymerizable compounds having two or more polymerizable functional groups in the molecule -

[0148] The polyfunctional polymerizable compound having two or more polymerizable functional groups in the above-mentioned molecule is not particularly limited as long as it has two or more polymerizable functional groups in the molecule, and can be appropriately selected according to the purpose. For example, a conventionally known polyfunctional polymerizable monomer or polyfunctional polymerizable oligomer can be appropriately used, but from the viewpoint of the influence on the injection stability, it is preferred to use a polyfunctional polymerizable monomer.

[0149] ---Multifunctional polymerizable compounds---

[0150] Examples of the polyfunctional polymerizable compound include pentaerythritol tri(meth)acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, pentaerythritol (meth)hexaacrylate, trimethylolpropane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, and the like. ester, hydroxypivalic acid neopentyl glycol di(meth)acrylate, tetramethylolmethane tri(meth)acrylate, dimethyloltricyclodecane di(meth)acrylate, modified glycerol tri(meth)acrylate, bisphenol A diglycidyl ether (meth)acrylate adduct, modified bisphenol A di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, hydroxypivalic acid neopentyl glycol (meth)acrylate adduct, 2-hydroxy-3-acryloxypropyl methacrylate, urethane acrylate oligomer, pentaerythritol tri(meth)acrylate hexamethylene diisocyanate urethane prepolymer, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate hexamethylene diisocyanate urethane prepolymer and the like.

[0151] These may be used alone or in combination of two or more.

[0152] The number of functional groups in the polyfunctional polymerizable compound is preferably from difunctional to hexafunctional, and particularly preferably from difunctional to trifunctional.

[0153] The content of the multifunctional polymerizable compound is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 60% by mass or more and 80% by mass or less, relative to the total amount of the composition B. When the content of the multifunctional polymerizable compound is 50% by mass or more relative to the total amount of the composition B, the scratch resistance of the composition B after immersion in hot water can be improved. In addition, the adhesion between the cured product of the composition A after immersion in an alkaline solution and the composition B can be made more excellent.

[0154] ---Other ingredients---

[0155] Examples of the other components include other polymerizable compounds, surfactants, polymerization initiators, polymerization accelerators, colorants, organic solvents, and other components.

[0156] ---Other polymerizable compounds---

[0157] As other polymerizable compounds, urethane acrylate oligomer etc. are mentioned, for example.

[0158] By including the urethane acrylate oligomer in Composition B, the scratch resistance after immersion in an ethanol solution can be improved.

[0159] The urethane acrylate oligomer is not particularly limited and can be appropriately selected according to the purpose, and examples thereof include EBECRYL 294 / 25HD, EBECRYL 4220, EBECRYL 4513, EBECRYL 4740, EBECRYL 4820, EBECRYL 8465, EBECRYL 9260, EBECRYL 8701, KRM8667, EBECRYL 4666, EBECRYL 8405, EBECRYL 210, and EBECRYL 220 manufactured by Daicel Olonex, and CN series commercially available as functional urethane acrylate oligomers such as CN8885NS manufactured by Sartomer, etc. These may be used alone or in combination of two or more.

[0160] The content of the urethane acrylate oligomer is preferably 3% by mass or more and 10% by mass or less, and more preferably 3% by mass or more and 6% by mass or less, relative to the total amount of the composition B. When the content of the urethane acrylate oligomer is 3% by mass or more and 10% by mass or less relative to the total amount of the composition B, the scratch resistance after immersion in an ethanol solution and the ejection stability by an inkjet method can be improved.

[0161] From the viewpoint of improving the wettability of the active energy ray-curable composition B on the cured product of the composition A, the active energy ray-curable composition B preferably contains a surfactant.

[0162] The surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include TEGO (registered trademark) Rad 2300 (manufactured by EVONIK).

[0163] ---Polymerization initiator---

[0164] The active energy ray-curable composition B of the present invention may also contain a polymerization initiator. As a polymerization initiator, it is sufficient that the active species such as free radicals or cations can be generated by the energy of the active energy line, and the polymerization of the polymerizable compound (monomer or oligomer) can be initiated. As such a polymerization initiator, a known free radical polymerization initiator or cationic polymerization initiator, base generator, etc. can be used alone or in combination of two or more, wherein a free radical polymerization initiator is preferably used. In addition, in order to obtain a sufficient curing speed, the polymerization initiator preferably contains 5 to 20% by mass relative to the total mass (100% by mass) of the composition.

[0165] Examples of free radical polymerization initiators include aromatic ketones, acylphosphine oxide compounds, aromatic onium salt compounds, organic peroxides, thio compounds (thioxanthone compounds, phenylthio-containing compounds, etc.), hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, compounds having a carbon-halogen bond, and alkylamine compounds.

[0166] In addition, in addition to the above-mentioned polymerization initiator, a polymerization accelerator (sensitizer) can also be used. As the polymerization accelerator, there is no particular limitation, for example, preferably trimethylamine, methyl dimethanolamine, triethanolamine, p-diethylaminoacetophenone, ethyl p-dimethylaminobenzoate, p-dimethylaminobenzoic acid-2-ethylhexyl ester, N,N-dimethylbenzylamine and 4,4'-bis(diethylamino)benzophenone and other amine compounds, and its content can be appropriately set according to the polymerization initiator used and its amount.

[0167] ---Color---

[0168] The active energy ray-curable composition B of the present invention may also contain a color material. As the color material, various pigments or dyes may be used to impart a glossy color such as black, white, magenta, cyan, yellow, green, orange, gold or silver, depending on the purpose or required characteristics of the composition of the present invention. The amount of the color material contained can be appropriately determined by considering the desired color concentration or dispersibility in the composition, and although there is no particular regulation, it is preferably 0.1 to 20% by mass relative to the total mass (100% by mass) of the composition. In addition, the active energy ray-curable composition of the present invention may also be colorless and transparent without containing a color material. In this case, for example, it is preferable to use a protective layer for protecting an image.

