JP2020015847A - Printed matter, printed matter for cut processing, printed matter for sticking, and manufacturing method of printed matter - Google Patents

Abstract

To provide a printed matter having a cured film with a three-dimensional feeling, excellent in a cut processability, a flex resistance, and a scratch resistance.SOLUTION: A printed matter includes a substrate and a cured film on the substrate. The cured film is a film obtained by curing a curable type composition containing a monofunctional monomer whose glass-transition temperature is 90°C or higher of 30 mass% or more with regard to a total amount of a polymerizable compound, a monofunctional monomer whose glass-transition temperature is 30°C or lower of 30 mass% or more with regard to the total amount of the polymerizable compound and a polyfunctional monomer of 2-15 mass%, inclusive, with regard to the total amount of the polymerizable compound. The cured film is 40 μm thick or thicker. Preferably the polyfunctional monomer is a bifunctional monomer.SELECTED DRAWING: None

Description

  The present invention relates to a printed matter, a printed matter for cutting, a printed matter for pasting, and a method for producing a printed matter.

  In recent years, active energy ray-curable inkjet inks as curable compositions are excellent in substrate compatibility, quick drying, strength, etc., so decorative printing on various building materials, daily necessities, automotive goods, etc. Widely used for signature printing and display printing.

  For example, as a commercial use or an industrial use, the use of printing with an active energy ray-curable ink on a substrate to be processed is increasing. For example, in a printed material using a magnet sheet as a base material to be processed, cut processing may be performed in accordance with a pattern, or cut processing may be performed in terms of operation such as carrying or using as a panel. For this reason, an image (cured product) obtained by the active energy ray-curable ink is required to have a cut workability such that a crack does not run or chip even when cut. Further, there is also a demand for scratch resistance such that the image (cured product) and the sheet are not scratched even if the sheet is rubbed, and also bend resistant such that the sheet is not broken or peeled even when wound into a roll.

  In particular, in recent active energy ray-curable ink-jet inks, decorating in which surface irregularities are formed by laminating inks may be performed, and a three-dimensional image can be obtained.

  In order to achieve both workability such as bending resistance and abrasion resistance, for example, an ink containing a large proportion of a monofunctional photopolymerizable compound has been proposed (for example, see Patent Document 1). The printed material of this ink also supports stretchability at high temperatures. Further, an ink composition has been proposed in which a monofunctional monomer having a high glass transition temperature is used to achieve both hardness at normal temperature and stretchability at high temperature (for example, see Patent Document 2).

  In addition, a curable composition having excellent shear workability such as cut workability often has low stretchability, and an ink containing a large amount of a polyfunctional monomer is added to a punched portion, and a polyfunctional monomer is added to a stretched portion. There has been proposed a method of applying an ink containing a small amount of ink separately in a punched portion and a stretched portion (for example, see Patent Document 3).

  An object of the present invention is to provide a printed matter having a three-dimensionally cured film excellent in cut workability, bending resistance, and abrasion resistance.

  The printed matter of the present invention as a means for solving the problem has a substrate and a cured film on the substrate, and the cured film contains 30 masses of a monofunctional monomer having a glass transition temperature of 90 ° C or higher. % And a glass transition temperature of 30% by mass or more of a monofunctional monomer having a temperature of 30 ° C. or less, and a film obtained by curing a curable composition containing 2% by mass or more and 15% by mass or less of a polyfunctional monomer. Is 40 μm or more.

  According to the present invention, it is possible to provide a printed material having a three-dimensional cured film having excellent cut processing properties, bending resistance, and abrasion resistance.

FIG. 1 is a schematic diagram illustrating an example of a printing apparatus used in the present invention.

(Printed matter)
The printed matter of the present invention has a substrate and a cured film on the substrate, and the cured film has a glass transition temperature of at least 30% by mass of a monofunctional monomer having a glass transition temperature of 90 ° C. or more based on the total amount of the polymerizable compound. A curable composition containing a monofunctional monomer having a glass transition temperature of 30 ° C. or less based on the total amount of the polymerizable compound and 30% by mass or more based on the total amount of the polymerizable compound; The cured film has a thickness of 40 μm or more, and further includes other members as necessary.

The present inventors have studied the printed matter having a three-dimensional cured film excellent in cut workability, bending resistance, and scratch resistance, and have obtained the following knowledge.
For example, in the case of a conventional cured film made of active energy ray-curable ink, there is a problem that cut workability is deteriorated in an ink which has both flexibility at high temperature and hardness at room temperature.
Further, in the conventional method of producing a printed material using curable compositions having different compositions, there is a problem that the same curable composition cannot achieve both shearing workability and stretchability.

