JP2021091207A - Manufacturing method of printed matter, and manufacturing apparatus of printed matter - Google Patents

Abstract

To provide a manufacturing method of printed matters, which can efficiently manufacture printed matters having a concave-convex shape having high hardness and excellent solvent resistance.SOLUTION: A manufacturing method of printed matters comprising: a foaming liquid layer formation step of forming a foaming liquid layer by imparting a foaming agent-containing composition containing a polymerizable compound containing a foaming agent and a multifunctional monomer to a matter to be printed; a foaming suppression agent imparting step of selectively imparting a foaming suppression agent containing a polymerizable compound on the foaming liquid layer; a foaming suppression agent curing step of curing the imparted foaming suppression agent; a foaming step of foaming the foaming liquid layer, by heating the foaming liquid layer; and a foaming liquid layer curing step of curing by irradiating an electron beam after the foaming step.SELECTED DRAWING: Figure 1

Description

The present invention relates to a method for producing a printed matter and an apparatus for producing a printed matter.

Conventionally, wallpaper and building interior materials such as flooring materials have been used for the inner walls, floors, ceilings, etc. of buildings. As such an interior material for construction, there is known a material in which a printed layer on which a desired image is printed is produced, and a concavo-convex pattern is formed on the printed layer by embossing or the like to impart designability.

As a method for manufacturing an interior material for construction having the uneven pattern, for example, a foam layer containing a foaming agent is provided as a part of the interior material for construction, and the foam layer is foamed to obtain an uneven pattern (for example). For example, it has been proposed that the foamed layer is further embossed (see, for example, Patent Document 2).

Further, for example, a wallpaper obtained by printing a desired image on a foam layer by an inkjet method and foaming the foam layer has been proposed (see, for example, Patent Document 3).

An object of the present invention is to provide a method for producing a printed matter, which can efficiently produce a printed matter having a concavo-convex shape having high hardness and excellent solvent resistance.

In the method for producing a printed matter of the present invention as a means for solving the above-mentioned problems, a foaming agent-containing composition containing a polymerizable compound containing a foaming agent and a polyfunctional monomer is applied to a printed matter to form a foaming liquid layer. A foaming liquid layer forming step to be formed, a foaming inhibitor applying step of selectively applying a foaming inhibitor containing a polymerizable compound on the foaming liquid layer, and a foaming inhibitor curing to cure the applied foaming inhibitor. A step, a foaming step of heating the foaming liquid layer to foam the foaming liquid layer after the foaming inhibitor curing step, and a foaming liquid layer curing step of irradiating an electron beam to cure the foaming liquid layer after the foaming step. ,including.

According to the present invention, it is possible to provide a method for producing a printed matter, which can efficiently produce a printed matter having a concavo-convex shape having high hardness and excellent solvent resistance.

FIG. 1 is a schematic view showing an example of a printed matter manufacturing apparatus of the present invention used in the printed matter manufacturing method of the present invention. FIG. 2 is a schematic view showing an example of the printed matter manufacturing apparatus of the present invention used in the printed matter manufacturing method of the present invention in Example 2. FIG. 3 is a schematic view showing an example of a printed matter manufacturing apparatus used in the printed matter manufacturing method in Comparative Example 1. FIG. 4 is a schematic view showing an example of an electron beam irradiation device used in Examples and the like.

(Printed matter manufacturing method and printed matter manufacturing equipment)
The method for producing a printed matter of the present invention comprises a foaming liquid layer forming step of applying a foaming agent-containing composition containing a polymerizable compound containing a foaming agent and a polyfunctional monomer to a printed matter to form a foaming liquid layer. A foaming inhibitor applying step of selectively applying a foaming inhibitor containing a polymerizable compound on the foaming liquid layer, a foaming inhibitor curing step of curing the applied foaming inhibitor, and a foaming inhibitor curing step. Later, a foaming liquid layer forming step including a foaming step of heating the foaming liquid layer to foam the foaming liquid layer and a foaming liquid layer curing step of irradiating and curing the foaming liquid layer with an electron beam after the foaming step. It is more preferable to further include, more preferably, a precoat liquid layer forming step is further included, and if necessary, other steps are included.

The printed matter manufacturing apparatus of the present invention comprises a foaming liquid layer forming means for forming a foaming liquid layer by imparting a foaming agent-containing composition containing a polymerizable compound containing a foaming agent and a polyfunctional monomer to a printed matter. The foaming inhibitor applying means for imparting a foaming inhibitor containing a polymerizable compound to an arbitrary portion of the foaming liquid layer, the foaming inhibitor curing means for curing the applied foaming inhibitor, and the foaming liquid layer are heated. It is preferable to have a foaming means for foaming the foaming liquid layer and a foaming liquid layer curing means for curing by irradiating an electron beam after the foaming step, and further having a coloring material liquid layer forming means. It is more preferable to have a coating layer forming means, and if necessary, other means.

The method for producing a printed matter of the present invention can be preferably carried out by the apparatus for producing a printed matter of the present invention, the foaming liquid layer forming step can be performed by the foaming liquid layer forming means, and the foaming inhibitor applying step can suppress foaming. The foaming inhibitor curing step can be performed by the foaming inhibitor curing means, the foaming step can be performed by the foaming means, and the foaming liquid layer curing step can be performed by the foaming liquid layer curing means. The color material liquid layer forming step can be performed by the coloring material liquid layer forming means, the precoating liquid layer forming step can be performed by the precoating liquid layer forming means, and the other steps can be performed by other means. It can be carried out.

In the prior art, there is a problem that the hardness and solvent resistance of the uneven shape portion are insufficient in the building interior material (printed matter) having the uneven shape formed by foaming the foam layer.
Therefore, in the present invention, after foaming a foaming liquid layer in which foaming is suppressed at a portion that is not desired to be foamed by a foaming inhibitor, an electron beam is irradiated after the foaming step to cure the foaming liquid layer to form a foamed layer. By the manufacturing method of forming, it is possible to efficiently manufacture a printed matter having a concavo-convex shape having high hardness and excellent solvent resistance.

In one aspect of the invention, the foaming agent-containing composition is substantially free of polymerization initiator. According to this aspect, the types of materials that can be used for the foaming agent-containing composition are increased as compared with the conventional case, and the hardness and solvent resistance of the uneven shape portion are further improved.
Further, in another aspect of the present invention, the content of the polyfunctional monomer in the foaming agent-containing composition is 50% by mass or more with respect to the total amount of the polymerizable compound contained in the foaming agent-containing composition. ..
According to this aspect, since the foaming liquid layer is three-dimensionally crosslinked by electron beam irradiation, the hardness and solvent resistance of the uneven shape portion are further improved.

<Effervescent liquid layer forming step and foaming liquid layer forming means>
The foaming liquid layer forming step is a step of applying a foaming agent-containing composition containing a foaming agent and a polymerizable compound containing a polyfunctional monomer to a printed matter to form a foaming liquid layer, and is a step of forming a foaming liquid layer. It is carried out by the forming means. The foaming liquid layer may also be referred to as an "under layer" or the like.
The foaming liquid layer refers to a state before being given a liquid foaming agent-containing composition and cured by a curing step described later. Although the foaming agent-containing composition is a liquid, it has a certain degree of viscosity, so that the foaming agent-containing composition can be added to form a layered state.

The average thickness of the foaming liquid layer is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 50 μm or more and 300 μm or less.
The shape of the foaming liquid layer is not particularly limited and may be appropriately selected depending on the intended purpose.

<< Printed matter >>
The foaming agent-containing composition is applied to a printed matter.
The printed matter is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include the substrate itself described later and the precoat liquid layer described later.

<< Base material >>
The base material is not particularly limited and may be appropriately selected depending on the intended purpose. For example, plastic film, resin-impregnated paper, natural paper, synthetic paper made of synthetic fibers, sheets such as non-woven fabric, cloth, and wood. Examples thereof include fiber plates, metal plates, glass plates, and ceramic plates. Among these, a base material having water resistance is preferable.

