JP2009083302A - Method for producing printed matter and printed matter produced by the method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for more easily producing a printed matter having excellent color developability and high brightness due to polarization action in addition to the effect of embossing, and a printed matter produced by the method.
SOLUTION: A dry film of an aqueous varnish composition is provided on a part or the whole of a printed surface printed on a paper base material, and an active energy ray-curable overprint varnish composition is formed on the dry film with an active energy ray. A cured film cured by irradiation is provided. The aqueous varnish composition contains at least one selected from the group of pearl pigments, metal powder pigments, and glass flakes, an aqueous resin, a surface conditioner, and an aqueous solvent. The active energy ray-curable overprint varnish composition is such that γ ₁ is the surface tension of the dry film and γ ₂ is the surface tension of the active energy ray-curable overprint varnish composition, γ ₂ −γ ₁ ≧ 5 mN / m is satisfied.
[Selection figure] None

Description

  The present invention relates to a method for producing a printed material used for obtaining high added value such as good color development or high brightness feeling due to polarization action, together with the effect of processing the surface of the printed material with unevenness (embossing), and the method thereof It relates to printed matter manufactured in

  Conventionally, it has been known to obtain a printed material excellent in three-dimensional effect and deep design by forming a concavo-convex pattern, a so-called embossed pattern, on the surface of the printed material.

  Various methods for easily forming a concavo-convex pattern on the surface of a printed material have been proposed.

  For example, a method has been proposed in which a liquid-repellent ink is printed on the surface of a substrate, then coated with a crosslinkable transparent resin and cured, and then subjected to hot embossing using an embossed plate to form an uneven pattern (for example, , See Patent Document 1).

  Also, print the pattern on the base material using liquid repellent ink, then apply the coating agent that forms the embossed layer, and apply the coating on the printing surface by the liquid repellent action between the ink and the coating agent. A method of forming a concavo-convex pattern in accordance with a pattern by eliminating the agent layer has been proposed. More specifically, a method using a liquid repellent ink and an ionizing radiation curable coating agent (for example, patent literature) 2), a method using an aqueous or oil-based ink, an electron beam or an ultraviolet curable clear coating agent (see, for example, Patent Document 3), a water-based ink having a surface tension of 9 to 19 dyn / cm, and a surface tension of 24 to 30 dyn. A method using an aqueous topcoat coating agent of / cm (for example, see Patent Document 4) has been proposed.

JP 59-132975 A JP 05-086306 A Japanese Patent Laid-Open No. 06-278354 Japanese Patent Laid-Open No. 07-108752

  However, in recent years, not only the embossing effect of obtaining a printed material that is excellent in three-dimensional effect and deep design by simply forming a concavo-convex pattern on the printed material, but further cosmetics of the printed material are required. It is becoming.

  An object of the present invention is to provide a method for more easily producing a printed material having excellent color developability and high brightness due to polarization action in addition to the above-mentioned embossing effect, and a printed material produced by the method. It is.

  As a result of intensive studies to solve the above problems, the present inventors have provided a film containing at least one selected from the group of pearl pigments, metal powder pigments, and glass flakes on the printed surface, A cured film of an active energy ray-curable overprint varnish composition that can impart excellent color development and high brightness to the printed material, and further uses the difference in surface tension with the film to partially form irregularities. It has been found that the formation of the printed matter can have a three-dimensional effect and a deep design by forming, and the present invention has been completed.

The present invention prints a printing ink composition on a paper substrate, and provides a dry film of an aqueous varnish composition on a part or the whole of the printed surface, and an active energy ray-curable overprint varnish is formed on the dry film. Provide a cured film obtained by curing the composition by irradiation with active energy rays,
The aqueous varnish composition contains at least one selected from the group of pearl pigments, metal powder pigments, and glass flakes, an aqueous resin, a surface conditioner, and an aqueous solvent,
The active energy ray-curable overprint varnish composition satisfies the following formula (1), and is a method for producing a printed matter.
γ ₂ −γ ₁ ≧ 5 mN / m (1)

Here, γ ₁ is the surface tension of the dry film, and γ ₂ is the surface tension of the active energy ray-curable overprint varnish composition.