  Therefore, the inventors of the present invention have found that a monofunctional monomer having a glass transition temperature of 90 ° C. or more is 30% by mass or more, a monofunctional monomer having a glass transition temperature of 30 ° C. or less is 30% by mass or more, and a polyfunctional monomer is 2% by mass. By using the curable composition containing 15% by mass or less, even if the cured film has a three-dimensional appearance with a film thickness of 40 μm or more, it is possible to obtain strength suitable for use as the cured film. Therefore, when the printed material having the cured film is cut (cut), a cut workability capable of obtaining a smooth cut surface without cracking or chipping, a bending resistance that is hard to be broken or peeled even when the printed material is wound into a roll, and It has been found that a printed material having a cured film having excellent scratch resistance, which is hardly damaged even when the printed material is repeatedly rubbed, can be obtained.

<Substrate>
The structure, material, size, and shape of the substrate are not particularly limited, and can be appropriately selected depending on the purpose.

As the thickness of the substrate increases, cracks (cracks and cracks) are more likely to occur in the cured film when the printed material is bent. In particular, in a printed material having a base material having a thickness of 0.2 mm or more, and further, 0.4 mm or more and 3.0 mm or less, the printed surface is placed on the outside in a roll shape (shaft diameter is 5 cm or more and 10 cm or less). When winding, the printing surface is elongated and cracks are likely to occur. If the thickness of the substrate is less than 0.2 mm, the stretch of the printing surface is small even if it is bent, and if it exceeds 3.0 mm, the necessity of bending is eliminated. Therefore, printed matter using a substrate having a thickness of 0.2 mm or more, or a substrate having a thickness of 0.4 mm or more and 3.0 mm or less is often stored in the state of a roll wound in a roll shape, Demand for flex resistance is high.
Although it depends on the cutting method, it is preferable that the base material is based on the premise of cutting. Examples of the substrate premised on the cutting include a magnet sheet, a marking film, and the like. A highly flexible substrate such as a magnet sheet or a marking film can be cut with scissors or a cutting machine without using a special cutting device.

  The structure of the base material is not particularly limited and can be appropriately selected depending on the purpose. For example, a single-layer structure composed of a single material, a multilayer structure in which a plurality of single materials are stacked, and a plurality of types. And the like.

  The material of the base material is not particularly limited as long as it can be cut with scissors or a cutting machine, and can be appropriately selected depending on the purpose. Examples of the material include elastomers (chlorinated polyethylene, chlorosulfonated polyethylene, ethylene / acetic acid). Vinyl copolymer, ethylene / propylene rubber, nitrile rubber, acrylic rubber, chloroprene rubber, etc.), polyvinyl chloride, metallized film and the like.

The substrate is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include a magnet sheet having a film layer and a magnet layer, and a pressure-sensitive adhesive sheet having a film layer and a pressure-sensitive adhesive layer.
Examples of the adhesive sheet include a marking film and a cutting sheet.

  The surface shape of the base material is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include a smooth shape and an uneven shape.

<Curing film>
The cured film is a coating film obtained by curing the curable composition on a substrate.

<< Curable composition >>
The curable composition contains a polymerizable compound. The polymerizable compound includes a monofunctional monomer and a polyfunctional monomer. As the monofunctional monomer, a monofunctional monomer having a glass transition temperature of 90 ° C. or higher is 30% by mass or more based on the total amount of the polymerizable compound, and a monofunctional monomer having a glass transition temperature of 30 ° C. or lower is based on the total amount of the polymerizable compound. 30% by mass or more, contains the polyfunctional monomer in an amount of 2% by mass or more and 15% by mass or less based on the total amount of the polymerizable compound, and further contains other components as necessary.

  The monomer is a compound that causes a polymerization reaction by an active energy ray (ultraviolet ray, electron beam, or the like) or an active species generated by the active energy ray and cures. Depending on the number of functional groups, a monofunctional monomer or a polyfunctional monomer is used. And monomers. The monomer may be a polymerizable composition, and may contain a polymerizable oligomer or a polymerizable polymer (macromonomer). These may be used alone or in combination of two or more.

<Measurement of glass transition temperature (Tg)>
The glass transition temperature (Tg) of a monofunctional monomer refers to the glass transition temperature of a cured product of a homopolymer of a monofunctional monomer. Here, the glass transition temperature (Tg) has a catalog value of a manufacturer of the monofunctional monomer. In this case, the value is adopted, and when it does not exist, the value is measured by the differential scanning calorimetry (DSC) method as follows.

-Glass transition temperature (Tg) measurement method-
The polymerization of the polymerizable monomer can be performed by a general solution polymerization method.
A: A toluene solution of 10% by mass of a polymerizable monomer B: 5% by mass of azobisisobutyronitrile as a polymerization initiator
A and B are purged with nitrogen, sealed in a test tube, and shaken in a 60 ° C warm bath for 6 hours to synthesize a polymer. Thereafter, the polymer is reprecipitated in a solvent in which the polymerizable monomer is soluble and the polymer is insoluble (eg, methanol, petroleum ether, etc.), and the polymer is taken out by filtration. The obtained polymer is measured by DSC. As the DSC device, DSC 120U manufactured by Seiko Instruments is used, and the measurement can be performed at a measurement temperature of 30 ° C. to 300 ° C. and a heating rate of 2.5 ° C. per minute.