[0169] As the pigment, an inorganic pigment or an organic pigment may be used, and one kind may be used alone or two or more kinds may be used in combination.

[0170] As the inorganic pigment, for example, carbon black (CI Pigment Black 7) such as furnace black, lamp black, acetylene black, channel black, etc., iron oxide, and titanium oxide can be used.

[0171] Examples of organic pigments include azo pigments such as insoluble azo pigments, condensed azo pigments, azo lakes, and chelated azo pigments; polycyclic pigments such as phthalocyanine pigments, perylene and perylene pigments, anthraquinone pigments, quinacridone pigments, dioxane pigments, thioindigo pigments, isoindolinone pigments, and quinophthalone pigments; dye chelates (e.g., basic dye type chelates, acid dye type chelates, etc.); lake pigments (e.g., basic dye type lakes, acid dye type lakes, etc.); nitro pigments, nitroso pigments, aniline black, and daylight fluorescent pigments.

[0172] In addition, in order to improve the dispersibility of the pigment, a dispersant may be further included.

[0173] The dispersant is not particularly limited, and examples thereof include dispersants commonly used for preparing pigment dispersions such as polymer dispersants.

[0174] As the dye, for example, acid dyes, direct dyes, reactive dyes, and basic dyes can be used, and one of them may be used alone or two or more of them may be used in combination.

[0175] ---Organic solvents---

[0176] The active energy ray-curable composition B of the present invention may contain an organic solvent, but it is better not to contain it if possible. If it is a composition that does not contain an organic solvent, especially a volatile organic solvent (VOCfree: does not contain volatile organic compounds), the place where the composition is stored is safer and environmental pollution can be prevented. In addition, "organic solvent" can refer to general non-reactive organic solvents such as ether, ketone, xylene, ethyl acetate, cyclohexanone, toluene, etc., and should be distinguished from reactive monomers. In addition, "free" of organic solvent means that it is substantially not contained, preferably less than 0.1% by mass.

[0177] ---Other ingredients---

[0178] The active energy ray-curable composition B of the present invention may contain other known components as required. There are no particular restrictions on other components, and examples thereof include conventionally known polymerization inhibitors, leveling agents, defoaming agents, fluorescent whitening agents, penetration enhancers, wetting agents (humectants), fixing agents, viscosity stabilizers, mildewproofing agents, preservatives, antioxidants, ultraviolet absorbers, chelating agents, pH adjusters, and thickeners.

[0179] [Preparation of Active Energy Ray-Curable Composition B]

[0180] The above-mentioned active energy ray-hardening composition B can be prepared using the above-mentioned various components, and its adjustment means or conditions are not particularly limited. For example, the polymerization monomer, pigment, dispersant, etc. can be put into a disperser such as a ball mill, kitty mill, disk mill, pin mill, DYNO-MILL, etc., and the pigment dispersion can be prepared after dispersion, and it can be adjusted by further mixing the polymerization monomer, initiator, inhibitor, surfactant, etc. into the pigment dispersion.

[0181] The viscosity of the active energy ray-curable composition B of the present invention can be appropriately adjusted according to the application or means of use. Although there is no particular limitation, from the viewpoint of further improving the interaction between the substrate and the active energy ray-curable composition and showing better adhesion, it is preferably 40 MPa·s or less at 25°C, and more preferably 30 MPa·s or less.

[0182] The viscosity can be measured, for example, by a cone-plate rotational viscometer VISCOMETER TVE-25L manufactured by Toki Sangyo Co., Ltd., using a cone rotor (1°34'×R24) at a rotation speed of 50 rpm and constant temperature circulating water set at 25° C. The temperature of the circulating water can be adjusted using VISCOMATEV-150III.

[0183] The method for applying the active energy ray-curable composition B to the cured product of the composition A is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include coating with a bar coater, coating with a coating roller, and an inkjet method.

[0184] <Composition B curing step and composition B curing mechanism>

[0185] The composition B curing step is a step of curing the active energy ray-curable composition B.

[0186] The composition B curing mechanism is a mechanism for curing the active energy ray-curable composition B.

[0187] As the curing mechanism of the composition B, the same mechanism as the curing mechanism of the composition A can be used.

[0188] [Curing method of active energy ray-curable composition B]

[0189] As a method for curing the above-mentioned active energy ray-curable composition B by irradiating the above-mentioned active energy ray, for example, there can be listed (1) a method of curing the above-mentioned active energy ray-curable composition B by irradiating the above-mentioned active energy ray immediately after the above-mentioned active energy ray-curable composition B is applied, (2) a method of curing the above-mentioned active energy ray-curable composition B by irradiating the above-mentioned active energy ray after a certain period of time has passed after the above-mentioned active energy ray-curable composition B is applied, etc.

[0190] In particular, for the above-mentioned active energy ray-curable composition B arranged on the outermost surface, by (2) applying the above-mentioned active energy ray-curable composition B and then irradiating it with active energy rays after a certain period of time to cure it, the surface friction can be reduced, the scratch resistance after immersion in hot water can be made better, and a glossy image can be formed.

[0191] This is because, by curing the active energy ray-curable composition B as in (2), the active energy ray-curable composition B applied to the cured product of the composition A wets and spreads, thereby making the surface after curing smooth.

[0192] The time from application of the active energy ray-curable composition B to irradiation of the cured product of the composition A (elapsed time after application) is preferably 5 to 30 seconds, more preferably 5 to 20 seconds.

[0193] The step of imparting the active energy ray-curable composition B and the step of curing the active energy ray-curable composition B preferably include repeatedly performing the step of imparting the composition B and the step of curing the composition B in such a manner that two or more layers containing the cured product of the active energy ray-curable composition B are formed on the cured product of the composition A, and more preferably three or more layers are formed.

[0194] By forming two or more layers containing a cured product of the active energy ray-curable composition B, the cured product of the composition B can be made to exhibit extremely excellent scratch resistance after being immersed in hot water.

