JP6739225B2 - Matted printed matter and method for producing the same - Google Patents

Description

The present invention relates to a printed matter which gives a matt feeling, and a method for producing the same.

Conventionally, in the field of commercial printing, a coating process (aqueous varnish, UV clear) for applying a coating agent (also called varnish in the industry) to a printed material for the purpose of making the printed material cosmetic, or a printed material coated with an aqueous varnish Various surface treatments such as press processing for applying a mirror gloss to the printed matter by heating and pressing with a stainless steel plate having a mirror surface and laminating processing for laminating a film such as OPP or PET on the printed matter are carried out.

In recent years, attempts are being made to give printed materials a beauty and function to differentiate them from competing products. The reason for this is that the design, function, design and beauty of printed matter have a great influence on product sales.

A method called matte varnish processing is one of the methods of imparting beauty. This is one of the "painting processes".
“Coating” refers to a printed substrate coated with varnish, and the types of varnish include gloss type, semi-matte type, and matte type.

Generally, matte varnish processing is i) matte processing using a matte OP varnish on a printing cylinder. ii) In the case of owning an offset printing machine with a coater, water-based mat varnish processing is typical. iii) Water-based mat varnish processing with an off-line coater is typical.

The common point of the general mat processing described above is that a matting agent is used. For example, an invention using silica as a matting agent has been made (for example, Patent Document 1). The matting agent has a relatively high aspect ratio, and the matting particles are regularly exposed from the binder layer, and the diffused reflection of light is utilized to achieve the matting effect.

Therefore, scratching the coating film with a nail or the like, the exposed matting agent will be broken due to contact at the guard rail part etc. caused by flowing the matt printed matter to the can making line, and the convex surface part will be flat, Since the irregular reflection of light is reduced and the corresponding part becomes glossy, the problem that the part is scratched and becomes a defective product cannot be avoided.

Further, when performing mat processing with a "general UV offset printing machine" without using a roll coater, the only option is to use an ultraviolet curing mat OP varnish. Since the UV-curable matte OP varnish contains a matting agent, its transferability is inferior to that of color inks, and the printability such as blank residue and plate residue is extremely poor. Also, the finished coating film is about 1 to 2 μm, which is the same as the ink layer, and the matting property is weak, and there is a weak point in scratching.
Therefore, if you want to commercialize with high quality, when using a "general UV offset printing machine", in many cases, after printing, mat processing is performed using a roll coater in a separate offline process. In this case, transfer costs, outsourcing costs, There are currently high costs.
On the other hand, UV pseudo embossing can be mentioned, but a printing machine with an in-line coater is required, and this processing cannot be performed with an offset cylinder of a normal printing machine.
It is desired to establish a printed matter and a method for producing the same, which can easily perform matte processing by using an "offset cylinder of a general UV printer" without requiring a coating device.

JP, 2010-229302, A

INDUSTRIAL APPLICABILITY The present invention uses a "offset cylinder of a general UV printing machine" without using a coating device and utilizes cissing by two layers of an ultraviolet-curing type underprinting varnish layer and an ultraviolet-curing type overprinting varnish layer to obtain a matte finish. While exhibiting the visual effect of, while maintaining the printability such as a blank residue and a plate residue without impairing the feeling of blackness, a printed material that imparts a scratch-resistant matte processing that can also secure the abrasion resistance of the film and the same. It is an object to provide a manufacturing method.

As a result of intensive studies by the inventors, the fine coating film formed by repelling the UV-curable overprint varnish 2 with the underprint layer by the UV-curable underprint varnish 1 provided on the surface of the substrate and the printing layer Creates unevenness, reproduces the matte effect by diffuse reflection of light, retains printability such as blank and plate remaining without impairing the black feeling, and has scratch-resistant performance that can also secure abrasion resistance of the film Provided is a printed matter characterized by having both and a method for producing the same.

