JP7380083B2 - Printed matter manufacturing method and printed matter manufacturing device - Google Patents

Description

The present invention relates to a printed matter manufacturing method and a printed matter manufacturing apparatus.

2. Description of the Related Art Materials such as flooring and wallpaper that are printed with desired images and given a design by embossing or the like are used for the floors, interior walls, ceilings, etc. of buildings. Additionally, attempts have been made to improve the durability of flooring materials and wallpapers by coating them with ultraviolet (UV) curable materials, coating with electron beam curable materials, and the like.

Furthermore, in recent years, technology has been developed to print desired images on embossed flooring materials, wallpapers, etc. using an inkjet method. Such technology includes, for example, a foam layer, an image forming layer, and a surface protective layer, the foam layer containing a thermoplastic resin and a foaming agent, and the image forming layer and the surface protective layer being crosslinked by electron beam irradiation. Alternatively, a method for manufacturing curable foam wallpaper has been proposed (see, for example, Patent Document 1). Furthermore, in order to improve the surface strength, decorative sheets for wall coverings that have a foamed resin layer on a paper base material and that use a specific resin composition for the foamed resin layer have been proposed (for example, patented (See Reference 2).

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing a printed matter that can produce a printed matter with excellent durability that maintains excellent design and image quality due to the uneven shape over a long period of time.

The method for producing a printed matter of the present invention includes an intermediate layer forming step of forming an intermediate layer by applying an intermediate layer forming liquid onto a base material, and a volume expansion step of forming an intermediate layer by applying a volume expansion agent and a polymerizable compound a to the intermediate layer. a volume expansion agent-containing liquid layer forming step of applying a volume expansion agent-containing liquid to form a volume expansion agent-containing liquid layer; and an ink-receiving liquid layer forming liquid containing polymerizable compound b on the volume expansion agent-containing liquid layer. an ink-receiving liquid layer forming step of applying an ink-receiving liquid layer to form an ink-receiving liquid layer; and a pre-curing image formation step of applying an ink containing a coloring material and a polymerizable compound c to the ink-receiving liquid layer to form a pre-curing image. process.

According to the present invention, it is possible to provide a method for manufacturing a printed matter that can produce a printed matter with excellent durability that maintains the design and image quality due to the excellent uneven shape over a long period of time.

FIG. 1 is a conceptual diagram showing an example of an inkjet printing apparatus of the present invention.

(Printed matter manufacturing method and printed matter manufacturing device)
The method for producing a printed matter of the present invention includes an intermediate layer forming step of forming an intermediate layer by applying an intermediate layer forming liquid onto a base material, and a volume expansion step of forming an intermediate layer by applying a volume expansion agent and a polymerizable compound a to the intermediate layer. a volume expansion agent-containing liquid layer forming step of applying a volume expansion agent-containing liquid to form a volume expansion agent-containing liquid layer; and an ink-receiving liquid layer forming liquid containing polymerizable compound b on the volume expansion agent-containing liquid layer. an ink-receiving liquid layer forming step of applying an ink-receiving liquid layer to form an ink-receiving liquid layer; and a pre-curing image formation step of applying an ink containing a coloring material and a polymerizable compound c to the ink-receiving liquid layer to form a pre-curing image. and further includes other steps as necessary.
The printed matter manufacturing apparatus of the present invention includes an intermediate layer forming means for forming an intermediate layer by applying an intermediate layer forming liquid onto a base material, and a volume expanding means for forming an intermediate layer by applying an intermediate layer forming liquid onto a base material, and a volume expanding agent and a polymerizable compound a contained in the intermediate layer. a volume-expanding agent-containing liquid layer forming means for applying a volume-expanding agent-containing liquid to form a volume-expanding agent-containing liquid layer; and an ink-receiving liquid layer-forming liquid containing a polymerizable compound b on the volume-expanding agent-containing liquid layer. an ink receiving liquid layer forming means for forming an ink receiving liquid layer by applying an ink containing a coloring material and a polymerizable compound c to the ink receiving liquid layer; and, if necessary, other means.
The method for producing a printed matter of the present invention can be suitably carried out using the printed matter producing apparatus of the present invention, the intermediate layer forming step can be suitably carried out by the intermediate layer forming means, and the volume expansion The agent-containing liquid layer forming step can be suitably carried out by means of a volume expansion agent-containing liquid layer forming means, the ink-receiving liquid layer forming step can be suitably carried out by the ink-receiving liquid layer forming means, and the curing The pre-image forming step can be preferably performed by the pre-curing image forming means, and the other steps can be suitably performed by the other means.
In the present invention, "foaming" is sometimes referred to as an embodiment of "volume expansion."

The present inventors studied a method for manufacturing printed matter that can produce a printed matter with excellent durability that maintains the design quality and image quality due to the excellent uneven shape over a long period of time, and obtained the following knowledge.
In conventional technology, a foam layer is directly formed on a base material in order to obtain printed matter with an uneven shape, but the uneven shape of the foam layer itself reduces the contact area with the surface of the base material, resulting in a decrease in adhesion. That is, there is a problem that durability may be lowered.
In addition, in conventional technology, a layer containing a coloring material is formed on a cured non-foamed resin layer, so it is necessary to form a surface protective layer to improve the scratch resistance of the formed image, and the printed matter is There is a problem in that the number of steps and equipment required to obtain the results increases.

Therefore, the present inventors provided an intermediate layer on the surface of the base material, and on the intermediate layer, a liquid layer containing a volume expander, an ink receiving liquid layer containing a polymerizable compound, and a liquid layer containing a polymerizable compound. It has been found that by forming the pre-cured images in this order, it is possible to obtain printed matter with excellent durability that maintains excellent design and image quality due to the uneven shape over a long period of time.

<Intermediate layer forming process and intermediate layer forming means>
The intermediate layer forming step is a step of applying an intermediate layer forming liquid onto the base material to form an intermediate layer.
The intermediate layer forming means is a means for forming an intermediate layer by applying an intermediate layer forming liquid onto the base material.
The intermediate layer forming step can be suitably performed by the intermediate layer forming means.

-Base material-
The base material is not particularly limited and can be selected as appropriate depending on the purpose, for example, resin film, resin-impregnated paper, synthetic paper made of synthetic fibers, natural paper, sheets of nonwoven fabric, cloth, leather, etc. Examples include wood, metal sheets, glass plates, ceramic plates, etc.
Examples of the resin film include a polyester film; a polypropylene film; a polyethylene film; a plastic film such as nylon, vinylon, and acrylic, or a combination of the above films.
The resin film is not particularly limited and can be appropriately selected depending on the purpose, but from the viewpoint of strength, one that is uniaxially or biaxially stretched is preferable.
Examples of the nonwoven fabric include one in which polyethylene fibers are dispersed in a sheet shape and bonded under heat and pressure to form a sheet shape.
Examples of the wood include MDF, HDF, particle board, plywood such as veneer, and decorative board with a sheet bonded to the surface. The average thickness of these is preferably 2 mm or more and 30 mm or less.
Examples of the glass plate include float glass, colored glass, tempered glass, wired glass, frosted glass, frosted glass, and mirror glass. The average thickness of these is preferably 0.3 mm or more and 20 mm or less.

-Middle class-
The intermediate layer is not particularly limited as long as it can maintain adhesion to the base material even if a volume expansion layer is formed by volume expansion of a liquid layer containing a volume expansion agent, which will be described later. You can choose.

The intermediate layer forming liquid contains a polymerizable compound, a dispersed resin, a dissolved resin, and solid fine particles, and further contains other materials as necessary. These may be used alone or in combination of two or more.

The polymerizable compound is not particularly limited and can be appropriately selected depending on the purpose, and the same polymerizable compound a contained in the volume expansion agent-containing liquid described later can be used. Examples of the polymerizable compound include a polymerizable compound that yields a polymer with a low glass transition point, and a polymerizable compound that has a functional group such as a hydroxyl group, a carboxyl group, an epoxy group, a sulfo group, or a phosphor group at the end of the molecule. It will be done. These may be used alone or in combination of two or more.
Examples of polymerizable compounds from which a polymer with a low glass transition point can be obtained include polyethylene glycol (600) diacrylate (Tg: -42°C) as a compound containing an ethylene oxide skeleton, and tridecyl as a compound containing an alkyl linear chain. Examples include acrylate (Tg: -55°C) and isodecyl acrylate (Tg: -60°C). When the polymerizable compound is one that yields a polymer with a low glass transition point, the flexibility of the resulting intermediate layer can be improved, and the volume expansion caused by volume expansion of the volume expansion agent-containing liquid layer can be improved. Since the adhesion between the layer and the base material is improved, the durability of the resulting printed matter can be improved.
Examples of the polymerizable compound having a functional group such as a hydroxyl group, carboxyl group, epoxy group, sulfo group, or phospho group at the molecular terminal include 1,4-cyclohexanedimethanol monoacrylate, 2-acryloyloxyethyl succinate, 4 -hydroxybutyl acrylate glycidyl ether, 2-acrylamido-2-methylpropanesulfonic acid, 2-hydroxyethyl methacrylate acid phosphate and the like.
The content of the polymerizable compound relative to the total amount of the intermediate layer forming liquid is preferably 1% by mass or more and 99% by mass or less, more preferably 10% by mass or more and 95% by mass or less.

