JP6894560B1 - Light-shielding gravure ink composition, light-shielding printed matter, laminate, method of manufacturing light-shielding printed matter, manufacturing method of laminate, 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 gravure ink composition having high adhesion to a substrate. An acid modification containing an untreated aluminum pigment (A) having an average particle size of 10 μm or less and a thermoplastic resin (B1), wherein the thermoplastic resin (B1) has an acid value of 2 mgKOH / g or more. A light-shielding gravure ink composition comprising a vinyl chloride / vinyl acetate copolymer resin (b1) and a polyurethane resin (b2). [Selection diagram] None

Description

The present invention relates to a light-shielding gravure ink composition, 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 packaged products to be packaged are required to have a light-shielding property. 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 addition, when laminated, the light-shielding property tends to decrease.

Patent Document 1 is characterized in that at least a white first printing layer and a brown or silver second printing layer are provided on one side of a plastic film, and a sealant layer is provided via a colored resin layer. The packaging material is listed.

In Patent Document 2, 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 Patent Document 1 and Patent Document 2, since sufficient light-shielding property cannot be obtained with a single-layer printing ink layer, it is necessary to laminate printing ink layers having different hues, the process is complicated, and cosmeticity (cosmeticity ( Whiteness) is also impaired. Therefore, a single-layer printing ink layer or a colored adhesive layer has been proposed to ensure light-shielding properties.

Patent Document 3 includes a laminated material in which at least a base film layer and a heat-sealing resin layer are laminated, and further, a light-shielding film provided with a continuous printing film using printing ink is provided on any of the layers constituting the laminated material. Sexual laminates are listed.

Patent Document 4 describes a laminated film having a gas barrier property having a structure including at least a transparent vapor-deposited film layer, a printing substrate layer provided with a colored layer made of printing ink on the surface, and a sealant film layer. ..

Patent Document 5 describes a packaging material composed of a laminated body having at least a sealant layer laminated on a base film layer via an adhesive layer, and a colorant is blended in the adhesive layer. The packaging materials used are listed.

Since Patent Document 3 and Patent Document 4 form a colored printing ink layer, the appearance is restricted and the cosmetic property (whiteness) is impaired. Further, in Patent Document 5, since the printing ink layer and the coloring resin layer are not provided, the process can be simplified and the cost can be reduced, but a step of mixing the coloring agent with the adhesive is required separately. Further, in the actually disclosed example (Example), the problem is solved by forming a white coating film layer (that is, a white printing ink layer), and a single layer to four layers of white are used. A printing ink layer is essential. Since the printing ink layer has a colored adhesive layer on the printing ink layer, the appearance is also restricted and the cosmetic property (whiteness) is impaired.

Further, in Patent Documents 1 to 5, it cannot be said that the light-shielding property is sufficient, and the cosmetic property may be inferior. Further, the adhesion to the printing ink layer has not been evaluated and may be inferior. In addition, when laminated, the light-shielding property may deteriorate.

Japanese Unexamined Patent Publication No. 9-314719 Japanese Unexamined Patent Publication No. 2017-202613 Japanese Unexamined Patent Publication No. 10-305513 Japanese Unexamined Patent Publication No. 2003-311865 Japanese Unexamined Patent Publication No. 2004-189325

Therefore, an object of the present invention is to provide a light-shielding gravure ink composition which can provide a printed matter having high light-shielding property and whiteness and has high adhesion to a substrate without using an aluminum foil or an aluminum-deposited film. And.

The present inventors include an untreated aluminum pigment (A) having an average particle size of 10 μm or less and a thermoplastic resin (B1), and the thermoplastic resin (B1) has an acid value of 2 mgKOH / g or more. The present invention has been found that the above object can be achieved by the light-shielding gravure ink composition characterized by containing an acid-modified vinyl chloride / vinyl acetate copolymer resin (b1) and a polyurethane resin (b2). It came to be completed.