Examples of the plastic film include a polyester film; a polypropylene film; a polyethylene film; a plastic film such as nylon, vinylon, and acrylic, or a film obtained by laminating the films.
The plastic film is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably uniaxially or biaxially stretched from the viewpoint of strength.

The non-woven fabric is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include those obtained by spraying polyethylene fibers in a sheet shape and thermocompression bonding to form a sheet shape.

Examples of the wood fiber board include medium density fiber board (MDF), high density fiber board (HDF), particle board, plywood such as veneer, and decorative board with a sheet bonded to the surface.

The method for applying the foaming agent-containing composition is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a knife coating method, a nozzle coating method, a die coating method, a lip coating method, a comma coating method, etc. Gravure coating method, rotary screen coating method, reverse roll coating method, roll coating method, spin coating method, kneader coating method, bar coating method, blade coating method, casting method, dip method, curtain coating method, etc., inkjet The method and the like can be mentioned.

The shape of the base material is not particularly limited and may be appropriately selected depending on the intended purpose.
The average thickness of the base material is not particularly limited and may be appropriately selected depending on the intended purpose.

<< Composition containing foaming agent >>
The foaming agent-containing composition contains a polymerizable compound containing a foaming agent and a polyfunctional monomer, and further contains other components as necessary.
It is preferable that the foaming agent-containing composition does not substantially contain the polymerization initiator described below. The term "substantially free" means that the total amount of the foaming agent-containing composition is less than 1% by mass.
By using the foaming agent-containing composition containing no polymerization initiator, it is possible to prevent the entire foaming liquid layer from being cured in the foaming inhibitor curing step, which is a step performed before foaming described below, and the foaming liquid layer can be prevented from curing. The desired portion of the can be foamed. Further, by using the foaming agent-containing composition containing no polymerization initiator, it is possible to prevent a problem that all the foaming agent-containing compositions are cured and the uneven shape is not formed before the foaming step described later is performed. Since the foaming liquid layer curing step described later is performed by irradiating an electron beam, the foaming liquid layer can be cured even if a foaming agent-containing composition containing no polymerization initiator is used.

− Foaming agent −
The foaming agent is not particularly limited as long as it is a material whose volume expands when heated, and can be appropriately selected depending on the intended purpose. For example, a heat-expandable microcapsule, a heat-decomposable foaming agent, etc. Can be mentioned. Among these, as the foaming agent, heat-expandable microcapsules are preferable because they have a high volume expansion coefficient and can form uniform and small closed cells.

The thermally expandable microcapsules are particles having a core-shell structure in which a volume-expandable compound is wrapped with a thermoplastic resin. The thermoplastic resin in the outer shell begins to soften by heating, and the vapor pressure of the encapsulated volume-expandable compound. Is increased to a pressure sufficient to deform the particles, and the thermoplastic resin in the outer shell is stretched and expanded. Examples of the volume expansion compound include low boiling point aliphatic hydrocarbons.

The average particle size of the heat-expandable microcapsules is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 10 μm to 50 μm.

Commercially available products can be used as the heat-expandable microcapsules. Examples of the commercially available products include Advancel EM series manufactured by Sekisui Chemical Industry Co., Ltd., EML101, EM306, EM403 (average particle size: 12 μm to 35 μm), and AkzoNovel (sold by Nippon Phillite Co., Ltd. in Japan). Expancel series, 053-40DU, 920-40DU, 930-120DU (average particle size: 10 μm to 38 μm), Matsumoto Microsphere F, FN series, F-48D, FN-100MD, FN- Examples thereof include 80 GSD (average particle size: 9 μm to 20 μm), Kureha Microspheres H750, H850, and H1100 (average particle size: 20 μm to 45 μm) manufactured by Kureha Corporation. These may be used alone or in combination of two or more.

Examples of the thermally decomposable foaming agent include an organic foaming agent and an inorganic foaming agent.
Examples of the organic foaming agent include azodicarbonamide (ADCA), azobisisobutynitrile (AIBN), p, p'-oxybisbenzenesulfonyl hydrazide (OBSH), dinitrosopentamethylenetetramine (DPT) and the like. Can be mentioned. These may be used alone or in combination of two or more.
Examples of the inorganic foaming 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 foaming agent is preferably 1% by mass or more and 15% by mass or less with respect to the total amount of the foaming agent-containing composition.

<< Polymerizable compound >>
The polymerizable compound contains a polyfunctional monomer and may contain a monofunctional monomer.

The polyfunctional monomer is 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 glycol di (meth) acrylate of hydroxypivalate, polytetramethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and trimethylolpropane di (meth) acrylate. Meta) 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), the (n ≒ 23)], dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di methacrylate _{[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, 1,9-nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane dimethanol di (meth) acrylate, propylene oxide-modified bisphenol A di (meth) acrylate, polyethylene glycol di (meth) ) Acrylate, dipentaerythritol hexa (meth) acrylate, propylene oxide-modified tetramethylolmethanetetra (meth) acrylate, dipentaerythritol hydroxypenta (meth) acrylate, caprolactone-modified dipentaerythritol hydroxypenta (meth) acrylate, ditrimethylolpropane tetra (Meta) 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 trimethylol Propanetri (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, propile Noxide-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, triethylene glycol di Examples thereof include vinyl ether and ethoxylated (4) bisphenol di (meth) acrylate. These may be used alone or in combination of two or more.

The ratio [molecular weight / functional quantity] of the polyfunctional monomer to the molecular weight and the functional quantity is preferably 250 or more from the viewpoint of achieving both foamability and fastness (hardness and solvent resistance).
The content of the polyfunctional monomer in the foaming agent-containing composition is preferably 50% by mass or more, more preferably 90% by mass or more, based on the total amount of the polymerizable compound. The content of the polyfunctional monomer is preferably 100% by mass or less, more preferably 95% by mass or less, based on the total amount of the polymerizable compound. When the content of the polyfunctional monomer is 50% by mass or more with respect to the total amount of the polymerizable compound, there is an advantage that the hardness of the formed uneven shape and the solvent resistance are excellent.

The monofunctional monomer has 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, trimethylrolpropane (meth) acrylic acid benzoic acid ester, and (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, Examples thereof include benzyl vinyl ether, ethyloxetane methyl vinyl ether, hydroxybutyl vinyl ether, ethyl vinyl ether, ethoxy (4) nonylphenol (meth) acrylate, benzyl (meth) acrylate, and caprolactone (meth) acrylate. These may be used alone or in combination of two or more.
Among these, isobolonyl (meth) acrylate is preferable because it has a high glass transition temperature (Tg) and good fastness.
The content of the monofunctional monomer is preferably 0% by mass or more and 10% by mass or less with respect to the total amount of the foaming agent-containing composition.

-Other ingredients-
The other components are not particularly limited and may be appropriately selected depending on the intended purpose. For example, a filler, a foaming accelerator, a dispersant, a coloring material, an organic solvent, an antiblocking agent, a thickener, and an antiseptic. Agents, stabilizers, deodorants, fluorescent agents, UV blocking agents and the like can be mentioned.

--Filler ---
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, and the like. Examples thereof 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 preferable.

--Effervescence accelerator ---
The foaming accelerator is not particularly limited and may be appropriately selected depending on the intended purpose. For example, zinc naphthenate, zinc acetate, zinc propionate, zinc 2-ethylpentanoate, 2-ethyl-4-methyl Zinc pentanate, zinc 2-methylhexanoate, zinc 2-ethylhexanate, zinc isooctylate, zinc n-zinc 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 linolenate, zinc linoleate, zinc ricinolate, zinc benzoate, o, m or p -Zinc toluate, pt-zinc butyl benzoate, zinc salicylate, zinc phthalate, zinc salt of monoalkyl phthalate (C4-18) ester, zinc dehydroacetate, zinc dibutyldithiocarbamate, zinc aminocrotonate, 2 -Zinc salt of mercaptobenzothiazole, zinc pyrithione, zinc complex of urea or diphenylurea and the like. These may be used alone or in combination of two or more.

