JP7363221B2 - 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.

Conventionally, there have been decorative panels in which desired images such as wood grain or stone grain are printed on substrates such as medium density fiberboard (MDF) or plywood for the purpose of adding decorativeness to indoor and outdoor spaces. Decorative panels with a highly uneven structure are widely used because they provide a luxurious decorative effect with a three-dimensional three-dimensional effect.

In recent years, as digitalization has attracted attention as consumer needs have diversified, attempts have been made to realize decorative panels using an inkjet method. Such technology is used to manufacture foamed embossed sheets that have a foamed resin layer containing thermally expandable microcapsules on a base material and optionally provide a printed layer, with the aim of achieving both foaming ratio and strength. , a method of heating a foamed resin layer in stages has been proposed (for example, see Patent Document 1).

An object of the present invention is to provide a method for producing a printed matter in which high adhesiveness between the volume expansion layer and a base material can be obtained while maintaining a large average thickness of the volume expansion layer.

The method for producing printed matter of the present invention as a means for solving the above problems includes applying a curable composition containing a volume expander and a polymerizable compound to a base material to form a volume expander-containing liquid layer. an expanding agent-containing liquid layer forming step, and a volume expansion step of heating the volume expanding agent-containing layer obtained by curing the volume expanding agent-containing liquid layer to expand the volume of the volume expanding agent-containing layer to form a volume expanding layer. The method includes a layer forming step and a preheating step, which is either step (1) or (2) below.
(1) Before the volume expansion agent-containing liquid layer formation step, heating the base material. (2) After the volume expansion agent-containing liquid layer formation step and before the volume expansion layer formation step. , heating either the volume expansion agent-containing liquid layer or the volume expansion agent-containing layer;

According to the present invention, it is possible to provide a method for producing a printed matter in which high adhesiveness between the volume expansion layer and the base material can be obtained while maintaining a large average thickness of the volume expansion layer.

FIG. 1 is a schematic diagram showing the temperature change of the volume expansion agent-containing liquid layer or the volume expansion agent-containing layer during heating in (2) above. FIG. 2 is a schematic diagram showing an example of the printed matter manufacturing apparatus of the present invention. FIG. 3 is a schematic diagram showing another example of the printed matter manufacturing apparatus of the present invention. FIG. 4 is a schematic diagram showing another example of the printed matter manufacturing apparatus of the present invention. FIG. 5 is a schematic diagram showing another example of the printed matter manufacturing 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 a step of forming a volume-expanding agent-containing liquid layer by applying a curable composition containing a volume-expanding agent and a polymerizable compound to a base material to form a volume-expanding agent-containing liquid layer; A volume expansion layer forming step of heating a volume expansion agent-containing layer obtained by curing a volume expansion agent-containing liquid layer to expand the volume of the volume expansion agent-containing layer to form a volume expansion layer, and the following (1) and It includes a preheating step which is any of the steps in (2), and further includes other steps such as a coloring material layer forming step, a volume expansion suppressing liquid application step, a volume expansion agent containing layer forming step, etc. as necessary. include.
(1) Before the volume expansion agent-containing liquid layer formation step, heating the base material. (2) After the volume expansion agent-containing liquid layer formation step and before the volume expansion layer formation step. , heating either the volume expansion agent-containing liquid layer or the volume expansion agent-containing layer;

The printed matter manufacturing apparatus of the present invention includes a volume expanding agent-containing liquid layer forming means for forming a volume expanding agent-containing liquid layer by applying a curable composition containing a volume expanding agent and a polymerizable compound to a base material; A volume expansion layer forming means for heating a volume expansion agent-containing layer obtained by curing a volume expansion agent-containing liquid layer to expand the volume of the volume expansion agent-containing layer to form a volume expansion layer, and the following (1) and ( 2), and if necessary, other means such as a coloring material layer forming means, a volume expansion suppressing liquid applying means, a volume expansion agent containing layer forming means, etc. have
(1) A means for heating the base material before the volume expansion agent-containing liquid layer formation means; (2) A means for heating the base material after the volume expansion agent-containing liquid layer formation means and before the volume expansion layer formation means. , means for heating either the volume expansion agent-containing liquid layer or the volume expansion agent-containing layer.

The method for producing a printed matter of the present invention can be suitably carried out using the apparatus for producing a printed matter of the present invention, and the step of forming a liquid layer containing a volumetric expansion agent is preferably carried out by the means for forming a liquid layer containing a volumetric expansion agent. The volume expansion layer forming step can be suitably carried out by the volume expansion layer forming means, the preheating step can be carried out suitably by the preheating means, and the other steps can be carried out suitably by the volume expansion layer forming means. It can be suitably implemented by the other means mentioned above.

In conventional technology, the temperature range in which microspheres, which are volume expansion agents, can be foamed well is narrow. There is a problem that the volumetric expansion in the direction is not uniform.
In addition, the base material and the volume expansion layer are bonded together by the intermolecular force between the resin around the microspheres and the base material, and if the contact area between the resin and the base material decreases due to the volume expansion of the microspheres, Since the force is reduced, it is preferable not to foam the microspheres in the volume expansion agent-containing layer near the base material from the viewpoint of high adhesion between the base material and the volume expansion layer. However, the prior art does not disclose high adhesion between the base material and the volume expansion layer.

As a result of extensive studies, the inventors of the present invention found that instead of expanding the volume of the volume expansion agent in the volume expansion agent-containing layer with one heating, the volume expansion agent-containing liquid layer or volume expansion agent-containing layer is not expanded in volume with a first heating device. By temporarily stopping the heating after heating the layer, the volume expanding agent-containing liquid layer or the volume expanding agent-containing layer is heated while the temperature of the volume expanding agent-containing liquid layer or the volume expanding agent-containing layer is higher than room temperature. The temperature difference in the thickness direction of the layer is reduced, and then the second heating device is used to heat the layer to expand the volume of the volume expansion agent-containing layer, thereby maintaining the average thickness of the volume expansion layer and the base layer. It was discovered that high adhesion to the material could be obtained.

Therefore, in the present invention, a volume expanding agent-containing liquid layer forming step of applying a curable composition containing a volume expanding agent and a polymerizable compound to a base material to form a volume expanding agent-containing liquid layer; 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 expand the volume of the volume expansion agent-containing layer to form a volume expansion layer, and a preheating step. Accordingly, high adhesion between the volume expansion layer and the substrate can be obtained while maintaining a large average thickness of the volume expansion layer.