That is, the present invention
(1) An ink layer made of a light-shielding gravure ink composition is laminated on at least one surface of a plastic base film with a thickness of 0.3 to 5 μm, and a white ink layer made of a white ink composition is laminated on the ink layer. A printed layer having a thickness of 0.5 to 10 μm and a sealant layer or a sealing layer laminated on the printed layer.
The light-shielding gravure ink composition contains an oleic acid-treated aluminum pigment (A) having an average particle size of 10 μm or less by an atomizing method, and a thermoplastic resin (B1).
The thermoplastic resin (B1) is an acid value of 2 mg KOH / g or more in which a carboxyl group-modified vinyl chloride-vinyl acetate copolymer resin (b1), viewed contains a polyurethane resin (b2),
The white ink composition contains titanium dioxide (C) and a thermoplastic resin (B2), and the thermoplastic resin (B2) contains a vinyl chloride / vinyl acetate copolymer resin (b3) and a polyurethane resin (b4). , A laminate characterized in that the solid content weight ratio of the titanium dioxide (C) to the thermoplastic resin (B2) is (C) / (B2) = 60/40 to 90/10 .
(2) An ink composed of a light-shielding gravure ink composition is laminated on at least one surface of a plastic base film with a white ink layer made of a white ink composition having a thickness of 0.5 to 10 μm. It is a laminate formed by laminating a printing layer having a thickness of 0.3 to 5 μm and a sealant layer or a sealing layer on the printing layer.
The light-shielding gravure ink composition contains an oleic acid-treated aluminum pigment (A) having an average particle size of 10 μm or less by an atomizing method, and a thermoplastic resin (B1).
The thermoplastic resin (B1) contains a carboxyl group-modified vinyl chloride / vinyl acetate copolymer resin (b1) having an acid value of 2 mgKOH / g or more and a polyurethane resin (b2).
The white ink composition contains titanium dioxide (C) and a thermoplastic resin (B2), and the thermoplastic resin (B2) contains a vinyl chloride / vinyl acetate copolymer resin (b3) and a polyurethane resin (b4). , A laminate characterized in that the solid content weight ratio of the titanium dioxide (C) to the thermoplastic resin (B2) is (C) / (B2) = 60/40 to 90/10 .
(3) The process of preparing the plastic base film and
An ink layer made of a light-shielding gravure ink composition is printed on at least one of the plastic base film with a thickness of 0.3 to 5 μm, and a white ink layer made of a white ink composition is printed on the ink layer with a thickness of 0.5 to 0.5. A gravure printing process that forms a printing layer by printing with a film thickness of 10 μm,
Further, it is a method for manufacturing a laminated body including a laminating step of creating a sealant layer on the printed layer or a coating step of creating a seal layer.
The light-shielding gravure ink composition contains an oleic acid-treated aluminum pigment (A) having an average particle size of 10 μm or less by an atomizing method, and a thermoplastic resin (B1).
The thermoplastic resin (B1) contains a carboxyl group-modified vinyl chloride / vinyl acetate copolymer resin (b1) having an acid value of 2 mgKOH / g or more and a polyurethane resin (b2).
The white ink composition contains titanium dioxide (C) and a thermoplastic resin (B2), and the thermoplastic resin (B2) contains a vinyl chloride / vinyl acetate copolymer resin (b3) and a polyurethane resin (b4). A method for producing a laminate, wherein the solid content weight ratio of the titanium dioxide (C) to the thermoplastic resin (B2) is (C) / (B2) = 60/40 to 90/10 .
(4) The process of preparing the plastic base film and
A white ink layer made of a white ink composition is printed on at least one of the plastic base film with a thickness of 0.5 to 10 μm, and an ink layer made of a light-shielding gravure ink composition is printed on the white ink layer. A gravure printing process that forms a printing layer by printing with a film thickness of 3 to 5 μm,
Further, it is a method for manufacturing a laminated body including a laminating step of creating a sealant layer on the printed layer or a coating step of creating a seal layer.
The light-shielding gravure ink composition contains an oleic acid-treated aluminum pigment (A) having an average particle size of 10 μm or less by an atomizing method, and a thermoplastic resin (B1).
The thermoplastic resin (B1) contains a carboxyl group-modified vinyl chloride / vinyl acetate copolymer resin (b1) having an acid value of 2 mgKOH / g or more and a polyurethane resin (b2).
The white ink composition contains titanium dioxide (C) and a thermoplastic resin (B2), and the thermoplastic resin (B2) contains a vinyl chloride / vinyl acetate copolymer resin (b3) and a polyurethane resin (b4). , solid content weight ratio of the titanium dioxide (C) and the thermoplastic resin (B2) the production of the laminate you wherein the Ru (C) / (B2) = 60 / 40~90 / 10 der One ,
(5) In a packaging bag that requires a plastic base film, a white ink layer, an ink layer, and a sealant layer or a seal layer in order from the outer layer.
The white ink layer has a film thickness of 0.5 to 10 μm and
The titanium dioxide (C) and the thermoplastic resin (B2) are contained, and the thermoplastic resin (B2) contains a vinyl chloride / vinyl acetate copolymer resin (b3) and a polyurethane resin (b4), and the titanium dioxide (C) is contained. And the thermoplastic resin (B2) are formed of a white ink composition having a solid content weight ratio of (C) / (B2) = 60/40 to 90/10.
The ink layer has a film thickness of 0.3 to 5 μm and
It contains an oleic acid-treated aluminum pigment (A) having an average particle size of 10 μm or less by an atomizing method, and a thermoplastic resin (B1).
The thermoplastic resin (B1) is a light-shielding gravure ink composition containing a carboxyl group-modified vinyl chloride / vinyl acetate copolymer resin (b1) having an acid value of 2 mgKOH / g or more and a polyurethane resin (b2). Packaging bag , characterized by being formed,
(6) In the lid material that requires the plastic base film, the white ink layer, the ink layer, and the sealant layer or the seal layer in this order from the outer layer.
The white ink layer has a film thickness of 0.5 to 10 μm and
The titanium dioxide (C) and the thermoplastic resin (B2) are contained, and the thermoplastic resin (B2) contains a vinyl chloride / vinyl acetate copolymer resin (b3) and a polyurethane resin (b4), and the titanium dioxide (C) is contained. And the thermoplastic resin (B2) are formed of a white ink composition having a solid content weight ratio of (C) / (B2) = 60/40 to 90/10.
The ink layer has a film thickness of 0.3 to 5 μm and
It contains an oleic acid-treated aluminum pigment (A) having an average particle size of 10 μm or less by an atomizing method, and a thermoplastic resin (B1).
The thermoplastic resin (B1) is a light-shielding gravure ink composition containing a carboxyl group-modified vinyl chloride / vinyl acetate copolymer resin (b1) having an acid value of 2 mgKOH / g or more and a polyurethane resin (b2). A lid material characterized by being formed ,
(7) In a label that requires a plastic base film, a white ink layer, an ink layer, and a sealant layer or a seal layer in order from the outer layer.
The white ink layer has a film thickness of 0.5 to 10 μm and
The titanium dioxide (C) and the thermoplastic resin (B2) are contained, and the thermoplastic resin (B2) contains a vinyl chloride / vinyl acetate copolymer resin (b3) and a polyurethane resin (b4), and the titanium dioxide (C) is contained. And the thermoplastic resin (B2) are formed of a white ink composition having a solid content weight ratio of (C) / (B2) = 60/40 to 90/10.
The ink layer has a film thickness of 0.3 to 5 μm and
It contains an oleic acid-treated aluminum pigment (A) having an average particle size of 10 μm or less by an atomizing method, and a thermoplastic resin (B1).
The thermoplastic resin (B1) is a light-shielding gravure ink composition containing a carboxyl group-modified vinyl chloride / vinyl acetate copolymer resin (b1) having an acid value of 2 mgKOH / g or more and a polyurethane resin (b2). Labels characterized by being formed ,
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 to provide a light-shielding gravure ink composition having high adhesion to a substrate.