The dispersion type resin is not particularly limited and can be appropriately selected depending on the purpose, for example, acrylic resin, vinyl acetate resin, styrene-butadiene resin, vinyl chloride resin, acrylic-styrene resin. , butadiene resin, styrene resin, epoxy resin, etc. These may be used alone or in combination of two or more.
The particle diameter of the resin component in the dispersed resin is not particularly limited as long as it forms an emulsion, but is preferably 150 nm or less, more preferably 5 nm or more and 100 nm or less. As the dispersion type resin, commercially available products can be used, and examples of the commercially available products include Boncoat W-26 (manufactured by DIC Corporation) and Boncoat W-386 (manufactured by DIC Corporation). These may be used alone or in combination of two or more.
The solid content of the dispersed resin based on the total amount of the intermediate layer forming liquid is preferably 1% by mass or more and 99% by mass or less, more preferably 10% by mass or more and 95% by mass or less.

The soluble resin is not particularly limited as long as it is dissolved in a solvent, and can be appropriately selected depending on the purpose. For example, acrylic resin, urethane resin, etc. , ethyl acetate, butyl acetate, and other solvents. As the soluble resin, commercially available products can be used, and examples of the commercially available products include Finetac CT-3088, Finetac CT-3850, Finetac CT-5020, Finetac CT-5030, and Finetac CT. -6030, Quick Master SPS-900-LV, Quick Master SPS-945NT, Quick Master SPS-1040NT-25 (all manufactured by DIC Corporation). These may be used alone or in combination of two or more.
The content of the soluble resin based on the total amount of the intermediate layer forming liquid is preferably 1% by mass or more and 99% by mass or less, more preferably 10% by mass or more and 95% by mass or less.

The solid fine particles are particles different from the dispersed resin, and are not particularly limited as long as they can improve the wettability of the base material or suppress deformation of the intermediate layer, and may be appropriately selected depending on the purpose. I can do it. Examples of the solid fine particles include solid fine particles having hydroxyl groups on their surfaces. When the solid fine particles have hydroxyl groups on their surfaces, the wettability of the surface of the base material can be improved, and deformation of the intermediate layer can be suppressed, so that the base material and the volume expansion agent It is possible to improve the adhesion with the volume-expandable layer obtained by expanding the volume of the liquid layer.
Commercially available products can be used as the solid fine particles, and examples of the commercially available products include organosilica sol MA-ST-M, IPA-ST, and MEK-ST-UP (manufactured by Nissan Chemical Co., Ltd.). These may be used alone or in combination of two or more.
The solid content of the solid fine particles relative to the total amount of the intermediate layer forming liquid is preferably 1% by mass or more and 50% by mass or less, more preferably 5% by mass or more and 30% by mass or less.

The average thickness (application amount) of the intermediate layer is not particularly limited and can be appropriately selected depending on the purpose, and is preferably 5 μm or more, for example. When the average thickness (application amount) of the intermediate layer is 5 μm or more, the adhesion between the base material and the volume expansion layer can be improved. Note that the average thickness is the thickness after curing and drying. To find the average value of the average thickness (applied amount) of the intermediate layer, the intermediate layer is scraped off at five different locations, and the height from the base material to the surface of the intermediate layer is measured using, for example, a Keyence laser microscope VK- It can be obtained by measuring at X100 and calculating the average value.

The method for forming the intermediate layer on the base material is not particularly limited, and can be appropriately selected depending on the purpose. For example, knife coating method, nozzle coating method, die coating method, lip coating method, comma coating method, gravure coating method, rotary screen coating method, reverse roll coating method, roll coating method, spin coating method, kneader coating method, bar coating method Coating methods such as , blade coating method, casting method, dip method, curtain coating method, and inkjet method can be mentioned.
Furthermore, before forming the intermediate layer, it is preferable to subject the base material to a surface treatment such as corona treatment to improve the coating uniformity and adhesion of the intermediate layer.

<Volume expanding agent-containing liquid layer forming step and volume expanding agent-containing liquid layer forming means>
The volume expansion agent-containing liquid layer forming step is a step of applying a volume expansion agent-containing liquid containing a volume expansion agent and the polymerizable compound a to the intermediate layer to form a volume expansion agent-containing liquid layer.
The volume expansion agent-containing liquid layer forming means is a means for forming a volume expansion agent-containing liquid layer by applying a volume expansion agent-containing liquid containing a volume expansion agent and the polymerizable compound a to the intermediate layer.

The volume expansion agent-containing liquid contains a volume expansion agent and a polymerizable compound a, preferably contains a polymerization initiator, a polymerization accelerator, and a surfactant as necessary, and further contains other components as necessary. .
Examples of the volume expansion agent-containing liquid include thermosetting compositions and active energy ray curable compositions, but active energy ray curable compositions are more suitable from the viewpoint of durability of the uneven shape.

--Volume expansion agent--
The volume expansion agent is not particularly limited as long as it is a material that expands in volume when heated, and can be appropriately selected depending on the purpose, such as thermally expandable microcapsules, thermally decomposable foaming agents, etc. Examples include. Among these, thermally expandable microcapsules are preferred because they have a high volumetric expansion coefficient and can form small, uniform closed cells. In addition, below, a volume expansion agent may be called a foaming agent.

The thermally expandable microcapsules are particles with a core-shell structure in which the volume expander is wrapped in a thermoplastic resin, and when heated, the thermoplastic resin in the outer shell begins to soften, and the vapor pressure of the encapsulated foaming compound increases. The pressure builds up to be sufficient to deform the particles, causing the thermoplastic outer shell to stretch and expand. Examples of the foaming compound include low boiling point aliphatic hydrocarbons.

As the thermally expandable microcapsules, commercially available products can be used, and examples of the commercially available products include Advancecell EM series manufactured by Sekisui Chemical Co., Ltd. and ExpancellDU, WU, MB, SL, and FG manufactured by AkzoNovel. series (sold in Japan by Nippon Philite Co., Ltd.), Matsumoto Microsphere F and FN series manufactured by Matsumoto Yushi Seiyaku Co., Ltd., and Kureha Microsphere H750, H850, and H1100 manufactured by Kureha Corporation. These may be used alone or in combination of two or more.

Examples of the thermally decomposable blowing agent include organic blowing agents and inorganic blowing agents.
Examples of the organic blowing agent include azodicarboxylic acid amide (ADCA), azobisisobutylnitrile (AIBN), p,p'-oxybisbenzenesulfonylhydrazide (OBSH), and dinitrosopentamethylenetetramine (DPT). Can be mentioned. These may be used alone or in combination of two or more.
Examples of the inorganic blowing agent include hydrogen carbonates such as sodium hydrogen carbonate, carbonates, and combinations of hydrogen carbonates and organic acid salts. These may be used alone or in combination of two or more.

The content of the volume expansion agent with respect to the total amount of the volume expansion agent-containing liquid is not particularly limited and can be appropriately selected depending on the purpose, but it is 1% by mass with respect to the total amount of the volume expansion agent-containing liquid. It is preferably 20% by mass or less, more preferably 3% by mass or more and 15% by mass or less.

<<Polymerizable compound a>>
The polymerizable compound a is not particularly limited as long as it is a compound that can be polymerized by being given energy, and can be appropriately selected depending on the purpose. For example, monofunctional monomers, polyfunctional monomers, monofunctional monomers, etc. Examples include combinations of functional monomers and polyfunctional monomers.

-Monofunctional monomer-
The monofunctional monomer has, for example, one vinyl group, acryloyl group, or methacryloyl group in its molecular structure.
Examples of the monofunctional monomer include γ-butyrolactone (meth)acrylate, isobornyl (meth)acrylate, formalized trimethylolpropane mono(meth)acrylate, trimethylolpropane (meth)acrylic acid benzoate, (meth)acryloyl Morpholine, 2-hydroxypropyl (meth)acrylamide, N-vinylcaprolactam, N-vinylpyrrolidone, N-vinylformamide, cyclohexanedimethanol monovinyl ether, hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, dicyclopentadiene vinyl ether, tricyclodecane vinyl ether , benzyl vinyl ether, ethyloxetane methyl vinyl ether, hydroxybutyl vinyl ether, ethyl vinyl ether, ethoxy(4)nonylphenol (meth)acrylate, benzyl (meth)acrylate, caprolactone (meth)acrylate, and the like. These may be used alone or in combination of two or more.
Among these, isobornyl (meth)acrylate is preferred because it has a high glass transition temperature (Tg) and good fastness.
The content of the monofunctional monomer is preferably 80% by mass or more and 99.5% by mass or less, more preferably 90% by mass or more and 95% by mass or less, based on the total amount of the volume expansion agent-containing liquid.

