JP6864774B1 - Light-shielding printed matter, laminate, light-shielding printed matter manufacturing method, laminate manufacturing method and packaging bag, lid material, label - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a printed matter having high light-shielding property and whiteness without using an aluminum foil or an aluminum-deposited film, and to provide a light-shielding printed matter having high adhesion to a substrate, blocking resistance of the printed matter, and laminating suitability. To do. SOLUTION: A white ink layer laminated with a film thickness of 0.5 to 10 μm and a gray ink layer laminated with a film thickness of 0.5 to 5 μm on at least one surface of a base material layer. The white ink layer is a layer composed of a white ink composition and a white ink set containing a curing agent solution (d1) used together with the white ink composition, and the gray ink layer. Is a layer composed of a gray ink set containing a gray ink composition and a curing agent solution (d2) used together with the gray ink composition, the white ink set has specific conditions, and the gray ink set. Is a light-shielding printed matter characterized by forming a light-shielding layer having specific conditions. [Selection diagram] None

Description

The present invention relates to a light-shielding printed matter, a laminate, a method for producing a light-shielding printed matter, a method for producing a laminate, and a packaging bag, a lid material, and a label.

Conventionally, flexible packaging products such as packaging bags and packaging containers for storing various products such as foods and drinks and detergents have some contents that change or deteriorate due to external light, and these are filled. The packaging products to be used are required to have light-shielding properties. For this reason, aluminum foil and aluminum-deposited film are generally used, but the problem is that pinholes are likely to occur due to poor bending resistance, and that sparks occur when heated in a microwave oven. In addition, there is a problem that it reacts with a metal detector and interferes with the inspection of foreign matter (metal pieces, etc.). Further, the aluminum foil has problems that it is difficult to separate aluminum and incinerate it, which is not preferable in terms of the environment. Therefore, it has been proposed to replace aluminum foil and aluminum-deposited film by printing.

In Patent Document 1 and Patent Document 2, a packaging material containing a base material layer, a light-shielding printing layer, and a sealant layer from the outer side of the container to the inner side of the container when the bag is made into a container. A packaging material is described in which the light-shielding printing layer is at least a white solid layer obtained by solid printing and an achromatic layer formed by mixing white and black and solid printing.

In Patent Document 3, at least the first base material layer, the light-shielding layer, the barrier layer laminated on the light-shielding layer, and the sealant layer are laminated in this order, and the light-shielding layer is one or a plurality of white layers. And the gray color layer are laminated in order from the first base material layer side, and the gray color layer is a laminate containing titanium oxide and carbon black having an average particle size of 0.1 to 0.3 μm. Is described.

In both of these patent documents, a white layer and a gray layer are laminated, but one patent document 1 and patent document 2 describe that the total light transmittance is preferably 20% or less, and the other patent document 2. Patent Document 3 describes that the visible light transmittance is preferably 20% or less.

However, in recent years, there has been an increasing demand for light-shielding properties and concealing properties, and those having a transmittance lower than the above-mentioned transmittance, that is, those capable of completely blocking light (transmittance of about 3% or less) are desired. Further, in addition to these light-shielding performances, it is required to have high performance in terms of designability, cosmeticity (particularly whiteness), printability, and laminating suitability.

On the other hand, in Patent Documents 1 to 3, it is preferable that the transmittance is about the above-mentioned degree, and there is no study on lowering the transmittance than this. Further, as described above, the increasing importance of designability and cosmeticity (particularly whiteness) has not been examined, and there is no description or suggestion, and the whiteness may be inferior.

Further, as described in Patent Document 1 and Patent Document 2, if the thickness of the white layer or the gray layer is increased, the light-shielding property and the hiding property can be improved, but the offensive odor is generated because the white layer and the gray layer are not sufficiently dried. It is only stated that it may occur, and no study has been made on improving the light-shielding property and the hiding property without increasing the thickness, and neither on the printability nor the laminate suitability has been studied.

Similarly, in Patent Document 3, the white layer has a two-layer structure composed of two white layers laminated, but there is a description that a single layer may be used or three or more layers may be laminated, and the white layer may be laminated. It is considered that the whiteness is improved as a plurality of layers are laminated, but it is not realistic in terms of cost and work efficiency because the amount of white ink used and the number of units increase. In addition, printability and laminate suitability have not been examined.

Further, since the printed matter (laminated matter) on which the white layer or the gray layer is formed is generally in a wound state after printing, the printed matter and the base material are in contact with each other under pressure. Therefore, blocking resistance is also important. In addition, when laminated, the light-shielding property may decrease.

Japanese Unexamined Patent Publication No. 2014-94767 Japanese Unexamined Patent Publication No. 2017-100809 Japanese Unexamined Patent Publication No. 2017-202613

Therefore, the present invention can provide a printed matter having high light-shielding property and whiteness without using an aluminum foil or an aluminum-deposited film, and has high adhesion to a substrate, blocking resistance of the printed matter, and light-shielding suitability for laminating. The purpose is to provide printed matter.

The present inventors have a white ink layer laminated with a film thickness of 0.5 to 10 μm and a gray ink layer laminated with a film thickness of 0.5 to 5 μm on at least one surface of the base material layer. And are laminated in this order, and the white ink layer is a layer composed of a white ink set containing a white ink composition and a curing agent solution (d1) used together with the white ink composition, and the gray. The ink layer is a layer composed of a gray ink set containing a gray ink composition and a curing agent solution (d2) used together with the gray ink composition, and the white ink set has specific conditions and the gray. It has been found that the above object can be achieved by the light-shielding printed matter characterized in that the ink set forms a light-shielding layer having specific conditions, and the present invention has been completed.