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 gravure ink composition of the present invention (hereinafter, also simply referred to as “ink composition”) contains an untreated aluminum pigment (A) having an average particle size of 10 μm or less and a thermoplastic resin (B1).
The thermoplastic resin (B1) preferably contains an acid-modified vinyl chloride / vinyl acetate copolymer resin (b1) having an acid value of 2 mgKOH / g or more and a polyurethane resin (b2).

The untreated aluminum pigment (A) preferably has an average particle size of 10 μm or less. More preferably, the average particle size is 0.5 μm to 10 μm. If the average particle size exceeds 10 μm, the light-shielding property may be inferior. If it is smaller than 0.5 μm, the adhesion may be inferior. The particle size is the average particle size of the longest scale-shaped particle size, and is measured by a particle size distribution measuring device by light scattering or a method of directly observing with an electron microscope. The average particle size referred to here means the D50 particle size by the laser diffraction / scattering method.

Moreover, it is preferable that it is untreated. Unlike the aluminum paste in which the aluminum pigment is coated with an acrylic resin, the untreated form improves the affinity with the acid-modified vinyl chloride / vinyl acetate copolymer resin (b1) described later, and improves the adhesion. .. Further, since the resin coating treatment is not required, complicated steps can be omitted, which has a cost merit.

Further, the untreated aluminum pigment (A) preferably has an aspect ratio defined by [average particle size / average thickness] of 10 to 100, and more preferably 15 to 80. By setting the aspect ratio within the above range, the light-shielding property becomes good.