That is, according to the present invention, a printing layer using an ultraviolet curable ink is provided on a base material, and underprinting with an ultraviolet curable underprint varnish 1 is partially or entirely performed on the surfaces of the base material and the printing layer. A layer is provided, and an overprinting layer by the ultraviolet curing type overprinting varnish 2 is provided on the whole surface or a part of the base material, the printing layer and the underprinting layer, and the underprinting layer and the overprinting layer are provided. The overlapped portion is a printed matter characterized in that the overprinting layer becomes fine particles due to repelling, a matte visual effect is expressed, and the non-overlapped portion forms a continuous glossy film, and the above-mentioned ultraviolet curing The underprint varnish 1 contains a (meth)acrylate monomer and/or a (meth)acrylate oligomer, a resin, a photopolymerization initiator, an extender pigment, and an auxiliary agent, and the number average molecular weight of the auxiliary agent is 100,000 to Provided is a printed material, characterized by containing 0.5 to 15% by mass of varnish of 500,000 polydimethylsiloxane.

The present invention also provides a printed matter in which the UV-curable overprint varnish 2 contains the varnish 1 containing a (meth)acrylate monomer and/or a (meth)acrylate oligomer, a resin, a photopolymerization initiator, and an extender pigment. To do.

The present invention further provides a printed matter in which the UV-curable underprint varnish 1 and/or the UV-curable overprint varnish 2 contains titanium oxide in an amount of 0.1 to 5 mass% of the total amount of each varnish.

The invention also provides a method for producing a printed matter in which the undercoat layer formed by the UV-curable underprint varnish 1 and the overcoat layer formed by the UV-curable overprint varnish 2 are formed by offset printing.

According to the present invention, without using a coating device, the "offset cylinder of a general UV printing machine" is used, and repelling by two layers of an ultraviolet-curing type underprinting varnish layer and an ultraviolet-curing type overprinting varnish layer is used to remove scratches. It is possible to provide a printed matter to which strong matte processing is applied and a method for producing the same. In the case of a general-purpose OP mat varnish to which a matting agent is added in order to obtain a matte tone, both the mat processing with the "UV curable mat OP varnish" and the mat processing in a separate process using an offline coater have a relatively high aspect ratio. Since a matting agent is generally mixed in, the resulting coating film has a matte agent that irregularly projects from the binder to diffusely reflect light, thereby producing a matte feeling, and therefore, the nails and manufacturing process This is because the mat particles generated from the binder are broken and easily scratched by transportation after the package is molded.
From the situation in which the matting agent protrudes from the binder that can be seen in the OP matte varnish with the conventional matting agent (FIG. 1), the matting effect according to the present invention is repellent particles (FIG. 2) that exist in a shape close to a circle, and Due to the manufacturing process, the protrusions will not break and scratches will be less likely to occur.

It is a sketch drawing of the processing section of the application layer by general OP mat varnish which added the matting agent. It is a sketch of the processing cross section by cissing by two layers of the ultraviolet curing type underprinting varnish layer and the ultraviolet curing type overprinting varnish layer according to the present invention.

The present invention will be described in detail. Unless otherwise specified, all% and parts in the description are based on mass.

The printed matter of the present invention is provided with a printing layer using an ultraviolet curable ink on a substrate, and underprinting with an ultraviolet curable underprint varnish 1 partially or entirely on the surface of the substrate and the printing layer. A layer is provided, and an overprinting layer by the ultraviolet curing type overprinting varnish 2 is provided on the whole surface or a part of the base material, the printing layer and the underprinting layer, and the underprinting layer and the overprinting layer are provided. The overlapping portion is a printed matter characterized in that the overprinting layer becomes fine particles due to repellency to produce a matte visual effect, and the nonoverlapping portion has a continuous film to give a glossy tone. 1 contains a (meth)acrylate monomer and/or (meth)acrylate oligomer, a resin, a photopolymerization initiator, an extender pigment, and an auxiliary agent, and the number average molecular weight of the auxiliary agent is 100,000 to 500,000. It is characterized in that polydimethylsiloxane is contained in an amount of 0.5 to 15 mass% of the total amount of the varnish.

The underprinting layer of the UV-curable underprinting varnish 1 may be solidly formed over the entire surface, or may be partially formed in a dot shape or a design pattern shape. Similarly, the overprinting layer formed by the UV-curable overprinting varnish 2 may be formed in a solid pattern over the entire surface, or may be partially formed in a dot pattern or a design pattern.