That is, the present invention
(1) on at least one side of the substrate layer, and a white ink layer formed by laminating a film thickness of 0.5 to 10 [mu] m, both the gray ink layer formed by laminating a film thickness of 0.5~5μm It is made by stacking light-shielding layers including
The white ink layer is a layer composed of a white ink set containing a white ink composition and a curing agent solution (d1) used together with the white ink composition.
The gray ink layer is a layer composed of a gray ink set containing a gray ink composition and a curing agent solution (d2) used together with the gray ink composition.
The white ink set has the following conditions (a) to (c).
Shielding prints the gray ink set is characterized and Turkey that having a following conditions (d) - (g),
(A) The white ink composition contains titanium dioxide (a1), a vinyl chloride / vinyl acetate copolymer resin (b1), and a polyurethane resin (b2).
(A) The solid content weight ratio of the resin solid content (B1) obtained by combining titanium dioxide (a1), vinyl chloride / vinyl acetate copolymer resin (b1), and polyurethane resin (b2) is (a1). ) / (B1) = 80/20 to 90/10.
(C) The solid content weight ratio of the resin solid content (B1) and the isocyanate compound (D1) in the curing agent solution (d1) is (B1) / (D1) = 40/60 to 95/5. ..
(D) The gray ink composition contains titanium dioxide (a2), carbon black (a3), a vinyl chloride / vinyl acetate copolymer resin (b3), and a polyurethane resin (b4).
(E) The solid content weight ratio of titanium dioxide (a2) and carbon black (a3) is (a2) / (a3) = 70/30 to 99.5 / 0.5.
(F) The pigment solid content (A), which is a combination of titanium dioxide (a2) and carbon black (a3), the vinyl chloride / vinyl acetate copolymer resin (b3), and the polyurethane resin (b4) are combined. The solid content weight ratio with the resin solid content (B2) is (A) / (B2) = 80/20 to 90/10.
(G) The solid content weight ratio of the resin solid content (B2) and the isocyanate compound (D2) in the curing agent solution (d2) is (B2) / (D2) = 40/60 to 95/5. ..
(2) A laminate characterized by laminating a sealant layer or a seal layer on the light-shielding layer of the light-shielding printed matter according to (1).
(3) The process of preparing the base material layer and
A gravure printing step of creating a light-shielding layer containing both a white ink layer having a film thickness of 0.5 to 10 μm and a gray ink layer having a film thickness of 0.5 to 5 μm on at least one of the substrate layers. Including,
A step of preparing a white ink set containing a white ink composition used for the white ink layer and a curing agent solution (d1) used together with the white ink composition, and a step of preparing the white ink set.
A step of preparing a gray ink set containing a gray ink composition used for the gray ink layer and a curing agent solution (d2) used together with the gray ink composition is included.
The white ink set has the following conditions (a) to (c).
The method of manufacturing the light-shielding prints the gray ink set is characterized and Turkey that having a following conditions (d) - (g),
(A) The white ink composition contains titanium dioxide (a1), a vinyl chloride / vinyl acetate copolymer resin (b1), and a polyurethane resin (b2).
(A) The solid content weight ratio of the resin solid content (B1) obtained by combining titanium dioxide (a1), vinyl chloride / vinyl acetate copolymer resin (b1), and polyurethane resin (b2) is (a1). ) / (B1) = 80/20 to 90/10.
(C) The solid content weight ratio of the resin solid content (B1) and the isocyanate compound (D1) in the curing agent solution (d1) is (B1) / (D1) = 40/60 to 95/5. ..
(D) The gray ink composition contains titanium dioxide (a2), carbon black (a3), a vinyl chloride / vinyl acetate copolymer resin (b3), and a polyurethane resin (b4).
(E) The solid content weight ratio of titanium dioxide (a2) and carbon black (a3) is (a2) / (a3) = 70/30 to 99.5 / 0.5.
(F) The pigment solid content (A), which is a combination of titanium dioxide (a2) and carbon black (a3), the vinyl chloride / vinyl acetate copolymer resin (b3), and the polyurethane resin (b4) are combined. The solid content weight ratio with the resin solid content (B2) is (A) / (B2) = 80/20 to 90/10.
(G) The solid content weight ratio of the resin solid content (B2) and the isocyanate compound (D2) in the curing agent solution (d2) is (B2) / (D2) = 40/60 to 95/5. ..
(4) The process of preparing the base material layer and
A gravure printing step of creating a light-shielding layer containing both a white ink layer having a film thickness of 0.5 to 10 μm and a gray ink layer having a film thickness of 0.5 to 5 μm on at least one of the substrate layers.
Including a laminating process to create a sealant layer or a coating process to create a sealant layer,
A step of preparing a white ink set containing a white ink composition used for the white ink layer and a curing agent solution (d1) used together with the white ink composition, and a step of preparing the white ink set.
A step of preparing a gray ink set containing a gray ink composition used for the gray ink layer and a curing agent solution (d2) used together with the gray ink composition is included.
The white ink set has the following conditions (a) to (c).
Method for producing a laminate wherein the gray ink set is characterized and Turkey that having a following conditions (d) - (g),
(A) The white ink composition contains titanium dioxide (a1), a vinyl chloride / vinyl acetate copolymer resin (b1), and a polyurethane resin (b2).
(A) The solid content weight ratio of the resin solid content (B1) obtained by combining titanium dioxide (a1), vinyl chloride / vinyl acetate copolymer resin (b1), and polyurethane resin (b2) is (a1). ) / (B1) = 80/20 to 90/10.
(C) The solid content weight ratio of the resin solid content (B1) and the isocyanate compound (D1) in the curing agent solution (d1) is (B1) / (D1) = 40/60 to 95/5. ..
(D) The gray ink composition contains titanium dioxide (a2), carbon black (a3), a vinyl chloride / vinyl acetate copolymer resin (b3), and a polyurethane resin (b4).
(E) The solid content weight ratio of titanium dioxide (a2) and carbon black (a3) is (a2) / (a3) = 70/30 to 99.5 / 0.5.
(F) The pigment solid content (A), which is a combination of titanium dioxide (a2) and carbon black (a3), the vinyl chloride / vinyl acetate copolymer resin (b3), and the polyurethane resin (b4) are combined. The solid content weight ratio with the resin solid content (B2) is (A) / (B2) = 80/20 to 90/10.
(G) The solid content weight ratio of the resin solid content (B2) and the isocyanate compound (D2) in the curing agent solution (d2) is (B2) / (D2) = 40/60 to 95/5. ..
(5) In a packaging bag that requires a base material layer, a light-shielding layer including both a white ink layer and a gray ink layer, and a sealant layer or a seal layer in this order from the outer layer, the white ink layer becomes (1). Formed with the described white ink set and
A packaging bag characterized in that the gray ink layer is formed by the gray ink set according to (1).
(6) In a packaging bag that requires a base material layer, a light-shielding layer including both a white ink layer and a gray ink layer, and a sealant layer or a seal layer in this order from the outer layer, the white ink layer becomes (1). Formed with the described white ink set and
A lid material, wherein the gray ink layer is formed by the gray ink set according to (1).
(7) In a packaging bag that requires a base material layer, a light-shielding layer including both a white ink layer and a gray ink layer, and a sealant layer or a seal layer in this order from the outer layer, the white ink layer becomes (1). Formed with the described white ink set and
A label, characterized in that the gray ink layer is formed by the gray ink set according to (1).
It is about.

According to the present invention, it is possible to provide a printed matter having high light-shielding property and whiteness without using an aluminum foil or an aluminum-deposited film, and has high adhesion to a substrate, blocking resistance of the printed matter, and light-shielding property having laminating suitability. Printed matter can be provided.

Hereinafter, embodiments for carrying out the present invention will be described in detail. It should be noted that the present embodiment is only one embodiment for carrying out the present invention, and the present invention is not limited to the present embodiment, and various modifications and embodiments are made without departing from the gist of the present invention. Is possible.

The light-shielding printed matter of the present invention is a gray ink formed by laminating a white ink layer having a thickness of 0.5 to 10 μm and a thickness of 0.5 to 5 μm on at least one surface of a base material layer. A light-shielding layer including both layers is laminated, and the white ink layer is a layer composed of a white ink composition and a white ink set containing a curing agent solution (d1) used together with the white ink composition. The gray ink layer is a layer composed of a gray ink set containing the gray ink composition and a curing agent solution (d2) used together with the gray ink composition, and the white ink set has specific conditions. and Turkey said gray ink set have a certain conditions are preferred.

The white ink layer is preferably laminated with a film thickness of 0.5 to 10 μm, and more preferably with a film thickness of 0.8 to 8 μm. If the film thickness is smaller than 0.5 μm, the whiteness may be inferior. If the film thickness is larger than 10 μm, the blocking resistance, adhesion, and lamination strength may be inferior. By including the white ink layer, the effect of concealing the gray ink layer is exhibited and the whiteness is improved.

The gray ink layer is preferably laminated with a film thickness of 0.5 to 5 μm, and more preferably with a film thickness of 0.8 to 3 μm. If the film thickness is smaller than 0.5 μm, the light-shielding property may be inferior. If the film thickness is larger than 5 μm, the whiteness, blocking resistance, adhesion, and lamination strength may be inferior. By including the gray ink layer, a light-shielding effect is exhibited by a synergistic effect with the white ink layer, and the light-shielding property is improved.

The white ink set preferably contains a white ink composition and a curing agent solution (d1) used together with the white ink composition.

The curing agent solution (d1) preferably contains an isocyanate compound (D1) and a solvent (E1).
Examples of the isocyanate compound (D1) include tolylene diisocyanate, aromatic diisocyanates such as 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, 4, Polyisocyanates such as aliphatic diisocyanates such as 4'-dicyclohexyldiisocyanate and pentane-1,5-diisocyanate (stavioPDI) and modified products such as trimethylolpropane trimerics, isocyanurates, bullets, and allophanates. Hardeners can be mentioned. These can be used alone or in admixture of two or more. Commercially available products include 24A-100, 22A-75, TPA-100, TSA-100, TSS-100, TAE-100, TKA-100, P301-75E, E402-808, E405-70B, AE700-. 100, D101, D201, A201H (manufactured by Asahi Kasei Corporation), Mitec Y260A (manufactured by Mitsubishi Chemical Corporation), Coronate HX, Coronate HL, Coronate L (manufactured by Tosoh Corporation), Desmodur N75MPA / X (Co) Examples thereof include Covestro Japan Co., Ltd.) and LG Hardener C (manufactured by Tokyo Ink Co., Ltd.). Of these, aliphatic isocyanate compounds are more preferable.

Examples of the solvent (E1) used in the curing agent solution include aromatic hydrocarbon solvents such as toluene and xylene, aliphatic hydrocarbon solvents such as hexane, cyclohexane, methylcyclohexane and ethylcyclohexane, methanol, ethanol and isopropyl. Alcohol, normal propyl alcohol, 1-butanol, 2-butanol, isobutanol, tert-butanol and other alcohol solvents, ethyl acetate, n-propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, tert acetate -Ester solvents such as butyl, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol. Glycol ether-based solvents such as monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether and esterified products thereof can be mentioned. As the esterified product, acetates are mainly selected. For example, ethylene glycol monomethyl ether acetate, Examples thereof include ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate. Of these, toluene, ethyl acetate, n-propyl acetate, isopropyl alcohol, propylene glycol monomethyl ether, methyl ethyl ketone and the like are more preferable from the viewpoint of printability and versatility. These can be used alone or in admixture of two or more. Further, the solvent (E1) contained in the curing agent solution is preferably the same as the solvent used for general gravure ink.

The white ink set preferably has the following conditions (a) to (c).
(A) The white ink composition contains titanium dioxide (a1), a vinyl chloride / vinyl acetate copolymer resin (b1), and a polyurethane resin (b2).
(A) The solid content weight ratio of the resin solid content (B1) obtained by combining titanium dioxide (a1), vinyl chloride / vinyl acetate copolymer resin (b1), and polyurethane resin (b2) is (a1). ) / (B1) = 80/20 to 90/10.
(C) The solid content weight ratio of the resin solid content (B1) and the isocyanate compound (D1) in the curing agent solution (d1) is (B1) / (D1) = 40/60 to 95/5. ..