<Preheating process and preheating means>
The preheating step is one of the steps (1) and (2) below, and is carried out by a preheating means.
(1) Before the volume expansion agent-containing liquid layer formation step, heating the base material. (2) After the volume expansion agent-containing liquid layer formation step and before the volume expansion layer formation step. , heating either the volume expansion agent-containing liquid layer or the volume expansion agent-containing layer;

As for the heating in the above (2), when the preheating step is performed before the volume expansion agent-containing layer forming step, the volume expansion agent-containing liquid layer is heated, and the preheating step is performed before the volume expansion agent-containing layer forming step. When carried out after the containing layer forming step, the volume expansion agent containing layer is heated. Further, heating is preferably performed from the surface of the volume expansion agent-containing liquid layer or the volume expansion agent-containing layer opposite to the surface in contact with the base material.

FIG. 1 is a schematic diagram showing the temperature change of the volume expansion agent-containing liquid layer or the volume expansion agent-containing layer during heating in (2) above.
When the volume expansion agent-containing liquid layer or the volume expansion agent-containing layer is heated to a specific temperature (hereinafter sometimes referred to as T _S ), the volume expansion agent starts volume expansion. When it is further heated to a specific temperature (hereinafter sometimes referred to as _TM ), the average thickness of the volume expansion agent-containing liquid layer or volume expansion agent-containing layer reaches its maximum due to the volume expansion of the volume expansion agent. Become. When the temperature of the volume-expanding agent-containing liquid layer or the volume-expanding agent-containing layer is further heated to exceed _TM , cracks or irregular shapes occur in the volume-expanded volume-expanding agent, and the average thickness of the volume-expanding layer decreases.
When preheating is not performed, the surface opposite to the surface of the volume expansion agent-containing liquid layer or the volume expansion agent-containing layer that is in contact with the base material when heating is performed to expand the volume of the volume expansion agent-containing layer. (hereinafter sometimes referred to as T ₁ ) and the temperature of the volume expansion agent-containing liquid layer or the surface of the volume expansion agent-containing layer in contact with the base material (hereinafter sometimes referred to as T ₂ ) (Figure 1 ) increases with heating, and when T ₂ reaches the temperature at which the volume expansion agent starts to expand (hereinafter sometimes referred to as _TS ), T ₁ becomes the volume expansion layer. Since the temperature exceeds the temperature at which the thickness of the layer becomes maximum (hereinafter sometimes referred to as _TM ), the average thickness of the volume expansion layer decreases.
In the present invention, T ₁ and T ₂ are reduced by preheating the volume expansion agent-containing liquid layer or the volume expansion agent-containing layer and temporarily stopping the heating. Here, since T ₁ , which has a higher temperature than T ₂ , has a faster temperature drop rate than T ₂ , the difference between T ₁ and T ₂ decreases when T ₁ and T ₂ are higher than room temperature. By performing heating again, when T ₂ becomes T _S , the difference between T ₁ and T ₂ becomes smaller than when preheating is not performed, so while maintaining the average thickness of the volume expansion layer thick, High adhesion between the volume expansion layer and the base material can be obtained.

The preheating means is not particularly limited as long as it can raise the temperature of the base material, the volume expansion agent-containing liquid layer, or the volume expansion agent-containing layer by heating, and can be selected as appropriate depending on the purpose. For example, an infrared heater, a hot air heater, a heating roller, etc. can be used.

The preheating step includes heating any one of the base material, the volume expansion agent-containing liquid layer, and the volume expansion agent-containing layer to a temperature below the temperature at which the volume expansion of the volume expansion agent starts (hereinafter sometimes referred to as _TS ). It is preferable to heat the mixture to a temperature of T _S -10° C. or more and less than T _S . When the temperature is T _S -10°C or more, the temperature difference between T ₁ and T ₂ can be small and uniformly heated in the subsequent volume expansion layer forming step, and when the temperature is less than T _S , the volume expansion agent can be heated. It becomes easy to heat the volume expansion agent-containing liquid layer or the volume expansion agent-containing layer without causing volume expansion.

The heating includes the temperature T ₁ of the surface of the volume expansion agent-containing liquid layer or the surface of the volume expansion agent-containing layer opposite to the surface in contact with the base material, and the volume expansion agent-containing liquid layer or volume expansion agent-containing liquid layer in contact with the base material. Preferably, the layer is heated such that the temperature T ₂ of the surface thereof is T ₁ −T ₂ <10° C. Thereby, higher adhesiveness between the volume expansion layer and the base material can be obtained while maintaining a larger average thickness of the volume expansion 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 forming a volume expansion agent-containing liquid layer by applying a curable composition containing a volume expansion agent and a polymerizable compound, and includes a volume expansion agent-containing liquid layer forming means. Implemented by

The curable composition containing the volume expander and polymerizable compound is preferably applied onto a substrate.

<<Base material>>
The base material is not particularly limited and can be selected as appropriate depending on the purpose, such as resin film, resin-impregnated paper, synthetic paper made of synthetic fibers, natural paper, sheets of nonwoven fabric, construction materials, Examples include cloth, leather, wood, metal sheets, glass plates, ceramic plates, etc. Among these, durable base materials are preferred, and building materials are more preferred.

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, it is preferably uniaxially or biaxially stretched.

The nonwoven fabric is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include a sheet formed by dispersing polyethylene fibers and bonding them under heat.

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.

The building materials include, for example, thermosetting resins, fiber plates, particle boards used for flooring, wallpaper, interior materials, wallboard materials, baseboards, ceiling materials, columns, etc., or on the surface of the above materials. Examples include those provided with a decorative board of thermosetting resin, olefin, polyester, PVC, etc.

The method for applying the curable composition onto the substrate is not particularly limited and can be appropriately selected depending on the purpose, such as knife coating method, nozzle coating method, die coating method, lip coating method, Coating methods such as comma coat method, gravure coat method, rotary screen coat method, reverse roll coat method, roll coat method, spin coat method, kneader coat method, bar coat method, blade coat method, cast method, dip method, curtain coat method, etc. Examples include manufacturing methods, inkjet methods, etc.

The average thickness of the volume expansion agent-containing liquid layer is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 50 μm or more, more preferably 80 μm or more, even more preferably 100 μm or more, and 100 μm or more and 150 μm or less. is particularly preferred.
When the average thickness of the volume expansion agent-containing liquid layer is 50 μm or more, a volume expansion layer with unevenness can be formed, and an excellent design can be imparted due to the uneven shape.