-Monofunctional monomer having a glass transition temperature of 90 ° C or higher-
A monofunctional monomer having a glass transition temperature of 90 ° C. or higher can increase the glass transition temperature of a cured film formed from the curable composition, and can improve the hardness at room temperature. Therefore, the abrasion resistance of the cured film formed from the curable composition can be improved.

  The monofunctional monomer having a glass transition temperature of 90 ° C. or higher is not particularly limited and can be appropriately selected depending on the intended purpose. Examples include N-vinyl-ε-caprolactam, isobornyl acrylate, adamantyl acrylate, 2-methyl-2-adamantyl acrylate, dicyclopentenyl acrylate, dicyclopentanyl acrylate, and the like. These may be used alone or in combination of two or more. Among these, acryloylmorpholine and isobornyl acrylate are preferred.

  The content of the monofunctional monomer having a glass transition temperature of 90 ° C. or higher is 30% by mass or more based on the total amount of the polymerizable compound, and preferably 30% by mass or more and 68% by mass or less.

-Monofunctional monomer having a glass transition temperature of 30 ° C or less-
Since a monofunctional monomer having a glass transition temperature of 30 ° C. or less can provide a flexible segment in a polymer constituting a cured film, the cut processing property and the bending resistance of the cured film formed from the curable composition can be improved. Can be improved.

  The monofunctional monomer having a glass transition temperature of 30 ° C. or lower is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include benzyl acrylate, cyclohexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl) methyl acrylate, tetrahydrofurfuryl acrylate, (3-ethyloxetane-3-yl) methyl (meth) acrylate, isostearyl acrylate, cyclic trimethylol And propane formal acrylate and phenoxyethyl acrylate. Among these, cyclohexyl acrylate and benzyl acrylate are preferred. These may be used alone or in combination of two or more. By including a monofunctional monomer having a glass transition temperature of 30 ° C. or lower, cut workability and bending resistance of a cured product of the curable composition can be improved.

  The content of the monofunctional monomer having a glass transition temperature of 30 ° C. or less is 30% by mass or more, preferably 30% by mass or more and 68% by mass or less based on the total amount of the polymerizable compound.

  The content of these monofunctional monomers is preferably from 85% by mass to 98% by mass, more preferably from 88% by mass to 95% by mass, based on the total amount of the polymerizable compound. When the content of the monofunctional monomer is 85% by mass or more, the bending resistance can be improved, and when it is 98% by mass or less, the scratch resistance is easily obtained, and the scratch resistance is improved. Therefore, even if 30% or more of a monofunctional monomer having a high glass transition temperature (Tg of 90 ° C. or more) is added, cut workability can be obtained.

-Polyfunctional monomer-
Examples of the polyfunctional monomer include a bifunctional monomer, a trifunctional monomer, and a monomer having a higher number of functional groups.
The polyfunctional monomer is not particularly limited and can be appropriately selected depending on the intended purpose. For example, 1,9-nonanediol diacrylate, neopentyl glycol di (meth) acrylate, (poly) ethylene glycol di (meth) A) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene Glycol di (meth) acrylate, (poly) tetramethylene glycol di (meth) acrylate, propylene oxide (PO) adduct of bisphenol A di (meth) acrylate, ethoxylated neopentyl glycol (Meth) acrylate, propoxylated neopentyl glycol di (meth) acrylate, ethylene oxide (EO) adduct of bisphenol A di (meth) acrylate, pentaerythritol tri (meth) acrylate, EO-modified pentaerythritol tri (meth) acrylate, PO modified pentaerythritol tri (meth) acrylate, EO modified pentaerythritol tetra (meth) acrylate, PO modified pentaerythritol tetra (meth) acrylate, EO modified dipentaerythritol tetra (meth) acrylate, PO modified dipentaerythritol tetra (meth) acrylate Acrylate, trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, PO-modified trimethylol Pantri (meth) acrylate, EO-modified tetramethylolmethanetetra (meth) acrylate, PO-modified tetramethylolmethanetetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, trimethylolpropanetri ( (Meth) acrylate, tetramethylolmethanetetra (meth) acrylate, trimethylolethanetri (meth) acrylate, bis (4- (meth) acryloxypolyethoxyphenyl) propane, diallyl phthalate, triallyl trimellitate, 1,6- Hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,10-decanediol di (Meth) acrylate, neopentyl glycol hydroxypivalate di (meth) acrylate, tetramethylol methane tri (meth) acrylate, dimethylol tricyclodecane di (meth) acrylate, modified glycerin tri (meth) acrylate, bisphenol A diglycidyl ether (Meth) acrylic acid adduct, modified bisphenol A di (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol tri (meth) acrylate tolylene diisocyanate urethane prepolymer Pentaerythritol tri (meth) acrylate hexamethylene diisocyanate urethane prepolymer, ditrimethylolpropanate (Meth) acrylate, pentaerythritol tri (meth) acrylate hexamethylene diisocyanate urethane prepolymer, urethane acrylate oligomer, epoxy acrylate oligomer, polyester acrylate oligomer, polyether acrylate oligomer, and silicone acrylate oligomers and the like. These may be used alone or in combination of two or more.