The titanium dioxide (a1) may be of an anatas type or a rutile type. The average particle size is preferably 0.1 to 0.5 μm, more preferably 0.15 to 0.45 μm. The average particle size referred to here means the D50 particle size by the laser diffraction / scattering method, and the same applies to the following.

Such titanium dioxide is commercially available, and JR-301, JR-403, JR-405, JR600A, JR-605, JR-600E, JR-603, JR-805, JR-806, JR-701, Examples thereof include JRNC, JR-800, JR, JA-1, JA-C, and JA-3 (manufactured by Teika Co., Ltd.).

The vinyl chloride / vinyl acetate copolymer resin (b1) is obtained by subjecting a vinyl chloride monomer and a vinyl acetate monomer to a polymerization reaction, and the polymerization method can be produced by a conventionally known method. The method is not particularly limited, and any of solution polymerization, emulsion polymerization and suspension polymerization can be carried out.
Further, it may be a modified vinyl chloride / vinyl acetate copolymer resin, and has an unsaturated carbon-carbon double bond in the vinyl chloride monomer, the vinyl acetate monomer and one molecule, and has an acidic functional group or the like. A monomer having a hydroxyl group may be copolymerized.

Examples of the monomer having a hydroxyl group include alkyl alcohols, vinyl alcohols, ethylene glycol monoacrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, 2- (2-hydroxyethoxy) ethyl acrylate, and the like. Examples thereof include hydroxyalkyl acrylates such as (1-hydroxycyclohexyl) methyl acrylate, and among them, vinyl alcohol and hydroxyalkyl acrylate are more preferable.

Examples of the acidic functional group include a carboxyl group, a sulfonic acid group, a mercapto group, a lactone group, a phenol group, a quinone and the like, and the carboxyl group is more preferable.

Examples of monomers having a carboxyl group include (meth) acrylic acid, acetic acid, propionic acid, butyric acid, valeric acid, isovaleric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, caprylic acid, which are examples of monocarboxylic acids. Examples thereof include lauric acid, myristyl acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, benzoic acid and salicylic acid. Examples of dicarboxylic acids include malic acid, itaconic acid, (anhydrous) maleic acid, phthalic acid, oxalic acid, glutaric acid, malonic acid, terephthalic acid, fumaric acid, isophthalic acid, adipic acid, sebacic acid, succinic acid, etc. Be done. Of these, (maleic anhydride) maleic anhydride is more preferable.

Such a vinyl chloride / vinyl acetate copolymer resin (b1) is commercially available, and is commercially available, VINNOL E15 / 45, VINNOL H15 / 42, VINNOL E15 / 45A, VINNOL E15 / 48A, VINNOL E22 / 48A, VINNOL H15 /. 45M, VINNOL H30 / 48M (manufactured by Wacker Chemie), Solvine C, Solvine CL, Solvine A, Solvine AL, Solvine TA5R, Solvine TAO, Solvine M5, Solvine M5R (manufactured by Nissin Chemical Industry Co., Ltd.), Kanevinyl M100 , Kanevinyl HM515, Kanevinyl T5DA (manufactured by Kaneka Corporation) and the like.

The polyurethane resin (b2) may be obtained by reacting a polyol with a polyisocyanate and a chain extender.

Examples of the polyol include polyether polyols, low molecular weight polyols, polyester polyols, polycarbonate polyols, polybutadiene glycols, glycols, acrylic polyols and the like. These polyols can be used alone or in admixture of two or more. Examples of the polyisocyanate include aromatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates. These polyisocyanates can be used alone or in admixture of two or more. Examples of the chain extender include polyamine compounds containing two or more primary or secondary amino groups in one molecule, hydrazide compounds, and low molecular weight polyols having a molecular weight of less than 600. These chain extenders can be used alone or in admixture of two or more. In the urethanization reaction, it is preferable to use a solvent for reaction control, and it is more preferable that the solvent is inert to the isocyanate group or has low activity. Examples of the solvent that can be used include aromatic solvents such as toluene and xylene, aliphatic solvents such as hexane, cyclohexane, methylcyclohexane and ethylcyclohexane, ketone solvents such as acetone, methylethylketone, methylisobutylketone and cyclohexanone, and acetic acid. Ester solvents such as ethyl, n-propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, glycol solvents such as propylene glycol monomethyl ether, methanol, ethanol, isopropanol, Examples thereof include alcohol solvents such as normal propanol and butanol. These solvents can be used alone or in admixture of two or more. In addition, additives may be added as needed. Examples of the additive include an antioxidant, a light stabilizer, an antioxidant, an ultraviolet absorber, a metal deactivator, a reaction retarder and the like. These additives can be added alone or in combination of two or more. Further, it can be appropriately added before and after the reaction or during the reaction.

The solid content weight ratio of the titanium dioxide (a1), the vinyl chloride / vinyl acetate copolymer resin (b1), and the resin solid content (B1) obtained by combining the polyurethane resin (b2) is (a1). ) / (B1) = 80/20 to 90/10, more preferably 82/28 to 88/12. If the ratio of titanium dioxide (a1) is less than 80, the whiteness may be inferior, and if it is more than 90, the lamination strength may be inferior.

The solid content weight ratio of the resin solid content (B1) and the isocyanate compound (D1) in the curing agent solution (d1) is (B1) / (D1) = 40/60 to 95/5. It is preferably 50/50 to 85/15. If the ratio of the resin solid content (B1) is less than 40, the blocking resistance may be inferior, and if it is more than 95, the lamination strength may be inferior.

The gray ink set is preferably a layer containing the gray ink composition and the curing agent solution (d2) used together with the gray ink composition.

The curing agent solution (d2) preferably contains an isocyanate compound (D2) and a solvent (E2), similarly to the curing agent solution (d1).

As the isocyanate compound (D2) and the solvent (E2), the same ones as those of the isocyanate compound (D1) and the solvent (E1) can be used.

The gray ink set preferably has the following conditions (d) to (g).
(D) The gray ink composition contains titanium dioxide (a2), carbon black (a3), a vinyl chloride / vinyl acetate copolymer resin (b3), and a polyurethane resin (b4).
(E) The solid content weight ratio of titanium dioxide (a2) and carbon black (a3) is (a2) / (a3) = 70/30 to 99.5 / 0.5.
(F) The pigment solid content (A), which is a combination of titanium dioxide (a2) and carbon black (a3), the vinyl chloride / vinyl acetate copolymer resin (b3), and the polyurethane resin (b4) are combined. The solid content weight ratio with the resin solid content (B2) is (A) / (B2) = 80/20 to 90/10.
(G) The solid content weight ratio of the resin solid content (B2) and the isocyanate compound (D2) in the curing agent solution (d2) is (B2) / (D2) = 40/60 to 95/5. ..

As the titanium dioxide (a2), the same titanium dioxide (a1) as described above can be used.

As the carbon black (a3), furnace black, thermal lamp black, acetylene black, channel black and the like can be used.
The average particle size of carbon black is preferably 8 nm to 100 nm, more preferably 10 nm to 80 nm.

Such carbon blacks are commercially available, and examples thereof include MA11 (manufactured by Mitsubishi Chemical Corporation) and BLACK PEARLS 430 (manufactured by Cabot Corporation).

The solid content weight ratio of the titanium dioxide (a2) and the carbon black (a3) is preferably (a2) / (a3) = 70/30 to 99.5 / 0.5, and is 80 /. It is preferably 20 to 99/1. If the ratio of the carbon black (a3) is larger than 30, the whiteness may be inferior, and if it is less than 0.5, the light-shielding property may be inferior.

As the vinyl chloride / vinyl acetate copolymer resin (b3), the same one as the vinyl chloride / vinyl acetate copolymer resin (b1) described above can be used.

As the polyurethane resin (b4), the same polyurethane resin (b2) as described above can be used.

The pigment solid content (A), which is a combination of the titanium dioxide (a2) and the carbon black (a3), the vinyl chloride / vinyl acetate copolymer resin (b3), and the polyurethane resin (b4) are combined. It is preferable that the solid content weight ratio with the resin solid content (B2) is (A) / (B2) = 80/20 to 90/10. If the ratio of the pigment solid content (A) is less than 80, the light-shielding property may be inferior, and if it is more than 90, the lamination strength may be inferior.

The solid content weight ratio of the resin solid content (B2) and the isocyanate compound (D2) in the curing agent solution (d2) is (B2) / (D2) = 40/60 to 95/5. It is preferably 50/50 to 85/15. If the ratio of the resin solid content (B2) is less than 40, the blocking resistance may be inferior, and if it is more than 95, the lamination strength may be inferior.