The untreated aluminum pigment (A) is preferably contained in the ink composition as a solid content in an amount of 1 to 95% by mass, more preferably 5 to 85% by mass. If the amount of the aluminum material is less than 1% by mass, the light-shielding property may be inferior, and if it exceeds 95% by mass, the adhesion may be inferior.

The thermoplastic resin (B1) preferably contains an acid-modified vinyl chloride / vinyl acetate copolymer resin (b1) having an acid value of 2 mgKOH / g or more and a polyurethane resin (b2).

The acid-modified vinyl chloride / vinyl acetate copolymer resin (b1) preferably has an acid value of 2 mgKOH / g or more, and more preferably in the range of 3 to 30 mgKOH / g. When it is within the above range, the adhesion is good.
The acid value is the number of mg of potassium hydroxide required to neutralize the acid group contained in 1 g of the resin, and is a value measured by JIS K0070.

The acid-modified vinyl chloride / vinyl acetate copolymer resin (b1) contains a vinyl chloride monomer, a vinyl acetate monomer, and a monomer having an unsaturated carbon-carbon double bond in one molecule and having an acidic functional group. The polymerization reaction is carried out, and the polymerization method can be produced by a conventionally known method, and the production method is not particularly limited, and any of solution polymerization, emulsion polymerization and suspension polymerization can be used. be able to. 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 carboxyl group-modified vinyl chloride / vinyl acetate copolymer resin (b1) is commercially available, and is commercially available. VINNOL H15 / 45M, VINNOL H30 / 48M (manufactured by Wacker Chemie), Solvine M5, Solvine M5R (Nisshin Kagaku). Examples include (manufactured by Kogyo Co., Ltd.) and Kanevinyl T5DA (manufactured by Kaneka Corporation).

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 antioxidants, light stabilizers, hydrolysis inhibitors, ultraviolet absorbers, metal deactivators, reaction retarders 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.

It is preferable that the acid-modified vinyl chloride / vinyl acetate copolymer resin (b1) and the polyurethane resin (b2) have a solid content weight ratio of (b1) / (b2) = 5/95 to 95/5. .. If the ratio of the acid-modified vinyl chloride / vinyl acetate copolymer resin (b1) is less than 5, the adhesion is lowered.

The thermoplastic resin (B1) may contain other resins. 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, non-acid-modified vinyl chloride-vinyl acetate copolymer, 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, polyether sulfone resin, polyether ketone resin, modified polyphenylene ether resin, polyphenylene sulfone resin, polyimide resin, polyamideimide resin, amorphous poly Arilate resin, polyether ether ketone resin, acrylic emulsion, urethane emulsion, polyvinyl alcohol resin, ethylene-vinyl alcohol resin, polylactic acid and the like are preferable. These resins may be one kind or two or more kinds.

In the light-shielding gravure ink composition of the present invention, the untreated aluminum pigment (A) and the thermoplastic resin (B1) have a solid content weight ratio of (A) / (B1) = 95/5 to 5/95. It is preferable that there is, and it is more preferable that (A) / (B1) = 85/15 to 15/80. If (A) is larger than 95, the adhesion is inferior because the resin content is small, and if it is smaller than 5, the light-shielding property is lowered because the pigment content is small.
The solid content in the ink composition is preferably in the range of 2 to 55% 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 55% by mass, the fluidity is poor and it becomes difficult to make ink.

In the light-shielding gravure ink composition of the present invention, 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 45 to 98% by mass. If it is less than 45% 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.

The ink composition contains 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, a tackifier, and the like. It 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.

In the light-shielding printed matter of the present invention, the light-shielding gravure ink composition may form a light-shielding printed layer formed by laminating an ink layer with a thickness of 0.3 to 5 μm on at least one surface of a plastic base film. preferable. The film thickness of the ink layer is more preferably 0.5 to 4 μm. If it is thinner than 0.3 μm, the light-shielding property is lowered. If it is thicker than 5 μm, the adhesion is poor.

The light-shielding printed matter of the present invention contains titanium dioxide (C) and a thermoplastic resin (B2) on the ink layer, and the thermoplastic resin (B2) is a vinyl chloride / vinyl acetate copolymer resin (b3) and polyurethane. From a white ink composition containing the resin (b4) and having a solid content weight ratio of the titanium dioxide (C) to the thermoplastic resin (B2) of (C) / (B2) = 60/40 to 90/10. It is preferable to form a light-shielding layer formed by laminating white ink layers having a thickness of 0.5 to 10 μm. By forming a white ink layer on the light-shielding layer, the whiteness is improved. By improving the whiteness, there is an effect that the visibility is improved. The film thickness of the white ink layer is more preferably 0.6 to 8 μm. If it is smaller than 0.5 μm, the whiteness is lowered. If it is larger than 10 μm, the adhesion is poor.