According to the present invention, without using a coating device, the "offset cylinder of a general UV printing machine" is used, and repelling by two layers of an ultraviolet-curing type underprinting varnish layer and an ultraviolet-curing type overprinting varnish layer is used to remove scratches. It is possible to provide a printed matter to which strong matte processing is applied and a method for producing the same.

The UV-curable underprint varnish 1 contains a (meth)acrylate monomer and/or a (meth)acrylate oligomer, a resin, a photopolymerization initiator, an extender pigment, and an auxiliary agent, and has a number average molecular weight of the auxiliary agent. 100,000 to 500,000 polydimethylsiloxane is contained in an amount of 0.5 to 15% by mass of the total amount of the varnish.

The UV-curable underprint varnish 1 and the UV-curable overprint varnish 2 may be arbitrarily selected from the (meth)acrylic monomer and/or (meth)acrylic oligomer used. In addition, in this invention, "(meth)acryl" is a general term for acryl and methacryl.

Examples of monofunctional (meth)acrylates include ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, and hexadecyl. (Meth)acrylate, octadecyl (meth)acrylate, isoamyl (meth)acrylate, isodecyl (meth)acrylate, isostearyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, methoxyethyl (meth)acrylate, butoxy Ethyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, nonylphenoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, glycidyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate , 2-hydroxy-3-phenoxypropyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, diethylaminoethyl (meth)acrylate, nonylphenoxyethyl tetrahydrofurfuryl (meth)acrylate, caprolactone-modified tetrahydrofurfuryl ( Examples thereof include (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and dicyclopentenyloxyethyl (meth)acrylate.

Examples of the bifunctional or higher functional (meth)acrylate include 1,4-butanediol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, and 1,6-hexanediol di(meth)acrylate. ) Acrylate, neopentyl glycol di(meth)acrylate, 2-methyl-1,8-octanediol di(meth)acrylate, 2-butyl-2-ethyl-1,3-propanediol di(meth)acrylate, tricyclodecanedi Such as methanol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate Dihydric alcohol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, tris(2-hydroxyethyl)isocyanurate di(meth)acrylate, neopentyl glycol 4 mol per mol Di(meth)acrylate of diol obtained by adding ethylene oxide or propylene oxide, di(meth)acrylate of diol obtained by adding 2 moles of ethylene oxide or propylene oxide to 1 mole of bisphenol A, and trimethylolpropane Of trivalent or higher polyhydric alcohols such as tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, poly(meth)acrylate of dipentaerythritol, etc. Tri(meth)acrylate of poly(meth)acrylate, triol obtained by adding 3 mol or more of ethylene oxide or propylene oxide to 1 mol of glycerin, and 3 mol or more of ethylene oxide or propylene oxide added to 1 mol of trimethylolpropane. Obtained by adding 4 moles or more of ethylene oxide or propylene oxide to 1 mole of bisphenol A, or poly(meth)acrylate of polyoxyalkylene polyol such as di(meth)acrylate of diol. ) Acrylate and the like can be mentioned.

As the polymerizable oligomer, in addition to the amine-modified acrylate described above, polyester (meth)acrylate, polyether (meth)acrylate, polyolefin (meth)acrylate, polystyrene (meth)acrylate, epoxy (meth)acrylate, urethane (meth) Acrylate etc. are mentioned.

From the viewpoint of suitably curing UV curable offset ink with low energy such as UV-LED light source, it is better to use UV curable monomer with higher reactivity, which is trifunctional or higher, in consideration of curability and film strength. However, if the adhesion to a printing substrate such as a film for flexible packaging and the flexibility of a film that suppresses the cracking of the ink cured film are prioritized, a monofunctional to trifunctional weight average is obtained. It is more preferable to use an acrylate having a molecular weight of 1,000 or less.

The (meth)acrylic monomer and/or (meth)acrylic oligomer component used in the UV-curable underprint varnish 1 and the UV-curable overprint varnish 2 used in the printed matter of the present invention are shown in the examples below, but are preferably Is contained in an amount of 50 to 90% by mass, more preferably 60 to 85% by mass, based on the total amount of the ink.