-Polyfunctional monomer-
The polyfunctional monomer is, for example, a compound having two or more vinyl groups, acryloyl groups, or methacryloyl groups in its molecular structure.
Examples of the polyfunctional monomer include ethylene glycol di(meth)acrylate, neopentyl hydroxypivalate glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, and triethylene glycol di(meth)acrylate. (Meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol dimethacrylate [CH ₂ = CH-CO-(OC ₂ H ₄ ) n-OCOCH=CH ₂ (n≒9), same (n≒14) , same (n≒23)], dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol dimethacrylate [CH ₂ =C(CH ₃ )-CO-(OC ₃ H ₆ ) _n -OCOC(CH ₃ )=CH ₂ (n≒7)], 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate ) acrylate, 1,9-nonanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, propylene oxide modified bisphenol A di(meth)acrylate, polyethylene glycol di(meth)acrylate meth)acrylate, dipentaerythritol hexa(meth)acrylate, propylene oxide-modified tetramethylolmethanetetra(meth)acrylate, dipentaerythritol hydroxypenta(meth)acrylate, caprolactone-modified dipentaerythritol hydroxypenta(meth)acrylate, ditrimethylolpropane Tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethylene oxide modified trimethylolpropane tri(meth)acrylate, propylene oxide modified trimethylolpropane tri(meth)acrylate, caprolactone modified tri(meth)acrylate Methylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, ethoxylated neopentyl glycol di(meth)acrylate, propylene oxide modified neopentyl glycol di( meth)acrylate, propylene oxide modified glyceryl tri(meth)acrylate, polyester di(meth)acrylate, polyester tri(meth)acrylate, polyester tetra(meth)acrylate, polyester penta(meth)acrylate, polyester poly(meth)acrylate, polyurethane Di(meth)acrylate, polyurethane tri(meth)acrylate, polyurethane tetra(meth)acrylate, polyurethane penta(meth)acrylate, polyurethane poly(meth)acrylate, triethylene glycol divinyl ether, cyclohexanedimethanol divinyl ether, diethylene glycol divinyl ether, Examples include triethylene glycol divinyl ether, ethoxylated (4) bisphenol di(meth)acrylate, and the like. These may be used alone or in combination of two or more.

[Molecular weight/functional number] in the polyfunctional monomer is preferably 250 or more. When the [molecular weight/functional number] of the polyfunctional monomer is 250 or more, both the designability (volume expandability) and robustness of the resulting printed matter can be achieved.

The content of the polyfunctional monomer in the volume expansion agent-containing liquid is not particularly limited and can be appropriately selected depending on the purpose, but it is 0.5 mass based on the total amount of the polymerizable compound a. % or more and 20% by mass or less, more preferably 5% by mass or more and 10% by mass or less. When the content of the polyfunctional monomer is 10% by mass or less based on the total amount of the polymerizable compound a, both designability (volume expandability) and robustness can be achieved.

The content of the polymerizable compound a in the volume expansion agent-containing liquid is not particularly limited and can be appropriately selected depending on the purpose; It is preferably 90% by mass or less, more preferably 70% by mass or more and 85% by mass or less. When the content is 70% by mass or more, the adhesiveness of the volume expansion agent in the volume expansion layer is increased, and even after volume expansion (volume expansion layer described below), peeling of the volume expansion layer from the intermediate layer and the base material is suppressed. It is possible to improve the durability of printed matter produced.

--Polymerization initiator--
Examples of the polymerization initiator include thermal polymerization initiators, photopolymerization initiators, and the like. Among these, photopolymerization initiators are more preferred from the viewpoint of design due to the uneven shape and durability of image quality.
The photopolymerization initiator may be any photopolymerization initiator as long as it can generate active species such as radicals and cations with the energy of active energy rays and initiate polymerization of the polymerizable compound. As the polymerization initiator, known radical polymerization initiators, cationic polymerization initiators, base generators, etc. can be used alone or in combination of two or more types. Among these, radical polymerization initiators are used. It is preferable to do so.
In order to obtain a sufficient curing speed, the content of the polymerization initiator is preferably 1% by mass or more and 20% by mass or less, and 5% by mass or more and 15% by mass or less, based on the total amount of the volume expansion agent-containing liquid. More preferred.
Examples of the radical polymerization initiator include aromatic ketones, acylphosphine oxide compounds, aromatic onium salt compounds, organic peroxides, thio compounds (e.g., thioxanthone compounds, thiophenyl group-containing compounds, etc.), hexaarylbylene compounds, etc. Examples include imidazole compounds, ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, compounds having a carbon-halogen bond, and alkylamine compounds.

The polymerization accelerator (sensitizer) is not particularly limited and can be appropriately selected depending on the purpose, for example, trimethylamine, methyldimethanolamine, triethanolamine, p-diethylaminoacetophenone, p-dimethylamino Examples include amine compounds such as ethyl benzoate, 2-ethylhexyl p-dimethylaminobenzoate, N,N-dimethylbenzylamine, and 4,4'-bis(diethylamino)benzophenone.
The content of the polymerization accelerator is not particularly limited and may be appropriately set depending on the polymerization initiator used and its amount.

The surfactant is not particularly limited and can be selected as appropriate depending on the purpose, for example, glycerin fatty acid ester, sorbitan fatty acid ester, polyethylene glycol fatty acid ester, glyceryl monostearate, glyceryl monooleate, Glycerin fatty acid esters such as diglyceryl stearate and diglyceryl monoisostearate, glycol fatty acid esters such as propylene glycol monostearate, sorbitan fatty acid esters such as sorbitan monostearate and sorbitan monooleate, sucrose stearate, POE ( 4.2) Lauryl ether, POE (40) hydrogenated castor oil, POE (10) cetyl ether, POE (9) lauryl ether, POE (10) oleyl ether, monooleic acid POE (20) sorbitan, monolauric acid POE (6) ) sorbitol, POE (15) cetyl ether, monopalmitic acid POE (20) sorbitan, POE (15) oleyl ether, POE (100) hydrogenated castor oil, POE (20) POP (4) cetyl ether, POE (20) cetyl Ether, POE (20) oleyl ether, POE (20) stearyl ether, POE (50) oleyl ether, POE (25) cetyl ether, POE (25) lauryl ether, POE (30) cetyl ether, POE (40) cetyl ether etc. These may be used alone or in combination of two or more.
The content of the surfactant is preferably 0.1% by mass or more and 2% by mass or less based on the total amount of the volume expansion agent-containing liquid.

--Other ingredients--
The other components are not particularly limited and can be selected as appropriate depending on the purpose, such as fillers, volume expansion promoters, thickeners, preservatives, stabilizers, deodorizers, fluorescent agents, and ultraviolet rays. Examples include blocking agents.

Examples of the filler include aluminum hydroxide, magnesium hydroxide, barium hydroxide, calcium carbonate, magnesium carbonate, calcium sulfate, barium sulfate, ferrous hydroxide, basic zinc carbonate, basic lead carbonate, silica sand, Examples include clay, talc, silicas, titanium dioxide, and magnesium silicate. These may be used alone or in combination of two or more. Among these, calcium carbonate, magnesium carbonate, aluminum hydroxide, and magnesium hydroxide are preferred.

The volume expansion accelerator is not particularly limited and can be appropriately selected depending on the purpose, for example, zinc naphthenate, zinc acetate, zinc propionate, zinc 2-ethylpentanoate, 2-ethyl-4- Zinc methylpentanoate, zinc 2-methylhexanoate, zinc 2-ethylhexanoate, zinc isooctylate, zinc n-octylate, zinc neodecanoate, zinc isodecanoate, zinc n-decanoate, zinc laurate, zinc myristate , zinc palmitate, zinc stearate, zinc isostearate, zinc 12-hydroxystearate, zinc behenate, zinc oleate, zinc linoleate, zinc linoleate, zinc ricinoleate, zinc benzoate, o, m or Zinc p-toluate, zinc p-t-butylbenzoate, zinc salicylate, zinc phthalate, zinc salt of monoalkyl phthalate (C4-18) ester, zinc dehydroacetate, zinc dibutyldithiocarbamate, zinc aminocrotonate, Examples include zinc salts of 2-mercaptobenzothiazole, zinc pyrithione, and zinc complexes of urea or diphenylurea. These may be used alone or in combination of two or more.

Examples of the thickener include polycyanoacrylate, polylactic acid, polyglycolic acid, polycaprolactone, polyacrylic acid alkyl ester, polymethacrylic acid alkyl ester, and the like. These may be used alone or in combination of two or more.

Examples of the preservative include those that are conventionally used and do not initiate polymerization of monomers, such as potassium sorbate, sodium benzoate, sorbic acid, and chlorocresol. These may be used alone or in combination of two or more.

Examples of the stabilizer serve to suppress polymerization of monomers during storage, and include anionic stabilizers, free radical stabilizers, and the like.
Examples of anionic stabilizers include metaphosphoric acid, maleic acid, maleic anhydride, alkylsulfonic acids, phosphorus pentoxide, iron (III) chloride, antimony oxide, 2,4,6-trinitrophenol, thiol, alkylsulfonyl , alkyl sulfone, alkyl sulfoxide, alkyl sulfite, sultone, sulfur dioxide, sulfur trioxide, and the like.
Examples of free radical stabilizers include hydroquinone, catechol, or derivatives thereof.