[0195] When forming two or more layers containing a cured product of the active energy ray-curable composition B, it is preferred to cure each layer each time it is applied. That is, in each layer, it is preferred to perform a curing step after performing an application step.

[0196] For example, when two compositions, namely, compositions B1 and B2, are applied as the active energy ray-curable composition B, it is preferred that B1 is applied first to the cured product of the active energy ray-curable composition A applied to the substrate, and after B1 is cured, B2 is applied and cured. In addition, B1 and B2 may be different compositions or the same composition.

[0197] In addition, when forming two or more layers containing a cured product of the active energy ray-curable composition B, the method for curing each layer is not particularly limited and can be appropriately selected according to the purpose. The curing method may be different for each layer or the same for each layer.

[0198] <Other processes and other organizations>

[0199] The other steps are not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include a composition C providing step and a composition C curing step.

[0200] The other mechanism is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include a composition C imparting mechanism and a composition C curing mechanism.

[0201] The composition C imparting step is a step of imparting an active energy ray-curable composition C different from the active energy ray-curable composition A and the active energy ray-curable composition B to the cured product of the active energy ray-curable composition A.

[0202] The active energy ray-curable composition C is not particularly limited as long as it is a composition that is a different combination from the active energy ray-curable composition A and the active energy ray-curable composition B, and can be appropriately selected according to the purpose. The active energy ray-curable composition C preferably contains a compound having a polymerizable functional group that can be cured by active energy rays.

[0203] The composition C imparting means is a means for imparting an active energy ray-curable composition C different from the composition A and the composition B to the cured product of the active energy ray-curable composition A.

[0204] As the composition C applying means, the same means as the composition A applying means can be used.

[0205] The composition C curing step is a step of curing the active energy ray-curable composition C.

[0206] The composition C curing mechanism is a mechanism for curing the active energy ray-curable composition C.

[0207] As the curing mechanism of the composition C, the same mechanism as the curing mechanism of the composition A can be used.

[0208] By performing the composition C imparting step and the composition C curing step after the composition A curing step and before the composition B imparting step, an image having a structure in which the cured product of composition A, the cured product of composition C, and the cured product of composition B are stacked in this order can be formed.

[0209] In addition, by performing the composition C imparting step and the composition C curing step after the composition B curing step, an image having a structure in which the cured product of composition A, the cured product of composition B, and the cured product of composition C are stacked in this order can be formed.

[0210] Here, as an example of an image forming apparatus, an example of an apparatus having an inkjet system as a mechanism for applying the compositions A and B and an irradiation section for irradiating active energy rays as a mechanism for curing the compositions A and B will be described.

[0211] The image forming apparatus may be provided with an active energy ray-curable composition by a device including a head unit for spraying the active energy ray-curable composition and an irradiation section for irradiating the active energy ray to cure the active energy ray-curable composition sprayed from the head unit.

[0212] By controlling the lighting and extinguishing of the irradiation section, it is possible to control whether the active energy ray-curable composition is cured by irradiation with active energy rays immediately after application or by curing after a certain period of time.

[0213] For example, in a device in which the head unit and the irradiation section are connected, the active energy ray-curable composition can be cured immediately after being applied by ejecting the active energy ray-curable composition from the head unit while the irradiation section is always lit.

[0214] In order to prevent the applied active energy ray-curable composition from being irradiated with active energy rays, the active energy ray-curable composition is ejected from the above-mentioned nozzle unit while the above-mentioned irradiation part is turned off, and then the above-mentioned irradiation part is turned on to irradiate the active energy rays. In this way, the composition can be applied and cured after a certain period of time.

[0215] Hereinafter, the imaging method and the imaging apparatus of the present invention will be described with reference to the accompanying drawings.

[0216] Figure 1 Shown is an example of an image forming apparatus including an inkjet ejection mechanism.

[0217] It should be noted that, in the imaging device of the present invention, Figure 1 In the following description, each color active energy ray-curable ink of yellow, magenta, cyan, and black can be replaced by the above-mentioned active energy ray-curable composition A, the above-mentioned active energy ray-curable composition B1, the above-mentioned active energy ray-curable composition B2, the above-mentioned active energy ray-curable composition B3, ..., and the compositions are sequentially applied to the cured products of each composition to produce a stacked structure.

[0218] The ink is ejected onto the recording medium 22 supplied from the supply roller 21 by the ink cartridges containing yellow, magenta, cyan and black active energy ray-hardening inks and the color printing units 23a, 23b, 23c and 23d of the ejection heads.

[0219] Thereafter, the ink is irradiated with active energy rays from the light sources 24a, 24b, 24c, and 24d for curing the ink to cure the ink and form a color image.

[0220] Thereafter, the recording medium 22 is conveyed toward the processing unit 25 and the printed matter take-up roller 26 .

[0221] Each of the printing units 23a, 23b, 23c, and 23d may be provided with a heating mechanism to liquefy the ink in the ink ejecting portion. In addition, a mechanism may be provided to cool the recording medium to room temperature by contact or non-contact as needed.

[0222] In addition, as an inkjet recording method, any one of the following can be applied as long as it is a serial method in which the nozzle can be moved to eject ink onto a recording medium that moves intermittently according to the width of the nozzle, or a line method in which the recording medium is continuously moved and ink is ejected onto the recording medium from a nozzle held in a certain position.

[0223] The recording medium 22 is not particularly limited, and may be paper, film, metal, or composite materials thereof, or may be sheet-shaped. In addition, the recording medium 22 may be capable of single-sided printing or double-sided printing.

[0224] Furthermore, the irradiation of active energy rays from the light sources 24a, 24b, and 24c may be weakened or omitted, and active energy rays may be irradiated from the light source 24d after printing of multiple colors. This can achieve energy saving and cost reduction.

[0225] The recorded matter recorded by the ink of the present invention includes not only the matter printed on a flat and smooth surface such as ordinary paper or resin film material, but also the matter printed on a surface with projections and depressions, or the matter printed on a surface made of various materials such as metal or ceramics. In addition, by stacking two-dimensional images, a partially three-dimensional image (an image composed of two-dimensional and three-dimensional images) or a three-dimensional object can be formed.