  The content of the polyfunctional monomer is 2% by mass or more and 15% by mass or less, preferably 5% by mass or more and 12% by mass or less based on the total amount of the polymerizable compound. Within this range, scratch resistance and cut workability can be imparted. When the content of the polyfunctional monomer is less than 2% by mass, the scratch resistance is reduced. Alternatively, when a monofunctional monomer having a high Tg is used, even if the abrasion resistance does not decrease, there occurs a problem that the cut workability is reduced and the cut surface is not smooth. On the other hand, if the content of the polyfunctional monomer exceeds 15% by mass, in particular, the bending resistance and the cut processability deteriorate, and the material cracks when bent or chipped when cut. Alternatively, when a polyfunctional monomer having a high molecular weight is employed, the viscosity tends to be too high even if the bending resistance and the cut processing property are not easily reduced.

  The number of functional groups of the polyfunctional monomer is preferably 2 to 6 functional groups, and more preferably a bifunctional monomer. The smaller the number of functional groups, the lower the viscosity, and the lower the viscosity of the surface liquid, so that it is suitable for inkjet printing.

-Other components-
Other components include, for example, a polymerization initiator, a coloring material, an organic solvent, and the like.

<Polymerization initiator>
The curable composition may contain a polymerization initiator. The polymerization initiator may be any as long as it is capable of generating active species such as radicals and cations by the energy of active energy rays and initiating polymerization of a 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. Among them, a radical polymerization initiator is used. Is preferred. Further, in order to obtain a sufficient curing rate, the polymerization initiator is preferably contained in an amount of 5% by mass to 20% by mass based on the total mass (100% by mass) of the composition.
Examples of the radical polymerization initiator include aromatic ketones, acylphosphine oxide compounds, aromatic onium salt compounds, organic peroxides, thio compounds (thioxanthone compounds, thiophenyl group-containing compounds, etc.), hexaarylbiimidazole compounds, Examples include ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, compounds having a carbon-halogen bond, and alkylamine compounds.
Further, in addition to the polymerization initiator, a polymerization accelerator (sensitizer) can be used in combination. Examples of the polymerization accelerator are not particularly limited. For example, trimethylamine, methyldimethanolamine, triethanolamine, p-diethylaminoacetophenone, ethyl p-dimethylaminobenzoate, 2-ethylhexyl p-dimethylaminobenzoate, N, Amine compounds such as N-dimethylbenzylamine and 4,4′-bis (diethylamino) benzophenone are preferable, and the content thereof may be appropriately set according to the polymerization initiator used and its amount.

<Color material>
The curable composition may contain a coloring material. As the coloring material, various pigments for imparting glossy colors such as black, white, magenta, cyan, yellow, green, orange, gold and silver, etc., depending on the purpose and required characteristics of the curable composition of the present invention. And dyes can be used. The content of the coloring material may be appropriately determined in consideration of a desired color concentration, dispersibility in the curable composition, and the like, and is not particularly limited, but is preferably based on the total mass of the composition (100% by mass). Preferably it is 0.1% by mass to 20% by mass. The curable composition may be colorless and transparent without containing a coloring material, and in that case, it is suitable, for example, as an overcoat layer for protecting an image.
As the pigment, an inorganic pigment or an organic pigment can be used, and one kind may be used alone, or two or more kinds 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.
As the organic pigment, for example, insoluble azo pigments, condensed azo pigments, azo lakes, azo pigments such as chelate azo pigments, phthalocyanine pigments, perylene and perinone pigments, anthraquinone pigments, quinacridone pigments, dioxane pigments, thioindigo pigments, isoindolinone pigments, quinophthalones Polycyclic pigments such as pigments, dye chelates (eg, basic dye type chelates, acid dye type chelates, etc.), dye lakes (eg, basic dye type lakes, acid dye type lakes, etc.), nitro pigments, nitroso pigments, Aniline black and daylight fluorescent pigments.
Further, a dispersant may be further included in order to improve the dispersibility of the pigment. The dispersant is not particularly limited, and includes, for example, a dispersant commonly used for preparing a pigment dispersion such as a polymer dispersant.
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.