The volume expansion agent-containing liquid can be prepared using the various components mentioned above, and the preparation means and conditions are not particularly limited. It can be prepared by dispersing it in a dispersing machine such as a pin mill or a dyno mill, and then mixing a polymerization initiator, a surfactant, and the like.
The static surface tension of the volume expansion agent-containing liquid can be measured by a plate method or a ring method using, for example, an automatic surface tension meter DY-300 manufactured by Kyowa Interface Science. The static surface tension may be adjusted as appropriate depending on the purpose and application means, but is preferably 15 mN/m or more and 50 mN/m or less at 25°C.
Further, the viscosity of the volume expansion agent-containing liquid is measured, for example, using a rheometer MCR301 manufactured by Anton Paar using a cone plate CP25-1 at a shear rate of 10/s and appropriately setting the temperature in the range of 20°C to 65°C. be able to. The viscosity may be adjusted as appropriate depending on the purpose and application means, but it is preferably 10 mPa·s or more and 20,000 mPa·s or less at 25°C.

There is no particular restriction on the means for applying the volume expansion agent-containing liquid onto the intermediate layer to form the volume expansion agent-containing liquid layer, and it can be appropriately selected depending on the purpose. For example, knife coating method, nozzle coating method, die coating method, lip coating method, comma coating method, gravure coating method, rotary screen coating method, reverse roll coating method, roll coating method, spin coating method, kneader coating method, bar coating method Coating methods such as , blade coating method, casting method, dip method, curtain coating method, and inkjet method can be mentioned.

The amount of the volume-expanding agent-containing liquid applied (average thickness of the volume-expanding agent-containing liquid layer) is not particularly limited and can be appropriately selected depending on the purpose. preferable. The average thickness referred to here is the average thickness after curing and before volumetric expansion. To find the average value of the average thickness, scrape off the volume expansion layer (including the intermediate layer) at five different locations, and calculate the height from the base material of that part to the surface of the volume expansion agent-containing liquid layer, for example. It is obtained by measuring with a laser microscope VK-X100 manufactured by Keyence Corporation and calculating the average value by dividing the average thickness of the intermediate layer.
Further, before forming the volume expansion agent-containing liquid layer, it is preferable to perform a surface treatment such as corona treatment on the surface of the intermediate layer to improve coating uniformity and adhesion of the volume expansion layer.

<Ink receiving liquid layer forming step and ink receiving liquid layer forming means>
The ink-receiving liquid layer forming step is a step of applying an ink-receiving liquid layer-forming liquid containing the polymerizable compound b onto the volume expansion agent-containing liquid layer to form an ink-receiving liquid layer.
The ink-receiving liquid layer forming means is a means for forming an ink-receiving liquid layer by applying an ink-receiving liquid layer-forming liquid containing the polymerizable compound b onto the volume expansion agent-containing liquid layer.
The ink-receiving liquid layer forming step can be suitably carried out by the ink-receiving liquid layer forming means.

-Ink receiving liquid layer forming liquid-
The ink-receiving liquid layer forming liquid is a liquid for forming an ink-receiving liquid layer for receiving the ink described below, and contains a polymerizable compound b, a polymerization initiator, a polymerization accelerator, a surfactant, It is preferable to contain a pigment, and further contain other components as necessary.
As the polymerizable compound b, the same compound as the polymerizable compound a can be used.
Regarding the polymerization initiator, the polymerization accelerator, the surfactant, and other components, the same ones as those used for the volume expansion agent-containing liquid can be used.
By containing the polymerizable compound b, the ink-receiving liquid layer forming liquid can be cured immediately, thereby suppressing image disturbances such as beading and bleeding, and producing printed matter with excellent image quality.

In addition, the static surface tension of the ink receiving liquid layer forming liquid may be adjusted as appropriate depending on the use and the means of application, but the static surface tension of the ink receiving liquid layer forming liquid may be adjusted as appropriate depending on the use and the means of application. is preferred.
Further, the viscosity of the ink-receiving liquid layer forming liquid may be adjusted as appropriate depending on the purpose and application means, but it is preferably 10 mPa·s or more and 20,000 mPa·s or less at 25°C.

The ink-receiving liquid layer forming liquid can be prepared by mixing the various components mentioned above, and the preparation means and conditions are not particularly limited. Pigment dispersion is prepared by dispersing the pigment in a dispersing machine such as a ball mill, kitty mill, disc mill, pin mill, or dyno mill.Additionally, polymerizable monomers, initiators, polymerization inhibitors, surfactants, etc. are added to the pigment dispersion. It can be prepared by mixing.

The method for applying the ink-receiving liquid layer forming liquid onto the volume expansion agent-containing liquid layer is not particularly limited, and can be appropriately selected depending on the purpose. For example, knife coating method, nozzle coating method, die coating method, lip coating method, comma coating method, gravure coating method, rotary screen coating method, reverse roll coating method, roll coating method, spin coating method, kneader coating method, bar coating method Coating methods such as , blade coating method, casting method, dip method, curtain coating method, and inkjet method can be mentioned.

The average thickness of the ink-receiving liquid layer after curing and before volumetric expansion is not particularly limited as long as it can obtain printed matter with stable high image quality and robustness regardless of the substrate, and it can be selected as appropriate depending on the purpose. For example, the thickness is preferably 1 μm or more, more preferably 1 μm or more and 100 μm or less, and even more preferably 30 μm or more and 50 μm or less.
The average thickness of the ink-receiving liquid layer after curing and before volume expansion is determined by scraping off the layer after curing and before volume expansion at five different locations, and then removing the layer from the volume expansion agent-containing liquid layer and the ink-receiving liquid layer. It can be obtained by observing the cross section of the layer with, for example, a laser microscope VK-X100 manufactured by Keyence Corporation, measuring the average thickness of the ink-receiving liquid layer after curing, and calculating the average value.

<Pre-curing image forming step and pre-curing image forming means>
The pre-curing image forming step is a step of applying an ink containing a coloring material and a polymerizable compound c to the ink-receiving liquid layer to form a pre-curing image.
The pre-curing image forming means is a means for applying an ink containing a coloring material and a polymerizable compound c to the ink-receiving liquid layer to form a pre-curing image.
The pre-curing image forming step can be suitably carried out by the pre-curing image forming means.
Note that the "uncured image" in the present invention includes everything printed using the ink (letters, figures, symbols, photographs, solid images, etc.).
In the pre-curing image forming step, the ink is applied to the surface of the ink-receiving liquid layer.

-ink-
The ink preferably contains the polymerizable compound c, a polymerization initiator, and a coloring material, and further contains other components as necessary.

--Polymerizable compound c--
As the polymerizable compound c, the same compound as the polymerizable compound a can be used.
It is preferable that the polymerizable compound c in the ink contains a monofunctional monomer and a polyfunctional monomer.
The content of the polymerizable compound c is not particularly limited and can be appropriately selected depending on the purpose. For example, the content of the polymerizable compound c is preferably 70% by mass or more and 95% by mass or less based on the total amount of the ink.
By containing the polymerizable compound c in the ink, it is possible to obtain a printed matter having an image with excellent fastness.

--Polymerization initiator--
As the polymerization initiator, the same one as in the ink receiving liquid layer forming liquid can be used.

--Color material--
The coloring material may be a variety of glossy colors such as black, magenta, cyan, yellow, green, orange, purple, white, gold or silver, depending on the purpose and required characteristics of the ink in the present invention. Pigments can be used.
The content of the coloring material may be appropriately determined in consideration of the desired color density, dispersibility in the ink, etc., and is not particularly limited, but is 0.1% by mass or more and 20% by mass based on the total amount of the ink. The following are preferred.
As the coloring material, inorganic pigments and organic pigments can be used. These may be used alone or in combination of two or more.
As the inorganic pigment, for example, carbon blacks (C.I. Pigment Black 7) such as furnace black, lamp black, acetylene black, and channel black, iron oxide, and titanium oxide can be used.
Examples of the organic pigments include azo pigments such as insoluble azo pigments, condensed azo pigments, azo lakes, and chelate azo pigments, phthalocyanine pigments, perylene and perinone pigments, anthraquinone pigments, quinacridone pigments, dioxane pigments, thioindigo pigments, isoindolinone pigments, Polycyclic pigments such as quinophthalone pigments, dye chelates (e.g., basic dye type chelates, acidic dye type chelates, etc.), dyeing lakes (e.g., basic dye type lakes, acidic dye type lakes, etc.), nitro pigments, nitroso pigments , aniline black, etc.
Further, in order to improve the dispersibility of the pigment, a dispersant may be further included.
The dispersant is not particularly limited, but includes, for example, dispersants commonly used for preparing pigment dispersions such as polymer dispersants.