[0226] Figure 2 FIG. 1 is a schematic diagram of another example of an imaging device (three-dimensional image forming device) according to the present invention.

[0227] Figure 2 The imaging device 39 adopts a head unit for arranging inkjet heads (which can be moved in the AB direction), and sprays a first active energy ray-hardening composition from the head unit 30 for the modeling object, and sprays a second active energy ray-hardening composition having a composition different from the first active energy ray-hardening composition from the head units 31, 32 for the support body, and these compositions are hardened and stacked at the same time by adjacent ultraviolet irradiation mechanisms 33, 34.

[0228] More specifically, for example, the process of spraying a second active energy ray-hardening composition onto the object supporting base plate 37 from the support head units 31, 32, forming a first support body layer having a storage portion after irradiation and curing with active energy rays, and then spraying a first active energy ray-hardening composition from the object head unit 30 in the storage portion to form a first object layer after irradiation and curing with active energy rays, is repeated multiple times by lowering the platform 38 that can move in the up and down directions according to the number of stacking times, so as to produce a three-dimensional object 35 after stacking the support body layer and the object layer.

[0229] Thereafter, the support layered portion 36 is removed as necessary.

[0230] In addition, Figure 2 In the figure, only one nozzle unit 30 for molding is provided for convenience of illustration, but in the imaging device of the present invention, two or more nozzle units 30 for molding are provided. Figure 2 The nozzle unit 30 for molding described in the invention is configured as a nozzle unit 30A for molding that sprays active energy ray-curable composition A, a nozzle unit 30B1 for molding that sprays active energy ray-curable composition B1, a nozzle unit 30B2 for molding that sprays active energy ray-curable composition B2, and a nozzle unit 30B3 for molding that sprays active energy ray-curable composition B3. The compositions sprayed (applied) from these nozzle units 30 for molding are cured by an ultraviolet irradiation mechanism to form a cured product of each composition. By adopting Figure 2 The image forming apparatus described in can repeatedly spray (apply) and cure each active energy ray-curable composition to form a modeled object layer.

[0231] <Application>

[0232] The use of the active energy ray-curable composition of the present invention is not particularly limited to the fields in which active energy ray-curable materials are generally used, and can be appropriately selected according to the purpose. For example, molding resins, coatings, adhesives, insulating materials, release agents, coating materials, sealing materials, various anti-corrosive materials, various optical materials, etc. can be listed.

[0233] Furthermore, the active energy ray-curable composition of the present invention can be used not only as ink to form a two-dimensional text or image, or a pattern coating of various base materials, but also as a three-dimensional modeling material to form a three-dimensional image (three-dimensional modeling object). The three-dimensional modeling material can be used as a binder between powder particles, the powder particles can be used in a powder lamination method for repeatedly curing and laminating powder layers to form three-dimensional models, and can also be used as a binder for a three-dimensional image (three-dimensional modeling object). Figure 2 It is used as a three-dimensional construction material (model material) or a supporting member (support material) of the layered modeling method (light modeling method) shown.

[0234] (Combination of active energy ray-curable composition)

[0235] The combination of the active energy ray-curable composition of the present invention includes an active energy ray-curable composition A containing a polymerizable monomer having a phosphate group and a polyester resin, and an active energy ray-curable composition B containing a multifunctional polymerizable compound having two or more polymerizable functional groups in the molecule, and may also contain other materials as needed.

[0236] The active energy ray-curable composition A and the active energy ray-curable composition B in the combination of the active energy ray-curable composition of the present invention are the same as described in the image forming method and the image forming apparatus of the present invention.

[0237] [Example]

[0238] Examples of the present invention are described below, but the scope of the present invention is not limited to these examples.

[0239] (Preparation of Pigment Dispersion)

[0240] [Preparation of black pigment dispersion]

[0241] 15 parts by mass of a black pigment (trade name: MOGUL-E (carbon black), manufactured by Orion Co., Ltd.), 5 parts by mass of a dispersant (trade name: BYK167, manufactured by BYK-Chemie Co., Ltd.) and 80 parts by mass of tetrahydrofurfuryl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.) were added to a 300 mL ball mill filled with zirconium oxide beads having a particle size of 2 mm (filling ratio: 43 vol%), and dispersed at 70 rpm for 180 hours at a dispersion temperature of 25°C to prepare a black pigment dispersion.

[0242] [Preparation of white pigment dispersion]

[0243] 110 parts by mass of titanium oxide A (trade name: TCR-52, manufactured by Sakai Chemical Co., Ltd., surface treatment: Al2O3) (Al2O3), 10 parts by mass of BYKJET-9151 (manufactured by BYK-Chemie Japan Co., Ltd.) and 100 parts by mass of tetrahydrofurfuryl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.) were added to a 500 mL ball mill filled with zirconia beads with a particle size of 2 mm (filling rate: 45 volume %), and dispersed at 70 rpm and a dispersion temperature of 25°C for 48 hours.

[0244] Then, the mixture was placed in a 1 L sand mill filled with zirconia beads having a diameter of 0.1 mm (filling ratio: 80% by volume), and dispersed at a peripheral speed of 8 m / sec and a dispersion temperature of 25° C. for 3 hours to prepare a white pigment dispersion.

[0245] (Preparation Examples A-1 to A-23)

[0246] - Preparation of active energy ray-curable compositions A-1 to A-23 -

[0247] The compositions shown in Tables 1 to 5 were mixed and stirred according to a conventional method to prepare active energy ray-curable compositions A-1 to A-23.

[0248] Specifically, first, the monomers, polyester resin, polymerization inhibitor, surfactant, and, if necessary, pigment dispersion are mixed and stirred to dissolve the polyester resin and polymerization inhibitor. Next, a polymerization initiator is added and mixed and stirred to dissolve the polymerization initiator to obtain an active energy ray-curable composition.