  In addition, the present invention is characterized in that an aqueous printing ink composition is used as the printing ink composition.

  Further, the present invention is characterized in that the dry film is provided by printing or coating the aqueous varnish composition on the printing surface and then drying it.

Further, in the present invention, the cured film is provided by printing or coating the active energy ray-curable overprint varnish composition, and then curing it by irradiation with active energy rays.
Printing of the printing ink composition, printing or coating of the aqueous varnish composition, and printing or coating of the active energy ray-curable overprint varnish composition are performed in an inline manner using a gravure plate. And

  Moreover, this invention is a printed matter manufactured by said manufacturing method of printed matter, and the uneven | corrugated pattern was formed in the surface.

  According to the present invention, there is provided a dry film of an aqueous varnish composition containing at least one selected from the group of pearl pigments, metal powder pigments, and glass flakes, an aqueous resin, a surface conditioner, and an aqueous solvent, Furthermore, by forming a cured film obtained by curing an active energy ray-curable overprint varnish composition having a surface tension satisfying specific conditions, it is possible to impart excellent color development and high brightness to the printed matter. Furthermore, the printed matter can have a three-dimensional effect and a deep design.

  Moreover, according to this invention, it is preferable to use a water-based printing ink composition as said printing ink composition.

  According to the invention, it is preferable that the dry film is provided by printing or coating the aqueous varnish composition on the printing surface and then drying it.

  According to the invention, the cured film is provided by printing or coating the active energy ray-curable overprint varnish composition, and then curing it by irradiation with active energy rays. At this time, printing of the printing ink composition, printing or coating of the aqueous varnish composition, and printing or coating of the active energy ray-curable overprint varnish composition are performed in-line using a gravure plate. Thus, it becomes possible to print easily and at high speed with one printing machine.

  Further, according to the present invention, a printed matter having a concavo-convex pattern formed on the surface thereof, which is produced by the method for producing a printed matter described above, has excellent color developability and high brightness, A printed matter having a deep design property can be provided.

Hereinafter, the present invention will be described in more detail.
In the method for producing a printed material of the present invention, first, a printing ink composition is printed on a paper substrate.

  Next, a dry film of the aqueous varnish composition is provided on a part or the whole of the printed surface, and the active energy ray-curable overprint varnish composition is cured on the dry film by irradiation with active energy rays. A film is provided.

  The aqueous varnish composition used at this time contains at least one selected from the group of pearl pigments, metal powder pigments, and glass flakes, an aqueous resin, a surface conditioner, and an aqueous solvent.

Moreover, the active energy ray-curable overprint varnish composition satisfies the following formula (1).
γ ₂ −γ ₁ ≧ 5 mN / m (1)

Here, γ ₁ is the surface tension of the dry film, and γ ₂ is the surface tension of the active energy ray-curable overprint varnish composition.

  The printed matter produced by such a production method has a three-dimensional effect and a deep design by embossing, and also has excellent color developability and high brightness feeling due to the film.

[Paper base]
Examples of the paper base material to be printed include paper base materials such as paper such as coated paper, coated cardboard, and synthetic paper.

[Printing ink composition]
Printing ink compositions for printing on paper substrates include printing ink compositions such as aqueous gravure printing ink compositions, aqueous flexographic printing ink compositions, inkjet printing ink compositions, and offset printing ink compositions. Can be mentioned.

  Conventionally used various printing ink compositions can be used without any problem as the printing ink composition, but it is preferable to use a water-based printing ink composition from the environmental viewpoint.

  Below, the aqueous | water-based gravure printing ink composition is demonstrated in detail as an aqueous | water-based printing ink composition printed on a paper base material.

  The aqueous gravure printing ink composition contains a pigment, an aqueous resin, and an aqueous solvent, and an additive is added as necessary.