As an example of a raw material resin used in the UV-curable underprint varnish 1 and the UV-curable overprint varnish 2 used in the printed matter of the present invention, a dialsophthal series resin (DAP resin), a die soup series (die soup up A, die soup up). S and Daiso Dup K, both manufactured by Daiso Co., Ltd.) can be used because they have excellent film strength.
Other examples include resin oligomers having a polymerizing group, which have higher reactivity than non-reactive resins having no polymerizing group in the molecule (inert resin), and examples of resin oligomers having a polymerizing group include: Epoxy acrylates, aliphatic acrylates, polyester acrylates, urethane acrylates, etc. may be mentioned and these may be used in combination. Various publicly known and used binder resins can be used. The binder resin described here refers to all resins having an affinity and dispersibility with an appropriate extender pigment and having the rheological properties required for a varnish. For example, a non-reactive resin is a diallyl phthalate resin. , Epoxy resin, polyurethane resin, polyester resin, petroleum resin, rosin ester resin, poly(meth)acrylic acid ester, cellulose derivative, vinyl chloride-vinyl acetate copolymer, polyamide resin, polyvinyl acetal resin, butadiene-acrylonitrile copolymer Examples of the binder resin compound include a combination thereof, or an epoxy acrylate compound, a urethane acrylate compound, a polyester acrylate compound or the like having at least one or more polymerizable groups in a resin molecule. They may be used, or any one or more of them may be used in combination.

As the photopolymerization initiator used in the printed matter of the present invention, when exposed to an ultraviolet light source having a wavelength range of 350 to 420 nm, for example, an α-aminoalkylphenone compound, an α-hydroxyketone compound, for the purpose of sensitizing effect, The curability can be maintained by using small amounts of various photopolymerization initiators such as an acylphosphine oxide-based compound, a thioxanthone-based compound, and a dialkylaminobenzophenone-based compound. However, by using these photopolymerization initiators together, curability can be maintained but yellowing and offensive odor cannot be avoided, and there is a trade-off relationship between curability and yellowing/offensive odor.

As the α-aminoalkylphenone photopolymerization initiator, 2-methyl-1-[4-(methylthio)phenyl]-2-monofolinopropan-1-one and the like have a number average molecular weight (279.4), 2 -Benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 (number average molecular weight: 366.5), 2-(dimethylamino)-2-(4-methyl-benzyl)-1-( 4-morpholin-4-yl-phenyl)-butan-1-one (number average molecular weight: 380.5) and the like can be mentioned, and any one or more of these may be contained, and a plurality of them may be used in combination. ..

Examples of the α-hydroxyketone photopolymerization initiator include 1-hydroxy-cyclohexyl-phenyl-ketone (number average molecular weight: 204.3), 2-hydroxy-2-methyl-1-phenyl-propan-1-one (number Average molecular weight: 164.2), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl}-2-methyl-propan-1-one (number average Molecular weight: 340.4), oligo(2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone) (number average molecular weight: 424.57), 2-hydroxy-1-{4 -[4-(2-hydroxy-2-methylpropionyl)phenoxy]phenyl}-2-methylpropanone (number average molecular weight: 342.39) and the like, and any one or more of these may be contained, You may use in combination of multiple.

Examples of the acylphosphine oxide-based polymerization initiator include bis-(2,6-dichlorobenzoyl)phenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-2,5-dimethylphenylphosphine oxide and bis- (2,6-dichlorobenzoyl)-4-propylphenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-1-naphthylphosphine oxide, bis-(2,6-dimethoxybenzoyl)phenylphosphine oxide, Bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis-(2,6-dimethoxybenzoyl)-2,5-dimethylphenylphosphine oxide, bis-(2,4 ,6-Trimethylbenzoyl)phenylphosphine oxide and other bisacylphosphine oxides, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2,6-dimethoxybenzoyl-diphenylphosphine oxide, 2,6-dichloro Monoacylphosphine oxides such as benzoyl-diphenylphosphine oxide, 2,4,6-trimethylbenzoyl-phenylphosphinic acid methyl ester, 2-methylbenzoyl-diphenylphosphine oxide, pivaloylphenylphosphinic acid isopropyl ester Among these, bisacylphosphine oxides such as 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and bis-(2,4,6-trimethylbenzoyl)phenylphosphine oxide are ultraviolet rays. Having a UV absorption wavelength that matches the emission wavelength region of the light emitting diode is more preferable in that suitable curability can be obtained, and the yellowing of the cured film and the odor of the photopolymerization initiator itself are small.