[0249] The stirring was performed at room temperature using a stirrer, Sany Electric (manufactured by Shinto Scientific Co., Ltd.).

[0250] Table 1

[0251]

[0252] Table 2

[0253]

[0254] Table 3

[0255]

[0256] Table 4

[0257]

[0258] Table 5

[0259]

[0260] (Preparation Examples B-1 to B-11)

[0261] - Preparation of active energy ray-curable compositions B-1 to B-11 -

[0262] The compositions shown in Tables 6 and 7 were mixed and stirred according to a conventional method to prepare active energy ray-curable compositions B-1 to B-11.

[0263] Specifically, first, the polymerizable compounds, polymerization inhibitors, and surfactants are mixed and stirred, and then, if necessary, the pigment dispersion is mixed and stirred. Next, a polymerization initiator is added, and the mixture is mixed and stirred to dissolve the polymerization initiator, thereby obtaining an active energy ray-curable composition B.

[0264] The stirring was performed at room temperature using a stirrer, Sany Electric (manufactured by Shinto Scientific Co., Ltd.).

[0265] Table 6

[0266]

[0267] Table 7

[0268]

[0269] In addition, the details of the materials used in the preparation of the active energy ray-curable compositions A and B are as follows.

[0270] [Polymerizable monomer having a phosphate group]

[0271] SR9051NS: Made by Sartomer, number of polymerizable functional groups: 3

[0272] SR9050NS: Made by Sartomer, number of polymerizable functional groups: 1

[0273] Light acrylate P-1A(N): manufactured by Kyoeisha Chemical Co., Ltd. Number of polymerizable functional groups: 1 Compound name: 2-acryloyloxyethyl acid phosphate

[0274] [Polyester resin]

[0275] UVAD-081: Made by Osaka Soda Co., Ltd., a polyester resin with an average molecular weight of 1400 and an unsaturated bond

[0276] UVAD-085: Made by Osaka Soda Co., Ltd., a polyester resin with a number average molecular weight of 2000 and an unsaturated bond

[0277] [Other polymerizable compounds]

[0278] Tetrahydrofurfuryl acrylate: manufactured by Osaka Organic Chemical Industry Co., Ltd., VISCOAT#150

[0279] Cyclic trimethylolpropane formal monoacrylate: manufactured by Osaka Organic Chemical Industry Co., Ltd., VISCOAT#200

[0280] ·Dipropylene glycol diacrylate: manufactured by Tokyo Chemical Industry Co., Ltd.

[0281] Trimethylolpropane triacrylate: manufactured by Osaka Organic Chemical Industry Co., Ltd., VISCOAT#295

[0282] Dipentaerythritol hexaacrylate, manufactured by Daicel Ornex Co., Ltd.

[0283] KRM8667: Urethane acrylate oligomer, manufactured by Daicel Ornex Co., Ltd.

[0284] [Polymerization initiator]

[0285] ·omniradTPO: made by IGM

[0286] ·omnirad819:Made by IGM

[0287] [Polymerization inhibitor]

[0288] ·BHT: Made by Tokyo Chemical Industry Co., Ltd.

[0289] [Surfactant]

[0290] TEGO (registered trademark) WET270: Made by EVONIK

[0291] TEGO (registered trademark) Rad2300: Made by EVONIK

[0292] (Example 1)

[0293] Using the obtained composition A of Preparation Example A-1 and the composition B of Preparation Examples B-1 to B-3, evaluation samples (printed material 1) were prepared in the "printing device", "conditions for imparting and curing active energy ray-curable composition A", and "conditions for imparting and curing active energy ray-curable composition B" shown below.

[0294] [Printing device]

[0295] Each active energy ray-curable composition was filled in an inkjet head MH5420 (manufactured by Ricoh Co., Ltd.) and a metal halide lamp (brightness 1 W / cm 2 ) in an inkjet printing device. The printing speed of the inkjet printing device is 0.8 m / s.

[0296] <Conditions for providing and curing the active energy ray-curable composition A>

[0297] [Conditions for providing active energy ray-curable composition A]

[0298] The gap between the nozzle and the substrate surface is 1 mm, and the adhesion amount is 1.5 mg / cm 2 The active energy ray-curable composition A was applied to a glass substrate (S9213, manufactured by Matsunami Glass Industry Co., Ltd.) under the printing conditions of 600 dpi×1200 dpi resolution, 8 passes, and bidirectional printing, so as to print a 4 cm square solid image.

[0299] [Curing Conditions of Active Energy Ray-Curable Composition A]

[0300] After 10 seconds have passed since the active energy ray curable composition A was applied to the substrate, the metal halide lamp was lit, and the carriage was scanned in a state where the active energy ray curable composition A was not applied (the composition was not ejected from the nozzle), and the printed solid image (the image of composition A-1) was irradiated with active energy rays to cure the solid image. That is, after the composition A was applied to the substrate, the composition A was cured over a period of time.

[0301] In this example, this curing condition is recorded as "glossy".

[0302] <Conditions for providing and curing the active energy ray-curable composition B>

[0303] The active energy ray-curable composition B was provided and cured in the order of active energy ray-curable compositions B-3, B-2, and B-1 on the cured product of the active energy ray-curable composition A-1 as shown below.

[0304] [Conditions for providing active energy ray-curable composition B-3]

[0305] Under the same conditions as those for applying the active energy ray-curable composition A, the active energy ray-curable composition B-3 was applied to the cured product of the active energy ray-curable composition A-1.

[0306] [Curing conditions of active energy ray-curable composition B-3]

[0307] After the active energy ray curable composition B-3 was applied to the cured product of the active energy ray curable composition A-1, the metal halide lamp was immediately lit, and the carriage was scanned in a state where the active energy ray curable composition was applied (the composition was ejected from the nozzle), and the printed solid image (the image of the active energy ray curable composition B-3) was irradiated with active energy rays to cure it. That is, after the active energy ray curable composition B-3 was applied to the cured product (layer) of the active energy ray curable composition A-1, the active energy ray curable composition B-3 was cured without a time interval.