--Other ingredients--
The other components are not particularly limited and can be selected as appropriate depending on the purpose, such as organic solvents, surfactants, polymerization inhibitors, leveling agents, antifoaming agents, optical brighteners, and penetration promoters. agents, wetting agents (humectants), fixing agents, viscosity stabilizers, rust preventives, preservatives, antioxidants, ultraviolet absorbers, and the like.
It is preferable not to include the organic solvent if possible. If the composition does not contain the above-mentioned organic solvent, especially a volatile organic solvent (VOC (Volatile Organic Compounds) free), the safety of the place where the composition is handled will be further increased, and it is also possible to prevent environmental pollution. becomes. Note that "organic solvent" refers to general non-reactive organic solvents such as ether, ketone, xylene, ethyl acetate, cyclohexanone, and toluene, and should be distinguished from reactive monomers. be. Moreover, "not containing" an organic solvent means substantially not containing it, and preferably less than 0.1% by mass.

The ink can be prepared using the various components mentioned above, and the preparation method and conditions are not particularly limited, but for example, polymerizable monomers, pigments, dispersants, etc. Pigment dispersion is prepared by putting it into a dispersing machine such as a mill, pin mill, or dyno mill, and dispersing it. It is prepared by further mixing a polymerizable monomer, an initiator, a polymerization inhibitor, a surfactant, etc. with the pigment dispersion. can do.

The static surface tension of the ink may be adjusted as appropriate depending on the purpose and application means, but it is preferably 20 mN/m or more and 55 mN/m or less at 25°C.
Further, the viscosity of the ink may be adjusted as appropriate depending on the purpose and application means, but it is preferably 1 mPa·s or more and 100 mPa·s or less at 25°C.

There is no particular restriction on the means for applying the ink onto the ink-receiving liquid layer to form an image, and it can be selected as appropriate depending on the purpose. This is preferable because it can be flexibly adapted to patterns.
In the inkjet method, for example, as a drive method for the ejection head, an on-demand head using a piezoelectric element actuator using PZT or the like, a method that applies thermal energy, an actuator that uses electrostatic force, etc. is used. Alternatively, a continuous injection type charge control type head or the like may be used.

The ink may be of three, four, or more types depending on the coloring material (pigment) contained, and each ink is applied by a separate inkjet head. Alternatively, a head may be used in which one head has a plurality of nozzle rows and each nozzle row ejects different types of ink. The head nozzle density required for each color changes depending on the desired image resolution and number of scans. Examples of the head nozzle density include 240 npi (nozzle per inch), 300 npi, 600 npi, and 1,200 npi.

The total amount of the ink applied to the ink-receiving liquid layer is preferably 3 μL/cm ² or less. When the total amount of the ink applied onto the ink-receiving liquid layer is 3 μL/cm ² or less, coalescence, color mixing, and deterioration of color gamut can be suppressed.

The ejection speed of the ink droplets is preferably 5 m/s or more and 15 m/s or less. When the ejection speed of the ink droplets is 5 m/s or more and 15 m/s or less, stable ejection can be performed.

The dot density (image resolution) of the ejected droplets is preferably 240 dpi x 240 dpi (dots per inch) or more.

The average thickness of the image formed by the ink after curing is not particularly limited and can be appropriately selected depending on the purpose, and is preferably 1 μm or more and 20 μm or less, more preferably 1 μm or more and 10 μm or less.
Further, in the present invention, it is preferable that the average thickness of the image formed with the ink is thinner than the average thickness of the ink-receiving liquid layer formed with the ink-receiving liquid layer forming liquid. The ink is added to the ink receiving liquid layer forming liquid by making the average thickness of the image formed by the ink thinner than the average thickness of the ink receiving liquid layer formed by the ink receiving liquid layer forming liquid. can be embedded, resulting in highly durable printed matter. The difference between the average thickness of the ink-receiving liquid layer formed by the ink-receiving liquid layer forming liquid and the average thickness of the image formed by the ink is preferably 100 μm or less.
Furthermore, in the present invention, it is preferable that the sum of the average thickness of the ink-receiving liquid layer formed by the ink-receiving liquid layer forming liquid and the average thickness of the image formed by the ink is 1 μm or more and 100 μm or less. When the sum of the average thickness of the ink receiving liquid layer formed by the ink receiving liquid layer forming liquid and the average thickness of the image formed by the ink is 1 μm or more and 100 μm or less, stable and high Prints with high image quality and robustness can be obtained.
The average thickness can be determined by, for example, scraping off the cured ink layer (image) and the ink-receiving liquid layer at five different locations, and measuring the height from the base material to the surface of the image (ink layer) at that part, for example. It can be obtained by measuring with a laser microscope VK-X100 manufactured by Keyence Corporation and calculating the average value.

<Other processes and other means>
The other steps are not particularly limited and can be selected as appropriate depending on the purpose, for example, a volume expansion suppressing liquid application step, a transparent layer formation step, a curing step, a volume expansion layer formation step, an embossing step, Examples include a bending process.
The other means are not particularly limited and can be selected as appropriate depending on the purpose, for example, volume expansion suppressing liquid applying means, transparent layer forming means, curing means, volume expansion layer forming means, embossing means, Examples include bending means.
The other steps can be suitably carried out by the other means.

<<Volume expansion suppressing liquid applying step and volume expansion suppressing liquid applying means>>
The volume expansion suppressing liquid applying step is a step of applying a volume expansion suppressing liquid to a predetermined region of the volume expansion agent-containing liquid layer.
The volume expansion suppressing liquid applying means is a means for applying the volume expansion suppressing liquid to a predetermined region of the volume expansion agent-containing liquid layer.
When performing the volume expansion suppressing liquid application step, it is preferably performed after the formation of the volume expansion agent-containing liquid layer and before the formation of the ink receiving liquid layer.

-Volume expansion suppressing liquid-
The volume expansion suppressing liquid contains a polymerizable compound, and further contains other components such as a polymerization initiator and a surfactant, if necessary.

Examples of the polymerizable compound include polyfunctional monomers and polyfunctional oligomers. As the polymerizable compound, the same compounds as those used in the volume expansion agent-containing liquid can be used, such as 1,6-hexanediol di(meth)acrylate, 1,3-butylene glycoldi Examples include acrylate, 1,4-butanediol diacrylate, diethylene glycol diacrylate, neopentyl glycol diacrylate, and dipropylene glycol diacrylate. Alternatively, a mixture of different polyfunctional monomers, a mixture of a polyfunctional monomer and a monofunctional monomer, a mixture of a polyfunctional oligomer and a monofunctional monomer, a mixture of a monofunctional monomer, a polyfunctional monomer, or a polyfunctional oligomer is used. be able to.
Since the volumetric expansion suppressing liquid contains a polyfunctional polymerizable compound, it is three-dimensionally crosslinked by applying energy, so the volumetric expansion suppressing liquid is applied to any region of the volumetric expansion agent-containing liquid layer and energy is applied. By doing so, it is possible to accurately control whether or not the volumetric expansion is performed (whether or not the area is subjected to volumetric expansion), and it is possible to provide printed matter with an excellent design due to the uneven shape.

The predetermined area in the volume expansion agent-containing liquid layer to which the volume expansion suppressing liquid is applied can be specified, for example, based on data on the uneven shape of the printed matter to be manufactured. In the volume expansion suppressing liquid applying step, for example, the volume expansion suppressing liquid is applied to a portion that is a concave portion (a region in which the volume expansion agent-containing liquid layer is not caused to expand) based on the uneven shape data of the printed matter to be manufactured. By bringing them into contact with each other, the volume expansion of the volume expansion agent-containing layer (the volume expansion agent-containing liquid layer after curing) in the volume expansion layer forming step described later can be suppressed, and an arbitrary uneven shape can be formed.

As the polymerization initiator, the surfactant, and the other components, the same ones as those used in the volume expansion agent-containing liquid can be used.

The static surface tension of the volume expansion suppressing liquid may be adjusted as appropriate depending on the purpose and application means, but is preferably 20 mN/m or more and 55 mN/m or less at 25°C.
Further, the viscosity of the volumetric expansion suppressing liquid may be adjusted as appropriate depending on the purpose and application means, but it is preferably 1 mPa·s or more and 100 mPa·s or less at 25°C.

The method for applying the volumetric expansion suppressing liquid is not particularly limited and can be selected as appropriate depending on the purpose, but the inkjet method is flexible and compatible with various volumetric expansion patterns (volume expansion suppressing patterns). This is preferable because it can be done.
As the inkjet method, for example, as a drive method of the ejection head, an on-demand head using a piezoelectric element actuator using PZT or the like, a method that applies thermal energy, an actuator that uses electrostatic force, etc. may be used. Alternatively, a continuous injection type charge control type head or the like may be used.

The amount of the volumetric expansion suppressing liquid applied is not particularly limited and can be appropriately selected depending on the purpose. Various patterns can be obtained. The amount of the volume expansion suppressing liquid applied is preferably, for example, 3 μL/cm ² or less with respect to the surface of the volume expansion agent-containing liquid layer.

The ejection speed of the droplets of the volumetric expansion suppressing liquid is preferably 5 m/s or more and 15 m/s or less. When the ejection speed of the droplets of the volumetric expansion suppressing liquid is 5 m/s or more and 15 m/s or less, stable ejection can be performed.