The total addition rate of the photopolymerization initiator is preferably 0.1 to 15% by mass based on the total amount of the varnish. When the addition amount is less than 0.1% by mass, the drying property is deteriorated, while when the addition amount is more than 15% by mass, the amount of the photopolymerization initiator becomes excessive and the fluidity of the varnish is impaired, which is not preferable.

The extender pigment used in the UV-curable underprint varnish 1 and the UV-curable overprint varnish 2 used in the printed matter of the present invention is used for adjusting fluidity of the varnish, preventing misting during printing, preventing penetration into a paper substrate, etc. Widely used for the purpose of improving physical properties and imparting functionality. Examples of the extender pigment include publicly known and used organic pigments for coloring, and examples thereof include extender pigments for printing inks listed in "Handbook of Pigments (edited by the Japan Pigment Technology Association)", such as calcium carbonate and magnesium carbonate. , Kaolin clay, talc, bentonite, mica, barium sulfate, silica and aluminum hydroxide can be used.

The content ratio of the extender pigment is preferably 0.5 to 30% by mass, and more preferably 1.0 to 20% by mass based on the total amount of the varnish. When the extender pigment content is less than 0.5% by mass, no effect is observed on the emulsion stability and the emulsification fluidity during printing, and when it is more than 30% by mass, the fluidity and transferability of the varnish are impaired, which is not preferable. ..

In the printed matter of the present invention, polydimethylsiloxane having a number average molecular weight of 100,000 to 500,000, which is a special silicon, is added to the undercoat varnish coating portion of the UV curable underprint varnish 1 in an amount of 0.5 to 15% by mass based on the total amount of the varnish. By adding it, a matte feeling can be expressed by applying the gloss type ultraviolet curable type overprinting varnish 2 onto the underprinting varnish 1. As the polydimethyl siloxane, those sold under the name such as dimethyl silicone oil can be used. It should be noted that silicone acrylate and modified silicone oil do not provide the effect equivalent to polydimethylsiloxane. Even if a matte feeling is obtained, sufficient scratch resistance, abrasion resistance, and ink fluidity cannot be obtained. When the number average molecular weight of the polydimethylsiloxane is 100,000 or less, a matt feeling is not obtained, while when the number average molecular weight is 500,000 or more, the dispersion in the underprint varnish is insufficient and the fluidity of the ink is poor. It tends to decrease. On the other hand, if it is less than 0.1% by mass of the total amount of the varnish, a matte feeling is not obtained, and if it exceeds 15% by mass, the fluidity of the ink tends to decrease.
Further, the range of the kinematic viscosity of the polydimethylsiloxane having the number average molecular weight of 100,000 to 500,000 at 25° C. is preferably 90,000 to 550,000 mm ² /S.

In the printed matter of the present invention, a wax can be added for the purpose of improving the curability of the varnished part. Examples of the wax include paraffin wax, carnauba wax, beeswax, microcrystalline wax, polyethylene wax, polyethylene oxide wax, polytetrafluoroethylene wax, amide wax, and other waxes, and C8 to C18 waxes such as coconut oil fatty acid and soybean oil fatty acid. Fatty acids in the range can be mentioned. Among them, powder type or particle type polyolefin wax represented by polyethylene wax and oxidized polyethylene wax is preferable because good varnish fluidity and curability can be obtained. Further, with respect to the UV-curable underprint varnish 1 and the UV-curable overprint varnish 2 used in the present invention, the total amount of the wax used is preferably in the range of 0.1 to 5% by mass based on the total amount of the varnish.

In the production of the printed matter of the present invention, as other blends of the above-mentioned components, a polymerization inhibitor, a dye, an organic solvent, an antistatic agent, a defoaming agent, a viscosity modifier, a light resistance stabilizer, a weather resistance stabilizer, if necessary. Additives such as heat stabilizers, antioxidants, leveling agents, and pigment dispersants can be used.