<<Curable composition>>
The curable composition contains a volume expander and a polymerizable compound, preferably contains a polymerization initiator and a surfactant if necessary, and further contains other components if necessary.
Examples of the curable composition include active energy ray curable compositions, but active energy ray curable compositions are more suitable from the viewpoint of the durability of the design due to the uneven shape.

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

The thermally expandable microcapsules are particles with a core-shell structure in which a volume-expanding compound 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 volume-expanding compound increases. This creates enough pressure to deform the particles, causing the thermoplastic outer shell to stretch and expand. Examples of the volume expansion 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 volume expansion agent include organic volume expansion agents and inorganic volume expansion agents.
Examples of the organic volume expanding agent include azodicarboxylic acid amide (ADCA), azobisisobutylnitrile (AIBN), p,p'-oxybisbenzenesulfonylhydrazide (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 volume expanding 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 expanding agent is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 1% by mass or more and 20% by mass or less, and 5% by mass based on the total amount of the curable composition. The content is more preferably 15% by mass or less.

<<Polymerizable compound>>
The polymerizable compound 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 monomers and polyfunctional monomers.

-Monofunctional monomer-
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, 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 curable composition.

-Polyfunctional 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 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] of 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 curable composition is not particularly limited and can be appropriately selected depending on the purpose, but is 10% by mass or less, and 1% by mass based on the total amount of the polymerizable compound. The following are preferred. Further, the content of the polyfunctional monomer is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, based on the total amount of the polymerizable compound. When the content of the polyfunctional monomer is 10% by mass or less based on the total amount of the polymerizable compound, there is an advantage that both designability (volume expandability) and robustness can be achieved.

-Polymerization initiator-
Examples of the polymerization initiator include photopolymerization initiators. 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 such polymerization initiators, known radical polymerization initiators, cationic polymerization initiators, base generators, etc. can be used singly or in combination of two or more. Among these, radical polymerization initiators It is preferable to use
In order to obtain a sufficient curing rate, the content of the polymerization initiator is preferably 1% by mass or more and 20% by mass or less, more preferably 5% by mass or more and 15% by mass or less, based on the total amount of the curable composition. .
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.

Moreover, in addition to the polymerization initiator, a polymerization accelerator (sensitizer) can also be used in combination.
The polymerization accelerator is not particularly limited and can be appropriately selected depending on the purpose, for example, trimethylamine, methyldimethanolamine, triethanolamine, p-diethylaminoacetophenone, ethyl p-dimethylaminobenzoate, Examples 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 depending on the polymerization initiator used and its amount.

-Other ingredients-
The other components are not particularly limited and can be appropriately selected depending on the purpose, such as fillers, volume expansion promoters, dispersants, colorants, organic solvents, antiblocking agents, thickeners, Examples include preservatives, stabilizers, deodorizing agents, fluorescent agents, and ultraviolet blocking agents.

--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, 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.

--Volume expansion accelerator--
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.

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

--Preservative--
The preservatives include those that are conventionally used and do not initiate polymerization of monomers, such as potassium sorbate, sodium benzoate, sorbic acid, and chlorocresol.

--Stabilizer--
The stabilizer serves the purpose of inhibiting polymerization of monomers during storage, and includes 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.

<Preparation of curable composition>
The curable composition used in the present invention can be prepared using the various components described above, and the preparation means and conditions are not particularly limited.

<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 the volume expansion suppressing liquid to a portion of the volume expansion agent-containing liquid layer where the volume expansion is not desired, and is carried out by a volume expansion suppressing liquid applying means.

The volume expansion suppressing liquid includes a polyfunctional polymerizable compound, a polymerization initiator, and the like.
As the polyfunctional polymerizable compound, the same polyfunctional monomer as in the curable composition of the liquid layer containing a volume expander can be used, such as 1,6-hexanediol di(meth)acrylate, Examples include 1,3-butylene glycol diacrylate, 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.
When the volume expansion suppressing liquid contains a polyfunctional polymerizable compound, the polyfunctional polymerizable compound is three-dimensionally crosslinked by energy application, so the polyfunctional polymerizable compound can be applied to any location of the volume expansion agent-containing liquid layer. By applying energy, it is possible to control the volume expansion on and off, and there is an advantage that it is possible to give printed matter an excellent design due to the uneven shape.
As the polymerization initiator, the same one as the polyfunctional monomer in the curable composition of the volume expansion agent-containing liquid layer can be used, such as a photopolymerization initiator.

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 an 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. may be used. Alternatively, a continuous injection type charge control type head or the like may be used.
The amount of the volume expansion suppressing liquid applied is not particularly limited and can be appropriately selected depending on the purpose, but it is 0.04 pL/μm ² to 2.8 pL/to the surface area of the volume expansion agent-containing liquid layer. μm ² is preferred.

<Volume expanding agent-containing layer forming step and volume expanding agent-containing layer forming means>
The volume-expanding agent-containing layer forming step is a step of applying energy to the volume-expanding agent-containing liquid layer to form the volume-expanding agent-containing layer, and is carried out by a volume-expanding agent-containing layer forming means.
Examples of the energy include active energy rays.

The volume expansion agent-containing liquid layer is cured by irradiating the volume expansion agent-containing liquid layer with the active energy rays.

-Active energy rays-
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 or more at an irradiation distance of 2 mm.
In the case of the electron beam, it is preferable that the acceleration 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.

The average thickness of the volume expansion agent-containing layer is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 50 μm or more, more preferably 80 μm or more, even more preferably 100 μm or more, and 100 μm or more and 150 μm or less. Particularly preferred.
When the average thickness of the volume-expanding agent-containing layer is 50 μm or more, a volume-expanding layer with unevenness can be formed, and an excellent design can be imparted due to the uneven shape.

<Coloring material layer forming process and coloring material layer forming means>
The coloring material layer forming step is a step of forming a coloring material layer by applying a coloring material composition containing a coloring material, and is performed by a coloring material layer forming means.

<<Coloring material composition>>
The coloring material composition contains a coloring material, and preferably contains a polymerizable compound and a polymerization initiator from the viewpoint of design due to the uneven shape and durability of image quality, and further contains other components as necessary. Contains.

-Coloring material-
The coloring material may include various pigments that impart glossy colors such as black, white, magenta, cyan, yellow, green, orange, gold, and silver, depending on the purpose and required characteristics of the coloring material composition in the present invention. or dye 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 may be 0.1% by mass based on the total amount of the coloring material composition. It is preferably 20% by mass or less, more preferably 1% by mass or more and 10% 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.
Examples of the inorganic pigment include carbon blacks (C.I. Pigment Black 7) such as furnace black, lamp black, acetylene black, and channel black, iron oxide, and titanium oxide.
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, daylight fluorescent pigments, 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.
As the dye, for example, acidic dyes, direct dyes, reactive dyes, and basic dyes can be used, and one type may be used alone or two or more types may be used in combination.