--Thickener ---
Examples of the thickener include polycyanoacrylate, polylactic acid, polyglycolic acid, polycaprolactone, polyacrylic acid alkyl ester, polymethacrylic acid alkyl ester and the like.

--Preservatives ---
Examples of the preservative include those that have been conventionally used and do not initiate the polymerization of monomers, such as potassium sorbate, sodium benzoate, sorbic acid, and chlorocresol.

--Stabilizer ---
The stabilizer serves the purpose of suppressing the polymerization of the monomer during storage, and examples thereof include an anionic stabilizer and a free radical stabilizer. The former are metaphosphoric acid, maleic acid, maleic anhydride, alkylsulfonic acid, phosphorus pentoxide, iron (III) chloride, antimony oxide, 2,4,6-trinitrophenol, thiol, alkylsulfonyl, alkylsulfone, alkylsulfoxide. , Alkyl sulfone, sulfone, sulfur dioxide, sulfur trioxide, etc., the latter containing hydroquinone, catechol, or derivatives thereof.

<Viscosity>
The viscosity of the foaming agent-containing composition used in the present invention may be appropriately adjusted according to the application and the means of application, and is not particularly limited, but is 5,000 mPa · s or more and 200,000 mPa · s or less at 25 ° C. preferable. When the viscosity is within the above range, dripping is less likely to occur when the foaming agent-containing composition is applied to form the foaming liquid layer, and a foaming liquid layer having a desired thickness can be obtained. Further, when the foaming inhibitor described below is applied, the hardness can be such that the foaming inhibitor can be applied at a desired position.
As a method for measuring the viscosity, it can be measured with a general rotary viscometer. For example, when the viscosity is 5,000 mPa · s to 66,000 mPa · s, it can be measured by a Brookfield rotary digital viscometer (KT-DV1401 for high rotation, manufactured by Cortec). When the viscosity is equal to or higher than the above numerical range, it can be measured by a Brookfield rotary digital viscometer (KT-DV1402 for high rotation, manufactured by Cortec).

<Preparation of foaming agent-containing composition>
The foaming agent-containing composition used in the present invention can be prepared by using the above-mentioned various components, and the preparation means and conditions thereof are not particularly limited.

<Formation of foaming inhibitor and means for applying foaming inhibitor>
The foaming inhibitor applying step is a step of selectively applying the foaming inhibitor onto the foaming liquid layer described above, and is carried out by the foaming inhibitor applying means.
The selective application on the foaming liquid layer means that the foaming portion and the non-foaming portion on the foaming liquid layer are selected and imparted to the non-foaming portion in the previous period. It can be said that this is applied to a portion of the foaming liquid layer that is not desired to be foamed.

The predetermined region in the foaming liquid layer to which the foaming inhibitor is applied (that is, the portion where foaming of the foaming liquid layer is not desired) can be specified, for example, based on the data of the uneven shape of the printed matter to be manufactured. In the foaming inhibitor applying step, for example, the foaming inhibitor is applied to and brought into contact with a portion that is a recess (a region where the foaming liquid layer is not foamed) in the data of the uneven shape in the printed matter to be manufactured, which will be described later. It is possible to suppress the foaming of the foaming liquid layer in the foaming step to form an arbitrary uneven shape.

The method of applying the foaming inhibitor to the foaming liquid layer is not particularly limited and may be appropriately selected depending on the intended purpose, but the inkjet method flexibly responds to various foaming patterns (suppressing patterns). It is preferable because it can be done.
As the inkjet method, for example, as the drive method of the discharge head, an on-demand type head using a piezoelectric element actuator using PZT or the like, a method of applying thermal energy, an actuator using electrostatic force, or the like is used. Alternatively, a continuous injection type charge control type head or the like can be used.

<< Foaming inhibitor >>
The foaming inhibitor preferably contains a polymerizable compound, more preferably further contains a polymerization initiator, and if necessary, contains other components.
It is preferable that the foaming inhibitor contains a polymerization initiator because it can cure a desired place before irradiation with an electron beam, which will be described later, and can form an uneven shape.

-Polymerizable compound-
As the polymerizable compound, the same compound as the above-mentioned foaming agent-containing composition can be used. Of these, polyfunctional monomers are preferred.
Since the polymerizable compound is a polyfunctional monomer, the polyfunctional monomer is three-dimensionally crosslinked by applying energy. Therefore, by applying the polyfunctional monomer to an arbitrary place in the foaming liquid layer and applying energy, the foaming agent is used. There is an advantage that the on / off of volume expansion can be controlled, and the printed matter can be given a design property due to an excellent uneven shape.

--Polymerization initiator ---
The polymerization initiator may be one that can generate active species such as radicals and cations by the energy of the active energy ray and initiate the polymerization of the polymerizable compound (monomer or oligomer). As such a polymerization initiator, known radical polymerization initiators, cationic polymerization initiators, base generators and the like can be used alone or in combination of two or more, and among these, radical polymerization initiators. It is preferable to use. Further, the polymerization initiator is preferably contained in an amount of 5% by mass or more and 20% by mass or less based on the total amount of the foaming inhibitor in order to obtain a sufficient curing rate.
Examples of the radical polymerization initiator include aromatic ketones, acylphosphine oxide compounds, aromatic onium salt compounds, organic peroxides, thio compounds (for example, thioxanthone compounds, thiophenyl group-containing compounds, etc.), and hexaarylbiimidazole. Examples thereof include compounds, ketooxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, compounds having a carbon halogen bond, alkylamine compounds and the like.

Further, in addition to the above-mentioned polymerization initiator, a polymerization accelerator (sensitizer) can also be used in combination.
The polymerization accelerator is not particularly limited and may be appropriately selected depending on the intended purpose. For example, trimethylamine, methyldimethanolamine, triethanolamine, p-diethylaminoacetophenone, ethyl p-dimethylaminobenzoate, p- Examples thereof include amine compounds such as -2-ethylhexyl 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 according to the polymerization initiator to be used and its amount.

-Other ingredients-
As the other component, the same foaming agent-containing composition as described above can be used.

<Expanding inhibitor curing step and foaming inhibitor curing means>
The foaming inhibitor curing step is a step of curing the foaming inhibitor, and is carried out by the foaming inhibitor curing means.
The foaming inhibitor curing step cures the foaming inhibitor that has permeated the surface of a predetermined portion of the foaming liquid layer (that is, a portion of the foaming layer that is not desired to be foamed) and the thickness direction of the portion. That is, a part of the foaming liquid layer is cured by the foaming inhibitor curing step, and the foaming of the foaming liquid layer is suppressed. In addition, a part of the precoat liquid layer described later may be cured by the foaming inhibitor curing step.
As the foaming inhibitor curing means, a means for curing by irradiating ultraviolet rays is preferable.

-Ultraviolet irradiation-
Mercury-free irradiation is strongly desired from the viewpoint of environmental protection, and replacement with a GaN-based semiconductor ultraviolet light emitting device is extremely useful industrially and environmentally. Further, the ultraviolet light emitting diode (UV-LED) and the ultraviolet laser diode (UV-LD) are compact, have a long life, have high efficiency, and are low in cost, and are preferable as an ultraviolet light source.

The ultraviolet irradiation conditions are not particularly limited and may be appropriately selected depending on the intended purpose, but it is preferable to use an irradiation device capable of irradiating with an intensity of 6 W / cm or more at an irradiation distance of 2 mm.