The printing base material used for the printed matter of the present invention is not particularly limited, and is used for printing, for example, catalogs, posters, leaflets, CD jackets, direct mail, pamphlets, cosmetics and beverages, pharmaceuticals, toys, packages of devices and the like. Fine paper, coated paper, art paper, imitation paper, paper such as thin paper and cardboard, various synthetic papers, polyester resin, acrylic resin, vinyl chloride resin, vinylidene chloride resin, polyvinyl alcohol, polyethylene, polypropylene, polyacrylonitrile, ethylene vinyl acetate Copolymers, ethylene vinyl alcohol copolymers, ethylene methacrylic acid copolymers, films or sheets of nylon, polylactic acid, polycarbonate, etc., cellophane, aluminum foil, and various other base materials conventionally used as printing base materials. I can name it.

The production of the active energy ray-curable offset ink composition described in the present invention is carried out in the same manner as in the conventional active energy ray-curable offset ink composition Violet, the (meth)acrylate monomer, the binder resin, the photopolymerization initiator, and the extender pigment. It is produced by blending a polymerization inhibitor, other additives and the like with stirring with a mixer or the like, and kneading the meat with a disperser such as a three-roll mill or a bead mill.

Hereinafter, the present invention will be specifically described with reference to examples. Hereinafter, “parts” and “%” are based on mass.
The number average molecular weight (in terms of polystyrene) of the present invention was measured by GPC (gel permeation chromatography) using an HLC8220 system manufactured by Tosoh Corporation under the following conditions.
Separation column: Four TSKgel GMH _HR- N manufactured by Tosoh Corporation are used. Column temperature: 40°C. Mobile layer: Tetrahydrofuran manufactured by Wako Pure Chemical Industries, Ltd. Flow rate: 1.0 ml/min. Sample concentration: 1.0% by weight. Sample injection volume: 100 microliters. Detector: differential refractometer.

[Method for producing UV-curable underprint varnish 1]
Various UV-curable underprint varnishes were prepared by kneading the varnishes of Production Comparative Examples 1 to 8 according to the compositions of Tables 1 and 2 and the compositions of Production Examples 1 to 9 and Tables 3 and 4 with a three-roll mill. Obtained. The numerical values in Tables 1 to 4 are% by mass.

[Production Method of Ultraviolet Curing Overprint Varnish 2]
According to the composition of Production Example 10 in Table 2, the overprint varnish 2 was obtained by kneading with a three-roll mill. As a reference example, a matte OP varnish containing ZEST PQHT (vinyl chloride resin) as a matting agent added in an amount of 5% by mass based on the total amount of the varnish was similarly kneaded according to Reference Production Example 1 in Table 4.

[Method for producing printed matter]
Using a simple color developing machine (RI tester, manufactured by Hoei Seiko Co., Ltd.), UV ink ink is uniformly spread on the rubber roll and metal roll of the RI tester using 0.10 ml of ink, and coated cardboard (manufactured by Oji Materia Co., Ltd.). On the surface of a UF coat having a surface area of 350 g/m ^{2 of} tsubo, color was applied so as to be uniformly applied over an area of 200 cm ² to prepare a color-developed product. The RI tester is a tester that spreads ink on paper or film, and can adjust the amount of ink transfer and printing pressure.
After the ink was applied, the developed material was irradiated with ultraviolet rays (UV), which is an active energy ray, to cure the ink film. Using a UV irradiator equipped with an air-cooled metal halide lamp (output 120 W/cm1 lamp) and a belt conveyor (made by Eye Graphics Co., with a cold mirror), put the developed product on the conveyor and directly under the lamp (irradiation distance 11 cm). Was passed at a speed of 40 meters per minute to cure the ink film.
Underprinting varnish obtained in paragraph [0043] on the surface of the black printed matter with a simple coatability machine, using the ink 0.10 ml, uniformly stretched on a rubber roll and metal roll RI tester, of 200 cm ² A color-developed product was prepared by performing color development so that the color was uniformly applied over the area. After the ink was applied, the developed material was irradiated with ultraviolet rays (UV), which is an active energy ray, to cure the ink film. Using a UV irradiation device equipped with an air-cooled metal halide lamp (output 120 W/cm1 lamp) and a belt conveyor, put the developed material on the conveyor and pass it directly under the lamp (irradiation distance 11 cm) at a speed of 40 meters per minute. To cure the ink film.
Further, the overprint varnish obtained in paragraph [0044] was uniformly spread on a rubber roll and a metal roll of the RI tester by using a simple color spreading machine and 0.10 ml of ink, and applied uniformly over an area of 200 cm ^2. The color was developed as described above to prepare a color-developed product. After the ink was applied, the developed material was irradiated with ultraviolet rays (UV), which is an active energy ray, to cure the ink film. Using a UV irradiation device equipped with an air-cooled metal halide lamp (output 120 W/cm1 lamp) and a belt conveyor, put the developed material on the conveyor and pass it directly under the lamp (irradiation distance 11 cm) at a speed of 40 meters per minute. To cure the ink film.