Further, the light-shielding printed matter of the present invention contains titanium dioxide (C) and a thermoplastic resin (B2) between the plastic base film and the ink layer, and the thermoplastic resin (B2) is vinyl chloride / vinyl acetate. It contains a copolymer resin (b3) and a polyurethane resin (b4), and the weight ratio of the titanium dioxide (C) to the thermoplastic resin (B2) is (C) / (B2) = 60/40 to 90/10. It is preferable to form a light-shielding layer formed by laminating a white ink layer made of the white ink composition having a thickness of 0.5 to 10 μm. Similar to the above, the whiteness is improved by forming the white ink layer on the light-shielding layer. Further, as a structure of the laminated body, another base material can be laminated between the base material plastic film and the ink layer via a dry laminate or the like.

The titanium dioxide (C) used in the white ink composition may be anatase type or rutile type. The average particle size is preferably 0.1 to 0.5 μm, more preferably 0.15 to 0.45 μm.

Such titanium dioxide is commercially available, 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.).

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

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

The acid-modified vinyl chloride / vinyl acetate copolymer resin (b3) and the polyurethane resin (b4) are preferably (b3) / (b4) = 95/5 to 5/95 in terms of solid content weight ratio. .. If the ratio of the acid-modified vinyl chloride / vinyl acetate copolymer resin (b3) is less than 5, the adhesion is lowered.

The thermoplastic resin (B2) may contain other resins. 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, non-acid-modified vinyl chloride-vinyl acetate copolymer, 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, polyether sulfone resin, polyether ketone resin, modified polyphenylene ether resin, polyphenylene sulfone resin, polyimide resin, polyamideimide resin, amorphous poly Arilate resin, polyether ether ketone resin, acrylic emulsion, urethane emulsion, polyvinyl alcohol resin, ethylene-vinyl alcohol resin, polylactic acid and the like are preferable. These resins may be one kind or two or more kinds.

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 a vapor-deposited polyamide film, various coating films coated with polyvinylidene chloride resin, polyvinyl alcohol resin, polyacrylic acid resin, etc., a coextrusion film of PET and nylon, and a 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. 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 laminating an ink layer on at least one surface of the base material layer. 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 may be an ink layer alone (base material layer / ink layer / DL / other base material, etc.) laminated with a light-shielding gravure ink composition, but the ink layer and the white ink composition are laminated. It may include a white ink layer. Further, in addition to the light-shielding layer, another ink layer formed by laminating with another gravure ink composition may be laminated (other ink layer / base material layer / (white ink layer) / ink layer / white). Ink layer / DL / other base materials, etc.). Further, since the light-shielding layer is formed by being coated by a gravure printing method, not only full solid printing but also partial printing is possible. Depending on the final packaging mode, the ink layer and the white ink layer may change the arrangement position of the printing base material for forming the light-shielding layer, and the formation order of the ink layer and the white ink layer may change. is there. That is, for example, after forming a light-shielding layer such as a base material layer / ink layer / white ink layer, another base material is laminated by dry lamination or the like (base material layer / ink layer / white ink layer / DL / other). It may be configured as a base material), or after forming a light-shielding layer such as a base material layer / white ink layer / ink layer, another base material is laminated by dry lamination or the like (base material layer / white ink layer / ink). It may be configured as a layer / DL / other base material). Further, by using a printing machine having a reversing mechanism, it is possible to obtain a light-shielding printed matter having a structure having various other ink layers. For example, after forming a light-shielding printing layer such as a base material layer / ink layer / other ink layer, it is inverted to form another ink layer, and then another base material is laminated by dry laminating or the like (another group). It may be configured as a material / DL / other ink layer / base material layer / ink layer / other ink layer / DL / other base material). Further, it may be another base material / DL / white ink layer / base material layer / ink layer or base material layer / white ink layer / ink layer / white ink layer / DL / other base material.

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 a light-shielding layer on the base material layer, and a 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.

In the laminate of the present invention, it is preferable to laminate a sealant layer or a seal layer on the light-shielding layer of the light-shielding printed matter. 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. A layer that is preferably or formed as a seal layer by coating an agent or the like can be mentioned.

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 base material layer 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), or extruded. Resin coating by 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.

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 for 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.

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 a hot melt coating 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.