<Foam process and foaming means>
The foaming step is a step of heating the foaming liquid layer to foam the foaming liquid layer, and is carried out by a foaming means. By heating the entire foam layer, the foam layer other than the portion where the foam inhibitor is cured foams. Since the foaming liquid layer is not cured by ultraviolet irradiation in the foaming inhibitor curing step, the foaming liquid layer is sufficiently cured by the foaming step.
The foaming means is a means for foaming the foaming liquid layer by heating, and examples thereof include an infrared heater, a warm air heater, and a heating roller.
The heating temperature is not particularly limited as long as it is at least the thermal decomposition temperature of the foaming agent, and can be appropriately selected depending on the intended purpose, but is preferably 100 ° C. or higher and 200 ° C. or lower.

<Effervescent liquid layer curing step and foaming liquid layer curing means>
The foaming liquid layer curing step is a step of irradiating an electron beam after the foaming step to cure the foaming liquid layer, and is carried out by the foaming liquid layer curing means.
The foam layer curing means is a means for performing electron beam irradiation.

The conditions for curing the foam layer are not particularly limited and may be appropriately selected depending on the intended purpose.
The acceleration voltage is preferably 120 keV to 250 keV, and the dose is preferably 15 kGy to 50 kGy. The dose refers to a value at a position where the distance from the electron beam irradiator is the longest in the object to be cured.

<Color material liquid layer forming process and coloring material liquid layer forming means>
The color material liquid layer forming step is a step of applying a color material-containing composition containing a color material and a polymerizable compound to form a color material liquid layer, and is carried out by a color material liquid layer forming means. The color material liquid layer may be referred to as a "printing layer", an "image layer", or the like.
The color material liquid layer forming step is preferably performed after the foaming liquid layer curing step.
The coloring material-containing composition is preferably applied to the foamed layer, which is a cured product of the foamed liquid layer, but may be applied to the foamed liquid layer.

The method for applying the colorant-containing composition is not particularly limited and may be appropriately selected depending on the intended purpose. However, the inkjet method is capable of productivity and flexible support for a wide variety of small lots. Is preferable.
As the inkjet method, for example, as the drive method of the discharge head, an on-demand type head using a piezoelectric element actuator using PZT or the like, a method of applying thermal energy, an actuator using electrostatic force, or the like is used. Alternatively, a continuous injection type charge control type head or the like can be used.

The coloring material-containing composition preferably contains a coloring material and a polymerizable compound, and if necessary, contains other components such as a polymerization initiator.

-Polymerizable compound-
As the polymerizable compound, the same compound as the above-mentioned foaming agent-containing composition can be used.
The polymerizable compound in the color material-containing composition preferably contains a monofunctional monomer, and may contain a polyfunctional monomer.

-Color material-
The color material-containing composition used in the present invention may contain a color material. The color material-containing composition may be colorless and transparent without containing a color material, and in that case, for example, it is suitable as an overcoat layer for protecting an image.
As the coloring material, various colors such as black, white, magenta, cyan, yellow, green, orange, and glossy colors such as gold and silver are imparted according to the purpose and required characteristics of the coloring material-containing composition in the present invention. Pigments and dyes can be used.
The content of the coloring material may be appropriately determined in consideration of the desired color density, dispersibility in the composition, etc., and is not particularly limited, but is 0.1% by mass with respect to the total amount of the coloring material-containing composition. It is preferably 20% by mass or more and 20% by mass or less.
As the pigment, an inorganic pigment or an organic pigment can be used, and one type may be used alone or two or more types may be used in combination.
As the inorganic pigment, for example, carbon black (CI pigment black 7) such as furnace black, lamp black, acetylene black, and channel black, iron oxide, and titanium oxide can be used.
Examples of organic pigments include azo pigments such as insoluble azo pigments, condensed azo pigments, azolakes and chelate azo pigments, phthalocyanine pigments, perylene and perinone pigments, anthraquinone pigments, quinacridone pigments, dioxane pigments, thioindigo pigments, isoindolinone pigments and quinophthalones. Polycyclic pigments such as pigments, dye chelate (for example, basic dye type chelate, acidic dye type chelate, etc.), dyeing lake (for example, basic dye type lake, acidic dye type lake, etc.), nitro pigment, nitroso pigment, Examples include aniline black and daylight fluorescent pigments.
Further, in order to improve the dispersibility of the pigment, a dispersant may be further contained.
The dispersant is not particularly limited, and examples thereof include dispersants commonly used for preparing pigment dispersions such as polymer dispersants.
As the dye, for example, an acid dye, a direct dye, a reactive dye, and a basic dye can be used, and one type may be used alone or two or more types may be used in combination.

-Other ingredients-
As the other component, the same composition as the foaming agent-containing composition can be used. Further, as the polymerization initiator, the same one as the above-mentioned foaming inhibitor can be used.

-Preparation of color material-containing composition-
The color material-containing composition used in the present invention can be prepared by using the above-mentioned various components, and the preparation means and conditions thereof are not particularly limited, but for example, a polymerizable monomer, a pigment as a color material, and a dispersant. Etc. are put into a disperser such as a ball mill, a kitty mill, a disc mill, a pin mill, a dyno mill, etc. and dispersed to prepare a pigment dispersion liquid, and further, a polymerizable monomer, a polymerization initiator, a polymerization inhibitor, etc. are added to the pigment dispersion liquid. It can be prepared by mixing a surfactant or the like.

-Viscosity of colorant-containing composition-
The viscosity of the coloring material-containing composition used in the present invention may be appropriately adjusted according to the application and the application means, and is not particularly limited. For example, when a discharge means for discharging the composition from a nozzle is applied. The viscosity in the range of 20 ° C. to 65 ° C., preferably the viscosity at 25 ° C. is preferably 3 mPa · s or more and 40 mPa · s or less, more preferably 5 mPa · s or more and 15 mPa · s or less, and 6 mPa · s or more and 12 mPa · s. The following are particularly preferred. Further, it is particularly preferable that the viscosity range is satisfied without containing the organic solvent. For the above viscosity, a cone rotor (1 ° 34'x R24) was used with a cone plate type rotational viscometer VISCOMETER TVE-22L manufactured by Toki Sangyo Co., Ltd., the rotation speed was 50 rpm, and the temperature of constant temperature circulating water was 20 ° C. It can be appropriately set and measured in the range of ~ 65 ° C. VISCOMATE VM-150III can be used to adjust the temperature of the circulating water.

<Pre-coating liquid layer forming step and pre-coating liquid layer forming means>
The precoat liquid layer forming step is a step of applying a precoat layer composition containing a polymerizable compound on the base material to form a precoat liquid layer, and is carried out by a precoat liquid layer forming means. To.
The precoat liquid layer forming step is preferably performed before the foaming liquid layer forming step.
The precoat liquid layer becomes a precoat layer through the curing step. The precoat layer may also be referred to as a primer layer.
By forming the precoat liquid layer, it is possible to obtain the effect of improving the adhesion of the foamed liquid layer to the substrate and vividly expressing the color of the color material layer which is the cured color material liquid layer.

The shape of the precoat liquid layer is not particularly limited and may be appropriately selected depending on the intended purpose. The line coating liquid layer may be formed on the entire surface of the base material, or may be formed on a part of the surface of the base material.
The average thickness of the precoat liquid layer is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 3 μm to 50 μm.

The method for applying the precoat composition is not particularly limited and may be appropriately selected depending on the intended purpose, but is not particularly limited and may be appropriately selected according to the intended purpose. For example, the 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, blade coating method, Examples include a coating method such as a casting method, a dip method, and a curtain coating method, and an inkjet method.

<< Pre-coating layer composition >>
The precoat layer composition contains a polymerizable compound and, if necessary, other components.

-Polymerizable compound-
As the polymerizable compound, the same compound as the above-mentioned foaming agent-containing composition can be used.
The polymerizable compound in the precoat layer composition preferably contains an ultraviolet ray or an active energy curable monomer, and may contain a thermosetting monomer.