[Evaluation method of printed matter 1: Matte property (gloss value)]
The gloss value at a reflection angle of 60° was measured on the obtained printed matter using a gloss meter (manufactured by Multi-Gloss 268 Konica Minolta). As an aptitude value, 5 to 22 are regarded as acceptable products.

[Printed material evaluation method 2: Matte property (visual evaluation)]
The printed matter obtained was visually evaluated for matte feeling.
◎: The matte feeling is very strong.
○: A matte feeling is strong.
Δ: The matte feeling is weak.
X: No matte feeling is observed.

[Evaluation method of printed matter 2: Blackness]
The obtained printed material was visually evaluated for blackness.
◯: Blackness is equivalent to that of a normal matte OP varnish printed matter.
Δ: The blackness is slightly inferior to that of a matte OP varnish printed matter.
X: Blackness is clearly inferior to that of a matte OP varnish printed matter.

[Printed material evaluation method 3: abrasion resistance]
Using a Gakushin-type friction resistance tester, the printed matter obtained by applying a quality paper of 500 g was rubbed 500 times, and the degree of removal of the coating film was evaluated.
○: The coating film is partially scratched. No more than 5 scratches.
B: A part of the coating film is scratched. The number of scratches is 5 or more. Δ: Scratches are seen in 30% or more of the coating film area.
Δ×: Scratches are seen in 50% or more of the coating film area.
X: A scratch is seen on the entire surface of the coating film area.

[Evaluation method of printed matter 4: Remaining blank/remaining printing plate]
After printing 1000 sheets with a UV offset printing machine manufactured by Komori Corporation, it was visually confirmed in the image area of the blanket/plate to evaluate the ink remaining condition.
◯: The amount of ink remaining on the blanket/plate is the same as that of normal UVOP varnish.
Δ: The amount of ink remaining on the blanket/plate is usually slightly larger than that of UVOP varnish.
X: The amount of ink remaining on the blanket/plate is usually larger than that of UVOP varnish.

[Evaluation method 5 of printed matter: ink fluidity]
The underprinting varnish 1 (ink) obtained in paragraph [0043] is used in a 25° C. environment with a parallel plate viscometer to compare the diameters of the ink films one minute after dropping a load of 115 g.
◯: Ink film diameter is 30 mm or more Δ: Ink film diameter is 25 to 30 mm
×: The diameter of the ink curtain is less than 25 mm