  As the pigment, various organic pigments and inorganic pigments can be used. Examples of organic pigments preferably used include various organic pigments such as azo lake, insoluble azo, phthalocyanine, and naphthol. Examples of inorganic pigments preferably used include various inorganic pigments such as titanium oxide, carbon black, dial, potassium carbonate, and barium sulfate.

  The amount of these pigments used is 1 to 20% by weight for organic pigments and 1 to 50% by weight for inorganic pigments with respect to the total amount of the aqueous gravure ink composition.

  Examples of the aqueous resin include an acrylic resin having an acid value of 5 to 300 dissolved in an aqueous solvent of a basic compound, a styrene-acrylic resin, a styrene-maleic acid resin, a styrene-acrylic-maleic acid resin, and a polyurethane resin. Water-soluble resins such as water-soluble resins, acrylic resin emulsions, styrene-acrylic resin emulsions, styrene-maleic acid resin emulsions, styrene-acrylic-maleic acid resin emulsions, and polyurethane resin emulsions.

  As an aqueous solvent, water is a basic component, and as an aqueous solvent, lower alcohols such as methanol, ethanol, normal propyl alcohol, and isopropyl alcohol, and glycols such as propylene glycol monomethyl ether may be used in combination with water.

  Furthermore, in the present invention, an additive such as a pigment dispersant, an antifoaming agent, a leveling agent, a lubricant, an antibacterial agent, an antifungal agent, an antiseptic, and waxes is added to the aqueous gravure printing ink composition as necessary. It can also be added.

  The aqueous gravure ink printing ink composition used in the present invention can be produced, for example, by the following method.

  Stir and knead pigments, water-based binder resins (mainly water-soluble resins), aqueous solvents and, if necessary, additives such as pigment dispersants using normal ink production equipment (eg ball mill, attritor, sand mill, etc.) After that, a predetermined material can be added and mixed.

[Aqueous varnish composition]
The aqueous varnish composition to be printed or applied on the printed surface side of the printed paper substrate is at least one selected from the group of pearl pigments, metal powder pigments, and glass flakes, aqueous resins, and surface conditioners. And an aqueous varnish composition containing an aqueous solvent.

  Examples of the pearl pigment include natural products such as fish scale foil, and synthetic products such as those obtained by coating the surface of natural mica with a metal oxide and those obtained by coating the surface of synthetic mica with a metal oxide. In general, synthetic products are often used in terms of availability, safety, and stability. Pearl pigments exhibit various color tones depending on the type of metal oxide coated on the mica surface and the coating film thickness. Examples of commercially available pearl pigments include the Iriodin series (Merck Japan Co., Ltd.).

  Examples of the metal powder pigment include various metal powder pigments such as aluminum powder, gold powder, silver powder, copper powder, and tin powder.

  Glass flakes include metal-coated glass flakes obtained by coating silver and nickel on the glass surface by electroless plating, and metal oxide coatings obtained by coating titanium dioxide by the liquid phase method on the surface of glass flakes. Examples include glass flakes. In the case of metal oxide coated glass flakes, colors such as silver, yellow, red, blue, and green can be obtained by changing the thickness of the titanium dioxide film.

  About at least 1 sort (s) selected from the group of these pearl pigments, metal powder pigments, and glass flakes, the usage-amount in an aqueous varnish composition is an aqueous varnish composition in total of a pearl pigment, a metal powder pigment, and glass flakes 3-20 mass% is preferable with respect to the whole quantity. In particular, when the amount used is 6 to 13% by mass, it is more preferable than the balance between fluidity and degree of polarization.

  Examples of the aqueous resin include an acrylic resin having an acid value of 5 to 300 dissolved in an aqueous solvent of a basic compound, a styrene-acrylic resin, a styrene-maleic acid resin, a styrene-acrylic-maleic acid resin, and a polyurethane resin. Water-soluble resins such as water-soluble resins, acrylic resin emulsions, styrene-acrylic resin emulsions, styrene-maleic acid resin emulsions, styrene-acrylic-maleic acid resin emulsions, and polyurethane resin emulsions.