-Other ingredients-
As the other component, the same composition as the foaming agent-containing composition can be used.

-Viscosity of precoat layer composition-
The viscosity of the precoat layer composition used in the present invention may be appropriately adjusted according to the application and the means of application, and is not particularly limited, but is preferably 5 mPa · s or more and 50,000 mPa · s or less at 25 ° C. When the viscosity is within the above range, dripping is less likely to occur when the precoat liquid layer is formed by applying the precoat layer composition, and a precoat liquid layer having a desired thickness can be obtained. In addition, it can have a hardness sufficient to impart the foaming liquid layer.
As the method for measuring the viscosity, it can be measured by the above-mentioned general rotary viscometer.

-Preparation of precoat layer composition-
The precoat layer composition used in the present invention can be prepared by using the above-mentioned various components, and the preparation means and conditions thereof are not particularly limited.

<Other processes and other means>
The other steps are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include an embossing step and a control step.
The other means are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include embossing means and control means.

<< Embossing process and embossing means >>
The embossing step is a step of forming an uneven pattern on the foamed gel layer of the object, and is carried out by the embossing means.
As the uneven pattern, a method such as embossing, chemical embossing, rotary screen processing, or raised printing, which is usually used for the purpose of imparting unevenness to wallpaper, decorative material, or the like, can be selectively used.
Examples of the embossing step include processing using an embossing plate, chemical embossing, a rotary screen, and a method of imparting unevenness by heap printing.

The embossing means may be either a means of embossing with a cooling roller after heating or a means of embossing at once using a hot roller embossing.
The embossing depth by the embossing is preferably 0.08 mm or more and 0.50 mm or less. When the embossing depth is 0.08 mm or more, a three-dimensional effect can be obtained, and when it is 0.50 mm or less, the abrasion strength of the surface can be improved.

Here, the apparatus for producing the printed matter of the present invention used in the method for producing the printed matter of the present invention will be described in detail with reference to the drawings.
FIG. 1 is a schematic view showing an example of a printed matter manufacturing apparatus of the present invention. The printed matter manufacturing apparatus 100 of FIG. 1 includes a coating roller 10 for applying a foaming agent-containing composition on a base material 19, a discharge head having a foaming inhibitor head 11 downstream thereof, an ultraviolet irradiation device 27, and an ultraviolet irradiation device 27. It has a heating device 18, an electron beam irradiation device 17, and a discharge head 16 including a black head 12, a cyan head 13, a magenta head 14, and a yellow head 15. In FIG. 1, 20 is a transport belt, 21 is a delivery roller facing the coating roller 10, and 22 is a take-up roller.

The base material 19 is conveyed in the direction of the arrow in FIG. 1 by winding the transport belt 20 by the take-up roller 22.
First, the foaming agent-containing composition is applied to the surface of the base material by the coating roller 10 to form a foaming liquid layer.
Next, the base material on which the foaming liquid layer is formed is scanned at a predetermined speed, and the foaming inhibitor is discharged from the foaming inhibitor head 11 to a portion of the foaming liquid layer where foaming is not desired. Next, the ultraviolet irradiation device 27 is used to irradiate the ultraviolet rays to cure the foaming inhibitor.
Next, when the foaming liquid layer having the cured foaming inhibitor is heated by the heating device 18, the foaming liquid layer foams. The foaming liquid layer after foaming is irradiated with an electron beam under predetermined irradiation conditions using an electron beam irradiating device 17 to cure the foaming liquid layer. Next, a black head 12, a cyan head 13, and a magenta head are used. A color material-containing composition for black, cyan, magenta, and yellow is discharged from each color head of 14 and the yellow head 15 by an inkjet method to form a color material liquid layer. Then, the color material liquid layer is irradiated with ultraviolet rays using the ultraviolet irradiation device 27 to cure the color material-containing composition, and a printed matter is obtained.

The printed matter produced by the method for producing a printed matter of the present invention and the printed matter manufacturing apparatus of the present invention has an uneven shape having high hardness and excellent solvent resistance, and has, for example, a floor material, a wallpaper, an interior material, and a building. It is suitable for applications such as building interior materials such as materials, wall materials, width wood, and ceiling materials.

(Printing set)
The printing set of the present invention includes a foaming agent-containing composition, a coloring material-containing composition, and a foaming inhibitor.
As the foaming agent-containing composition and the foaming inhibitor, the same ones as those of the foaming agent-containing composition and the foaming inhibitor described above can be used. The color material-containing composition contains a color material, and may contain other components if necessary. As for the coloring material and other components, the same coloring materials and other components as described above can be used.
The printing set of another aspect of the present invention comprises a foaming agent-containing composition, a colorant-containing composition, and a foaming inhibitor.
As the foaming agent-containing composition and the foaming inhibitor, the same ones as those of the foaming agent-containing composition and the foaming inhibitor described above can be used. The color material-containing composition contains a color material and a polymerizable compound, and may contain other components if necessary. As for the coloring material, the polymerizable compound, and other components, the same coloring materials, polymerizable compounds, and other components as described above can be used.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. However, "parts" represents "parts by mass" unless otherwise specified.

(Preparation Example 1)
<Preparation of foaming inhibitor>
Stir 100 parts of 1,6-hexanediol diacrylate (manufactured by Tomoe Engineering Co., Ltd.) as a polymerizable compound and 5 parts of a photopolymerization initiator (Omnirad TPO H, manufactured by IGM Resins BV). To obtain a foaming inhibitor.

(Preparation Example 2)
<Preparation of color material-containing composition A1 for black>
60 parts of acryloyl morpholine (manufactured by Tokyo Kasei Kogyo Co., Ltd.) as a polymerizable compound, 20 parts of benzyl acrylate (manufactured by Tokyo Kasei Kogyo Co., Ltd.), and SPECIAL BLACK 250 (black pigment, manufactured by BASF Japan) as a coloring material. A black colorant-containing composition A1 was prepared by stirring 40 parts.

(Preparation Example 3)
<Preparation of color material-containing composition A2 for cyan>
60 parts of acryloyl morpholine (manufactured by Tokyo Kasei Kogyo Co., Ltd.) as a polymerizable compound, 20 parts of benzyl acrylate (manufactured by Tokyo Kasei Kogyo Co., Ltd.), and IRGLITE BLUE GLVO (cyan pigment, manufactured by BASF Japan) as a coloring material. A cyanic colorant-containing composition A2 was prepared by stirring 40 parts.

(Preparation Example 4)
<Preparation of color material-containing composition A3 for magenta>
60 parts of acryloyl morpholine (manufactured by Tokyo Kasei Kogyo Co., Ltd.) as a polymerizable compound, 20 parts of benzyl acrylate (manufactured by Tokyo Kasei Kogyo Co., Ltd.), and CINQUASIA MAGENTA RT-355-D (magenta pigment, BASF) as a coloring material. A color material-containing composition A3 for magenta was prepared by stirring 40 parts (manufactured by Japan).

(Preparation Example 5)
<Preparation of color material-containing composition A4 for yellow>
60 parts of acryloyl morpholine (manufactured by Tokyo Kasei Kogyo Co., Ltd.) as a polymerizable compound, 20 parts of benzyl acrylate (manufactured by Tokyo Kasei Kogyo Co., Ltd.), and NOVOPERM YELLOW H2G (yellow pigment, manufactured by Clariant) 40 as a coloring material. The yellow colorant-containing composition A4 was prepared by stirring the portions.

(Preparation Example 6)
<Preparation of foaming agent-containing composition A>
Azodicarboxylic acid amide as a foaming agent with respect to 94% by mass of a polymerizable compound consisting of 90 parts by mass of isobornyl acrylate (manufactured by Tomoe Kogyo Co., Ltd.) and 10 parts by mass of trimethylolpropane triacrylate (manufactured by Tomoe Kogyo Co., Ltd.). The foaming agent-containing composition A was prepared by adding 3% by mass (manufactured by Eiwa Kasei Kogyo Co., Ltd.) and 3% by mass of zinc naphthenate (manufactured by Tokyo Kasei Kogyo Co., Ltd.) as a foaming accelerator and stirring the mixture.