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 device 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 and a printing layer obtained by printing the light-shielding gravure ink composition on at least one of the base material layers with a film thickness of 0.3 to 5 μm. It is preferable to include a gravure printing step for producing the above. The film thickness of the print layer is more preferably 0.5 to 4.5 μm. If it is thinner than 0.3 μm, the light-shielding property is lowered. If it is thicker than 5 μm, the adhesion is poor.

The method for producing a light-shielding printed matter of the present invention contains titanium dioxide (C) and a thermoplastic resin (B2) after the gravure printing step of creating the ink layer, and the thermoplastic resin (B2) is vinyl chloride acetic acid. It contains a vinyl copolymer resin (b3) and a polyurethane resin (b4), and the solid content weight ratio of the titanium dioxide (C) and the thermoplastic resin (B2) is (C) / (B2) = 60/40 to It is preferable to include a gravure printing step of printing a white ink layer composed of a white ink composition of 90/10 with a film thickness of 0.5 to 10 μm. The film thickness of the white ink layer is preferably 0.6 to 8 μm. If it is thinner than 0.5 μm, the whiteness is lowered. If it is thicker than 10 μm, the adhesion is poor. By including the white ink layer, the effect of concealing the ink layer is exhibited and the whiteness is improved.

In the method for producing a light-shielding printed matter of the present invention, titanium dioxide (C) and a thermoplastic resin (B2) are contained before the gravure printing step of preparing the ink layer, and the thermoplastic resin (B2) is made of vinyl chloride. It contains a vinyl acetate copolymer resin (b3) and a polyurethane resin (b4), and the weight ratio of the titanium dioxide (C) to the thermoplastic resin (B2) is (C) / (B2) = 60/40 to 90. It is preferable to include a gravure printing step of printing a white ink layer composed of a white ink composition of 1/10 with a film thickness of 0.5 to 10 μm. The film thickness of the white ink layer is preferably 0.6 to 8 μm. If it is thinner than 0.5 μm, the whiteness is lowered. If it is thicker than 10 μm, the adhesion is poor. By including the white ink layer, the effect of concealing the ink layer is exhibited and the whiteness is improved.

The method for producing a light-shielding printed matter includes a gravure printing step of printing a white ink layer composed of the ink layer and a white ink composition, and a gravure printing step of printing another ink layer composed of another gravure ink composition. It may be included, and it is more preferable that it is produced by a gravure printing process using a multicolor gravure printing machine. Further, a gravure printing machine having a reversing mechanism may be used.

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 proof property, pinhole resistance, 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 and a gravure in which an ink layer composed of a light-shielding gravure ink composition is printed on at least one of the base material layers with a thickness of 0.3 to 5 μm. It may include a printing step and a laminating step to create a sealant layer or a coating step to create a sealing 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.

Further, after the gravure printing step of creating the ink layer, titanium dioxide (C) and a thermoplastic resin (B2) are contained, and the thermoplastic resin (B2) is a vinyl chloride / vinyl acetate copolymer resin (b3). And polyurethane resin (b4), and the solid content weight ratio of the titanium dioxide (C) and the thermoplastic resin (B2) is (C) / (B2) = 60/40 to 90/10. A gravure printing step of printing a white ink layer made of an object with a film thickness of 0.5 to 10 μm may be included.

Further, before the gravure printing step of preparing the ink layer, titanium dioxide (C) and a thermoplastic resin (B2) are contained, and the thermoplastic resin (B2) is a vinyl chloride / vinyl acetate copolymer resin (b3). ) And the polyurethane resin (b4), and the solid content weight ratio of the titanium dioxide (C) and the thermoplastic resin (B2) is (C) / (B2) = 60/40 to 90/10. A gravure printing step of printing a white ink layer composed of the composition with a film thickness of 0.5 to 10 μm may be included.

The packaging bag of the present invention is a packaging bag that requires a base material layer, a light-shielding layer, and a sealant layer or a seal layer in order from the outer layer, in which the light-shielding layer is formed of the light-shielding gravure ink composition. Is preferable.

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, and a sealant layer or a seal layer in order from the outer layer, and the light-shielding layer is formed of the light-shielding gravure ink composition. Is preferable. 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 of food, quantity, container to be sealed, equipment, environment, etc., and may be attached or adhered with heat seal (heat pressure seal), surface seal, adhesive, etc. 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, and a sealant layer or a seal layer in order from the outer layer, in which the light-shielding layer is formed of the light-shielding gravure ink composition. Is preferable.
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. The adhesive layer or adhesive layer is any material such as a rubber-based adhesive material or an acrylic resin-based adhesive material that is in close contact with the base material layer or other base material and the release layer, and the release layer can be easily peeled off. But it may be. The release layer may be a polyethylene film, a polyester film, or paper (release paper).