[0308] In this embodiment, this curing condition is expressed as "matte".

[0309] [Conditions for providing active energy ray-curable composition B-2]

[0310] The active energy ray-curable composition B-2 was applied to the cured product of the active energy ray-curable composition B-3 under the same conditions as those for applying the active energy ray-curable composition A.

[0311] [Curing Conditions of Active Energy Ray-Curable Composition B-2]

[0312] After applying the active energy ray-curable composition B-2 on the cured product (layer) of the active energy ray-curable composition B-3 under the same curing conditions as those of the active energy ray-curable composition B-3 (matte), the active energy ray-curable composition B-2 was cured without any interval.

[0313] [Conditions for providing active energy ray-curable composition B-1]

[0314] The active energy ray-curable composition B-1 was applied to the cured product of the active energy ray-curable composition B-2 under the same conditions as those for applying the active energy ray-curable composition A.

[0315] [Curing Conditions of Active Energy Ray-Curable Composition B-2]

[0316] After applying the active energy ray-curable composition B-1 to the cured product (layer) of the active energy ray-curable composition B-2 under the same curing conditions as those of the active energy ray-curable composition A-1 (glossy), the active energy ray-curable composition B-1 is cured over a certain period of time.

[0317] It should be noted that in Example 1, a layer of a cured product of each composition was prepared in the order of active energy ray-curable composition A-1, B-3, B-2, and B-1 on a substrate, and a printed material having four layers of cured products of active energy ray-curable compositions was prepared. That is, in Example 1, a printed material having a laminated structure consisting of layers of cured products of each composition in the order of substrate, active energy ray-curable composition A-1, B-3, B-2, and B-1 was obtained.

[0318] In this embodiment, the image printed under the curing condition of "glossy" has a "60° gloss" value of 80 or more measured by the following method. In addition, the image printed under the curing condition of "matte" has a "60° gloss" value of 30 or less measured by the following method.

[0319] - 60° gloss measurement method -

[0320] Ten sheets of TPPAPER (manufactured by NBS Ricoh Co., Ltd.) were stacked, and a sample for evaluation was placed thereon, and measurement was performed using micro-tri-gloss 4446 (manufactured by BYK).

[0321] The "60° gloss" of the active energy ray-curable composition A refers to the result of measuring a sample for evaluation consisting only of a cured product of the active energy ray-curable composition A separately prepared under the conditions described in [Conditions for providing the active energy ray-curable composition A] and [Conditions for curing the active energy ray-curable composition A].

[0322] The “60° gloss” of the active energy ray-curable composition B refers to the result of measuring the “60° gloss” of the layer of the active energy ray-curable composition B formed on the outermost surface of the evaluation sample (final printed product).

[0323] (Examples 2 to 39 and Comparative Examples 1 to 6)

[0324] In Example 1, printed materials (evaluation samples) 2 to 45 were obtained in the same manner as in Example 1, except that the combinations described in Tables 8 to 14 were changed to active energy ray-curable compositions A-1 to A-23 and active energy ray-curable compositions B-1 to B-11, and the printing method was changed to the one described in Tables 8 to 14.

[0325] In addition, one to three layers were printed in each of Examples and Comparative Examples for the active energy ray-curable composition B. When two or more layers of the active energy ray-curable composition B were printed, each layer was cured.

[0326] The printing method of the active energy ray-curable composition B other than the outermost layer was "matte".

[0327] It should be noted that the printing method of the outermost layer composition B described in Tables 8 to 14 refers to the printing method of the active energy ray-curable composition B arranged on the outermost layer when the active energy ray-curable composition A and the active energy ray-curable composition B are printed in an overlapping manner. For example, in the case of Example 1, the active energy ray-curable composition B on the outermost layer refers to the active energy ray-curable composition B-1, and in the case of Example 5, the active energy ray-curable composition B on the outermost layer refers to the active energy ray-curable composition B-4.

[0328] Next, the "initial scratch resistance", "scratch resistance after hot water immersion", "scratch resistance after ethanol immersion" and "scratch resistance after alkaline solution immersion" of the printed materials (evaluation samples) 1 to 45 obtained in Examples 1 to 39 and Comparative Examples 1 to 6, and the "jetting stability" of the active energy ray-curable composition A of Preparation Examples A-1 to A-23 were evaluated as follows. The results are shown in Tables 8 to 14.

[0329] (Initial scratch resistance)

[0330] The obtained printed material (evaluation sample) was subjected to a pencil hardness test according to JIS K5600-5-4 (scratch hardness: pencil method), and the presence or absence of image peeling was evaluated based on the following evaluation criteria. If the evaluation result is "C" or above, it is a level that has no problem in practical use.

[0331] In addition, the pencil hardness in this test refers to the pencil hardness when the image is not peeled off as the evaluation result. For example, in the evaluation of a certain sample, when the image is not peeled off in 5H but is peeled off in 6H, the pencil hardness of the sample is "5H" and the evaluation result is "A". It should be noted that "image peeling" in the evaluation criteria refers to the case where either "cured material A of the active energy ray-curable composition" or "cured material B of the active energy ray-curable composition" is peeled off.

[0332] [Evaluation criteria]

[0333] S: Pencil hardness 6H or above

[0334] A: Pencil hardness is above 4H and below 5H

[0335] B: Pencil hardness is above 2H and below 3H

[0336] C: Pencil hardness is F or higher and H or lower

[0337] D: Pencil hardness is below HB

[0338] (Abrasion resistance after hot water immersion)

[0339] The obtained printed matter (evaluation sample) was immersed in hot water heated to 90° C. or 80° C. for 20 minutes so that the image portion and the base material were completely immersed.

[0340] After immersion, the printed material (evaluation sample) was taken out, and water droplets attached to the image surface were immediately wiped off. A pencil hardness test according to JIS K5600-5-4 (scratch hardness: pencil method) was performed to evaluate the presence or absence of image peeling based on the following evaluation criteria. If the evaluation result is "C" or above, it is a level that has no problem in actual use.