(Preparation Example 7)
<Preparation of foaming inhibitor A>
Ethoxylation (4) Nonylphenol acrylate (manufactured by Tomoe Kogyo Co., Ltd.) 30 parts by mass and trimellitic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) as a foaming inhibitor 30 parts by mass to stir the foaming inhibitor A. Prepared.

(Adjustment example 8)
<Preparation of precoat layer composition A>
Precoat layer composition A is prepared by stirring 95 parts of an aliphatic acrylate (CN966J75, manufactured by Tomoe Engineering Co., Ltd.) and 5 parts of a photopolymerization initiator (Omnirad TPO H, manufactured by IGM Resins BV). did.

(Manufacturing Example 1)
<Preparation of Foaming Agent-Containing Composition 1>
A polymerizable compound consisting of 50 parts of isobornyl acrylate (manufactured by Tomoe Kogyo Co., Ltd.), which is a monofunctional monomer, and 50 parts of trimethylolpropane triacrylate (manufactured by Tomoe Kogyo Co., Ltd.), which is a polyfunctional monomer, as a foaming agent. 15 parts of microspheres (H750, average particle size: 20 μm, manufactured by Kureha Co., Ltd.) were added and stirred to obtain a foaming agent-containing composition 1.
The viscosity of the foaming agent-containing composition 1 was 30 mPa · s at 25 ° C. as measured by a Brookfield rotary digital viscometer (KT-DV1401 for high rotation, manufactured by Cortec).

(Manufacturing Example 2)
<Preparation of Foaming Agent-Containing Composition 2>
Microsphere (H750, Kureha Corporation) as a foaming agent in a polymerizable compound consisting of 5 parts of isobornyl acrylate (manufactured by Tomoe Kogyo Co., Ltd.) and 95 parts of urethane acrylate (CN975, manufactured by Sartmer Co., Ltd.) which is a polyfunctional monomer. (Manufactured) 15 parts were added and stirred to obtain a foaming agent-containing composition 2.
The viscosity of the foaming agent-containing composition 2 was measured at 25 ° C. in the same manner as above, and was 9,000 mPa · s at 25 ° C.

(Manufacturing Example 3)
<Preparation of Foaming Agent-Containing Composition 3>
Microsphere (H750, Kureha Corporation) as a foaming agent in a polymerizable compound consisting of 10 parts of isobornyl acrylate (manufactured by Tomoe Kogyo Co., Ltd.) and 90 parts of urethane acrylate (CN975, manufactured by Sartmer Co., Ltd.) which is a polyfunctional monomer. (Manufactured) 15 parts were added and stirred to obtain a foaming agent-containing composition 3.
The viscosity of the foaming agent-containing composition 3 was measured in the same manner as above and found to be 5,000 mPa · s at 25 ° C.

(Manufacturing Example 4)
<Preparation of Foaming Agent-Containing Composition 4>
A foaming agent by adding 10 parts of Microsphere (H750, manufactured by Kureha Corporation) as a foaming agent to a polymerizable compound consisting of 100 parts of urethane acrylate (CN975, manufactured by Sartmer Co., Ltd.), which is a polyfunctional monomer, and stirring the mixture. The containing composition 4 was obtained.
The viscosity of the foaming agent-containing composition 4 was 180,000 mPa · s at 25 ° C. as measured in the same manner as above.

(Manufacturing Example 5)
<Preparation of Foaming Agent-Containing Composition 5>
Microsphere (H750, Kureha Corporation) as a foaming agent in a polymerizable compound consisting of 5 parts of isobornyl acrylate (manufactured by Tomoe Kogyo Co., Ltd.) and 95 parts of urethane acrylate (CN959, manufactured by Sartmer Co., Ltd.) which is a polyfunctional monomer. (Manufactured) 10 parts were added and stirred to obtain a foaming agent-containing composition 5.
The viscosity of the foaming agent-containing composition 5 was measured in the same manner as above and found to be 150,000 mPa · s at 25 ° C.

(Manufacturing Example 6)
<Preparation of Foaming Agent-Containing Composition 6>
94% by mass of a polymerizable compound consisting of 90 parts by mass of urethane acrylate (Aronix M-1200 manufactured by Toa Synthetic Co., Ltd.) and 10 parts by mass of trimethylolpropane triacrylate (manufactured by Tomoe Kogyo Co., Ltd.), which is a polyfunctional monomer. A foaming agent-containing composition 6 was obtained by adding 10 parts of microspheres (H750, manufactured by Kureha Co., Ltd.) as a foaming agent and stirring the mixture. The viscosity of the foaming agent-containing composition 6 was measured in the same manner as above and found to be 250,000 mPa · s at 25 ° C.

(Manufacturing Example 7)
<Preparation of Foaming Agent-Containing Composition 7>
A polymerizable compound consisting of 50 parts of isobornyl acrylate (manufactured by Tomoe Kogyo Co., Ltd.), which is a monofunctional monomer, and 50 parts of trimethylolpropane triacrylate (manufactured by Tomoe Kogyo Co., Ltd.), which is a polyfunctional monomer, as a foaming agent. 15 parts of microspheres (FN-80GSD, average particle size: 6-10 μm, manufactured by Matsumoto Yushi Pharmaceutical Co., Ltd.) were added and stirred to obtain a foaming agent-containing composition 7.
The viscosity of the foaming agent-containing composition 7 was 40 mPa · s at 25 ° C. as measured by a Brookfield rotary digital viscometer (KT-DV1401 for high rotation, manufactured by Cortec).

(Example 1)
FIG. 1 is a schematic view showing a printed matter manufacturing apparatus of the present invention used in Example 1. The printed matter manufacturing apparatus 100 of FIG. 1 includes a coating roller 10 for applying a foaming agent-containing composition on a base material 19, a foaming inhibitor discharge head 11 downstream thereof, an ultraviolet irradiation device 27, and a heating device 18. It has an electron beam irradiation device 17, and a discharge head 16 including a black head 12, a cyan head 13, a magenta head 14, and a yellow head 15. In FIG. 1, 20 is a transport belt, 21 is a delivery roller facing the coating roller 10, and 22 is a take-up roller. The base material 19 is conveyed in the direction of the arrow in FIG. 1 by winding the transport belt 20 by the take-up roller 22.

As the ultraviolet irradiation device 27, an LED light source unit (LED Zero Solidcure, manufactured by Integration Technology Co., Ltd.) having a peak wavelength of 385 nm was used as a light source.

The heating device 18 was manufactured by combining the Lutex blower G series manufactured by Hitachi Industrial Equipment Systems Co., Ltd., the electric heater XS-2 for generating high-temperature hot air manufactured by Kansai Electric Heat Co., Ltd., and the high blow nozzle 50AL manufactured by Kansai Electric Heat Co., Ltd. A heating device adjusted to have a wind speed of 30 m / sec from the tip of the nozzle was used.

The electron beam irradiation device 17, using the EC 300/30/30 mA manufactured by Iwasaki Electric Co., in an inert gas blanket, as the inert gas source, a compressor with _{N 2} gas generator (Maxi-Flow30, Inhouse Gas Co. The gas was connected at a pressure of 0.2 MPa · s, N ₂ was allowed to flow at a flow rate of 2 L / min to 10 L / min, and the oxygen concentration was set to 500 ppm or less.

As the discharge head 16, a GEN4 head (MH2420) manufactured by Ricoh Printing Systems Co., Ltd. is used, and a foam inhibitor head 11, a black head 12, a cyan head 13, a magenta head 14, and a yellow head are used. The heads for each color were arranged in parallel, and the discharge head 16 was heated to 45 ° C., and the frequency was controlled so that drawing could be performed with a droplet size of 20 pL.