<Organic solvent>
The curable composition may include an organic solvent, but preferably does not include an organic solvent if possible. If the composition does not contain an organic solvent, in particular, a volatile organic solvent (VOC (Volatile Organic Compounds) free), the safety of the place where the composition is handled is further enhanced, and environmental pollution can be prevented. . The `` organic solvent '' is, for example, a general non-reactive organic solvent such as ether, ketone, xylene, ethyl acetate, cyclohexanone, and toluene, and should be distinguished from a reactive monomer. is there. Further, “not including” the organic solvent means that the organic solvent is not substantially contained, and preferably less than 0.1% by mass.

<Other ingredients>
The curable composition may contain other components as necessary. Other components are not particularly limited, and include, for example, conventionally known surfactants, polymerization inhibitors, leveling agents, defoamers, fluorescent brighteners, penetration enhancers, wetting agents (humectants), Examples include fixing agents, viscosity stabilizers, fungicides, preservatives, antioxidants, ultraviolet absorbers, chelating agents, pH adjusters, and thickeners.

The thickness (film thickness) of the cured film is not particularly limited and can be appropriately selected depending on the purpose. For example, the thickness is 40 μm or more, preferably 50 μm or more and 1,000 μm or less, and more preferably 100 μm or more and 500 μm or less. preferable. When the thickness (thickness) of the cured film is 40 μm or more, the resulting cured film can have a three-dimensional effect. When the thickness (film thickness) of the cured film is 1,000 μm or less, a printed material having excellent bending resistance against cracking, chipping, peeling off due to bending, and the like in the cutting process can be obtained.
The method of measuring the thickness of the cured film is not particularly limited and can be appropriately selected depending on the purpose.For example, a micro gauge or a palpation type step meter for comparing the thickness with the non-printed portion, the cross section of the printed material is used. A method of observing and measuring with a scanning electron microscope (SEM) is exemplified.

<Preparation of curable composition>
The curable composition can be prepared using the various components described above, and the preparation means and conditions are not particularly limited.For example, a polymerizable monomer, a pigment, a dispersant, and the like can be prepared by using a ball mill, a kitty mill, a disk mill, A pigment dispersion is prepared by putting the mixture in a dispersing machine such as a pin mill or a Dyno mill and dispersing the pigment dispersion, and the pigment dispersion is prepared by further mixing a polymerizable monomer, a polymerization initiator, a polymerization inhibitor, a surfactant, and the like. be able to.

<Viscosity>
The viscosity of the curable composition may be appropriately adjusted depending on the use and application means, and is not particularly limited. For example, when a discharge means for discharging the curable composition from a nozzle is used, 20 The viscosity in the range of from 65 ° C. to 65 ° C., desirably the viscosity at 25 ° C. to 50 ° C. is preferably 3 mPa · s to 40 mPa · s, more preferably 5 mPa · s to 15 mPa · s, and particularly preferably 6 mPa · s to 12 mPa · s. . It is particularly preferable that the viscosity range is satisfied without containing the organic solvent. The above viscosity was measured using a cone plate type rotary viscometer VISCOMMETER TV-22L manufactured by Toki Sangyo Co., Ltd., using a cone rotor (1 ° 34 ′ × R24), rotating at 50 rpm, and keeping the temperature of constant temperature circulating water at 20 ° C. It can be measured by appropriately setting it within the range of ~ 65 ° C. VISCOMATE VM-150III can be used for adjusting the temperature of the circulating water.

<Application>
The use of the curable composition of the present invention is not particularly limited as long as it is a field where an active energy ray-curable ink is generally used, and can be appropriately selected depending on the purpose.
Furthermore, the curable composition can be used as an ink to form not only two-dimensional characters and images, design coating films on various substrates, but also three-dimensional images (three-dimensional objects). It can also be used as a molding material.
As a three-dimensional modeling device for modeling a three-dimensional molded object using the curable composition, a known three-dimensional modeling device can be used, and is not particularly limited. For example, a storage unit, a supply unit, and a discharge unit of the composition And those provided with active energy ray irradiation means and the like.
Further, the printed matter using the curable composition of the present invention also includes a processed product obtained by processing the printed matter. The processed product is obtained, for example, by subjecting a cured product or a structure formed into a sheet to processing such as cutting, punching, and heat stretching. OA equipment, electrical and electronic equipment, meters such as cameras, panels for operation units, etc., are suitably used for applications that require processing after decorating the surface.
The substrate is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include plastic, metal, fiber, cloth, leather, ceramics, and composite materials thereof, and a viewpoint of workability. Therefore, a plastic substrate is preferred.

  As the printed matter having the curable composition of the present invention, not only those printed on a smooth surface such as a normal resin sheet, but also those printed on a printing surface having irregularities, various kinds of metals and ceramics and the like Also includes those printed on a printing surface made of a material.

(Printed material for cutting)
The printed matter for cutting according to the present invention comprises the printed matter of the present invention.