  The surface modifier is not particularly limited as long as it adjusts the surface tension of the aqueous varnish composition, but examples thereof include silicone oil, silicone surfactant, acetylene surfactant, and fluorine surfactant. it can.

  As an aqueous solvent, water may be used as a basic component, and as an aqueous solvent, lower alcohols such as methanol, ethanol, normal propyl alcohol, and isopropyl alcohol, and glycols such as propylene glycol monomethyl ether may be used in combination with water.

  If necessary, the aqueous varnish composition used in the present invention may further contain additives such as antifoaming agents, leveling agents, lubricants, antibacterial agents, antifungal agents, preservatives, waxes and the like. .

The aqueous varnish composition of the present invention can be produced, for example, by the following method.
At least one selected from the group consisting of pearl pigments, metal powder pigments, and glass flakes, an aqueous resin, an aqueous solvent, and other additives as necessary are stirred using a normal stirring device (for example, a disper). After that, a predetermined material can be added and mixed.

[Active energy ray-curable overprint varnish composition]
In the present invention, the active energy ray-curable overprint varnish composition is printed or coated on the dried film obtained by drying the aqueous varnish composition.

  As the active energy ray-curable overprint varnish composition, a composition satisfying the following surface tension conditions is used.

The conditions for the surface tension, the surface tension of the dried coating of the aqueous varnish composition formed on the printing surface as gamma _1, when the surface tension of the radiation-curable overprint varnish composition was gamma _2,
γ ₂ −γ ₁ ≧ 5 mN / m (1)
It is.

When the surface tension difference γ ₂ −γ ₁ is smaller than 5 mN / m, a good uneven pattern cannot be formed. Even if the surface tension difference γ ₂ −γ ₁ is considerably higher than 5 mN / m, there is no harmful effect on the development of the uneven pattern. Rather, the larger the difference, the finer the active energy ray-curable overprint varnish composition is. Since it is repelled, a good concavo-convex pattern is obtained, and 8 mN / m or more is more preferable. However, 15 mN / m is reasonable as the upper limit of the surface tension difference.

  As the active energy ray-curable overprint varnish composition, either a solvent type or an aqueous type can be used.

  The active energy ray-curable overprint varnish composition contains a photopolymerizable compound, a photopolymerizable initiator, a solvent or an aqueous solvent.

  Here, the photopolymerizable compound is preferably a photopolymerizable compound having at least one (meth) acryloyl group, and such a photopolymerizable compound has at least one (meth) acryloyl group in the molecule. A monomer, an oligomer, etc. are mentioned.

  Monomers having one (meth) acryloyl group in the molecule include alkyl (meth) acrylates such as ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, methyl acrylate, butyl acrylate and 2-ethylhexyl acrylate; benzyl methacrylate, benzyl Aralkyl (meth) acrylates such as acrylates; Alkoxyalkyl (meth) acrylates such as butoxyethyl methacrylate and butoxyethyl acrylate; Polyalkylene glycol monoalkyls such as diethylene glycol monoethyl ether, triethylene glycol monobutyl ether and dipropylene glycol monomethyl ether (Meth) acrylic esters of ether; hexaethylene glycol mono (Meth) acrylic esters of polyalkylene glycol monoaryl ethers such as phenyl ethers; isobornyl (meth) acrylates; glycerol mono (meth) acrylates; hydroxyalkyl (meth) alkyls such as 2-hydroxyethyl (meth) acrylate Chelates and the like can be mentioned.

  Examples of monomers having two or more (meth) acryloyl groups in the molecule include bisphenol A di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 1,3-butylene glycol di (meth) acrylate. , Diethylene glycol di (meth) acrylate, glycerol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tri Methylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate DOO, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, and the like that they have been modified with alkylene oxide can be exemplified.