[0341] In addition, the pencil hardness in this test refers to the pencil hardness when the image is not peeled off as the evaluation result. For example, in the evaluation of a certain sample, when the image is not peeled off in 5H but is peeled off in 6H, the pencil hardness of the sample is "5H" and the evaluation result is "A". It should be noted that "image peeling" in the evaluation criteria refers to the case where either "cured material A of the active energy ray-curable composition" or "cured material B of the active energy ray-curable composition" is peeled off.

[0342] [Evaluation criteria]

[0343] S: Pencil hardness 6H or above

[0344] A: Pencil hardness is above 4H and below 5H

[0345] B: Pencil hardness is above 2H and below 3H

[0346] C: Pencil hardness is F or higher and H or lower

[0347] D: Pencil hardness is below HB

[0348] (Abrasion resistance after ethanol immersion)

[0349] In the "scratch resistance after hot water immersion", the "scratch resistance after ethanol immersion" was evaluated based on the following evaluation criteria in the same manner as in the "scratch resistance after hot water immersion" except that the hot water (90°C or 80°C water) was changed to a 50 mass % ethanol aqueous solution prepared by diluting 99.5% ethanol (manufactured by Kanto Chemical Co., Ltd.) with ion-exchanged water and the immersion was continued for 1 hour. If the evaluation result is "C" or higher, it is a level that does not cause problems in actual use.

[0350] [Evaluation criteria]

[0351] S: Pencil hardness 6H or above

[0352] A: Pencil hardness is above 4H and below 5H

[0353] B: Pencil hardness is above 2H and below 3H

[0354] C: Pencil hardness is F or higher and H or lower

[0355] D: Pencil hardness is below HB

[0356] (Abrasion resistance after immersion in alkaline solution)

[0357] The obtained printed material (evaluation sample) was immersed in a 3 mass % sodium hydroxide aqueous solution heated to 80° C. for 20 minutes in such a manner that the image portion and the base material were completely immersed. The 3 mass % sodium hydroxide aqueous solution was prepared by dissolving sodium hydroxide (manufactured by Kanto Chemical Co., Ltd.) in ion exchange water. After the immersion, the printed material (evaluation sample) was taken out, and water droplets attached to the image surface were immediately wiped off, and a tape peeling test was performed.

[0358] The tape peeling test is to stick a tape (CT-24, manufactured by Nichiban Co., Ltd.) on the image part and press it firmly, then peel it off quickly in a direction of 90° to the image surface, and visually observe the image surface after peeling off the tape, and evaluate it according to the following evaluation criteria. It should be noted that "image peeling" in the evaluation criteria refers to the case where either "cured material A of the active energy ray-curable composition" or "cured material B of the active energy ray-curable composition" is peeled off.

[0359] [Evaluation criteria]

[0360] ◎: No peeling of the image is seen after the tape is peeled off

[0361] 〇: After the tape is peeled off, the image is slightly peeled off.

[0362] ×: The image peels off on the entire surface after the tape is peeled off or the image peels off when immersed in an alkaline solution

[0363] (Jet Stability of Active Energy Ray-Curable Composition A)

[0364] In an expansion type coating device EV2500 (manufactured by Ricoh Co., Ltd.) equipped with an inkjet head MH5420 (manufactured by Ricoh Co., Ltd.), the active energy ray-curable compositions of modulation examples A-1 to A-20 were filled respectively, and the spraying state was observed with a camera when the spraying was continued for 30 minutes while the heater of the nozzle was turned on to heat the composition in the nozzle. Evaluation was performed according to the following evaluation criteria.

[0365] Regarding the observation of the injection state, one row of the four rows of injection ports was observed.

[0366] [Evaluation criteria]

[0367] 0: Spray from all nozzles

[0368] △: The number of nozzles that did not eject was observed to be 1 or more and less than 30

[0369] ×: The number of nozzles where no ejection was observed was 30 or more

[0370] Table 8

[0371]

[0372] Table 9

[0373]

[0374] Table 10

[0375]

[0376] Table 11

[0377]

[0378] Table 12

[0379]

[0380] Table 13

[0381]

[0382] Table 14

[0383]

[0384] Regarding the evaluation of the scratch resistance after immersion in ethanol, although the 50% ethanol aqueous solution is shown in the Examples, the same results as those of the 50% ethanol aqueous solution were obtained in the case of the 30% ethanol aqueous solution and the 70% ethanol aqueous solution.

[0385] As embodiments of the present invention, for example, the following are described.

[0386] <1> An imaging method, characterized in that it includes: a composition A imparting step of imparting an active energy ray-curable composition A containing a polymerizable monomer having a phosphate group and a polyester resin to a substrate material; a composition A curing step of curing the active energy ray-curable composition A; a composition B imparting step of imparting an active energy ray-curable composition B containing a multifunctional polymerizable compound having two or more polymerizable functional groups in the molecule to a cured product of the active energy ray-curable composition A; and a composition B curing step of curing the active energy ray-curable composition B.

[0387] <2> according to <1> The imaging method, wherein: the active energy ray-curable composition A also contains a multifunctional polymerizable compound having two or more polymerizable functional groups in the molecule, and the content of the multifunctional polymerizable compound in the active energy ray-curable composition A is less than 25% by mass relative to the total amount of the composition A.

[0388] <3> according to <1> ~ <2> The imaging method described in any one of the preceding claims, wherein: the polyester resin is a polyester resin having an unsaturated bond.

[0389] <4> according to <1> ~ <3> The imaging method described in any one of the preceding claims, wherein: the content of the polyester resin is 3% by mass or more and 15% by mass or less relative to the total amount of the composition A.

[0390] <5> according to <1> ~ <4> The imaging method described in any one of the preceding claims, wherein: the number average molecular weight of the polyester resin is less than 2000.