-Polymerizable compound-
As the polymerizable compound, the same polymerizable compound as that of the curable composition in the volume expansion agent-containing liquid layer can be used.

-Polymerization initiator-
As the polymerization initiator, the same polymerization initiator as that of the curable composition in the volume expansion agent-containing liquid layer can be used.

<Other ingredients>
The other components are not particularly limited and can be appropriately selected depending on the purpose, such as organic solvents, surfactants, polymerization inhibitors, leveling agents, antifoaming agents, optical brighteners, Examples include penetration enhancers, wetting agents (humectants), fixing agents, viscosity stabilizers, antifungal agents, preservatives, antioxidants, ultraviolet absorbers, chelating agents, pH adjusters, thickeners, and the like.

--Organic solvent--
The coloring material composition used in the present invention may contain an organic solvent, but it is preferable not to contain it if possible. If the composition does not contain organic solvents, especially volatile organic solvents (VOC (Volatile Organic Compounds) free), the safety of the place where the composition is handled will be further improved, and it will also be possible to prevent environmental pollution. . 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.

-Preparation of coloring material composition-
The coloring material composition used in the present invention can be prepared using the various components described above, and the preparation means and conditions are not particularly limited. Pigment dispersion is prepared by dispersing the pigment into a dispersing machine such as a mill, disc mill, pin mill, or dyno mill.Additionally, a polymerizable compound, a polymerization initiator, a polymerization inhibitor, a surfactant, etc. are added to the pigment dispersion. It can be prepared by mixing.

<Viscosity>
The viscosity of the coloring material composition used in the present invention may be adjusted as appropriate depending on the purpose and application means, and is not particularly limited. For example, when applying a discharging means such as discharging the composition from a nozzle, The viscosity at 20°C to 65°C, preferably 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 or less. is particularly preferred. Further, it is particularly preferable that the viscosity range is satisfied without including the organic solvent. The above viscosity was measured using a cone plate rotational viscometer VISCOMETER TVE-22L manufactured by Toki Sangyo Co., Ltd. using a cone rotor (1°34' x R24) at a rotation speed of 50 rpm and a constant temperature circulating water temperature of 20°C. The temperature can be set and measured as appropriate in the range of ~65°C. VISCOMATE VM-150III can be used to adjust the temperature of circulating water.

There are no particular restrictions on the method for applying the coloring material composition onto the liquid layer containing the volume expansion agent, and the method can be selected as appropriate depending on the purpose. This is preferable because it allows for flexible adaptation.
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.

<Volume expansion layer forming step and volume expansion layer forming means>
The volume expansion layer forming step includes heating the volume expansion agent-containing layer obtained by curing the volume expansion agent-containing liquid layer to expand the volume of the volume expansion agent-containing layer to form a volume expansion layer. This step is carried out by means of forming a volumetrically expandable layer.
The volume expansion layer forming means is not particularly limited as long as it can expand the volume expansion agent by heating, and can be appropriately selected depending on the purpose. For example, an infrared heater, a hot air heater, a heating roller, etc. Can be mentioned.

The heating is preferably performed from the surface of the volume-expanding agent-containing layer opposite to the surface that is in contact with the base material. As a result, T ₁ becomes higher than T ₂ , so that only the volume expansion agent on the surface of the volume expansion agent-containing layer opposite to the surface in contact with the base material can be expanded in volume.

In the volume expansion layer forming step, the temperature _T1 of the surface of the volume expansion agent-containing layer opposite to the surface in contact with the base material is preferably heated to TS _or higher, and heated to a temperature higher than or equal to TS _and lower than or equal to _TM . It is more preferable to do so. When the temperature is T _S or more, the volume expansion agent in the volume expansion agent-containing layer can be expanded in volume, and when the temperature is T _M or less, the generation of cracks or irregular shapes in the volume expansion layer can be prevented. I can do it.

It is preferable that the heating is started when T ₁ and T ₂ of the volume expansion agent-containing layer are such that T ₁ -T ₂ <10°C. Thereby, when T ₂ becomes T _S , T ₁ becomes T _M , so that higher adhesion between the volume expansion layer and the base material can be obtained while keeping the average thickness of the volume expansion layer thicker.
The above T ₁ and the above T ₂ can be adjusted to T ₁ −T ₂ <10° C. by lowering the temperature of the volume expansion agent-containing liquid layer after the preheating step. There are no particular restrictions on the method of lowering the temperature of the volume expansion agent-containing liquid layer, and it can be selected as appropriate depending on the purpose. Examples include a method of performing a step of forming an agent-containing layer, a method of cooling a volume-expanding agent-containing liquid layer or a volume-expanding layer-containing layer using a cooling device after a preheating step, and the like.
The cooling device is not particularly limited as long as it can lower the temperature of the base material, the volume expansion agent-containing liquid layer, or the volume expansion agent-containing layer, and can be appropriately selected depending on the purpose. For example, a forced air cooling system can be used. , a cooling method using a chiller, a cooling method using a Peltier element, etc.

The heating is performed so that the temperature T ₂ of the surface of the volume-expanding agent-containing layer in contact with the base material and the temperature T _S at which volume expansion of the volume-expanding agent starts is |T ₂ -T _S |≦5°C. It is preferable to heat the volume-expanding agent-containing layer as follows. This prevents the volume expansion agent in the portion of the volume expansion agent-containing layer that is in contact with the base material from expanding in volume, and provides higher adhesion between the volume expansion layer and the base material.

The average thickness of the volume expansion layer is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 100 μm or more, more preferably 310 μm or more, even more preferably 400 μm or more, and 400 μm or more and 2,000 μm or less. Particularly preferred.
When the average thickness of the volumetric expansion layer is 100 μm or more, it is possible to form a volumetric expansion layer with a difference in unevenness due to the volumetric expansion suppressing liquid, and it is possible to provide an excellent design due to the uneven shape.

<Other processes and other means>
The other steps are not particularly limited and can be appropriately selected depending on the purpose, and include, for example, an embossing step, a control step, and the like.
The other means are not particularly limited and can be appropriately selected depending on the purpose, and include, for example, embossing means, control means, and the like.