  As an oligomer having at least one (meth) acryloyl group in the molecule, one obtained by appropriately polymerizing one or more of the above monomers, a polyester acrylate oligomer, an epoxy acrylate oligomer, a urethane acrylate oligomer, or the like is used. be able to.

  The photopolymerizable compound is appropriately selected and used so as to be a solvent-type or aqueous-type active energy ray-curable overprint varnish composition, preferably an oligomer alone or a combination of an oligomer and a monomer. Is preferred.

  As the photopolymerizable initiator, a photocleavable type and / or a hydrogen abstracting type that can be easily cleaved by irradiation with active energy rays to form two radicals, or a mixture thereof can be used.

  Specific examples of the photopolymerization initiator include benzoin isobutyl ether, 2,4-diethyl oxanthone, 2-isopropylthioxanthone, benzyl, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2-benzyl-2-dimethyl. Amino-1- (4-morpholinophenyl) -butan-1-one, bis (2,4,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, 1,2-octanedione, 1-hydroxycyclohexyl phenyl ketone, benzoin ethyl ether, benzyldimethyl ketal, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane- 1-one, benzophenone, 4-methylbenzene Zophenone, isophthalphenone, 4-benzoyl-4′-methyl-diphenyl sulfide, 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- ( p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piphenyl-4,6- Bis (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s- Triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (pipe Nyl) -6-triazine, 2,4-trichloromethyl (4'-methoxystyryl) -6-triazine 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl)- s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2 -Pipenyl-4,6-bis (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (Trichloromethyl) -s-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- ( Piperonyl) -6-triazine, 2,4-trichloromethyl (4'-methoxystyryl) -6-triazine, and the like. These can be used alone or in combination of two or more.

  Examples of the solvent include lower alcohols such as methanol, ethanol, normal propyl alcohol, and isopropyl alcohol, glycols such as propylene glycol monomethyl ether, ketones such as ethyl acetate, and esters.

  Examples of the aqueous solvent include water as a basic component, and other aqueous solvents such as methanol, ethanol, lower alcohols such as normal propyl alcohol and isopropyl alcohol, and glycols such as propylene glycol monomethyl ether in combination with water.

  In the active energy ray-curable overprint varnish composition, a sensitizer (compound) can be used in combination with a photopolymerization initiator in order to improve curability.

  Examples of the sensitizer include trimethylamine, methyldimethanolamine, triethanolamine, p-diethylaminoacetophenone, ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, N, N-dimethylbenzylamine, 9,10. -Dibutoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-bis (2-ethylhexyloxy) anthracene, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone Etc.

  In addition, the active energy ray-curable overprint varnish composition includes a slip agent, an antifoaming agent, a leveling agent, a lubricant, an antibacterial agent, an antifungal agent, an antiseptic agent, in order to improve the slipperiness of the obtained printed matter. Additives such as waxes can also be used.

  The active energy ray-curable overprint varnish composition used in the present invention can be produced, for example, by the following method.

  After stirring a photopolymerizable compound, a photopolymerization initiator, a solvent or an aqueous solvent, and other additives as necessary using a normal stirring device (for example, a disper), a predetermined material is added and mixed. Can be manufactured.

[Production method]
Below, the manufacturing method of the printed matter of this invention is demonstrated concretely. Note that the present invention is not limited to the specific method described below. According to the concept of the present invention, the printed matter has a three-dimensional effect and a deep design, and has excellent color development and high brightness. A method for producing a printed material is included in the scope of the present invention.

  First, various printing ink compositions are printed on a paper substrate using a gravure printing machine, flexographic printing machine, offset printing machine, ink jet printer or the like, and the printed surface is dried.

  Next, the above-mentioned aqueous varnish composition is printed on a part or the whole of the printing surface side of the paper substrate on which the image is printed by a printing machine, or a coating machine such as a roll coater, a flexo coater, a gravure coater, an air knife, etc. Is applied and dried to form a dry film. As the drying method, for example, a normal method such as natural drying or hot air blowing can be used.

  An active energy ray-curable overprint varnish composition that satisfies the surface tension condition described above is further printed or applied onto the provided dry film.