First, as the base material 19 ^{, the foaming agent-containing composition 1 is coated on the surface of a paper having a mass of 80 g / m 2} (Ostrich Diamond High Grade Plain Paper RJPH-03) by a coating roller 10 so that the average thickness is 100 μm. , A foaming liquid layer was formed.
Next, the base material on which the foaming liquid layer was formed was scanned at a speed of 15 m / min, and the foaming inhibitor was discharged from the foaming inhibitor head 11 to a portion of the foaming liquid layer where foaming was not desired. Next, the foaming inhibitor was cured using the ultraviolet irradiation device 27.
Next, when the obtained foaming liquid layer was heated at 170 ° C. for 10 seconds by the heating device 18, the foaming liquid layer was foamed.
Next, the foaming liquid layer was cured by irradiating the foaming liquid layer with an electron beam under irradiation conditions of an acceleration voltage of 30 kV and a dose of 30 kGy using an electron beam irradiation device 17.
In the electron beam irradiating device 17, as shown in FIG. 4, the electron beam 171 was applied so as to include all of the base material 19, the foaming liquid layer 191 and the foaming inhibitor 192.
Next, from the black head 12, the cyan head 13, the magenta head 14, and the yellow head 15, the color material-containing compositions A1 to A4 for black, cyan, magenta, and yellow are 25 by an inkjet method. % Images (1/4 width of each color film) were drawn to form a colorant liquid layer. After forming the color material liquid layer, the color material liquid layer was cured using the ultraviolet irradiation device 27. From the above, the printed matter of Example 1 was obtained.

(Example 2)
In Example 1, as shown in FIG. 2, a printed matter was obtained in the same manner as in Example 1 except that the ultraviolet irradiation device 27 was installed between the foam inhibitor head 11 and the heads 12 to 15 for each color. ..

(Example 3)
A printed matter was obtained in the same manner as in Example 1 except that the foaming agent-containing composition 1 was changed to the foaming agent-containing composition 2 having the above composition in Example 1.

(Example 4)
A printed matter was obtained in the same manner as in Example 1 except that the foaming agent-containing composition 1 was changed to the foaming agent-containing composition 3 having the above composition in Example 1.

(Example 5)
A printed matter was obtained in the same manner as in Example 1 except that the foaming agent-containing composition 1 was changed to the foaming agent-containing composition 4 having the above composition in Example 1.

(Example 6)
A printed matter was obtained in the same manner as in Example 1 except that the foaming agent-containing composition 1 was changed to the foaming agent-containing composition 5 having the above composition in Example 1.

(Example 7)
A printed matter was obtained in the same manner as in Example 1 except that the foaming agent-containing composition 1 was changed to the foaming agent-containing composition 6 having the above composition in Example 1.

(Example 8)
A printed matter was obtained in the same manner as in Example 1 except that the foaming agent-containing composition 1 was changed to the foaming agent-containing composition 7 having the above composition in Example 1.

(Example 9)
In Example 1, the base material was changed to a steel plate (electrogalvanized steel plate, thickness 5 mm, length 225 mm, width 300 mm, manufactured by Kuho Metal Mfg. Co., Ltd.), and 30 μm of the precoat layer composition A was applied onto the base material. A printed matter was obtained in the same manner as in Example 1 except that a step of curing with ultraviolet rays was added.

(Comparative Example 1)
A printed matter was produced using an apparatus as shown in FIG.
As a base material, the above-mentioned foaming agent-containing composition A is applied to the surface of a paper having a mass of 80 g / m ² (Ostrich Diamond High Grade Plain Paper RJPH-03) in the same manner as in Example 1 to form a foaming liquid layer. did.
Next, the base material on which the foaming liquid layer was formed was scanned at a speed of 15 m / min, and the foaming inhibitor A was discharged from the foaming inhibitor head 11 to a portion of the foaming liquid layer where foaming was not desired. Next, from the black head 12, the cyan head 13, the magenta head 14, and the yellow head 15, the color material-containing composition A1 for black, cyan, magenta, and yellow having the same composition as in Example 1. A 25% image (a quarter width of each color film) was drawn on A4 by an inkjet method to form a color material liquid layer.
Next, the foaming liquid layer and the coloring material liquid layer were irradiated with ultraviolet rays using an ultraviolet irradiation device 27 and cured.
Next, when the obtained cured product was heated at 170 ° C. for 10 seconds by the heating device 18, the heated portion of the foaming liquid layer foamed (the foaming step was performed). From the above, the printed matter of Comparative Example 1 was obtained.

(Comparative Example 2)
A printed matter of Comparative Example 2 was obtained in the same manner as in Example 1 except that the foaming step was performed after the foaming liquid layer curing step in Example 1.

The hardness and solvent resistance of the obtained printed matter of Examples 1 to 9 and Comparative Examples 1 and 2 were evaluated by the following methods. The evaluation results are shown in Table 1 below.

<Hardness>
Tested on the printed matter of Examples 1 to 9 and Comparative Examples 1 and 2 using a TQC spring load type scratch hardness tester (KT-SP0010, manufactured by Cortec) under the conditions of a tip diameter of 1 mm and a spring load of 3N. The hardness was evaluated according to the following evaluation criteria. The amount of dent was measured with a laser microscope (VKX100, manufactured by Keyence Co., Ltd.).

[Evaluation criteria]
〇: No dent is generated Δ: A dent of 0 μm or more and less than 50 μm is generated ×: A dent of 50 μm or more is generated

<Solvent resistance>
Ethanol (purity 99.5%) was sprayed on the printed matter of Examples 1 to 9 and Comparative Examples 1 and 2 and left to stand for 12 hours, and the solvent resistance was evaluated according to the following evaluation criteria.

[Evaluation criteria]
〇: No decrease in color development concentration due to contact liquid, no peeling from the base material can be confirmed Δ: Slight decrease in color development concentration due to contact liquid cannot be confirmed, no peeling from the base material can be confirmed ×: Due to contact liquid Decreased color density can be seen, or peeling from the substrate can be confirmed.

<Unevenness>
The printed matter of Examples 1 to 9 and Comparative Examples 1 and 2 were visually observed, and the unevenness was evaluated according to the following evaluation criteria.

[Evaluation criteria]
〇: Clear unevenness could be observed Δ: Concavo-convex shape could be observed, but not clear unevenness ×: No unevenness was formed

Examples 1 to 9 were printed matter having a concavo-convex shape having high hardness and excellent solvent resistance.
In addition, in Example 7, since the shape of the convex portion was higher than that in Examples 1 to 6, the uneven shape was not clear as compared with Examples 1 to 6 and the like. In Comparative Examples 1 and 2, not only the foaming inhibitor but also the foaming liquid layer was cured before heating, so that foaming could not be performed and an uneven shape could not be obtained. Further, in Comparative Example 2, since the uneven shape was not obtained at all, the hardness and the solvent resistance could not be evaluated.