<< Embossing process and embossing means >>
The embossing step is a step of forming an uneven pattern on the volume expansion layer and the coloring material layer, and is carried out by an embossing means.
As the uneven pattern, methods such as embossing, chemical embossing, rotary screen processing, or raised printing, which are usually used for the purpose of imparting unevenness to wallpaper, decorative materials, etc., can be selected and used.
Examples of the embossing process include a method of providing unevenness by using an embossing plate, chemical embossing, a rotary screen, or raised printing.

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

Here, the printed matter manufacturing apparatus of the present invention used in the printed matter manufacturing method of the present invention will be described in detail with reference to the drawings.
FIG. 2 is a schematic diagram showing an example of the printed matter manufacturing apparatus of the present invention. The printed matter manufacturing apparatus 100 shown in FIG. 2 includes a coating roller 10 for coating a curable composition on a substrate 19, a head 11 for a volumetric expansion suppressing liquid downstream of the coating roller 10, a heating device 18 for preheating, and a heating device 18 for preheating. It has an energy beam irradiation device 27, an ejection head 16 consisting of a black head 12, a cyan head 13, a magenta head 14, and a yellow head 15, and a heating device 28 for forming a volume expansion layer. In addition, in FIG. 2, 20 is a conveyance belt, 21 is a delivery roller facing the application roller 10, and 22 is a winding roller.

The base material 19 is conveyed in the direction of the arrow in FIG. 2 by being wound around the conveyor belt 20 by the winding roller 22 .
First, a curable composition is applied to the surface of the base material 19 using the application roller 10 to form a volume expansion agent-containing liquid layer.
Next, the base material 19 on which the volumetric expansion agent-containing liquid layer is formed is scanned at a predetermined speed, and the volumetric expansion suppressing liquid is applied from the volumetric expansion suppressing liquid head 11 to locations where the volumetric expansion of the volumetric expansion agent-containing liquid layer is not desired. Discharge to.
Next, the volume expansion agent-containing liquid layer is heated by the heating device 18 at T _{2 S} for 5 to 10 seconds to perform preheating. In addition, in the preliminary heating, the base material 19 may be heated in addition to the volume expansion agent-containing liquid layer.
Next, the volume expanding agent-containing liquid layer is cured by irradiating the volume expanding agent-containing liquid layer with active energy rays under predetermined irradiation conditions using the active energy ray irradiation device 27. form a layer.
Next, the color material compositions for black, cyan, magenta, and yellow are applied by an inkjet method from each color head 12 for black, head 13 for cyan, head 14 for magenta, and head 15 for yellow. Discharge to form a coloring material layer.
Next, when the obtained volumetric expansion agent-containing layer is heated by the heating device 28, the volumetric expansion agent-containing layer at the heated portion expands in volume, and while maintaining the average thickness of the volumetric expansion layer thick, Printed matter with high adhesion to the material can be obtained.
FIG. 3 is a schematic diagram showing another example of the printed matter manufacturing apparatus of the present invention. The printed matter manufacturing apparatus 100 shown in FIG. 3 includes a coating roller 10 for coating a curable composition onto a base material 19, a volume expansion suppressing liquid head 11 downstream of the coating roller 10, an active energy ray irradiation device 27, and a preheating device. a heating device 18 for forming a volume expansion layer, an ejection head 16 consisting of a black head 12, a cyan head 13, a magenta head 14, and a yellow head 15, and a heating device 28 for forming a volume expansion layer. In addition, in FIG. 3, 20 is a conveyance belt, 21 is a delivery roller facing the application roller 10, and 22 is a winding roller.

The base material 19 is transported in the direction of the arrow in FIG. 3 by being wound around the transport belt 20 by the winding roller 22.
First, a curable composition is applied to the surface of the base material 19 using the application roller 10 to form a volume expansion agent-containing liquid layer.
Next, the base material 19 on which the volumetric expansion agent-containing liquid layer is formed is scanned at a predetermined speed, and the volumetric expansion suppressing liquid is applied from the volumetric expansion suppressing liquid head 11 to locations where the volumetric expansion of the volumetric expansion agent-containing liquid layer is not desired. Discharge to.
Next, the volume expanding agent-containing liquid layer is cured by irradiating the volume expanding agent-containing liquid layer with active energy rays under predetermined irradiation conditions using the active energy ray irradiation device 27. form a layer.
Next, the volume expansion agent-containing layer is heated by the heating device 18 at T _{2 S} for 5 to 10 seconds to perform preheating. In addition, in the preliminary heating, the base material 19 may be heated in addition to the volume expansion agent-containing liquid layer.
Next, the color material compositions for black, cyan, magenta, and yellow are applied by an inkjet method from each color head 12 for black, head 13 for cyan, head 14 for magenta, and head 15 for yellow. Discharge to form a coloring material layer.
Next, when the obtained volumetric expansion agent-containing layer is heated by the heating device 28, the volumetric expansion agent-containing layer at the heated portion expands in volume, and while maintaining the average thickness of the volumetric expansion layer thick, Printed matter with high adhesion to the material can be obtained.
FIG. 4 is a schematic diagram showing another example of the printed matter manufacturing apparatus of the present invention. The printed matter manufacturing apparatus 100 shown in FIG. 4 includes a coating roller 10 for coating a curable composition onto a base material 19, a volume expansion suppressing liquid head 11 downstream thereof, an active energy ray irradiation device 27, and a coating roller 10 for coating a curable composition on a substrate 19. It has an ejection head 16 consisting of a head 12, a cyan head 13, a magenta head 14, and a yellow head 15, a heating device 18 for preheating, and a heating device 28 for forming a volume expansion layer. In addition, in FIG. 4, 20 is a conveyance belt, 21 is a delivery roller facing the application roller 10, and 22 is a winding roller.