(Printed material for pasting)
The printed matter for pasting of the present invention comprises at least one of the printed matter of the present invention and the printed matter for cutting.

<Manufacturing method of printed matter, printing apparatus>
The method for producing a printed matter of the present invention may use active energy rays, or may include heating.
In order to cure the curable composition with an active energy ray, the printing apparatus of the present invention includes an irradiation step for irradiating the active energy ray, and a curing unit of the present invention. And a storage unit for storing the mold composition, and the storage unit may store a storage container. Further, it may have a discharge step and discharge means for discharging the curable composition. The method of discharging is not particularly limited, and examples thereof include a continuous injection type and an on-demand type. Examples of the on-demand type include a piezo method, a thermal method, and an electrostatic method.
FIG. 1 is an example of a printing apparatus provided with an inkjet discharge unit. The ink is ejected onto the recording medium 22 supplied from the supply roll 21 by the respective color printing units 23a, 23b, 23c, and 23d each including an ink cartridge of an active energy ray-curable ink of each color of yellow, magenta, cyan, and black and an ejection head. Is done. After that, the ink is irradiated with active energy rays from light sources 24a, 24b, 24c, and 24d for curing the ink to cure the ink, thereby forming a color image. Thereafter, the recording medium 22 is transported to the processing unit 25 and the printed material take-up roll 26. Each of the printing units 23a, 23b, 23c, and 23d may be provided with a heating mechanism so that the ink is liquefied at the ink ejection unit. If necessary, a mechanism for cooling the recording medium to about room temperature by contact or non-contact may be provided. In addition, as an inkjet recording method, for a recording medium that moves intermittently according to the discharge head width, a serial method in which the head is moved to discharge ink onto the recording medium, or the recording medium is continuously moved, Any of a line method in which ink is ejected onto a recording medium from a head held at a fixed position can be applied.
The recording medium 22 is not particularly limited, but includes plastic, metal, fiber, cloth, leather, ceramics, a composite material thereof, and the like, and may be in a sheet shape. Further, a configuration that enables only one-sided printing or a configuration that enables double-sided printing may be employed.
Further, the active energy ray irradiation from the light sources 24a, 24b and 24c may be weakened or omitted, and after printing a plurality of colors, the active energy ray may be emitted from the light source 24d. Thereby, energy saving and cost reduction can be achieved.
As the printed matter of the curable composition of the present invention, not only those printed on a smooth surface such as a normal resin film, but also those printed on a printing surface having irregularities, and various materials such as metals and ceramics And those printed on the surface to be printed. In addition, by stacking two-dimensional images, it is possible to form an image (a two-dimensional and three-dimensional image) or a three-dimensional object partially having a three-dimensional effect.
In the present invention, the recording medium is synonymous with the base material.

<Curing means>
Means for curing the curable composition include heat curing and curing with active energy rays. Among these, curing with active energy rays is preferable.
The active energy rays used for curing the curable composition include, in addition to ultraviolet rays, electron beams, α-rays, β-rays, γ-rays, X-rays, etc. What is necessary is just to be able to provide the energy required for proceeding, 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. Further, in the case of ultraviolet irradiation, mercury-free is strongly desired from the viewpoint of environmental protection, and replacement with a GaN-based semiconductor ultraviolet light emitting device is very useful industrially and environmentally. Furthermore, ultraviolet light emitting diodes (UV-LEDs) and ultraviolet laser diodes (UV-LDs) are compact, have a long life, are highly efficient, and are low in cost, and are preferred as ultraviolet light sources.

  Hereinafter, examples of the present invention will be described, but the present invention is not limited to these examples. In this example, an example is shown in which an active energy ray-curable ink is used as the curable composition.

(Preparation Examples 1 to 20)
-Preparation of active energy ray-curable inks 1 to 20-
The active energy ray curable inks 1 to 20 were prepared by mixing and stirring the compositions shown in Tables 1 to 5.

(Example 1)
The obtained active energy ray-curable ink 1 of Preparation Example 1 was used as an ultraviolet illuminance at a printing speed of 840 mm / sec. Printed matter 1 was obtained by performing 8-pass printing with unidirectional printing (outbound only) at an arc of 1.0 W / cm ² and repeating printing to the film thickness (0.7 μm) shown in Table 1. Was.
The illuminance (W / cm ² ) was measured in the UVA region of UV Power Pack (registered trademark) II (manufactured by EIT).
As a base material, a magnet sheet (FP Magex magnet color sheet (manufactured by Magex Co., Ltd., white, thickness of magnet layer: 0.5 mm to 1.0 mm, film: PVC white)) was used.

(Examples 2 to 12 and Comparative Examples 1 to 8)
Printed products 2 to 20 were obtained in the same manner as in Example 1 except that the active energy ray-curable ink 1 was changed to the active energy ray-curable inks 2 to 20 shown in Tables 1 to 5.