In addition to the vinyl chloride / vinyl acetate copolymer resin (b1) and the polyurethane resin (b2), the vinyl chloride / vinyl acetate copolymer resin (b3) and the polyurethane resin (b4), other thermoplastic resins (B5) may be included. For example, cellacs, rosins, rosin-modified maleic acid resin, rosin-modified phenol resin, nitrified cotton, cellulose acetate, cellulose acetylpropionate, cellulose acetylbutyrate, rubber chloride, cyclized rubber, polyethylene resin, polypropylene resin, chloride. Vinyl resin, polyamide resin, ethylene- (meth) acrylic acid copolymer, polyester resin, polyvinylidene chloride resin, vinyl acetate resin, ketone resin, butyral resin, chlorinated polypropylene resin, chlorinated polyethylene resin, chlorinated ethylene vinyl acetate Resin, ethylene vinyl acetate resin, (meth) acrylic resin, styrene maleic acid resin, polystyrene resin, polyacetal resin, polycarbonate resin, casein, alkyd resin, acrylonitrile resin, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer , Polysulfone resin, polyether resin, polyethersulfone resin, polyether ketone resin, modified polyphenylene ether resin, polyphenylene sulfone resin, polyimide resin, polyamideimide resin, amorphous polyarylate resin, polyether ether ketone resin and the like are preferable. These resins may be one kind or two or more kinds.

The solid content of the pigment and the resin in each ink composition is preferably in the range of 2 to 60% by mass. If it is lower than 2% by mass, the coating amount at the time of printing is not sufficient, and if it exceeds 60% by mass, the fluidity is poor and it becomes difficult to make ink.

As the white ink composition and the gray ink composition, a solvent usually used for gravure ink can be used.
Examples of the solvent include aromatic hydrocarbon solvents such as toluene and xylene, aliphatic hydrocarbon solvents such as hexane, cyclohexane, methylcyclohexane and ethylcyclohexane, methanol, ethanol, isopropyl alcohol, normal propyl alcohol and 1-butanol. , 2-butanol, isobutanol, tert-butanol and other alcohol solvents, ethyl acetate, n-propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, tert-butyl acetate and other ester solvents, acetone. , Methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and other ketone solvents, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether. , Glycol ether-based solvents such as propylene glycol monobutyl ether and esterified products thereof are mentioned. As the esterified product, acetates are mainly selected, for example, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol. Examples thereof include monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate. Of these, toluene, ethyl acetate, n-propyl acetate, isopropyl alcohol, propylene glycol monomethyl ether, methyl ethyl ketone and the like are more preferable from the viewpoint of printability and versatility. These can be used alone or in admixture of two.
The solvent in the ink composition is preferably in the range of 40 to 98% by mass. If it is less than 40% by mass, the solid content increases, the fluidity deteriorates, and the ink production suitability is inferior. There is a risk that the shade (swimming phenomenon) of the ink will occur, the viscosity will decrease, and the pigment will easily settle.

Each of the ink compositions includes a coloring material, an inorganic filler, an organic filler, a defoaming agent, a leveling agent, an antiblocking agent, a wax, a pigment dispersant, an antistatic agent, a slip agent, a plasticizer, and a tackifier. Etc. can also be contained. Any known and commonly used ink composition can be appropriately selected as long as the characteristics of the ink composition are not impaired.

The coloring material may contain a pigment, a dye, or a mixture thereof.
Examples of pigments include inorganic pigments such as titanium dioxide, petals, barium sulfate, calcium carbonate, silica, zinc oxide, zinc sulfide, mica, talc, and pearl, phthalocyanine, insoluble azo, condensed azo, and dioxazine. Examples thereof include organic pigments such as anthraquinone-based, quinacridone-based, perylene-based, perinone-based, thioindigo-based, and carbon black, various other fluorescent pigments, metal powder pigments, and extender pigments. These pigments may be used alone or in combination of two or more. The dye is preferably one that dissolves or disperses in a solvent, and may be used alone or in combination of two or more. Above all, it is preferable to use a pigment from the viewpoint of durability.

The base material layer is preferably at least one selected from paper, plastic films or sheets, and laminates thereof. For example, polyester films such as polyethylene terephthalate (PET), polyethylene naphthalate and polybutylene terephthalate, polyolefin films such as polyethylene, polypropylene and ethylene-vinyl acetate, polystyrene films, alcohol films such as ethylene-vinyl alcohol and polyvinyl alcohol, and polyamide films. Alternatively, a transparent vapor-deposited polyester film or transparent film having a barrier layer in the middle, a polycarbonate film, a polyacrylonitrile film, a polyimide film, a cellophane, a moisture-proof cellophane, a PET film, or a polyamide film provided with a vapor-deposited layer such as alumina or silica. Examples thereof include vapor-deposited polyamide films, various coating films coated with polyvinylidene chloride resin, polyvinyl alcohol resin, polyacrylic acid resin, etc., PET and nylon coextruded films, and polylactic acid films. These may be either stretched or unstretched, and one type or two or more types may be laminated. Appropriate ones can be selected in consideration of mechanical strength and dimensional stability. Further, in order to improve the adhesion of the anchor coat layer and the laminate layer on the printed surface, a corona treatment, a low temperature plasma treatment, a frame treatment, a solvent treatment, a coating treatment or the like can be applied, or a pre-applied one can be selected. Among them, PET film, polypropylene film, polyamide film, coating film, transparent vapor-deposited polyester film or transparent vapor-deposited polyamide film, co-extruded film and the like are preferable. The thickness of the plastic base film is not particularly limited as long as it does not interfere with printability, winding suitability, etc., but is preferably 5 to 300 μm, more preferably 6 to 250 μm.

The paper base material layer preferably contains at least one selected from coated paper, uncoated paper, and a paper base material to which a plastic film or the like is bonded thereto. The paper base material may be one in which a thermoplastic resin or the like is laminated by a method such as dry laminating, non-solvent laminating or extrusion laminating, or a method of laminating via an adhesive or the like, and these may be appropriately combined. It may be a thing. Further, a laminate having heat-sealing properties can also be used as a paper base material. Examples of the method for imparting heat-sealing properties include laminating known sealant films, resin coating by extrusion laminating, coating of heat-sealing agents and hot melts, and heat-sealing resin processing by co-extrusion. A layer to which heat-sealing property is imparted by a method is also referred to as a heat-sealing layer. The thickness of the paper base material is not particularly limited as long as it does not interfere with printability, winding suitability, etc., but is preferably 5 to 800 μm, more preferably 6 to 600 μm.

The light-shielding layer is preferably formed by being coated by a gravure printing method. In particular, it is more preferably formed by coating by a gravure printing method using a multicolor gravure printing machine. The light-shielding layer includes a white ink layer laminated with a white ink set and a gray ink layer laminated with a gray ink set. The light-shielding layer may be a white ink layer laminated with a white ink set and a gray ink layer laminated with a gray ink set, but other inks laminated with the ink layer and another gravure ink composition. It may include layers. Depending on the final packaging mode, these ink layers may change the arrangement position of the printing base material for forming the light-shielding layer, and the formation order of these ink layers may change. That is, for example, after forming a light-shielding layer such as a base material layer / white ink layer / gray ink layer, another base material layer is laminated by dry lamination or the like (base material layer / white ink layer / gray ink layer / DL). / Other base material layer) may be used, or after forming a light-shielding layer such as a base material layer / gray ink layer / white ink layer, another base material layer is laminated by dry laminating or the like (base material layer). / Gray ink layer / white ink layer / DL / other base material).

In the laminated body of the present invention, a sealant layer or a seal layer may be laminated on the light-shielding layer. Examples of the sealant layer include a laminate having a heat-sealing property, a bonding of a known sealant film, and a resin coating by an extrusion lamination method. The sealing layer may be, for example, a heat-sealing agent or a hot melt. It is preferable that the seal layer is coated with an agent.

As the sealant layer, as long as the seal strength can be sufficiently secured, the bonding method is appropriately selected according to the printing substrate, application, composition and the like. For example, the light-shielding layer on the plastic base film is bonded to a known sealant film via an adhesive (dry laminating method, non-solvent laminating method, wet laminating method), heat-bonded (thermal laminating method), and the like. Resin coating by extrusion laminating (extrusion laminating method, coextrusion laminating method, PE sandwich laminating method) and the like can be preferably used. A laminate can be produced by using one of these methods or a combination of these methods.
The thickness of the sealant layer is not particularly limited, but is preferably 2 to 200 μm for the sealant film and 1 to 100 μm for the resin coating by the extrusion laminating method.

Examples of the sealant film include polyethylene, polypropylene, ethylene-vinyl acetate, polyolefin films such as copolymers thereof, co-pressed films and colored films thereof, polystyrene films, polyacrylonitrile films, ethylene-vinyl alcohol resin films, and the like. It may be either stretched or unstretched, and one type or two or more types may be laminated.

Examples of the resin that can be used for the resin coating by the extrusion laminating method include polyethylene resins such as LDPE, LLDPE, and HDPE, polypropylene resins, ethylene-vinyl acetate copolymers, ionomer resins, ethylene-acrylic acid copolymers, and ethylene-acrylic acids. Ethyl copolymer, ethylene-methyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl methacrylate copolymer, ethylene-propylene copolymer, methylpentene polymer, polyethylene or polypropylene with maleic acid or fumal Examples thereof include acid-modified polyolefin resins modified with an acid, polystyrene resins, and thermoplastic resins such as polybutylene terephthalate resin, and these resins may be one or more laminated.