[0391] <6> according to <1> ~ <5> The imaging method described in any one of the preceding claims, wherein: relative to the total amount of the composition A, the content of the polymerizable monomer having a phosphate group is 3% by mass or more and 10% by mass or less.

[0392] <7> according to <1> ~ <6> The imaging method described in any one of the preceding claims, wherein: the polymerizable monomer having a phosphate group is a multifunctional monomer having two or more polymerizable functional groups in the molecule.

[0393] <8> according to <7> The imaging method, wherein: the polymerizable monomer having a phosphate group is the multifunctional monomer having three polymerizable functional groups in the molecule.

[0394] <9> according to <1> to <8> The imaging method described in any one of the preceding claims, wherein: the content of the multifunctional polymerizable compound in the active energy ray-curable composition B is 50% by mass or more relative to the total amount of the composition B.

[0395] <10> according to <9> The imaging method, wherein: the content of the multifunctional polymerizable compound in the active energy ray-curable composition B is 60% by mass or more and 80% by mass or less relative to the total amount of the composition B.

[0396] <11> according to <1> ~ <10> The imaging method described in any one of the preceding claims, wherein: the method of imparting the active energy ray-curable composition A and the active energy ray-curable composition B is an inkjet method.

[0397] <12> according to <1> ~ <11> The imaging method according to any one of the preceding claims, comprising: repeatedly performing the composition B imparting step and the composition B curing step to form two or more layers containing a cured product of the active energy ray-curable composition B.

[0398] <13> according to <1> ~ <12> The imaging method according to any one of the above, wherein: the composition B curing step comprises imparting the active energy ray-curable composition B to the cured product of the active energy ray-curable composition A through the composition B imparting step, and then irradiating the active energy ray after 5 seconds or more to cure the active energy ray-curable composition B.

[0399] <14> according to <1> ~ <13> The imaging method according to any one of the above, wherein: the composition A curing step comprises imparting the active energy ray-curable composition A to the substrate through the composition A imparting step, and then irradiating the substrate with active energy rays after more than 5 seconds to cure the active energy ray-curable composition B.

[0400] <15> A combination of active energy ray-curable compositions, characterized in that it includes: an active energy ray-curable composition A, which contains a polymerizable monomer having a phosphate group and a polyester resin, and an active energy ray-curable composition B, which contains a multifunctional polymerizable compound having two or more polymerizable functional groups in the molecule.

[0401] <16> An imaging device, characterized in that it includes: a composition A imparting mechanism for imparting an active energy ray-curable composition A containing a polymerizable monomer having a phosphate group and a polyester resin to a base material; a composition A curing mechanism for curing the active energy ray-curable composition A; a composition B imparting mechanism for imparting an active energy ray-curable composition B containing a multifunctional polymerizable compound having two or more polymerizable functional groups in the molecule to a cured product of the active energy ray-curable composition A, and a composition B curing mechanism for curing the active energy ray-curable composition B.

[0402] According to the above <1> ~ <14> The imaging method described in any one of the above <15> The combination of the active energy ray-curable composition and the above <16> The imaging device can solve various problems in the prior art and achieve the purpose of the present invention.

Claims

1. An imaging method, characterized in that: include: a composition A applying step of applying an active energy ray-curable composition A containing a polymerizable monomer having a phosphate ester group and a polyester resin to a substrate; a composition A curing step of curing the active energy ray-curable composition A; a step of applying an active energy ray-curable composition B containing a multifunctional polymerizable compound having two or more polymerizable functional groups in its molecule to the cured product of the active energy ray-curable composition A; and A composition B curing step of curing the active energy ray-curable composition B.

2. The imaging method according to claim 1, wherein: The active energy ray-curable composition A further contains a multifunctional polymerizable compound having two or more polymerizable functional groups in the molecule. The content of the polyfunctional polymerizable compound in the active energy ray-curable composition A is 25% by mass or less relative to the total amount of the composition A.

3. The imaging method according to claim 1 or 2, wherein: The polyester resin is a polyester resin having an unsaturated bond.

4. The imaging method according to claim 1 or 2, wherein: The content of the polyester resin is 3% by mass or more and 15% by mass or less relative to the total amount of the composition A.

5. The imaging method according to claim 1 or 2, wherein: The number average molecular weight of the polyester resin is 2,000 or less.

6. The imaging method according to claim 1 or 2, wherein: The content of the polymerizable monomer having a phosphate group is 3% by mass or more and 10% by mass or less relative to the total amount of the composition A.

7. The imaging method according to claim 1 or 2, wherein: The polymerizable monomer having a phosphate group is a multifunctional monomer having two or more polymerizable functional groups in the molecule.

8. The imaging method according to claim 7, wherein: The polymerizable monomer having a phosphate group is the multifunctional monomer having three polymerizable functional groups in the molecule.

9. The imaging method according to claim 1 or 2, wherein: The content of the polyfunctional polymerizable compound in the active energy ray-curable composition B is 50% by mass or more relative to the total amount of the composition B.

10. The imaging method according to claim 9, wherein: The content of the polyfunctional polymerizable compound in the active energy ray-curable composition B is 60% by mass or more and 80% by mass or less relative to the total amount of the composition B.

11. The imaging method according to claim 1 or 2, wherein: The method of applying the active energy ray-curable composition A and the active energy ray-curable composition B is an inkjet method.

12. The imaging method according to claim 1 or 2, wherein: The method comprises repeatedly performing the composition B applying step and the composition B curing step to form two or more layers containing a cured product of the active energy ray-curable composition B.

13. The imaging method according to claim 1 or 2, wherein: The composition B curing step includes applying the active energy ray-curable composition B to the cured product of the active energy ray-curable composition A in the composition B applying step, and then irradiating the active energy ray after 5 seconds or more to cure the active energy ray-curable composition B.

14. The imaging method according to claim 1 or 2, wherein: The composition A curing step includes applying the active energy ray-curable composition A to the substrate in the composition A applying step, and then irradiating the substrate with active energy rays after 5 seconds or more to cure the active energy ray-curable composition B.

Images