  Next, in the printed materials 1 to 20 obtained in Examples 1 to 12 and Comparative Examples 1 to 8, “cut workability”, “bending resistance”, “scratch resistance”, and “ The “three-dimensional feeling” was measured and evaluated. The results are shown in Tables 1 to 5.

(Cut workability)
The obtained printed materials 1 to 20 were cut by a paper cutter PC-A3 (manufactured by Lion Office Equipment), and the cut printed materials were visually checked and evaluated according to the following evaluation criteria.

[Evaluation criteria]
：: The cut surface of the cured film is along the cut surface of the base material, and the cut surface of the cured film is smooth. △: The cut surface of the cured film is along the cut surface of the base material, but the cut of the cured film The cut surface of the cured film is not smooth due to a portion where the surface and the cut surface of the base material do not match. X: Chipping detached from the base material at the cut surface of the cured film, or a crack is generated in the cured film.

(Bending resistance)
According to JIS K 5600-5-1, the obtained printed materials 1 to 20 were subjected to a bending resistance test of 180 ° bending with the printing surface outside the bending by a cylindrical mandrel method. The printed matter after the test was visually checked and evaluated according to the following evaluation criteria.

[Evaluation criteria]
：: No cracks occurred at a mandrel diameter of 10 mm. Δ: Cracks occurred at a mandrel diameter of 10 mm, but no cracks occurred at 32 mm. ×: Cracks occurred at a mandrel diameter of 32 mm.

(Scratch resistance)
A pencil hardness test was performed on the obtained printed materials 1 to 20 as a scratch resistance test. The pencil hardness test was performed according to JIS K5600-5-4 scratch hardness (pencil method). As a device, a pencil hardness TQC WW tester manufactured by COTEC Co., Ltd. (dedicated to 750 g load) was used, and the pencil was attached to the printed surface at an angle of 45 ° with a load of 750 g to be pressed on the printed material at a speed of 0.5 mm / s. Was tested. The printed matter after the test was visually checked and evaluated according to the following evaluation criteria.

[Evaluation criteria]
：: No scratches visible to the naked eye at a pencil hardness of HB or higher. Δ: Scratches visible to the naked eye at a pencil hardness of B. ×: Scratches visible to the naked eye at a pencil hardness of 2B or less.

(3D effect)
In addition to the obtained printed materials 1 to 20, printing is performed by using the active energy ray-curable inks 1 to 20 of Preparation Examples 1 to 20 so that the thickness of the cured film described in Tables 1 to 5 is obtained. Printed products 1 'to 20' having an uneven surface of a portion and a non-print portion were obtained. The surface of the obtained printed matter was visually checked while holding it in a hand, and evaluated according to the following evaluation criteria.
[Evaluation criteria]
◎: Even when viewed from a distance of 5 m, a three-dimensional effect can be felt regardless of the angle. ○: A three-dimensional effect can be felt regardless of the angle. I can not feel it, it looks like a plane image

  The trade names and the names of the manufacturers of the components in Tables 1 to 5 are as follows.

<Monofunctional monomer>
<<< Monofunctional monomer having a glass transition temperature of 30 ° C. or less >>>
-Phenoxyethyl acrylate (PEA): manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name: Biscoat # 192, Tg: 2 ° C
・ Benzyl acrylate (BzA): manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name: Biscoat # 160, Tg: 6 ° C.
-Cyclic trimethylolpropane formal acrylate (CTFA): manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name: Biscoat # 200, Tg: 27 ° C
<<< Monofunctional monomer having a glass transition temperature of 90 ° C. or more >>>
-N-vinylcaprolactam (NVC): manufactured by Ashland, trade name: V-Cap TM, Tg: 90 ° C
-Isobornyl acrylate (IBXA): manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name: IBXA, Tg: 97 ° C
Acryloylmorpholine (ACMO): KJ Chemicals Co., Ltd., Tg: 145 ° C

<Polyfunctional monomer>
-1,9-nonanediol diacrylate (NDDA): manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name: Biscoat # 260
-Urethane acrylate (UA): manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name: Shikko UV-3010B

<Polymerization initiator>
-2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone: trade name: Irgacure 379, manufactured by BASF

<Color material>
・ Phthalocyanine copper: PB15: 4

  Next, the glass transition temperature of the monofunctional monomer used for preparing each active energy ray-curable ink was measured as follows.

<Measurement of glass transition temperature (Tg)>
The glass transition temperature (Tg) of a monofunctional monomer refers to the glass transition temperature of a cured film of a homopolymer of a monofunctional monomer, where the glass transition temperature (Tg) has a catalog value of a manufacturer of the monofunctional monomer. In this case, the value is adopted, and when it does not exist, the value is measured by the differential scanning calorimetry (DSC) method as follows.