As the seal layer, as long as the seal strength can be sufficiently ensured, the forming method is appropriately selected according to the printing substrate, the application, the configuration, and the like. For example, a heat sealant or hot melt coating, or a resin coating (direct laminating method) in which molten polypropylene is directly pressure-bonded to the printed surface can be preferably used. A laminate can be produced by using one of these methods or a combination of these methods. The thickness of the seal layer is not particularly limited, but is preferably 1 to 50 μm for hot melt adhesive coating and 0.01 to 30 μm for heat sealant coating.

Examples of heat sealant resins include vinyl acetate, cellacs, rosins, rosin-modified maleic acid resin, rosin-modified phenolic resin, nitrified cotton, cellulose acetate, cellulose acetylpropionate, cellulose acetylbutyrate, and chloride. Rubber, cyclized rubber, polyamide resin, vinyl chloride-vinyl acetate copolymer, polyester resin, ketone resin, butyral resin, chlorinated polypropylene resin, chlorinated polyethylene resin, chlorinated ethylene vinyl acetate resin, ethylene vinyl acetate resin, ( Meta) Examples thereof include thermoplastic resins such as acrylic resin, urethane resin, ethylene-vinyl alcohol resin, styrene maleic acid resin, casein, and alkyd resin, and these may be used alone or in combination of two or more. These resins are dissolved in a solvent, dissolved in an aqueous solution, or dispersed in water such as acrylic emulsions, urethane emulsions, ethylene-vinyl alcohol emulsions, polyethylene emulsions, polypropylene emulsions, and ethylene vinyl acetate emulsions. Can be mentioned.

In addition to the light-shielding layer, the light-shielding printed matter of the present invention imparts or enhances performance such as rigidity, waist, gas barrier property, aroma-retaining property, moisture-proof property, pinhole resistance, deadhole property, and linear cut property. The intermediate layer may be laminated. When the intermediate layer is provided, it is not always necessary to provide the light-shielding layer on the plastic base film, and the light-shielding layer may be provided on the intermediate layer.

Examples of the intermediate layer include a plastic film, a sheet, and a laminate thereof. Examples of the plastic film include polyester films such as polyethylene terephthalate (PET), polyethylene naphthalate and polybutylene terephthalate, polyolefin films such as polyethylene, polypropylene and ethylene-vinyl acetate, polystyrene films, and alcohol-based films such as ethylene-vinyl alcohol and polyvinyl alcohol. Barrier polyamide film with a film, polyamide film or barrier layer in the middle, polycarbonate film, polyacrylonitrile film, polyimide film, cellophane, moisture-proof cellophane, PET film or polyamide film with a vapor deposition layer such as alumina or silica. Examples thereof include polyester film or transparent vapor-deposited polyamide film, various coating films coated with polyvinylidene chloride resin, polyvinyl alcohol resin, polyacrylic acid resin and the like, PET and nylon coextrusion film, and polylactic acid film. These may be either stretched or unstretched, and one type or two or more types may be laminated. Appropriate ones can be selected in consideration of mechanical strength and dimensional stability. In order to improve the adhesion, the bonded surface can be subjected to corona treatment, low temperature plasma treatment, frame treatment, solvent treatment, coating treatment or the like, or a pre-treated one can be selected. The treatment is preferably double-sided treatment.
The intermediate layer may have a thickness of 5 to 300 μm, more preferably 6 to 250 μm, as long as it does not interfere with printability, winding suitability, and the like.

When an adhesive is used in the dry laminating method, non-solvent laminating method, wet laminating method, extrusion laminating method, etc., a commercially available adhesive may be used. Examples thereof include epoxy-based, polyester-based, polyethyleneimine-based, polybutadiene-based, water-based urethane-based, isocyanate-based, organic titanium-based, starch-based water-soluble adhesives, and water-based adhesives such as vinyl acetate emulsions. As a method of applying the adhesive for forming the sealant layer, a known application method can be used, for example, a roll coater, a reverse roll coater, a gravure coater, a micro gravure coater, a knife coater, a bar coater, and a wire bar coater. , Die coater, dip coater and the like can be used. The thickness of the adhesive is not particularly limited, but is preferably in the range of 0.001 to 10 μm, and particularly preferably in the range of 0.01 to 5 μm.

The light-shielding printed matter of the present invention is used for packaging, food preservation, retort, microwave oven, agriculture, civil engineering, fishery, automobile interior / exterior, ship, daily necessities, building material interior / exterior, and housing equipment. , Medical / medical equipment use, pharmaceutical use, home appliance use, furniture use, stationery / office supplies use, sales promotion use, commercial use, electrical and electronic industrial use, industrial material use, etc. Above all, it is more preferable to be used for packaging.

The method for producing a light-shielding printed matter of the present invention includes a step of preparing a base material layer, a white ink layer having a thickness of 0.5 to 10 μm on at least one of the base material layers, and a thickness of 0.5 to 5 μm. A white ink composition used for the white ink layer and a curing agent solution (d1) used together with the white ink composition, which comprises a gravure printing step of creating a light-shielding layer including both of the gray ink layers of the above. A step of preparing a white ink set containing the above, and a step of preparing a gray ink set containing the gray ink composition used for the gray ink layer and the curing agent solution (d2) used together with the gray ink composition. It includes the white ink set has the following conditions (a) to (c), the a Turkey gray ink set having a following conditions (d) - (g) are preferable.
(A) The white ink composition contains titanium dioxide (a1), a vinyl chloride / vinyl acetate copolymer resin (b1), and a polyurethane resin (b2).
(A) The solid content weight ratio of the resin solid content (B1) obtained by combining titanium dioxide (a1), vinyl chloride / vinyl acetate copolymer resin (b1), and polyurethane resin (b2) is (a1). ) / (B1) = 80/20 to 90/10.
(C) The solid content weight ratio of the resin solid content (B1) and the isocyanate compound (D1) in the curing agent solution (d1) is (B1) / (D1) = 40/60 to 95/5. ..
(D) The gray ink composition contains titanium dioxide (a2), carbon black (a3), a vinyl chloride / vinyl acetate copolymer resin (b3), and a polyurethane resin (b4).
(E) The solid content weight ratio of titanium dioxide (a2) and carbon black (a3) is (a2) / (a3) = 70/30 to 99.5 / 0.5.
(F) The pigment solid content (A), which is a combination of titanium dioxide (a2) and carbon black (a3), the vinyl chloride / vinyl acetate copolymer resin (b3), and the polyurethane resin (b4) are combined. The solid content weight ratio with the resin solid content (B2) is (A) / (B2) = 80/20 to 90/10.
(G) The solid content weight ratio of the resin solid content (B2) and the isocyanate compound (D2) in the curing agent solution (d2) is (B2) / (D2) = 40/60 to 95/5. ..

The film thickness of the white ink layer is preferably 0.5 to 10 μm, more preferably 0.8 to 8 μm. If the film thickness is smaller than 0.5 μm, the whiteness may be inferior. If the film thickness is larger than 10 μm, the blocking resistance, adhesion, and lamination strength may be inferior. By including the white ink layer, the effect of concealing the gray ink layer is exhibited and the whiteness is improved.

The thickness of the gray ink layer is preferably 0.5 to 5 μm, more preferably 0.8 to 3 μm. If the film thickness is smaller than 0.5 μm, the light-shielding property may be inferior. If the film thickness is larger than 5 μm, the whiteness, blocking resistance, adhesion, and lamination strength may be inferior. By including the gray ink layer, a light-shielding effect is exhibited by a synergistic effect with the white ink layer, and the light-shielding property is improved.

The white ink set preferably has the following conditions (a) to (c).
(A) The white ink composition contains titanium dioxide (a1), a vinyl chloride / vinyl acetate copolymer resin (b1), and a polyurethane resin (b2).
(A) The solid content weight ratio of the resin solid content (B1) obtained by combining titanium dioxide (a1), vinyl chloride / vinyl acetate copolymer resin (b1), and polyurethane resin (b2) is (a1). ) / (B1) = 80/20 to 90/10.
(C) The solid content weight ratio of the resin solid content (B1) and the isocyanate compound (D1) in the curing agent solution (d1) is (B1) / (D1) = 40/60 to 95/5. ..

The solid content weight ratio of the titanium dioxide (a1), the vinyl chloride / vinyl acetate copolymer resin (b1), and the resin solid content (B1) obtained by combining the polyurethane resin (b2) is (a1). ) / (B1) = 80/20 to 90/10, more preferably 82/28 to 88/12. If the ratio of titanium dioxide (a1) is less than 80, the whiteness may be inferior, and if it is more than 90, the lamination strength may be inferior.