The dot density (image resolution) of the ejected droplets is preferably 240 dpi x 240 dpi (dots per inch) or more.

<<Transparent layer forming step and transparent layer forming means>>
The transparent layer forming step is a step of applying a transparent layer forming liquid containing a polymerizable compound and not containing a coloring material onto the uncured image to form a transparent layer.
The transparent layer forming means is a means for forming a transparent layer by applying a transparent layer forming liquid containing a polymerizable compound and not containing a coloring material onto the uncured image.
The transparent layer forming step is performed after the pre-curing image forming step.
As the polymerizable compound, the same compounds as those used in the volume expansion agent-containing liquid can be used.
The method for applying the transparent layer forming liquid onto the uncured image is not particularly limited and can be appropriately selected depending on the purpose. A method can be used.
By forming the transparent layer on the pre-cured image, the storage stability of the formed pre-cured image and post-cured image can be improved.

<<Curing process and curing means>>
The curing step is a step of curing the volume expansion agent-containing liquid layer, the ink-receiving liquid layer, and the uncured image (ink layer) by external stimulation.
The curing means is a means for curing the volume expansion agent-containing liquid layer, the ink-receiving liquid layer, and the uncured image (ink layer) by external stimulation.
By curing the volume expansion agent-containing liquid layer, the ink-receiving liquid layer, and the uncured image (ink layer), an integrated cured product can be obtained. Note that the volume expansion agent-containing liquid layer, the ink-receiving liquid layer, and a layer obtained by curing the pre-curing image (ink layer) are respectively replaced by the volume-expanding agent-containing layer, the ink-receiving layer, and the post-curing image. It is sometimes called.

The external stimulus is not particularly limited and can be appropriately selected depending on the purpose, and includes, for example, active energy rays, heat, and the like.

The active energy rays include, in addition to ultraviolet rays, electron beams, α rays, β rays, γ rays, X rays, etc. that can impart the energy necessary to proceed with the polymerization reaction of the polymerizable components in the composition. It is good if there is one, and there is no particular limitation. In particular, when a high-energy light source is used, the polymerization reaction can proceed without using a polymerization initiator. Furthermore, in the case of ultraviolet irradiation, mercury-free devices are strongly desired from the viewpoint of environmental protection, and replacement with GaN-based semiconductor ultraviolet light-emitting devices is very useful both industrially and environmentally. Furthermore, ultraviolet light emitting diodes (UV-LEDs) and ultraviolet laser diodes (UV-LDs) are compact, long-life, highly efficient, and low-cost, and are preferred as ultraviolet light sources.

The curing conditions are not particularly limited and can be appropriately selected depending on the purpose, but in the case of ultraviolet rays, it is preferable to use an irradiation device that can irradiate with an intensity of 6 W/cm ^{2 or} more at an irradiation distance of 2 mm.
In the case of an electron beam, it is preferable that the accelerating voltage is such that a dose of 15 kGy or more is applied to the part farthest from the electron beam irradiation device to be cured.

<<Volume expansion layer forming step and volume expansion layer forming means>>
The volume expansion layer forming step is a step of heating the volume expansion agent-containing layer to form a volume expansion layer.
The volume expansion layer forming step is a means of heating the volume expansion agent-containing layer to form a volume expansion layer.
The volume expansion layer forming means is not particularly limited as long as it can volume expand the volume expansion agent in the volume expansion agent-containing layer by heating, and can be appropriately selected depending on the purpose, for example, Examples include infrared heaters, hot air heaters, heating rollers, and high-frequency dielectric heaters.
The heating temperature in the volume expansion layer forming step is not particularly limited as long as it is equal to or higher than the volume expansion temperature of the volume expansion agent, and can be appropriately selected depending on the purpose. For example, 100 ° C. or more and 250 ° C. or less is preferable. .

The timing of performing the volume expansion layer forming step is not particularly limited as long as it is after the volume expansion agent-containing liquid layer formation step, and can be appropriately selected depending on the purpose. More specifically, for example, as described above, in the volume expansion agent-containing liquid layer formation step, when applying energy to the volume expansion agent-containing liquid to harden it, the volume expansion layer formation step is performed at once. Alternatively, it may be performed after the formation of each layer (for example, the intermediate layer, the volume expansion agent-containing layer, and the cured image) is completed.

<< Embossing process and embossing means >>
The embossing process is a process of forming an uneven pattern on printed matter.
Embossing means is means for forming an uneven pattern on printed matter.
In the embossing process, methods such as embossing, chemical embossing, rotary screen processing, or raised printing, which are usually used for the purpose of adding unevenness to wallpaper, decorative materials, etc., can be selected and used as appropriate. can.

Examples of the embossing means include means for embossing with a cooling roller after heating, and means for embossing at once using a hot roller embossing.
The depth of embossing by embossing is preferably 0.08 mm or more and 0.50 mm or less. When the embossing depth is 0.08 mm or more, the three-dimensional effect can be improved, and when it is 0.50 mm or less, the surface abrasion strength can be improved.
Examples of the shape of the uneven pattern formed by embossing include woodgrain conduit grooves, stone plate surface unevenness, fabric surface texture, satin finish, grain, hairline, parallel grooves, and the like.

The printed matter produced by the printed matter manufacturing method of the present invention and the printed matter manufacturing apparatus of the present invention has excellent durability that maintains the design and image quality due to the excellent uneven shape over a long period of time. It is suitable for applications such as wallpaper, interior materials, wall materials, width lumber, ceiling materials, and architectural materials such as pillars.

Here, the printed matter manufacturing apparatus of the present invention will be described in detail with reference to the drawings.
FIG. 1 is a schematic diagram showing an example of a printed matter manufacturing apparatus of the present invention. The printed matter manufacturing apparatus 100 in FIG. 1 includes a roller coater 12 that applies an intermediate layer forming liquid onto a base material 11, a curtain coater 21 that applies a volume expansion agent-containing liquid onto the intermediate layer, and a volume expansion agent suppressing agent. A head 30 for applying a liquid by an inkjet method, an active energy ray irradiation device 31, a roller coater 32 for applying an ink receiving liquid layer forming liquid, and a head for black as a head for applying a plurality of inks by an inkjet method. 33a, a magenta head 33b, a cyan head 33c, a yellow head 33d, a discharge head unit consisting of a transparent layer forming liquid head (not shown), a second active energy ray irradiation device 34, and a heating device 20. ing. In addition, in FIG. 1, 36 is a conveyance belt, and 37 is a conveyance roller. The base material 11 is transported in the direction of the arrow in FIG. 1 by a transport belt 36 and transport rollers 37.
First, an intermediate layer is applied to the surface of the base material using a roller coater, and then a first active energy ray-curable composition is applied using a curtain coater 21 to form a liquid film (volume expanding agent-containing liquid layer) of a predetermined thickness. Form. Next, the base material on which the intermediate layer and the volume-expanding agent-containing liquid layer are formed is scanned at a predetermined speed, and the volume expansion-suppressing liquid corresponding to the uneven pattern is discharged from the head 30 onto the volume-expanding agent-containing liquid layer. Next, using the active energy ray irradiation device 31, the volumetric expansion suppressing liquid discharged into a predetermined area is cured by active energy rays.
In this way, the volume expansion agent-containing liquid layer is cured according to the uneven pattern, and the volume expansion agent-containing liquid layer is hardened by applying the volume expansion suppressing liquid, and the volume expansion agent-containing liquid layer is semi-cured without applying the volume expansion suppressing liquid. A liquid film of a predetermined thickness is formed with the ink-receiving liquid layer forming liquid on the swelling agent-containing liquid layer by a roller coater 32 . Next, ink corresponding to the image pattern is ejected from the heads 33a to 33d onto the ink receiving liquid layer to form a pre-cured image. Next, using the active energy ray irradiation device 34, active energy rays are irradiated under predetermined irradiation conditions to cure the ink receiving liquid layer and the uncured image.
Finally, the heating device 20 heats and volumetrically expands the volumetric expansion agent in the volumetric expansion agent-containing liquid layer on the printed matter on which a cured image is formed from the intermediate layer on the substrate 11, thereby forming an uneven shape.
The printed matter manufacturing apparatus 100 is configured as a single-pass printing apparatus in which the width that can be printed by the inkjet head is larger than the width of the substrate to be printed, and the number of scans is one. A multi-pass printing device may be configured that has a small width and is provided with a drive mechanism (head unit or substrate conveyance) that can perform multiple scans.

Examples of the present invention will be described below, but the present invention is not limited to these examples in any way.