The base material 19 is conveyed in the direction of the arrow in FIG. 4 by being wound around the conveyor belt 20 by the winding roller 22.
First, a curable composition is applied to the surface of the base material 19 using the application roller 10 to form a volume expansion agent-containing liquid layer.
Next, the base material 19 on which the volumetric expansion agent-containing liquid layer is formed is scanned at a predetermined speed, and the volumetric expansion suppressing liquid is applied from the volumetric expansion suppressing liquid head 11 to locations where the volumetric expansion of the volumetric expansion agent-containing liquid layer is not desired. Discharge to.
Next, the volume expanding agent-containing liquid layer is cured by irradiating the volume expanding agent-containing liquid layer with active energy rays under predetermined irradiation conditions using the active energy ray irradiation device 27. form a layer.
Next, the color material compositions for black, cyan, magenta, and yellow are applied by an inkjet method from each color head 12 for black, head 13 for cyan, head 14 for magenta, and head 15 for yellow. Discharge to form a coloring material layer.
Next, the volume expansion agent-containing layer is heated by the heating device 18 at T _{2 S} for 5 to 10 seconds to perform preheating. In addition, in the preliminary heating, the base material 19 may be heated in addition to the volume expansion agent-containing liquid layer.
Next, when the obtained volumetric expansion agent-containing layer is heated by the heating device 28, the volumetric expansion agent-containing layer at the heated portion expands in volume, and while maintaining the average thickness of the volumetric expansion layer thick, Printed matter with high adhesion to the material can be obtained.
FIG. 5 is a schematic diagram showing another example of the printed matter manufacturing apparatus of the present invention. The printed matter manufacturing apparatus 100 shown in FIG. 5 includes a heating device 18 for preheating, a coating roller 10 for coating a curable composition on a substrate 19, a head 11 for a volumetric expansion suppressing liquid downstream of the coating roller 10, and a head 11 for a volumetric expansion suppressing liquid. It has an energy beam irradiation device 27, an ejection head 16 consisting of a black head 12, a cyan head 13, a magenta head 14, and a yellow head 15, and a heating device 28 for forming a volume expansion layer. In addition, in FIG. 5, 20 is a conveyance belt, 21 is a delivery roller facing the application roller 10, and 22 is a winding roller.

The base material 19 is transported in the direction of the arrow in FIG. 5 by winding the transport belt 20 around the winding roller 22 .
First, the base material is heated by the heating device 18 at T _S for 5 to 10 seconds to perform preheating.
Next, a curable composition is applied to the surface of the base material 19 using the application roller 10 to form a volume expansion agent-containing liquid layer.
Next, the base material 19 on which the volumetric expansion agent-containing liquid layer is formed is scanned at a predetermined speed, and the volumetric expansion suppressing liquid is applied from the volumetric expansion suppressing liquid head 11 to locations where the volumetric expansion of the volumetric expansion agent-containing liquid layer is not desired. Discharge to.
Next, the volume expanding agent-containing liquid layer is cured by irradiating the volume expanding agent-containing liquid layer with active energy rays under predetermined irradiation conditions using the active energy ray irradiation device 27. form a layer.
Next, the color material compositions for black, cyan, magenta, and yellow are applied by an inkjet method from each color head 12 for black, head 13 for cyan, head 14 for magenta, and head 15 for yellow. Discharge to form a coloring material layer.
Next, when the obtained volumetric expansion agent-containing layer is heated by the heating device 28, the volumetric expansion agent-containing layer at the heated portion expands in volume, and while maintaining the average thickness of the volumetric expansion layer thick, Printed matter with high adhesion to the material can be obtained.

The printed matter produced by the printed matter manufacturing method of the present invention and the printed matter manufacturing apparatus of the present invention not only provides a printed matter having excellent design and image quality due to the uneven shape, but also has a long-lasting effect due to the excellent uneven shape. Since the design and image quality can be maintained, it is suitable for use as, for example, flooring materials, wallpapers, interior materials, wall materials, baseboards, ceiling materials, building materials such as pillars, and the like.

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

(Example 1)
Printed matter was manufactured using a printed matter manufacturing apparatus as shown in FIG.

As the ejection head 16, a GEN4 head (MH2420) manufactured by Ricoh Printing Systems Co., Ltd. is used, and it includes a head 11 for volume expansion suppressing liquid, a head 12 for black, a head 13 for cyan, a head 14 for magenta, and a head 14 for yellow. Five heads 15 were arranged in parallel, the ejection head 16 was heated to 45° C., and the frequency was controlled so that a droplet size of 20 pL could be drawn.
As the active energy ray irradiation device 17, EC300/30/30mA manufactured by Iwasaki Electric Co., Ltd. was used, and inside the inert gas blanket, an N ₂ gas generator with a compressor (Maxi-Flow30, Inhouse Gas) was used as an inert gas source. (manufactured by Nippon Steel & Co., Ltd.) was connected at a pressure of 0.2 MPa·s, N ₂ was flowed at a flow rate of 2 L/min to 10 L/min, and the oxygen concentration was set to be 500 ppm or less.

The heating devices 18 and 28 are a combination of 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 high blow nozzle 50AL manufactured by Kansai Dentsu Co., Ltd. The prepared heating device was adjusted so that the wind speed from the nozzle tip was 30 m/sec.

First, as the base material 19, the following curable composition A was applied to the surface of paper (Ostritch Diamond high-grade plain paper RJPH-03) with a mass of 80 g/m ² using a coating roller 10 so that the average thickness was 100 μm. Then, a liquid layer containing a volume expander was formed.
Next, the base material on which the volume expansion agent-containing liquid layer was formed is scanned at a speed of 15 m/min, and the following volume expansion suppression liquid A is applied from the volume expansion suppression liquid head 11 to increase the volume of the volume expansion agent-containing liquid layer. I vomited it where I didn't want it to.
Next, the volume expansion agent-containing liquid layer was heated at 180° C. for 10 seconds by the heating device 18 to perform preheating. Using an infrared thermography GTC400C manufactured by GOSCH, we measured the temperature of the surface of the liquid layer containing the volume expanding agent after preheating, which is opposite to the surface in contact with the base material. The temperature was below 138°C).
Next, the volume expanding agent-containing liquid layer is cured by irradiating active energy rays using the active energy ray irradiation device 27 under irradiation conditions of 30 kV and 30 kGy at an accelerating voltage to form a volume expanding agent-containing layer. did.
Next, from the black head 12, cyan head 13, magenta head 14, and yellow head 15, the following color material compositions A1 to A4 for black, cyan, magenta, and yellow are applied by an inkjet method. A 25% image (one-fourth the width of each color film) was drawn to form a coloring material layer.
Next, heating was performed at 180° C. for 10 seconds using the heating device 28 to cause volume expansion of the heated portion of the volume expansion agent-containing layer, thereby forming a volume expansion layer. Through the above steps, the printed matter of Example 1 was obtained. The average thickness of the volume expansion layer of the obtained printed matter was 480 μm, and when the surface of the volume expansion layer in contact with the base material was observed using an optical microscope, the volume of the surface of the volume expansion layer in contact with the base material was The swelling agent had not expanded in volume.