The solid content weight ratio of the resin solid content (B1) and the isocyanate compound (D1) in the curing agent solution (d1) is (B1) / (D1) = 40/60 to 95/5. It is preferably 50/50 to 85/15. If the ratio of the resin solid content (B1) is less than 40, the blocking resistance may be inferior, and if it is more than 95, the lamination strength may be inferior.

The gray ink set preferably has the following conditions (d) to (g).
(D) The gray ink composition contains titanium dioxide (a2), carbon black (a3), a vinyl chloride / vinyl acetate copolymer resin (b3), and a polyurethane resin (b4).
(E) The solid content weight ratio of titanium dioxide (a2) and carbon black (a3) is (a2) / (a3) = 70/30 to 99.5 / 0.5.
(F) The pigment solid content (A), which is a combination of titanium dioxide (a2) and carbon black (a3), the vinyl chloride / vinyl acetate copolymer resin (b3), and the polyurethane resin (b4) are combined. The solid content weight ratio with the resin solid content (B2) is (A) / (B2) = 80/20 to 90/10.
(G) The solid content weight ratio of the resin solid content (B2) and the isocyanate compound (D2) in the curing agent solution (d2) is (B2) / (D2) = 40/60 to 95/5. ..

The solid content weight ratio of the titanium dioxide (a2) and the carbon black (a3) is preferably (a2) / (a3) = 70/30 to 99.5 / 0.5, and is 80 /. It is preferably 20 to 99/1. If the ratio of the carbon black (a3) is larger than 30, the whiteness may be inferior, and if it is less than 0.5, the light-shielding property may be inferior.

The pigment solid content (A), which is a combination of the titanium dioxide (a2) and the carbon black (a3), the vinyl chloride / vinyl acetate copolymer resin (b3), and the polyurethane resin (b4) are combined. It is preferable that the solid content weight ratio with the resin solid content (B2) is (A) / (B2) = 80/20 to 90/10. If the ratio of the pigment solid content (A) is less than 80, the whiteness may be inferior, and if it is more than 90, the lamination strength may be inferior.

The solid content weight ratio of the resin solid content (B2) and the isocyanate compound (D2) in the curing agent solution (d2) is (B2) / (D2) = 40/60 to 95/5. It is preferably 50/50 to 85/15. If the ratio of the resin solid content (B2) is less than 40, the blocking resistance may be inferior, and if it is more than 95, the lamination strength may be inferior.

In the method for producing a light-shielding printed matter, a light-shielding layer including a white ink layer obtained by printing the white ink set and a gray ink layer obtained by printing the gray ink set may be created. A gravure printing step of creating another printing layer formed by printing another gravure ink composition may be included, and it is more preferable that the printing is performed by a gravure printing step using a multicolor gravure printing machine.
In addition to the light-shielding layer, a step of forming an intermediate layer for imparting or strengthening performance such as rigidity, waist, gas barrier property, aroma retention property, moisture resistance property, pinhole resistance property, dead hole property, and linear cut property is performed. It may be included.

The method for producing a laminate of the present invention includes a step of preparing a base material layer, a white ink layer having a thickness of 0.5 to 10 μm on at least one of the base material layers, and a thickness of 0.5 to 5 μm. It may include a gravure printing step of creating a light-shielding layer including both of the gray ink layers of the above, and a laminating step of creating a sealant layer or a coating step of creating a seal layer.
Examples of the step of forming the sealant layer include a step of laminating a laminate having heat-sealing property, a known sealant film, and a resin coating by extrusion laminating processing, and a coating step of forming the sealant layer. May be a process by coating a heat sealant or a hot melt agent.

The packaging bag of the present invention is a packaging bag that requires a base material layer, a light-shielding layer including both a white ink layer and a gray ink layer, and a sealant layer or a seal layer in this order from the outer layer. It is preferable that the white ink set is formed and the gray ink layer is formed by the gray ink set.

The packaging bag may be in any of well-known forms such as a two-sided seal, a three-sided seal, a four-sided seal, a pillow seal, a standing pouch, an envelope sticker, a gusset, and a fusing seal.

The lid material of the present invention is a lid material that requires a base material layer, a light-shielding layer including both a white ink layer and a gray ink layer, and a sealant layer or a seal layer in this order from the outer layer. It is preferable that the gray ink layer is formed by the white ink set and the gray ink layer is formed by the gray ink set. The form of the lid material may be any of well-known forms such as a cover, a lid, and a cap.

Further, it is preferable that the container is in close contact with the container to form a closed container. Adhesion to the container may be carried out manually, or a machine such as an automatic sealing device may be used. These may be appropriately selected depending on the type, form and size, quantity, sealed container, equipment, environment, etc. of the food, and may be attached or adhered with a heat seal (heat pressure seal), a surface seal, an adhesive, or the like. It may be done by a method using such as.
It is more preferable that the container is a bottomed tubular container. In this case, the lid material preferably covers the opening of the bottomed tubular container and is hermetically sealed, and more preferably hermetically sealed by heat sealing.
Examples of the resin used for the container include thermoplastic resins such as polyethylene-based, polypropylene-based, polyethylene terephthalate, polyvinyl chloride, polystyrene, and polyacrylonitrile.

The label of the present invention is a label that requires a base material layer, a light-shielding layer including both a white ink layer and a gray ink layer, and a sealant layer or a seal layer, in which the white ink layer is the white ink set. It is preferable that the gray ink layer is formed and the gray ink layer is formed by the gray ink set.
Further, a label can be obtained by forming an adhesive layer or an adhesive layer on the plastic base film on the other surface on which the light-shielding layer is formed or another base material, and further forming a release layer. As long as the adhesive layer or adhesive layer adheres to the release layer with a plastic base film or other base material such as a rubber adhesive material or an acrylic resin adhesive material, and the release layer can be easily peeled off. Either may be used. The release layer may be a polyethylene film, a polyester film, or paper (release paper).

The white ink composition and the gray ink composition can be produced by a known method by uniformly dissolving or dispersing titanium dioxide, carbon black, a thermoplastic resin, a coloring material, various additives and the like in a solvent. Dissolving or dispersing can be done with various stirrers or dispersions such as dissolvers, roll mills, ball mills, bead mills, sand mills, attritors, paint shakers, agitators, henshell mixers, colloid mills, pearl mills, ultrasonic homogenizers, wet jet mills, kneaders, homomixers, etc. You can use the machine. These devices may be used alone or in combination of two or more. If the ink composition contains air bubbles or coarse particles, it is preferable to remove them using a known filter, centrifuge, or the like in order to deteriorate printability and print quality.

The viscosity of each of the ink compositions is not particularly limited as long as it does not interfere with printing. Considering the manufacturing suitability and handling of the ink used in gravure printing, it is preferably 10 to 1,000 mPa · s at 25 ° C. If it is less than 10 mPa · s, the viscosity is too low and the pigment tends to settle, and if it is larger than 1,000 mPa · s, the fluidity is poor and the ink production is hindered or it is difficult to fill the container. It becomes. In this case, the measurement can be performed using a commercially available viscometer such as a Brookfield type viscometer or a cone plate type viscometer.

The white ink composition and the gray ink composition are preferably used in gravure printing and can be coated as they are, but depending on the coating conditions and the coating effect, Zahn Cup # 3 Co., Ltd. is diluted. It can be adjusted to a desired viscosity and used by diluting it with a diluting solvent. The viscosity in this case is preferably 10 to 40 seconds at 25 ° C. If it is less than 10 seconds, it is easy to swim, and if it is longer than 40 seconds, the transferability at the time of printing is deteriorated.

The diluting solvent may be any one as long as it can be used by adjusting the viscosity of the ink composition, and examples thereof include organic solvents and water, and commercially available ones can also be used, and there is no particular limitation. Commercially available products include WA735 solvent (alcohol-based solvent), TA52 solvent (alcohol-based solvent), PU533 solvent (toluene-containing solvent), PU515 solvent (non-toluene solvent), SL9155 solvent (non-toluene solvent), CN104 solvent. (Non-toluene solvent), AC372 solvent (non-toluene solvent), PP575 solvent (toluene-containing solvent), SL9164 solvent (non-ketone solvent), SL9170 solvent (non-ketone solvent) (Made) and so on.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In addition, the part in an Example and a comparative example represents a mass part, and% represents a mass%.

[Making white ink]
White ink set W1 (Manufacturing example 1)
Titanium dioxide (JR-805, D50 average particle size 0.29 μm, manufactured by Teika Co., Ltd.) 45 parts, polyurethane resin PU1 (solid content 30%, manufactured by Tokyo Ink Co., Ltd.) 15 parts, hydroxyl group-containing vinyl chloride / vinyl acetate Copolymer resin CL1 (solvine TAO, solid content 20%, manufactured by Nisshin Kagaku Kogyo Co., Ltd.) 15 parts, propyl acetate 20 parts, isopropyl alcohol 5 parts, ceramic beads 100 parts are charged and used in a paint shaker for 1 hour. After dispersing to obtain white ink w1, 10 parts of a curing agent solution (LG curing agent C, solid content 50%, manufactured by Tokyo Ink Co., Ltd.) was dispersed with a paint shaker for 10 minutes to obtain white. 110 copies of ink set W1 were obtained. Similarly, each white ink set of Production Examples 2 to 11 was prepared according to the formulations shown in Tables 1 and 2.