<Preparation of intermediate layer forming liquid 1>
10 parts by mass of 1,4-cyclohexanedimethanol monoacrylate (manufactured by Mitsubishi Chemical Corporation) as a polymerizable compound, 85 parts by mass of 2-acryloyloxyethyl phthalate (manufactured by Shin-Nakamura Chemical Co., Ltd.), and Omnirad TPO (IGM) as a polymerization initiator. Intermediate layer forming liquid 1 was prepared by stirring 5 parts by mass (manufactured by Resins).
The static surface tension of the intermediate layer forming liquid 1 at 25°C was 40 mN/m, and the viscosity at 25°C was 7,000 mPa·s.
Note that the static surface tension at 25° C. was measured by the plate method using an automatic surface tension meter DY-300 manufactured by Kyowa Interface Science. The viscosity at 25°C was measured using a rheometer MCR301 manufactured by Anton Paar, using a cone plate CP25-1, and setting a shear rate of 10/s and a temperature of 25°C. Hereinafter, static surface tension and viscosity were measured in the same manner.

<Preparation of volumetric expansion agent-containing liquid A1>
15 parts by mass of Kureha Microsphere (manufactured by Kureha Co., Ltd., H750) as a volume expansion agent, 40 parts by mass of isobornyl acrylate (manufactured by Tomoe Kogyo Co., Ltd.) as a polymerizable compound a, 2-acryloyloxyethyl phthalate (Shin Nakamura Chemical Co., Ltd.) A volume expander-containing liquid A1 was prepared by stirring 40 parts by mass of Omnirad TPO (manufactured by IGM Resins) as a polymerization initiator.
The static surface tension of the volume expansion agent-containing liquid A1 at 25°C was 33 mN/m, and the viscosity at 25°C was 130 mPa·s.

<Preparation of ink receiving liquid layer forming liquid A2>
94 parts by mass of 2-acryloyloxyethyl succinate (manufactured by Shin Nakamura Chemical Co., Ltd.) as a polymerizable compound b, 5 parts by mass of Omnirad TPO (manufactured by IGM Resins) as a polymerization initiator, and BYK-UV-3510 (manufactured by IGM Resins) as a surfactant. By stirring 1 part by mass (manufactured by BYK), an ink receiving liquid layer forming liquid A2 was prepared.
The static surface tension of the ink receiving liquid layer forming liquid A2 at 25°C was 20 mN/m, and the viscosity at 25°C was 190 mPa·s.

<Preparation of black ink A-Bk>
As the polymerizable compound c, 25 parts by mass of phenoxyethyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), 26 parts by mass of acryloylmorpholine (manufactured by Tokyo Chemical Industry Co., Ltd.), and 35 parts by mass of trimethylolpropane ethoxy triacrylate (manufactured by Daicel Allnex Corporation) Parts by mass, 5 parts by mass of Omnirad TPO (manufactured by IGM Resins) as a polymerization initiator, 2 parts by mass of Solsperse 32000 (manufactured by Lubrizol) as a surfactant/dispersant, SPECIAL BLACK 350 (black pigment, manufactured by BASF Japan) as a coloring material. A black ink A-Bk was prepared by stirring 7 parts by mass (manufactured by a commercial manufacturer).
The static surface tension of the black ink A-Bk at 25°C was 24 mN/m, and the viscosity at 25°C was 25 mPa·s.

<Preparation of magenta ink A-M>
As the polymerizable compound c, 25 parts by mass of phenoxyethyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), 26 parts by mass of acryloylmorpholine (manufactured by Tokyo Chemical Industry Co., Ltd.), and 35 parts by mass of trimethylolpropane ethoxy triacrylate (manufactured by Daicel Allnex Corporation) Parts by mass, 5 parts by mass of Omnirad TPO (manufactured by IGM Resins) as a polymerization initiator, 2 parts by mass of Solsperse 32000 (manufactured by Lubrizol) as a surfactant/dispersant, CINQUASIA MAGENTA RT-355-D (magenta pigment) as a coloring material. , manufactured by BASF Japan) were stirred to prepare magenta inks AM.
The static surface tension of the magenta ink A to M at 25°C was 24 mN/m, and the viscosity at 25°C was 25 mPa·s.

<Preparation of cyan ink A-C>
As the polymerizable compound c, 25 parts by mass of phenoxyethyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), 26 parts by mass of acryloylmorpholine (manufactured by Tokyo Chemical Industry Co., Ltd.), and 35 parts by mass of trimethylolpropane ethoxy triacrylate (manufactured by Daicel Allnex Corporation) parts by mass, 5 parts by mass of Omnirad TPO (manufactured by IGM Resins) as a polymerization initiator, 2 parts by mass of Solsperse 32000 (manufactured by Lubrizol) as a surfactant/dispersant, IRGALITE BLUE GLVO (cyan pigment, manufactured by BASF Japan) as a coloring material. Cyan ink A-C was prepared by stirring 40 parts by mass of (manufactured by) Co., Ltd.).
The static surface tension of the cyan ink A to C at 25°C was 24 mN/m, and the viscosity at 25°C was 25 mPa·s.

<Preparation of yellow ink AY>
As the polymerizable compound c, 25 parts by mass of phenoxyethyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), 26 parts by mass of acryloylmorpholine (manufactured by Tokyo Chemical Industry Co., Ltd.), and 35 parts by mass of trimethylolpropane ethoxy triacrylate (manufactured by Daicel Allnex Corporation) Parts by mass, 5 parts by mass of Omnirad TPO (manufactured by IGM Resins) as a polymerization initiator, 2 parts by mass of Solsperse 32000 (manufactured by Lubrizol) as a surfactant/dispersant, NOVOPERM YELLOW H2G (yellow pigment, manufactured by Clariant) as a coloring material. ) Yellow ink AY was prepared by stirring 40 parts by mass.
The static surface tension of the yellow ink AY at 25°C was 24 mN/m, and the viscosity at 25°C was 25 mPa·s.

Next, the printed matter manufacturing apparatus 100 shown in FIG. Printed matter 1 was obtained using ink AC and yellow ink AY in the following manner.
Using a roller coater 12 (manufactured by Matsuo Sangyo Co., Ltd., Easy Proof), an intermediate layer forming liquid is applied onto a 9 mm thick MDF (medium density fiberboard, NP Wood manufactured by Sumitomo Forestry Co., Ltd.) base material 11. It was applied to a thickness of 5 μm. After drying in an oven (not shown), a volume expanding agent-containing layer forming liquid was applied onto the intermediate layer to a thickness of 100 μm using a curtain coater 21 (manufactured by Chefura, laboratory flow coater). Thereafter, using an active energy ray irradiation device 31 (manufactured by Hamamatsu Photonics, linear irradiation type UV-LED light source GJ-75), UV irradiation is performed from a position 10 mm away from the base material surface to harden the volume expansion agent-containing liquid layer. Ta.
Next, the ink-receiving liquid layer forming liquid was applied onto the cured volume expansion agent-containing liquid layer to a thickness of 6 μm using a roller coater 32 (manufactured by Matsuo Sangyo Co., Ltd., Easy Proof).
Next, this base material is scanned at a speed of 15 m/min, and a black ink head 33a is used as the ink ejection heads 14 to 17 using GEN5 heads (MH5420, 150 npi x 4 rows) manufactured by Ricoh Industries Co., Ltd. , the magenta ink head 33b, the cyan ink head 33c, and the yellow ink head 33d are heated to 40° C. to ink black ink A-Bk, magenta ink A-M, cyan ink A-C, and yellow ink AY. , a droplet volume of 7 pL and a droplet speed of 7 m/s were ejected, and a solid image was created at a dot density of 25% for each color at 600 dpi x 600 dpi.
Next, the pre-cured image was similarly cured using the active energy ray irradiation device 34 used to cure the liquid layer containing the volume expansion agent. The time from ejection of the yellow ink to curing was set to 6 seconds.
Finally, the mixture was heated and foamed using a heating device 35. The heating device was created by combining Lutex Blower G series manufactured by Hitachi Industrial Equipment Systems Co., Ltd., electric heater XS-2 for generating high-temperature hot air manufactured by Kansai Dentsu Co., Ltd., and Kansai Dentsu Co., Ltd. High Blow Nozzle 50AL. was adjusted so that the wind speed from the nozzle tip was 30 m/sec and the temperature at the nozzle tip was 200°C. Through the above steps, printed matter 1 was obtained.

(Example 2)
A printed matter 2 was obtained in the same manner as in Example 1, except that the intermediate layer forming liquid 1 was changed to the following intermediate layer forming liquid 2.

<Adjustment of intermediate layer forming liquid 2>
As a polymerizable compound, 10 parts by mass of 2-acrylamido-2-methylpropanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 85 parts by mass of 2-acryloyloxyethyl phthalate (manufactured by Shin-Nakamura Chemical Co., Ltd.), and Omnirad as a polymerization initiator. Intermediate layer forming liquid 2 was prepared by stirring 5 parts by mass of TPO (manufactured by IGM Resins).
The static surface tension of the intermediate layer forming liquid 2 at 25°C was 40 mN/m, and the viscosity at 25°C was 6,000 mPa·s.

(Example 3)
In Example 1, the intermediate layer forming liquid 1 was changed to the intermediate layer forming liquid 3 of Boncourt W-26 (manufactured by DIC Corporation) as a dispersion type resin, and after coating the intermediate layer forming liquid 3, it was heated in an oven at 100°C. Printed matter 3 was obtained in the same manner as in Example 1 except that it was dried for a minute.