  Coating of the active energy ray-curable overprint varnish composition uses a coating machine such as a roll coater, a flexo coater, a gravure coater, or an air knife.

  Next, for example, the active energy ray-curable overprint varnish composition that has been printed and applied using a light irradiation device is irradiated with active energy rays to obtain a cured film.

  For example, the active energy ray curable overprint varnish composition is irradiated with the active energy ray using an active energy ray irradiation device equipped with a high-pressure mercury lamp, a metal halide lamp, an LED lamp, or the like. The printed material is dried simultaneously with the irradiation of the active energy ray. The drying here can be performed by heat generated by irradiation with active energy rays, without forced drying.

  In this way, by providing a dry film and a cured film, a concavo-convex pattern is formed on the printed surface, the printed matter has a three-dimensional effect and a deep design, and an excellent color developability and a high brightness feeling are formed. be able to.

  Furthermore, it is preferable to carry out in-line using a water gravure printing ink composition as a printing ink composition which is a preferred example of the method for producing a printed material, and using a gravure printing machine having a gravure plate as a printing machine.

  First, after printing an image on a paper substrate with a gravure printing machine having a gravure plate using an aqueous gravure printing ink composition, the printing surface is dried using a drying device provided in the printing machine. The aqueous varnish composition described above is printed on a part or the entire surface of the printing surface with a gravure printing machine having a gravure printing plate, and dried using a drying device provided in the printing machine.

  On the dried film obtained by drying, the active energy ray-curable overprint varnish composition that satisfies the surface tension condition described above is printed by a gravure printing machine having a gravure printing plate.

  Next, the active energy ray-curable overprint varnish composition is irradiated with an active energy ray and cured using a light irradiation device provided in the gravure printing machine. For example, an active energy ray irradiating apparatus equipped with a high-pressure mercury lamp, a metal halide lamp, an LED lamp or the like is used to irradiate an active energy ray to cure the active energy ray-curable overprint varnish composition. Simultaneously with curing, the printed material is dried by heat generated by irradiation with active energy rays.

  In this way, an uneven pattern can be formed on the printing surface to give the printed matter a three-dimensional effect and a deep design, and an excellent color development and high brightness can be formed.

  The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Unless otherwise specified, “%” means “mass%” and “part” means mass part.

<Water-based gravure ink composition 1>
Grampia GCR black 1000 (manufactured by Sakata Inks) was used.

<Aqueous varnish composition>
Aqueous varnish composition 1
Pearl pigment: Iriolidine 211 (manufactured by Merck Japan) 15.0 parts Acrylic emulsion (aqueous resin): Nippon SX7 (manufactured by Nippon Zeon) 62.9 parts Polyethylene wax: WPE-W400 (manufactured by Mitsui Chemicals) 3.0 parts Silicone oil (surface conditioner) ): TW-4000 (manufactured by Kyoeisha Chemical Co., Ltd.) 9.0 parts Isopropyl alcohol 10.1 parts Total 100.0 parts

After blending to achieve the above blending composition, the mixture was stirred and mixed with a disper. To 100 parts of the obtained mixture, 50 parts of a diluting solvent (isopropyl alcohol: water = 7: 3) was added and diluted 50% to obtain an aqueous varnish composition having a viscosity of 17 seconds.
Viscosity was measured at 25 ° C. using Zaan Cup R # 3 manufactured by Kosei Co., Ltd.

Aqueous varnish composition 2
An aqueous varnish composition 2 was obtained using the same materials and the same production conditions as the aqueous varnish composition 1 except that the pearl pigment was changed from Iriodin 211 to Iriodin 223 (manufactured by Merck Japan). The viscosity was 17 seconds.

Aqueous varnish composition 3
An aqueous varnish composition 3 was obtained using the same materials and the same production conditions as the aqueous varnish composition 1 except that the pearl pigment was changed from Iriodin 211 to Iriodin 231 (manufactured by Merck Japan). The viscosity was 17 seconds.