<Preparation of curable composition A>
A volume expanding agent is added to 94 parts by mass of a polymerizable compound consisting of 90 parts by mass of methoxytriethylene glycol #400 acrylate (manufactured by Shin Nakamura Chemical Co., Ltd.) and 10 parts by mass of trimethylolpropane triacrylate (manufactured by Tomoe Kogyo Co., Ltd.). 3% by mass of azodicarboxylic acid amide (manufactured by Eiwa Kasei Kogyo Co., Ltd., temperature T _S at which volumetric expansion starts: 138°C) as a volume expansion accelerator, and 3% by mass of zinc naphthenate (manufactured by Tokyo Kasei Kogyo Co., Ltd.) as a volumetric expansion accelerator. A curable composition A was prepared by adding and stirring.

<Volume expansion suppression liquid A>
As the volumetric expansion suppressing liquid A, a liquid consisting of a polyfunctional monomer (1,6-hexanediol diacrylate) was used.

<Preparation of black coloring material composition A1>
60 parts by mass of acryloylmorpholine (manufactured by Tokyo Chemical Industry Co., Ltd.), 20 parts by mass of benzyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), and 40 parts by mass of SPECIAL BLACK 250 (black pigment, manufactured by BASF Japan) as a coloring material. By stirring, black coloring material composition A1 was prepared.

<Preparation of cyan coloring material composition A2>
60 parts by mass of acryloylmorpholine (manufactured by Tokyo Chemical Industry Co., Ltd.), 20 parts by mass of benzyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), and 40 parts by mass of IRGALITE BLUE GLVO (cyan pigment, manufactured by BASF Japan) as a coloring material. By stirring, cyan coloring material composition A2 was prepared.

<Preparation of magenta coloring material composition A3>
60 parts by mass of acryloylmorpholine (manufactured by Tokyo Chemical Industry Co., Ltd.), 20 parts by mass of benzyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), and CINQUASIA MAGENTA RT-355-D (magenta pigment, manufactured by BASF Japan) as a coloring material. A magenta coloring material composition A3 was prepared by stirring 40 parts by mass.

<Preparation of yellow coloring material composition A4>
Stir 60 parts by mass of acryloylmorpholine (manufactured by Tokyo Chemical Industry Co., Ltd.), 20 parts by mass of benzyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), and 40 parts by mass of NOVOPERM YELLOW H2G (yellow pigment, manufactured by Clariant) as a coloring material. By doing so, yellow coloring material composition A4 was prepared.

(Example 2)
In Example 1, a printed matter manufacturing apparatus as shown in FIG. 3 was used, except that the preheating was performed after the formation of the volume expansion agent-containing layer and before the formation of the coloring material layer. Printed matter was produced in the same manner. Using an infrared thermometer GTC400C manufactured by GOSCH, we measured the temperature of the surface of the volume-expanding agent-containing layer opposite to the surface in contact with the base material after preheating. (below 138°C). The average thickness of the volume expansion layer of the obtained printed matter was 560 μm, and when the surface of the volume expansion layer in contact with the base material was observed using an optical microscope, the volume of the surface of the volume expansion layer in contact with the base material was The swelling agent had not expanded in volume.

(Example 3)
Example 1 was carried out in the same manner as in Example 1, except that preheating was performed after the formation of the color material layer and before the formation of the volume expansion layer using the printed matter manufacturing apparatus as shown in FIG. A printed matter was produced. Using an infrared thermometer GTC400C manufactured by GOSCH, we measured the temperature of the surface of the volume-expanding agent-containing layer opposite to the surface in contact with the base material after preheating. (below 138°C). The average thickness of the volume expansion layer of the obtained printed matter was 520 μm, and when the surface of the volume expansion layer in contact with the base material was observed using an optical microscope, the volume of the surface of the volume expansion layer in contact with the base material was The swelling agent had not expanded in volume.

(Example 4)
In Example 1, using the printed matter manufacturing apparatus as shown in FIG. 5, preheating was performed before the formation of the volume expansion agent-containing liquid layer, and the base material was heated in the preheating. A printed matter was produced in the same manner as in Example 1. When the temperature of the base material after preheating was measured using an infrared thermography GTC400C manufactured by GOSCH, it was found to be 135°C (lower than 138°C, the temperature at which volume expansion of the volume expansion agent starts). The average thickness of the volume expansion layer of the obtained printed matter was 490 μm, and when the surface of the volume expansion layer in contact with the base material was observed using an optical microscope, the volume of the surface of the volume expansion layer in contact with the base material was The swelling agent had not expanded in volume.

(Comparative example 1)
In Example 1, a printed matter was produced in the same manner as in Example 1, except that preheating was not performed. The average thickness of the volume expansion layer of the obtained printed matter was 200 μm, and when the surface of the volume expansion layer in contact with the base material was observed using an optical microscope, it was found that the volume expansion agent on the surface of the volume expansion layer in contact with the base material was observed. had not expanded in volume.

(Comparative example 2)
In Comparative Example 1, a printed matter was produced in the same manner as in Comparative Example 1, except that the heating at 180° C. for 10 seconds by the heating device 28 was changed to heating at 180° C. for 30 seconds. The average thickness of the volume expansion layer of the obtained printed matter was 400 μm, and when the surface of the volume expansion layer in contact with the base material was observed using an optical microscope, the volume of the surface of the volume expansion layer in contact with the base material was The swelling agent had expanded in volume.

Next, the durability of the image quality of each of the obtained printed matter of Examples 1 to 4 and Comparative Examples 1 to 2 was evaluated as follows. The results are shown in Table 1.

<How to evaluate durability of image quality>
After scratching the surface of the obtained printed matter with a cutter, spray water, ethanol, acetone, and toluene on it and leave it for 12 hours.The surface of the printed matter was rubbed 10 times with paper, and the image area after rubbing and the degree of volume expansion were measured. The durability of the image quality was determined by microscopic and visual observation using the following criteria.
[Evaluation criteria]
A: Very good level with no peeling of the volumetrically expandable layer from the base material B: Very good level with almost no peeling of the volumetrically expandable layer from the base material C: Peeling of the volumetrically expandable layer from the base material D: Peeling of the volumetric expansion layer has spread over the entire abrasion area, but it is at an impractical level.