[Making gray ink]
Gray ink set G1 (Manufacturing example 12)
Titanium dioxide (JR-805, D50 average particle size 0.29 μm, manufactured by Teika Co., Ltd.) 45 parts, carbon black (MA11, D50 average particle size 29 nm, manufactured by Mitsubishi Chemical Co., Ltd.) 1 part, polyurethane resin PU1 (solid) Min 30%, manufactured by Tokyo Ink Co., Ltd. 15 parts, hydroxyl group-containing vinyl chloride / vinyl acetate copolymer resin CL1 (solvine TAO, solid content 20%, manufactured by Nissin Chemical Industry Co., Ltd.) 15 parts, propyl acetate 19 A part, 5 parts of isopropyl alcohol, and 100 parts of ceramic beads were prepared and dispersed in a paint shaker for 1 hour to obtain gray ink g1, and then a curing agent solution (LG curing agent C, solid content 50%, Tokyo ink (Tokyo ink). (Manufactured by Co., Ltd.) 8 parts were dispersed in a paint shaker for 10 minutes to obtain 108 parts of gray ink set G1. Similarly, each gray ink of Production Examples 12 to 26 was prepared according to the formulations shown in Tables 3 and 4.

[Making light-shielded printed matter]
A 150L 40μm laser plate is attached to the gravure calibrator GRAVO-PROOF (product number: CM-W, manufactured by Nissho Gravure Co., Ltd.), and the white ink W1 of Production Example 1 is diluted solvent (MEK 40 parts, propyl acetate 40 parts, isopropyl alcohol 20). Part), Zahn Cup No. After adjusting the viscosity to 17 seconds in 3, print on a PET film (E-5102, abbreviation: PET, manufactured by Toyobo Co., Ltd.) with a thickness of 2.0 μm, and then replace with a 150 L30 μm laser plate and white. On the ink printing surface, gray ink G1 was mixed with the same diluting solvent to make Zahn Cup No. After adjusting the viscosity to 17 seconds in No. 3, printing was performed with a film thickness of 1.3 μm to obtain a light-shielded printed matter PR1. Similarly, as shown in Tables 5 and 6, the white ink, the gray ink, and the film thickness were changed to obtain light-shielding printed matter PR2 to PR19, PR25, PR27, PR29, and PR35, respectively.

Further, the base material was replaced with Pyrene P-2161 (abbreviation: OPP, manufactured by Toyobo Co., Ltd.) of a stretched polypropylene film having a thickness of 20 μm, and white ink W1 and gray ink G1 were printed to obtain a light-shielding printed matter PR20. Similarly, as shown in Tables 5 and 6, the white ink, the gray ink, and the film thickness were changed to obtain light-shielding printed matter PR26, PR28, and PR31, respectively.

Further, the base material was replaced with Bonil RX (abbreviation: nylon, manufactured by Kojin Film & Chemicals Co., Ltd.), which is a nylon film having a thickness of 15 μm, and white ink W1 and light-shielding ink G4 were printed to obtain a light-shielding printed matter PR21. .. Similarly, as shown in Tables 5 and 6, the white ink, the gray ink, and the film thickness were changed to obtain light-shielding printed matter PR23, PR30, PR32, and PR34, respectively.

Further, the base material is replaced with Barrierlocks 1011SBR2 (abbreviation: transparent vapor-deposited PET, manufactured by Toray Film Processing Co., Ltd.), which is a transparent vapor-deposited PET film having a thickness of 12 μm, and white ink W1 and light-shielding ink G4 are printed to print the light-shielding printed matter PR22. Got Similarly, as shown in Tables 5 and 6, the white ink, the gray ink, and the film thickness were changed to obtain light-shielding printed matter PR24 and PR33, respectively.

The light-shielding printed matter of Examples 1 to 22 and Comparative Examples 1 to 13 were evaluated for whiteness, light-shielding property, adhesion, and blocking resistance, and are shown in Tables 5 and 6.

<Whiteness>
Spread black paper, place the printed matter on it so that the white ink layer side is on the upper side, and use a spectrophotometric densitometer (X-Rite extract, manufactured by X-Rite) for 5 printed surfaces of the printed matter. , Brightness (L ^* ) was measured and the average value was evaluated. It was judged that the larger the brightness (L ^* ) value, the better the whiteness. The whiteness was evaluated on a two-point scale: ◯: the brightness (L ^* ) value was 75 or more, and ×: the brightness (L ^{*) value was less than 75.}

<Light-shielding property>
Prepare three sample pieces obtained by cutting the printed matter into a size of 2 cm x 3 cm, and use a haze meter (HAZE-GARD II, Toyo Seiki Seisakusho Co., Ltd.) based on JIS K 7361-1.1997. The total light transmittance was measured and the average value was evaluated. It was judged that the lower the value of the total light transmittance, the better the light-shielding property. The light-shielding property was evaluated on a two-point scale of: ◯: total light transmittance value was less than 2%, and ×: total light transmittance value was 2% or more.

<Adhesion>
Adhesive tape (18 mm, manufactured by Nichiban Co., Ltd.) was attached to the printed surface of the light-shielding printed matter and rapidly peeled off at an angle of 90 degrees. The peeled state of the peeled printed surface was visually observed and the adhesion was evaluated. .. Those with no peeling on the printed surface were judged to have good adhesion. The adhesion was evaluated on a two-point scale: ◯: not peeling at all, ×: peeling even a little.

<Blocking resistance>
Two light-shielding printed matter is cut into a size of 3 cm × 3 cm, the printed surface and the non-printed surface are overlapped, and ^{after applying a load of 5 N / cm 2} at 50 ° C. for 24 hours, the printed surface and the non-printed surface are applied. The peeling resistance when the overlapped portion was peeled off was measured, and the state of the surface of the printed surface after the peeling was observed. The evaluation was made in two stages: ◯: no ink peeling and no peeling resistance, and ×: ink peeling was observed and peeling resistance was present.

[Creation of laminate]
Takelac A-525 / Takenate A-52 (abbreviation: DL, manufactured by Mitsui Chemicals, Inc.) is coated on the light-shielding layer of the light-shielding printed matter PR1 with A-Bar OSP-10 (manufactured by OSG System Products Co., Ltd.). Then, emblem ONMB-RT (abbreviation: NY, manufactured by Unitika Co., Ltd.), which is a nylon film with a thickness of 15 μm, is bonded, and further, CPP 60 μm Trefan NO ZK93KM (abbreviation: CPP, manufactured by Toray Film Processing Co., Ltd.) is attached. After bonding, aging was carried out at 50 ° C. for 72 hours to obtain a laminated product LAM1 of PR1 / DL / NY / DL / CPP.
Similarly, in place of the light-shielded printed matter PR2 to PR19, PR25, PR27, PR29 and PR35, laminates LAM2 to LAM19, LAM25, LAM27, LAM29 and LAM35 were obtained, respectively.

Takelac A-969V / A-5 (abbreviation: DL, manufactured by Mitsui Chemicals, Inc.) is coated on the light-shielding layer of the light-shielding printed matter PR20 with A-Bar OSP-10 (manufactured by OSG System Products Co., Ltd.). , TUX-HC (abbreviation: LLDPE, manufactured by Mitsui Chemicals Tohcello Co., Ltd.), which is a linear low-density polyethylene film with a thickness of 60 μm, is affixed, and then aged at 40 ° C. for 24 hours to PR20 / DL / LLDPE. LAM20 was obtained.
Similarly, in place of the light-shielded printed matter PR26, PR28 and PR31, laminated bodies LAM26, LAM28 and LAM31 were obtained, respectively.

Takelac A-620 / Takenate A-65 (abbreviation: DL, manufactured by Mitsui Chemicals, Inc.) is coated on the light-shielding layer of the light-shielding printed matter PR21 with A-Bar OSP-10 (manufactured by OSG System Products Co., Ltd.). After laminating CMPS008C (abbreviation: EP film, manufactured by Mitsui Chemicals Tohcello Co., Ltd.), which is a co-pressing film with a thickness of 30 μm, aging is performed at 35 ° C. for 48 hours to PR21 / DL / nylon / DL / CPP. LAM21 was obtained.
Similarly, in place of the light-shielded printed matter PR23, PR30, PR32 and PR34, laminates LAM23, LAM30, LAM32 and LAM34 were obtained, respectively.