Aqueous varnish composition 4
An aqueous varnish composition 4 was obtained using the same materials and the same production conditions as the aqueous varnish composition 1 except that aluminum powder 231 (manufactured by Merck), which is a metal powder pigment, was used instead of the pearl pigment. The viscosity was 17 seconds.

Aqueous varnish composition 5
Aqueous varnish composition except that the silicone oil as a surface conditioner: TW-4000 is changed from 9.0 parts to 5 parts, and the acrylic emulsion as a water-based resin: Nippon SX7 is changed from 62.9 parts to 66.9 parts Aqueous varnish composition 5 was obtained using the same materials and the same production conditions as for product 1. The viscosity was 16 seconds.

Aqueous varnish composition 6
Silicone oil: TW-4000 was changed from 9.0 parts to 2 parts, and Nippon SX7 was changed from 62.9 parts to 69.9 parts. Thus, an aqueous varnish composition 6 was obtained. The viscosity was 16 seconds.

Aqueous varnish composition 7
Except for changing the pearl pigment from 15.0 parts to 10.5 parts and changing NIPPOL SX7 from 62.9 parts to 66.4 parts, the same materials and the same production conditions as the aqueous varnish composition 1, An aqueous varnish composition 7 was obtained. The viscosity was 16 seconds.

Aqueous varnish composition 8
Except for changing the pearl pigment from 15.0 parts to 18.0 parts and changing NIPPOL SX7 from 62.9 parts to 59.9 parts, the same materials and the same production conditions as the aqueous varnish composition 1, An aqueous varnish composition 8 was obtained. The viscosity was 16 seconds.

Aqueous varnish composition 9
An aqueous varnish composition 9 was obtained using the same materials and the same production conditions as those of the aqueous varnish composition 1 except that the pearl pigment was changed to 0 part and the NP SX7 was changed from 62.9 parts to 71.9 parts. The viscosity was 16 seconds.

<Active energy ray-curable overprint varnish composition>
UV-curable overprint varnish composition 1
Epoxy acrylate oligomer (photopolymerizable compound):
Laromar 8986 (BASF) 65.0 parts Photopolymerization initiator: Irgacure 184 (CIBA) 4.0 parts Silicon slip agent: Granol 410 (Kyoeisha Chemical Co., Ltd.) 0.2 parts Ethanol 25.0 parts Total 100.0 parts

After blending to achieve the above blending composition, the mixture was stirred and mixed with a disper. 20 parts of a diluting solvent (ethanol) was added to 100 parts of the obtained mixture to dilute it by 20% to obtain an ultraviolet curable overprint varnish composition 1 having a viscosity of 16 seconds.
Viscosity was measured at 25 ° C. using Zaan Cup R # 3 manufactured by Kosei Co., Ltd.

・ UV curable overprint varnish composition 2
An ultraviolet curable overprint varnish composition 2 was obtained using the same materials and the same production conditions as the ultraviolet curable overprint varnish composition 1 except that ethanol as a solvent was changed to isopropyl alcohol. The viscosity was 16 seconds.

・ UV curable overprint varnish composition 3
An ultraviolet curable overprint varnish composition 3 was obtained using the same materials and the same production conditions as the ultraviolet curable overprint varnish composition 1 except that ethanol as the solvent was changed to ethyl acetate. The viscosity was 16 seconds.
Ink compositions for aqueous gravure printing, aqueous varnish compositions 1 to 9, and ultraviolet curable overprint varnish compositions 1 to 3 were produced in-line by the following method so as to have the combinations shown in Table 1, and Examples 1 to 9 The printed matter of Comparative Examples 1-2 was obtained.