(Example 4)
In Example 1, the intermediate layer forming liquid 1 was changed to the intermediate layer forming liquid 4 of Finetac CT-5020 (manufactured by DIC Corporation) as a soluble resin, and after applying the intermediate layer forming liquid 4, it was heated in an oven at 100 ° C. Printed matter 4 was obtained in the same manner as in Example 1, except that it was dried for 1 minute.

(Example 5)
A printed matter 5 was obtained in the same manner as in Example 1, except that the intermediate layer forming liquid 1 was changed to the following intermediate layer forming liquid 5.

<Adjustment of intermediate layer forming liquid 5>
By stirring 90 parts by mass of Boncoat W-26 (manufactured by DIC Corporation) as a dispersed resin and 10 parts by mass of organosilica sol IPA-ST-UP (manufactured by Nissan Chemical Co., Ltd.) as solid particles, the intermediate layer forming liquid 5 was prepared. Prepared.

(Example 6)
A printed matter 6 was obtained in the same manner as in Example 1, except that the intermediate layer forming liquid 1 was changed to the following intermediate layer forming liquid 6.

<Adjustment of intermediate layer forming liquid 6>
By stirring 90 parts by mass of Finetac CT-5020 (manufactured by DIC Corporation) as a soluble resin and 10 parts by mass of organosilica sol MEK-ST-UP (manufactured by Nissan Chemical Co., Ltd.) as solid particles, an intermediate layer forming liquid 6 was prepared. was prepared.

(Comparative example 1)
Printed matter 7 was obtained in the same manner as in Example 1, except that the volume expansion agent-containing liquid was applied directly to the base material without forming an intermediate layer.

Next, the "durability" of each of the obtained printed materials 1 to 7 of Examples 1 to 6 and Comparative Example 1 was evaluated as follows. The evaluation results are shown in Table 2.

<Durability>
The adhesion (durability) of the printed matter was evaluated using a cross-cut method. Use a cutter to make cuts in the printed material so that 5 x 5 grids are formed with a width of 1 mm, and use adhesive tape (manufactured by Cortech, product name: CCI-1) with an adhesive strength of 10 ± 1 N/25 mm width based on JIS K5600. Attach the attached tape) to the entire surface of the printed material and peel it off from the printed material for 0.5 seconds to 1 second at an angle as close to 60° as possible. The ratio of the residual rate of the volume expansion layer and the printed layer of the remaining printed matter was measured and evaluated based on the following evaluation criteria.

[Evaluation criteria]
◎: The residual rate of the volumetric expansion layer and the printed layer is 90% or more. ○: The residual rate of the volumetric expansion layer and the printed layer is 50% or more and less than 90%. ×: The residual rate of the volumetric expansion layer and the printed layer is less than 50%.

From the results in Table 2, it was found that the printed matter of Examples 1 to 6 had better durability than the printed matter of Comparative Example 1.

Aspects of the present invention are, for example, as follows.
<1> An intermediate layer forming step of applying an intermediate layer forming liquid onto the base material to form an intermediate layer;
A volume expansion agent-containing liquid layer forming step of forming a volume expansion agent-containing liquid layer by applying a volume expansion agent-containing liquid containing a volume expansion agent and a polymerizable compound a to the intermediate layer;
an ink-receiving liquid layer forming step of forming an ink-receiving liquid layer by applying an ink-receiving liquid layer-forming liquid containing polymerizable compound b onto the volume expansion agent-containing liquid layer;
This method of producing a printed matter is characterized by comprising a pre-curing image forming step of applying an ink containing a coloring material and a polymerizable compound c to the ink-receiving liquid layer to form a pre-curing image.
<2> The method for producing a printed matter according to <1>, wherein the intermediate layer forming liquid contains at least one of a polymerizable compound, a dispersed resin, a dissolved resin, and solid fine particles.
<3> The polymerizable compound is a polymerizable compound that yields a polymer with a low glass transition point, and a polymerizable compound that has at least a hydroxyl group, a carboxyl group, an epoxy group, a sulfo group, and a phosphor group at the molecular terminal. The method for producing a printed matter according to at least one of the above items <2>.
<4> The polymerizable compound having at least a hydroxyl group, a carboxyl group, an epoxy group, a sulfo group, and a phospho group at the molecular terminal is 1,4-cyclohexanedimethanol monoacrylate, 2-acryloyloxyethyl succinate, 4- The method for producing a printed matter according to any one of <2> to <3> above, which is hydroxybutyl acrylate glycidyl ether and 2-acrylamido-2-methylpropanesulfonic acid.
<5> The dispersion type resin is an acrylic resin, a vinyl acetate resin, a styrene-butadiene resin, a vinyl chloride resin, an acrylic-styrene resin, a butadiene resin, a styrene resin, or an epoxy resin. The method for producing a printed matter according to any one of <2> to <4>.
<6> The above-mentioned <2> to <5>, wherein the soluble resin is a resin such as an acrylic resin or a urethane resin dissolved in a solvent such as methyl ethyl ketone, dioxane, hexane, ethyl acetate, or butyl acetate. This is a method for producing a printed matter according to any one of the above.
<7> The method for producing a printed matter according to any one of <2> to <6>, wherein the solid fine particles have hydroxyl groups on their surfaces.
<8> From <1> above, further comprising a curing step of irradiating and curing at least one of the volume expansion agent-containing liquid layer, the ink-receiving liquid layer, and the uncured image with active energy rays. The method for producing a printed matter according to any one of <7>.
<9> The method for producing a printed matter according to <8>, wherein the active energy ray is at least one of ultraviolet rays and electron beams.
<10> Any one of <1> to <9> above, further comprising a volume expansion layer forming step of heating the volume expansion agent-containing layer obtained by curing the volume expansion agent-containing liquid layer to form a volume expansion layer. This is a method for producing a printed matter as described in .
<11> Intermediate layer forming means for forming an intermediate layer by applying an intermediate layer forming liquid onto the base material;
A volume expansion agent-containing liquid layer forming means for forming a volume expansion agent-containing liquid layer by applying a volume expansion agent-containing liquid containing a volume expansion agent and a polymerizable compound a to the intermediate layer;
an ink-receiving liquid layer forming means for forming an ink-receiving liquid layer by applying an ink-receiving liquid layer-forming liquid containing polymerizable compound b onto the volume expansion agent-containing liquid layer;
The apparatus for producing a printed matter is characterized by comprising a pre-curing image forming means for applying an ink containing a coloring material and a polymerizable compound c to the ink-receiving liquid layer to form a pre-curing image.

According to the printed matter manufacturing method described in <1> to <10> above and the printed matter manufacturing apparatus described in <11> above, various conventional problems can be solved and the object of the present invention can be achieved. .

11 Base material 12, 32 Application roller 21 Curtain coater 30 Volume expansion suppressing liquid head 31, 34 Active energy ray irradiation device 33a Head for black 33b Head for magenta 33c Head for cyan 33d Head for yellow 35 Heating device 36 Conveyor belt 37 Conveyance roller

Patent No. 5195999 Japanese Patent Application Publication No. 2007-291596

Claims (5)

an intermediate layer forming step of forming an intermediate layer by applying an intermediate layer forming liquid on the base material;
A volume expansion agent-containing liquid layer forming step of forming a volume expansion agent-containing liquid layer by applying a volume expansion agent-containing liquid containing a volume expansion agent and a polymerizable compound a to the intermediate layer;
an ink-receiving liquid layer forming step of forming an ink-receiving liquid layer by applying an ink-receiving liquid layer-forming liquid containing polymerizable compound b onto the volume expansion agent-containing liquid layer;
A method for producing a printed matter, comprising a pre-curing image forming step of applying an ink containing a coloring material and a polymerizable compound c to the ink-receiving liquid layer to form a pre-curing image. The method for producing a printed matter according to claim 1, wherein the intermediate layer forming liquid contains at least one of a polymerizable compound, a dispersed resin, a soluble resin, and solid fine particles. Any one of claims 1 to 2, further comprising a curing step of irradiating and curing at least one of the volume expansion agent-containing liquid layer, the ink-receiving liquid layer, and the uncured image with active energy rays. The method for manufacturing printed matter described in . The method for manufacturing a printed matter according to any one of claims 1 to 3, further comprising a volume expansion layer forming step of heating the volume expansion agent-containing layer obtained by hardening the volume expansion agent- containing liquid layer to form a volume expansion layer. . an intermediate layer forming means for forming an intermediate layer by applying an intermediate layer forming liquid onto the base material;
A volume expansion agent-containing liquid layer forming means for forming a volume expansion agent-containing liquid layer by applying a volume expansion agent-containing liquid containing a volume expansion agent and a polymerizable compound a to the intermediate layer;
an ink-receiving liquid layer forming means for forming an ink-receiving liquid layer by applying an ink-receiving liquid layer-forming liquid containing polymerizable compound b onto the volume expansion agent-containing liquid layer;
An apparatus for producing a printed matter, comprising: a pre-curing image forming means for applying an ink containing a coloring material and a polymerizable compound c to the ink-receiving liquid layer to form a pre-curing image.

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