Takelac A-620 / Takenate A-65 (abbreviation: DL, manufactured by Mitsui Chemicals, Inc.) is coated on the light-shielding layer of the light-shielding printed matter PR22 with A-Bar OSP-10 (manufactured by OSG System Products Co., Ltd.). After laminating CMPS008C (abbreviation: EP film, manufactured by Mitsui Chemicals Tohcello Co., Ltd.), which is a co-pressed film with a thickness of 30 μm, aging was performed at 35 ° C. for 48 hours to form a laminate of PR24 / DL / EP film. LAM22 was obtained.
Similarly, in place of the light-shielded printed matter PR24 and PR33, laminated bodies LAM24 and LAM33 were obtained, respectively.

<Light shielding after laminating>
Prepare three sample pieces obtained by cutting the laminate into a size of 2 cm x 3 cm, and use a haze meter (HAZE-GARD II, Toyo Seiki Seisakusho Co., Ltd.) based on JIS K 7361-1.1997, respectively. The total light transmittance of was measured and the average value was evaluated. It was judged that the lower the value of the total light transmittance, the better the light-shielding property. The light-shielding property was evaluated on a two-point scale of: ◯: total light transmittance value was less than 3%, and ×: total light transmittance value was 3% or more.

According to Tables 5 and 6, it is clear that the light-shielding printed matter of Examples 1 to 22 is excellent in whiteness, light-shielding property, adhesion, and blocking resistance. In addition, it is clear that the light-shielding property of the laminated body hardly deteriorates even after laminating.
A light-shielding printed matter (PR35) in which a white light-shielding layer and a gray-colored layer similar to Patent Document 3 are laminated is clearly inferior in whiteness and cosmeticity, and is also inferior in light-shielding property. Further, it is clear that the laminated body (LAM38) is also inferior in light-shielding property when laminated.
It is clear that the light-shielding printed matter of Comparative Examples 1 to 12 is inferior in any of whiteness, light-shielding property, adhesion, and blocking resistance.

Claims (7)

A light-shielding layer containing both a white ink layer laminated with a film thickness of 0.5 to 10 μm and a gray ink layer laminated with a film thickness of 0.5 to 5 μm on at least one surface of the base material layer. the formed by laminating,
The white ink layer is a layer composed of a white ink set containing a white ink composition and a curing agent solution (d1) used together with the white ink composition.
The gray ink layer is a layer composed of a gray ink set containing a gray ink composition and a curing agent solution (d2) used together with the gray ink composition.
The white ink set has the following conditions (a) to (c).
Shielding prints the gray ink set is characterized and Turkey that having a following conditions (d) - (g).
(A) The white ink composition contains titanium dioxide (a1), a vinyl chloride / vinyl acetate copolymer resin (b1), and a polyurethane resin (b2).
(A) The solid content weight ratio of the resin solid content (B1) obtained by combining titanium dioxide (a1), vinyl chloride / vinyl acetate copolymer resin (b1), and polyurethane resin (b2) is (a1). ) / (B1) = 80/20 to 90/10.
(C) The solid content weight ratio of the resin solid content (B1) and the isocyanate compound (D1) in the curing agent solution (d1) is (B1) / (D1) = 40/60 to 95/5. ..
(D) The gray ink composition contains titanium dioxide (a2), carbon black (a3), a vinyl chloride / vinyl acetate copolymer resin (b3), and a polyurethane resin (b4).
(E) The solid content weight ratio of titanium dioxide (a2) and carbon black (a3) is (a2) / (a3) = 70/30 to 99.5 / 0.5.
(F) The pigment solid content (A), which is a combination of titanium dioxide (a2) and carbon black (a3), the vinyl chloride / vinyl acetate copolymer resin (b3), and the polyurethane resin (b4) are combined. The solid content weight ratio with the resin solid content (B2) is (A) / (B2) = 80/20 to 90/10.
(G) The solid content weight ratio of the resin solid content (B2) and the isocyanate compound (D2) in the curing agent solution (d2) is (B2) / (D2) = 40/60 to 95/5. .. A laminate characterized by laminating a sealant layer or a seal layer on the light-shielding layer of the light-shielding printed matter according to claim 1. The process of preparing the base layer and
A gravure printing step of creating a light-shielding layer containing both a white ink layer having a film thickness of 0.5 to 10 μm and a gray ink layer having a film thickness of 0.5 to 5 μm on at least one of the substrate layers. Including,
A step of preparing a white ink set containing a white ink composition used for the white ink layer and a curing agent solution (d1) used together with the white ink composition, and a step of preparing the white ink set.
A step of preparing a gray ink set containing a gray ink composition used for the gray ink layer and a curing agent solution (d2) used together with the gray ink composition is included.
The white ink set has the following conditions (a) to (c).
Method for producing a light-shielding printed matter the gray ink set is characterized and Turkey that having a following conditions (d) - (g).
(A) The white ink composition contains titanium dioxide (a1), a vinyl chloride / vinyl acetate copolymer resin (b1), and a polyurethane resin (b2).
(A) The solid content weight ratio of the resin solid content (B1) obtained by combining titanium dioxide (a1), vinyl chloride / vinyl acetate copolymer resin (b1), and polyurethane resin (b2) is (a1). ) / (B1) = 80/20 to 90/10.
(C) The solid content weight ratio of the resin solid content (B1) and the isocyanate compound (D1) in the curing agent solution (d1) is (B1) / (D1) = 40/60 to 95/5. ..
(D) The gray ink composition contains titanium dioxide (a2), carbon black (a3), a vinyl chloride / vinyl acetate copolymer resin (b3), and a polyurethane resin (b4).
(E) The solid content weight ratio of titanium dioxide (a2) and carbon black (a3) is (a2) / (a3) = 70/30 to 99.5 / 0.5.
(F) The pigment solid content (A), which is a combination of titanium dioxide (a2) and carbon black (a3), the vinyl chloride / vinyl acetate copolymer resin (b3), and the polyurethane resin (b4) are combined. The solid content weight ratio with the resin solid content (B2) is (A) / (B2) = 80/20 to 90/10.
(G) The solid content weight ratio of the resin solid content (B2) and the isocyanate compound (D2) in the curing agent solution (d2) is (B2) / (D2) = 40/60 to 95/5. .. The process of preparing the base layer and
A gravure printing step of creating a light-shielding layer containing both a white ink layer having a film thickness of 0.5 to 10 μm and a gray ink layer having a film thickness of 0.5 to 5 μm on at least one of the substrate layers.
Including a laminating process to create a sealant layer or a coating process to create a sealant layer,
A step of preparing a white ink set containing a white ink composition used for the white ink layer and a curing agent solution (d1) used together with the white ink composition, and a step of preparing the white ink set.
A step of preparing a gray ink set containing a gray ink composition used for the gray ink layer and a curing agent solution (d2) used together with the gray ink composition is included.
The white ink set has the following conditions (a) to (c).
Method for producing a laminate wherein the gray ink set is characterized and Turkey that having a following conditions (d) - (g).
(A) The white ink composition contains titanium dioxide (a1), a vinyl chloride / vinyl acetate copolymer resin (b1), and a polyurethane resin (b2).
(A) The solid content weight ratio of the resin solid content (B1) obtained by combining titanium dioxide (a1), vinyl chloride / vinyl acetate copolymer resin (b1), and polyurethane resin (b2) is (a1). ) / (B1) = 80/20 to 90/10.
(C) The solid content weight ratio of the resin solid content (B1) and the isocyanate compound (D1) in the curing agent solution (d1) is (B1) / (D1) = 40/60 to 95/5. ..
(D) The gray ink composition contains titanium dioxide (a2), carbon black (a3), a vinyl chloride / vinyl acetate copolymer resin (b3), and a polyurethane resin (b4).
(E) The solid content weight ratio of titanium dioxide (a2) and carbon black (a3) is (a2) / (a3) = 70/30 to 99.5 / 0.5.
(F) The pigment solid content (A), which is a combination of titanium dioxide (a2) and carbon black (a3), the vinyl chloride / vinyl acetate copolymer resin (b3), and the polyurethane resin (b4) are combined. The solid content weight ratio with the resin solid content (B2) is (A) / (B2) = 80/20 to 90/10.
(G) The solid content weight ratio of the resin solid content (B2) and the isocyanate compound (D2) in the curing agent solution (d2) is (B2) / (D2) = 40/60 to 95/5. .. The white according to claim 1 in a packaging bag that requires a base material layer, a light-shielding layer including both a white ink layer and a gray ink layer, and a sealant layer or a seal layer in this order from the outer layer. Formed with an ink set and
A packaging bag characterized in that the gray ink layer is formed by the gray ink set according to claim 1. The white ink layer according to claim 1 in a lid material that requires a base material layer, a light-shielding layer including both a white ink layer and a gray ink layer, and a sealant layer or a seal layer in this order from the outer layer. Formed with an ink set and
A lid material, wherein the gray ink layer is formed by the gray ink set according to claim 1. The white ink according to claim 1, wherein the label requires a base material layer, a light-shielding layer including both a white ink layer and a gray ink layer, and a sealant layer or a seal layer in this order from the outer layer. Formed as a set and
A label characterized in that the gray ink layer is formed by the gray ink set according to claim 1.