-Glass transition temperature (Tg) measurement method-
Polymerization of the polymerizable monomer was performed by a general solution polymerization method.
A: A toluene solution of 10% by mass of a polymerizable monomer B: 5% by mass of azobisisobutyronitrile as a polymerization initiator
A and B were purged with nitrogen, sealed in a test tube, and shaken in a 60 ° C. warm bath for 6 hours to synthesize a polymer. Thereafter, the polymer was reprecipitated in a solvent in which the polymerizable monomer was soluble and the polymer was insoluble (for example, methanol, petroleum ether, etc.), and the polymer was taken out by filtration. The obtained polymer was subjected to DSC measurement. As a DSC apparatus, DSC120U manufactured by Seiko Instruments was used, and the measurement was performed at a measurement temperature of 30 ° C to 300 ° C and a heating rate of 2.5 ° C per minute.

Aspects of the present invention are, for example, as follows.
<1> having a substrate and a cured film on the substrate,
The cured film is composed of a monofunctional monomer having a glass transition temperature of 90 ° C. or higher based on the total amount of the polymerizable compound, and a monofunctional monomer having a glass transition temperature of 30 ° C. or lower based on the total amount of the polymerizable compound. % Or more, and a film obtained by curing a curable composition containing 2% by mass or more and 15% by mass or less based on the total amount of the polymerizable compound,
The printed matter is characterized in that the thickness of the cured film is 40 μm or more.
<2> The printed matter according to <1>, wherein the polyfunctional monomer is a bifunctional monomer.
<3> Any one of <1> to <2>, wherein the monofunctional monomer having a glass transition temperature of 90 ° C. or higher is at least one of N-vinyl-ε-caprolactam, isobornyl acrylate, and acryloylmorpholine. Printed matter described in 1.
<4> The monofunctional monomer having a glass transition temperature of 30 ° C. or less is at least one of phenoxyethyl acrylate, benzyl acrylate, and cyclic trimethylolpropane formal acrylate, according to any one of <1> to <3>. Printed matter.
<5> The printed matter according to any one of <1> to <4>, wherein the thickness of the base material is 0.2 mm or more.
<6> The printed material according to any one of <1> to <5>, wherein the base material is a magnet sheet.
<7> The printed matter according to any one of <1> to <6>, wherein the cured film has a thickness of 50 μm or more and 1,000 μm or less.
<8> A printed matter for cutting, comprising the printed matter according to any one of <1> to <7>.
<9> A printed material for pasting, comprising: the printed material according to any one of <1> to <7>; and the printed material for cutting according to <8>.
<10> Manufacture of at least one of the printed matter according to any one of <1> to <7>, the printed matter for cutting according to <8>, and the printed matter for pasting according to <9>. This is a method for producing a printed matter.

  Production of the printed matter according to any one of <1> to <7>, the printed matter for cutting according to <8>, the printed matter for pasting according to <9>, and the printed matter according to <10>. According to the method, the above problems in the related art can be solved and the object of the present invention can be achieved.

Japanese Patent No. 5265916 JP 2007-56232 A JP 2012-219212 A

Claims (10)

A substrate, having a cured film on the substrate,
The cured film is composed of a monofunctional monomer having a glass transition temperature of 90 ° C. or higher based on the total amount of the polymerizable compound, and a monofunctional monomer having a glass transition temperature of 30 ° C. or lower based on the total amount of the polymerizable compound. % Or more, and a film obtained by curing a curable composition containing 2% by mass or more and 15% by mass or less based on the total amount of the polymerizable compound,
A printed matter, wherein the thickness of the cured film is 40 μm or more.   The printed matter according to claim 1, wherein the polyfunctional monomer is a bifunctional monomer.   The printed matter according to any one of claims 1 to 2, wherein the monofunctional monomer having a glass transition temperature of 90 ° C or higher is at least one of N-vinyl-ε-caprolactam, isobornyl acrylate, and acryloylmorpholine.   The printed matter according to any one of claims 1 to 3, wherein the monofunctional monomer having a glass transition temperature of 30 ° C or lower is at least one of phenoxyethyl acrylate, benzyl acrylate, and cyclic trimethylolpropane formal acrylate.   The printed matter according to any one of claims 1 to 4, wherein the thickness of the substrate is 0.2 mm or more.   The printed matter according to any one of claims 1 to 5, wherein the base material is a magnet sheet.   The printed matter according to any one of claims 1 to 6, wherein the thickness of the cured film is 50 µm or more and 1,000 µm or less.   A printed material for cutting, comprising the printed material according to any one of claims 1 to 7.   A printed matter for pasting, comprising the printed matter according to any one of claims 1 to 7 and the printed matter for cutting according to claim 8. A method for producing a printed matter, characterized by producing at least one of the printed matter according to any one of claims 1 to 7, the printed matter for cutting according to claim 8, and the printed matter for pasting according to claim 9. .