Examples of aspects of the present invention are as follows.
<1> A volume expanding agent-containing liquid layer forming step of applying a curable composition containing a volume expanding agent and a polymerizable compound to a base material to form a volume expanding agent-containing liquid layer;
heating the volume expansion agent-containing layer obtained by hardening the volume expansion agent-containing liquid layer to expand the volume of the volume expansion agent-containing layer to form a volume expansion layer;
Furthermore, it has a preheating step,
The method for producing a printed matter is characterized in that the preheating step is one of the steps (1) and (2) below.
(1) Before the volume expansion agent-containing liquid layer formation step, heating the base material. (2) After the volume expansion agent-containing liquid layer formation step and before the volume expansion layer formation step. , a step of heating either the volume expansion agent-containing liquid layer or the volume expansion agent-containing layer <2> The method for producing a printed matter according to <1> above, wherein the preheating step is (2).
<3> In the preheating step, either the volume expansion agent-containing liquid layer or the volume expansion agent-containing layer is heated to a temperature lower than a temperature T _S at which volume expansion of the volume expansion agent starts. This is a method for producing printed matter.
<4> The printed matter according to <1>, wherein the preheating step is (1) above, and in the preheating step, the base material is heated to a temperature lower than a temperature T _S at which volume expansion of the volume expansion agent starts. This is a manufacturing method.
<5> The volume expansion layer forming step includes temperature T 1 of the surface of the volume expansion agent-containing layer opposite to the surface in contact with the base material, and temperature T ₁ of the surface of the volume expansion agent-containing layer in contact with the base material. The method for producing a printed matter according to any one of <1> to <4>, which starts when the temperature T ₂ becomes T ₁ -T ₂ <10°C.
<6> In the volume expansion layer forming step, the temperature T ₂ of the surface of the volume expansion agent-containing layer in contact with the base material and the temperature T _S at which volume expansion of the volume expansion agent starts are |T ₂ - The method for producing a printed matter according to any one of <1> to <5>, wherein the volume expansion agent-containing layer is heated so that T _S |≦5°C.
<7> The method for producing a printed matter according to any one of <1> to <6>, wherein the heating temperature is T _S -10°C or more and T _S or less.
<8> Any one of <1> to <7> above, comprising a volume expanding agent-containing layer forming step of irradiating the volume expanding agent-containing liquid layer with active energy rays to form the volume expanding agent-containing layer. This is a method for producing a printed matter as described in .
<9> The method for producing a printed matter according to any one of <1> to <8>, wherein the volume expansion agent-containing layer has an average thickness of 50 μm or more and 150 μm or less.
<10> The method for producing a printed matter according to any one of <1> to <9>, wherein the volume expansion agent is a thermally expandable microcapsule.
<11> A volume expanding agent-containing liquid layer forming means for forming a volume expanding agent-containing liquid layer by applying a curable composition containing a volume expanding agent and a polymerizable compound to a base material;
a volume expansion layer forming means for heating the volume expansion agent-containing layer obtained by hardening the volume expansion agent-containing liquid layer to expand the volume of the volume expansion agent-containing layer to form a volume expansion layer;
Furthermore, it has a preheating means,
The apparatus for producing printed matter is characterized in that the preheating means is one of the means (1) and (2) below.
(1) A means for heating the base material before the volume expansion agent-containing liquid layer formation means; (2) A means for heating the base material after the volume expansion agent-containing liquid layer formation means and before the volume expansion layer formation means. , means for heating either the volume-expanding agent-containing liquid layer or the volume-expanding agent-containing layer <12> Irradiating the volume-expanding agent-containing liquid layer with active energy rays to heat the volume-expanding agent-containing layer. The apparatus for manufacturing a printed matter according to item <11> above has a volume expansion agent-containing layer forming means.

According to the method for producing printed matter according to any one of <1> to <10> and the apparatus for producing printed matter according to any one of <11> to <12>, problems in the past can be solved and The purpose of the invention can be achieved.

10 Application roller 11 Head for volumetric expansion suppressing liquid 12 Head for black 13 Head for cyan 14 Head for magenta 15 Head for yellow 16 Discharge head 18 Heating device 19 Base material 20 Conveyance belt 21 Delivery roller 22 Winding roller 27 Active energy ray irradiation Device 28 Heating device 100 Printed matter manufacturing device

Japanese Patent Application Publication No. 9-109303

Claims (7)

A volume expanding agent-containing liquid layer forming step of forming a volume expanding agent-containing liquid layer by applying a curable composition containing a volume expanding agent and a polymerizable compound to a base material;
heating the volume expansion agent-containing layer obtained by hardening the volume expansion agent-containing liquid layer to expand the volume of the volume expansion agent-containing layer to form a volume expansion layer;
Furthermore, before the volume expansion agent-containing liquid layer forming step, the printed matter comprises a preheating step of heating the base material to a temperature lower than a temperature T S at which volume expansion of the volume expansion agent starts _. Manufacturing method . In the volume expansion layer forming step, the temperature T of the surface of the volume expansion agent-containing layer opposite to the surface in contact with the base material is ₁ and the temperature T of the surface of the volume expansion agent-containing layer in contact with the base material. ₂ Toga, T ₁ -T ₂ The method for producing printed matter according to claim 1, which starts when the temperature is <10°C. In the volume expansion layer forming step, the temperature T of the surface of the volume expansion agent-containing layer in contact with the base material is ₂ and the temperature T at which the volume expansion of the volume expansion agent starts. _S Toga, ｜T ₂ -T _S 3. The method for producing a printed matter according to claim 1, wherein the volume expansion agent-containing layer is heated to a temperature of |≦5°C. The production of a printed matter according to any one of claims 1 to 3, comprising a volume expansion agent-containing layer forming step of irradiating the volume expansion agent-containing liquid layer with active energy rays to form the volume expansion agent-containing layer. Method. The method for producing a printed matter according to any one of claims 1 to 4, wherein the average thickness of the volume expansion agent-containing layer is 50 μm or more and 150 μm or less. A volume expanding agent-containing liquid layer forming means for forming a volume expanding agent-containing liquid layer by applying a curable composition containing a volume expanding agent and a polymerizable compound to a base material;
a volume expansion layer forming means for heating the volume expansion agent-containing layer obtained by hardening the volume expansion agent-containing liquid layer to expand the volume of the volume expansion agent-containing layer to form a volume expansion layer;
Furthermore, before the volume expansion agent-containing liquid layer forming means, the base material is heated to a temperature T at which the volume expansion of the volume expansion agent starts. _S 1. An apparatus for producing printed matter, characterized in that it has a preheating means for heating the printed material to a temperature lower than that of the preheating means. 7. The apparatus for manufacturing a printed matter according to claim 6, further comprising a volume expansion agent-containing layer forming means for forming the volume expansion agent-containing layer by irradiating the volume expansion agent-containing liquid layer with active energy rays.