The light-shielding gravure ink composition can be produced by a known method by uniformly dissolving or dispersing an untreated aluminum pigment, a thermoplastic resin, a coloring material, various additives and the like in a solvent. Dissolution or dispersion 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 You can use the machine. These devices may be used alone or in combination of two or more. When bubbles or coarse particles are contained in the ink composition, it is preferable to remove them by using a known filter, centrifuge or the like in order to deteriorate the printability and the quality of the printed matter.

The viscosity of the ink composition 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 ink composition is preferably used for gravure printing and can be coated as it is, but depending on the coating conditions and coating effect, Zahn Cup # 3 (manufactured by Dilution Co., Ltd.) can be used. It can be adjusted to a desired viscosity and used by diluting 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.

At the time of printing, a curing agent can be added to the ink composition if necessary. For example, tolylene diisocyanate, aromatic diisocyanates such as 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, 4,4'-dicyclohexyldiisocyanate, Examples thereof include aliphatic diisocyanates such as pentane-1,5-diisocyanate (stavioPDI) and polyisocyanate-based curing agents such as modified products such as trimethylolpropane trimerics, isocyanurates, bullets and allophanates thereof. 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 include Bestro Japan Co., Ltd.) and LG Hardener C (manufactured by Tokyo Ink Co., Ltd.).

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%.

[Preparation of acid-modified vinyl chloride / vinyl acetate copolymer resin]
20 parts of carboxyl group-modified vinyl chloride / vinyl acetate copolymer resin (solvine M5, acid value 5.9 mgKOH / g, manufactured by Nissin Chemical Industry Co., Ltd.) and 80 parts of methyl ethyl ketone (MEK) are placed in a beaker at 600 rpm. The mixture was stirred for 30 minutes to obtain 100 parts of a carboxyl group-modified vinyl chloride / vinyl acetate copolymer resin CL1 having a solid content of 20%.
Similarly, using a carboxyl group-modified vinyl chloride / vinyl acetate copolymer resin (Kanevinyl T5DA, acid value 6.5 mgKOH / g, manufactured by Kaneka Co., Ltd.), a carboxyl group-modified vinyl chloride / acetic acid having a solid content of 20% is used. Using vinyl copolymer resin CL2, hydroxyl group-containing vinyl chloride / vinyl acetate copolymer resin (solvine TAO, acid value 0 mgKOH / g, hydroxyl value 98 mgKOH / g, manufactured by Nisshin Chemical Industry Co., Ltd.), solid content 20 Using% hydroxyl group-containing vinyl chloride / vinyl chloride copolymer resin CL3 and unmodified vinyl chloride / vinyl acetate copolymer resin (solvine CL, acid value 0 mgKOH / g, manufactured by Nisshin Kagaku Kogyo Co., Ltd.) , A vinyl chloride / vinyl acetate copolymer resin CL4 having a solid content of 20% was obtained.

[Preparation of untreated aluminum pigment]
Using 100 g of raw material aluminum powder, 3 g of oleic acid, and 500 mL of mineral spirit produced by the atomizing method as raw materials, they were charged into a ball mill together with 5 kg of a 3.2φ bearing ball and pulverized to obtain a slurry.
After completion of the pulverization, the slurry was sieved to 37 μm to remove coarse particles, and then the excess solvent was removed by a filter press to obtain a cake having a heating residue of 90% by mass.
The obtained cake was transferred into a vertical mixer, mineral spirit was added, and the mixture was mixed for 15 minutes to obtain an aluminum paste A1 containing an untreated aluminum pigment. The untreated aluminum pigment in the paste was a non-leaving type, had a solid content of 65% by mass, and had a D50 average particle size of 7 μm.

[Preparation of light-shielding gravure ink composition]
Light-shielding ink G1 (Example 1)
Carboxy-modified vinyl chloride / vinyl acetate copolymer resin CL1 25 parts, polyurethane resin PU1 (solid content 30%, manufactured by Tokyo Ink Co., Ltd.) 30 parts, aluminum paste A1 (untreated aluminum pigment, solid content 65%, D50) (Average particle size 7 μm) 15 parts, 30 parts of propyl acetate, and 100 parts of ceramic beads were charged and dispersed with a paint shaker for 1 hour to prepare the light-shielding ink G1 of Example 1. Similarly, the light-shielding inks of Examples 2 to 5 and Comparative Examples 1 to 6 were prepared according to the formulations shown in Tables 1 and 2.