Examples of aspects of the present invention are as follows.
<1> A foaming liquid layer forming step of applying a foaming agent-containing composition containing a polymerizable compound containing a foaming agent and a polyfunctional monomer to form a foaming liquid layer.
A step of applying a foaming inhibitor, which selectively applies a foaming inhibitor containing a polymerizable compound onto the foaming liquid layer, and a step of applying the foaming inhibitor.
A foaming inhibitor curing step for curing the applied foaming inhibitor, and
After the foaming inhibitor curing step, a foaming step of heating the foaming liquid layer to foam the foaming liquid layer,
A method for producing a printed matter, which comprises a foaming liquid layer curing step of irradiating an electron beam to cure after the foaming step.
<2> The method for producing a printed matter according to <1>, further comprising a step of forming a color material liquid layer, which comprises applying a color material-containing composition containing a color material and a polymerizable compound to form a color material liquid layer. is there.
<3> Any of the above <1> to <2> further comprising a step of forming a precoat liquid layer by applying a composition for a precoat layer containing a polymerizable compound on a base material to form a precoat liquid layer. It is a manufacturing method of the printed matter described in 1.
<4> The method for producing a printed matter according to any one of <1> to <3>, wherein the foaming inhibitor is cured by irradiating ultraviolet rays in the foaming inhibitor curing step.
<5> The method for producing a printed matter according to any one of <1> to <4>, wherein the foaming agent-containing composition does not substantially contain a polymerization initiator.
<6> The printed matter according to any one of <1> to <5>, wherein the content of the polyfunctional monomer in the foaming agent-containing composition is 50% by mass or more with respect to the total amount of the polymerizable compound. It is a manufacturing method of.
<7> The method for producing a printed matter according to any one of <1> to <6>, wherein the foaming inhibitor contains a polymerization initiator.
<8> The method for producing a printed matter according to any one of <1> to <7>, wherein the foaming inhibitor and the coloring material-containing composition are applied by an inkjet method.
<9> The method for producing a printed matter according to any one of <1> to <6>, wherein the foaming agent contains heat-expandable microcapsules.
<10> The method for producing a printed matter according to any one of <1> to <9>, wherein the foaming agent-containing composition has a viscosity at 25 ° C. of 5,000 mPa · s or more and 200,000 mPa · s or less. ..
<11> A foaming liquid layer forming means for forming a foaming liquid layer by applying a foaming agent-containing composition containing a polymerizable compound containing a foaming agent and a polyfunctional monomer.
A foaming inhibitor applying means for selectively applying a foaming inhibitor containing a polymerizable compound to an arbitrary portion on the foaming liquid layer, and a foaming inhibitor applying means.
A foaming inhibitor curing means for curing the applied foaming inhibitor,
A foaming means for heating the foaming liquid layer to foam the foaming liquid layer, and
An apparatus for producing a printed matter, which comprises a foaming liquid layer curing means for curing by irradiating an electron beam after foaming.
<12> The printed matter manufacturing apparatus according to <11>, further comprising a color material liquid layer forming means for forming a color material liquid layer by applying a color material-containing composition containing a color material and a polymerizable compound. is there.
<13> The printed matter manufacturing apparatus according to any one of <11> to <12>, wherein the foaming inhibitor curing means is a means for irradiating ultraviolet rays to cure the foaming inhibitor.
<14> The printed matter according to any one of <11> to <13>, wherein the content of the polyfunctional monomer in the foaming agent-containing composition is 50% by mass or more with respect to the total amount of the polymerizable compound. Manufacturing equipment.
<15> The apparatus for producing a printed matter according to any one of <11> to <14>, wherein the foaming inhibitor contains a polymerization initiator.
<16> The printed matter manufacturing apparatus according to any one of <11> to <15>, wherein the means for applying the foaming inhibitor and the colorant-containing composition is a means for applying by an inkjet method.
<17> The apparatus for producing a printed matter according to any one of <11> to <16>, wherein the foaming agent-containing composition has a viscosity at 25 ° C. of 5,000 mPa · s or more and 200,000 mPa · s or less. ..
<18> The method for producing a printed matter according to any one of <11> to <17>, wherein the foaming agent contains heat-expandable microcapsules.
<19> It is characterized by containing a foaming agent-containing composition containing a polymerizable compound containing a foaming agent and a polyfunctional monomer, a coloring material-containing composition containing a coloring material, and a foaming inhibitor containing a polymerizable compound. It is a set for printing.
<20> Includes a foaming agent-containing composition containing a polymerizable compound containing a foaming agent and a polyfunctional monomer, a coloring material-containing composition containing a coloring material and a polymerizable compound, and a foaming inhibitor containing a polymerizable compound. It is a printing set characterized by this.

The method for producing a printed matter according to any one of <1> to <10>, the apparatus for producing a printed matter according to any one of <11> to <18>, and any one of the above <19> to <20>. The printing set described in the above can solve the above-mentioned problems in the past and achieve the above-mentioned object of the present invention.

10 Coating roller 11 Foaming inhibitor head 12 Black head 13 Cyan head 14 Magenta head 15 Yellow head 16 Discharge head 17 Electron beam irradiation device 18 Heating device 19 Base material 20 Conveyance belt 21 Sending roller 22 Winding roller 27 Ultraviolet irradiation device 100 Printed matter manufacturing device

JP-A-2007-308869 Japanese Patent No. 5195999 JP-A-2017-105162

Claims (14)

A foaming liquid layer forming step of applying a foaming agent-containing composition containing a polymerizable compound containing a foaming agent and a polyfunctional monomer to a printed matter to form a foaming liquid layer.
A step of applying a foaming inhibitor, which selectively applies a foaming inhibitor containing a polymerizable compound onto the foaming liquid layer, and a step of applying the foaming inhibitor.
A foaming inhibitor curing step for curing the applied foaming inhibitor, and
After the foaming inhibitor curing step, a foaming step of heating the foaming liquid layer to foam the foaming liquid layer,
A method for producing a printed matter, which comprises a foaming liquid layer curing step of irradiating an electron beam to cure after the foaming step. The method for producing a printed matter according to claim 1, further comprising a step of forming a color material liquid layer, which comprises applying a color material-containing composition containing a color material and a polymerizable compound to form a color material liquid layer. The method for producing a printed matter according to any one of claims 1 to 2, further comprising a step of forming a precoat liquid layer by applying a precoat layer composition containing a polymerizable compound on a base material to form a precoat liquid layer. .. The method for producing a printed matter according to any one of claims 1 to 3, wherein in the foaming inhibitor curing step, the foaming inhibitor is cured by irradiating ultraviolet rays. The method for producing a printed matter according to any one of claims 1 to 4, wherein the foaming agent-containing composition does not substantially contain a polymerization initiator. The method for producing a printed matter according to any one of claims 1 to 5, wherein the content of the polyfunctional monomer in the foaming agent-containing composition is 50% by mass or more with respect to the total amount of the polymerizable compound. The method for producing a printed matter according to any one of claims 1 to 6, wherein the foaming inhibitor contains a polymerization initiator. The method for producing a printed matter according to any one of claims 1 to 7, wherein the foaming inhibitor and the coloring material-containing composition are applied by an inkjet method. The method for producing a printed matter according to any one of claims 1 to 8, wherein the foaming agent contains heat-expandable microcapsules. The method for producing a printed matter according to any one of claims 1 to 9, wherein the foaming agent-containing composition has a viscosity at 25 ° C. of 5,000 mPa · s or more and 200,000 mPa · s or less. A foaming liquid layer forming means for forming a foaming liquid layer by imparting a foaming agent-containing composition containing a polymerizable compound containing a foaming agent and a polyfunctional monomer to a printed matter.
A foaming inhibitor applying means for selectively applying a foaming inhibitor containing a polymerizable compound to an arbitrary generation site on the foaming liquid layer, and a foaming inhibitor applying means.
A foaming inhibitor curing means for curing the applied foaming inhibitor,
A foaming means for heating the foaming liquid layer to foam the foaming liquid layer, and
An apparatus for producing a printed matter, which comprises a foaming liquid layer curing means for curing by irradiating an electron beam after foaming. The apparatus for producing a printed matter according to claim 11, further comprising a means for forming a color material liquid layer by imparting a color material-containing composition containing a color material and a polymerizable compound to form a color material liquid layer. For printing, which comprises a foaming agent-containing composition containing a polymerizable compound containing a foaming agent and a polyfunctional monomer, a coloring material-containing composition containing a coloring material, and a foaming inhibitor containing a polymerizable compound. set. It is characterized by containing a foaming agent-containing composition containing a polymerizable compound containing a foaming agent and a polyfunctional monomer, a coloring material-containing composition containing a coloring material and a polymerizable compound, and a foaming inhibitor containing a polymerizable compound. A set for printing.

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