・ Printing conditions Printing machine: Toshiba gravure printing machine Base material: Coated ball CRC210g (manufactured by Rengo Co., Ltd.)
Drying: 80 ° C / 75m ³
UV irradiation: Z-8 (high pressure mercury) 120W x 5 lamps Printing speed: 80m / min

・ Printing procedure As a gravure plate, a 175 screen screen gravure roll (plate depth: 35 μm) is prepared by helio electronic engraving, and a gravure printing machine is used to form an aqueous gravure printing ink composition on a paper substrate. The product (Granpia GCR Black 1000, manufactured by Sakata Inks) was solid-printed and then heat-dried.

  Using the same gravure roll as described above, the aqueous varnish composition was solid-printed on the printed surface and dried to obtain a dry film.

  Subsequently, the ultraviolet curable overprint varnish composition was solid-printed using a 150 degree screen line (plate depth 40 μm) beer roll, and then cured and dried by ultraviolet irradiation to obtain a cured film.

<Evaluation>
(surface tension)
The surface tension of the dried film and the surface tension of the ultraviolet curable overprint varnish composition were measured by the following measurement method, and the difference (γ ₂ −γ ₁ ) was determined. The results are shown in Table 1.

・ Method for measuring surface tension of dry film The surface tension of the dry film is determined according to JIS K 6768 (plastic film and paper-wetting test method). Measured using “Liquid”.

-Measuring method of surface tension of ultraviolet ray curable overprint varnish composition It measured at 25 degreeC using the platinum plate with the surface tension meter (Kyowa Kagaku Co., Ltd. make, model A3).

(Evaluation of unevenness of printed materials of Examples 1 to 7 and Comparative Examples 1 and 2)
The unevenness of the printed materials of Examples 1 to 7 and Comparative Examples 1 and 2, the fineness of the uneven pattern, polarized light emission, and glitter were visually evaluated. The evaluation results are shown in Table 1.

・ Concavity and convexity of printed matter ○: A surface with a clear concavo-convex pattern was obtained. Δ: A surface with a concavo-convex pattern was unclear. ×: A concavo-convex pattern was hardly obtained.

・ The fineness of the uneven pattern ◎: The printed pattern is fine ○: The printed pattern is slightly rough △: The printed pattern is rough

・ Polarization and glitter (high brightness)
○: Polarized color and / or sparkle x: Polarized color and / or no glitter

  Since Comparative Example 1 did not contain any of the pearl pigment, the metal powder pigment, and the glass flakes, neither polarized color development nor high brightness (brilliant feeling) was observed. In Comparative Example 2, since the difference in surface tension was smaller than 3.1 and 5, no uneven pattern was formed on the printed matter, and the design was inferior.

  On the other hand, all of the examples were able to impart excellent color development and high brightness to the printed material, and further, the printed material could have a three-dimensional effect and a deep design.

Claims (5)

A printing ink composition is printed on a paper substrate, and a dry film of an aqueous varnish composition is provided on a part or all of the printed surface, and an active energy ray-curable overprint varnish composition is activated on the dry film. Provide a cured film cured by irradiation with energy rays,
The aqueous varnish composition contains at least one selected from the group of pearl pigments, metal powder pigments, and glass flakes, an aqueous resin, a surface conditioner, and an aqueous solvent,
The active energy ray-curable overprint varnish composition satisfies the following formula (1).
γ ₂ −γ ₁ ≧ 5 mN / m (1)
Here, γ ₁ is the surface tension of the dry film, and γ ₂ is the surface tension of the active energy ray-curable overprint varnish composition.   The method for producing a printed matter according to claim 1, wherein an aqueous printing ink composition is used as the printing ink composition.   The method for producing a printed matter according to claim 1 or 2, wherein the dry film is provided by printing or coating the aqueous varnish composition on the printed surface and then drying the composition. The cured film is provided by printing or coating the active energy ray-curable overprint varnish composition, and then curing it by irradiation with active energy rays.
Printing of the printing ink composition, printing or coating of the aqueous varnish composition, and printing or coating of the active energy ray-curable overprint varnish composition are performed in an inline manner using a gravure plate. A method for producing a printed matter according to claim 3   A printed matter produced by the method for producing a printed matter according to claim 1, wherein a concavo-convex pattern is formed on the surface.