The raw materials and abbreviations shown in Tables 1 to 4 are shown below.
-ZEST PQHT: Tokuyama vinyl chloride resin-Calcium carbonate PC: Shiraishi Calcium Co., Ltd. primary particle size 1500 NM (major axis)
High filler: hydrous magnesium silicate high filler (talc) #5000PJ, manufactured by Matsumura Sangyo Co., Ltd.-Titanium CR58-2: Chlorinated rutile titanium oxide, average particle diameter 28 (μm), oil absorption 18, Ishihara. Sangyo Co., Ltd./Daiso Dup A: Diacrylic phthalate resin, Daiso/Aronix M-7300K: Polyester acrylate, Toagosei Co., Ltd./DPHA: MIRAMER M-600, Dipentaerythritol Hexaacrylate, MIWON SR355NS: Ditrimethylolpropane tetraacrylate (DITMPTA), Sartomer Co., MIRAMER M-240: Bisphenol A (EO modified) diacrylate, Toyo Chemicals Co., Ltd. MIRAMER M-3130: Trimethylolpropane (EO modified) ) Triacrylate, manufactured by Toyo Chemicals Co., Ltd. IRGACURE 907: α-aminoalkylphenone photopolymerization initiator, 2-methyl-1-[4-(methylthio)phenyl]-2-monofolinopropane-1- ON and the like have a number average molecular weight (279.4), manufactured by BASF, IRGACURE 184:1-hydroxysiloxyhexyl phenyl ketone, manufactured by BASF, S-381-N1: polyethylene wax, manufactured by Shamrock, TEGO RAD 2700, silicone Acrylate (number average molecular weight: 7,000), Evonik Silicon KF-96 100CS: silicone oil having a dimethylsiloxane structure, Shin-Etsu Chemical Co., Ltd. Silicon TSF-451-6M, silicone oil having a dimethylsiloxane structure (Number average molecular weight: 60,000), kinematic viscosity 60,000 mm ² /S, Silicon TSF-451-10M manufactured by Tanac Co., Ltd., silicone oil having a dimethylsiloxane structure (number average molecular weight: 100,000), kinematic viscosity 100,000 mm ² / S, (Ltd.) Tanakku Ltd. silicon TSF-451-50M, silicone oil having a dimethyl siloxane structure (number average molecular weight: 500,000), kinematic viscosity 500,000 ² / S, ( Silicon TSF-451-60M manufactured by Tanac Co., Ltd., silicone oil having a dimethylsiloxane structure (number average molecular weight: 600,000), kinematic viscosity 600,000 mm ² /S, manufactured by Tanac Co., Q-1301: Nitrosamine-based polymerization initiator, manufactured by Wako Pure Chemical Industries, Ltd.

The evaluation results are shown in Tables 5 and 6.

In the portion where the underprinting layer of the UV-curable underprinting varnish 1 produced using the plate cylinder of the offset printing machine and the overprinting layer of the UV-curable overprinting varnish 2 overlap, the overprinting layer becomes fine particles due to repelling, While exhibiting a matte visual effect, the wear resistance of the film can be ensured while maintaining the printability such as blank residue and plate residue without impairing the black feeling.
Further, as shown in Reference Example, in a printed matter which uses a matte OP varnish containing a matting agent and is subjected to an extremely general matte processing using a varnish coater, although a matte visual effect is obtained, abrasion resistance is obtained. Is not obtained, and the printability such as a blank residue and a plate residue is poor.

1. Coated cardboard as a printing substrate (350 g/m ^{2 of} tsubo)
2. General OP matte varnish layer 3. Matting agent 4. 4. UV curable underprint varnish layer of the present invention UV-curable topcoat varnish layer by cissing

Claims (4)

A printing layer using an ultraviolet-curable ink is provided on the substrate, and an underprinting layer of the ultraviolet-curing underprinting varnish 1 is provided partially or entirely on the surfaces of the substrate and the printing layer. On the base material, the printing layer and the underprinting layer, an overprinting layer of the UV-curable overprinting varnish 2 is entirely or partially provided, and a portion where the underprinting layer and the overprinting layer overlap is overprinted. A printed matter, characterized in that the layers become fine particles due to repellency to develop a matte visual effect, and non-overlapping portions form a continuous film with a glossy tone.
The UV-curable underprint varnish 1 contains a (meth)acrylate monomer and/or (meth)acrylate oligomer, a resin, a photopolymerization initiator, an extender pigment, and an auxiliary agent, and the auxiliary agent has a number average molecular weight of 100. A printed matter comprising 5,000 to 500,000 of polydimethylsiloxane in an amount of 0.5 to 15% by mass based on the total amount of the varnish.
The printed matter according to claim 1, wherein the UV-curable overprint varnish 2 is a varnish 2 containing a (meth)acrylate monomer and/or a (meth)acrylate oligomer, a resin, a photopolymerization initiator, and an extender pigment.
Further, the ultraviolet curable under- Varnish 1 and / or the ultraviolet-curable overprinting varnish 2, claim 1 or 2 prints according containing titanium oxide 0.1 to 5% by weight of the varnish total amount.
Subbing layer by ultraviolet curable underprinting varnish 1 above, and the overcoat layer by the ultraviolet curable overprinting varnish 2, a method for manufacturing a printed material according to claim 1, formed by the offset printing.

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