[Making white ink]
White ink W1 (Production example 1)
Titanium dioxide (JR-805, D50 average particle size 0.29 μm, manufactured by Teika Co., Ltd.) 45 parts, polyurethane resin PU (solid content 30%, manufactured by Tokyo Ink Co., Ltd.) 15 parts, vinyl chloride / vinyl acetate co-weight Combined resin CL (solvine CL, solid content 20%, manufactured by Nisshin Kagaku Kogyo Co., Ltd.) 15 parts, propyl acetate 20 parts, isopropyl alcohol 5 parts, ceramic beads 100 parts were charged and dispersed for 1 hour with a paint shaker. The white ink W1 was produced. Similarly, each white ink of Production Examples 2 to 6 was prepared according to the formulation shown in Table 3.

[Manufacturing of gray ink] (Production example 7)
Titanium dioxide (JR-805, D50 average particle size 0.29 μm, manufactured by Teika Co., Ltd.) 37 parts, carbon black (MA11, D50 average particle size 29 nm, manufactured by Mitsubishi Chemical Co., Ltd.) 0.7 parts, polyurethane resin PU (Solid content 30%, manufactured by Tokyo Ink Co., Ltd.) 50 parts, 1.2 parts of propyl acetate, 2.5 parts of isopropyl alcohol, 8.6 parts of ethyl acetate, 100 parts of ceramic beads were prepared and 1 with a paint shaker. Gray ink was prepared by time dispersion.

[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 1.9 μm, and then replace with a 150 L30 μm laser plate and white. On the ink printing surface, the light-shielding ink G1 was added to the Zahn Cup No. 1 with the same diluting solvent. 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 4 and 5, the light-shielding ink and the film thickness are changed, and the light-shielding printed matter PR2, PR6, PR7, PR8, PR9, PR13, PR14, PR15, PR20, PR21, PR24, PR25, PR26 and PR27, respectively. Got
Further, the ink was changed to the gray ink of Production Example 7 to obtain a light-shielding printed matter PR30.
Further, instead of the 150L 30μm laser plate, the light-shielding ink G1 was used in the same diluting solvent to obtain Zahn Cup No. After adjusting the viscosity to 17 seconds in step 3, printing was performed with a film thickness of 1.2 μm, and then, instead of the 150 L40 μm laser plate, white ink W1 was applied to the light-shielding ink printing surface with the same diluting solvent to obtain Zahn Cup No. After adjusting the viscosity to 17 seconds in step 3, printing was performed with a film thickness of 1.9 μm to obtain a light-shielding printed matter PR10 (light-shielding ink was printed first, and white ink was printed on it).
Further, instead of the 150L 30μm laser plate, the light-shielding ink G1 was used in the same diluting solvent to obtain Zahn Cup No. After adjusting the viscosity to 17 seconds in step 3, printing was performed with a film thickness of 1.3 μm to obtain a light-shielding printed matter PR11 (only light-shielding ink was printed). Similarly, as shown in Tables 4 and 5, the light-shielding ink and the film thickness were changed to obtain light-shielding printed matter PR12, PR28 and PR29, respectively.

Further, the base material layer was printed with white ink W1 and light-shielding ink G3 instead of pyrene P-2161 (abbreviation: OPP, manufactured by Toyobo Co., Ltd.) of a stretched polypropylene film having a thickness of 20 μm to obtain a light-shielding printed matter PR3. .. Similarly, as shown in Table 5, the light-shielding ink and the film thickness were changed to obtain light-shielding printed matter PR18, PR22 and PR23, respectively.
Further, it was changed to LG-FK light-shielding gray H (abbreviation: light-shielding gray, manufactured by Tokyo Ink Co., Ltd.) to obtain a light-shielding printed matter PR31.

Further, the base material layer is printed with white ink W1 and light-shielding ink G4 instead of Barrierlocks 1011SBR2 (abbreviation: transparent thin-film PET, manufactured by Toray Film Processing Co., Ltd.), which is a transparent vapor-filmed PET film having a thickness of 12 μm. Obtained PR4. Similarly, as shown in Table 5, the light-shielding ink and the film thickness were changed to obtain light-shielding printed matter PR16 and PR19.

Further, the base material layer is printed with white ink W1 and light-shielding ink G5 instead of Bonnil RX (abbreviation: nylon, manufactured by Kojin Film & Chemicals Co., Ltd.) of a nylon film having a thickness of 15 μm to obtain a light-shielding printed matter PR5. It was. Similarly, as shown in Table 5, the light-shielding ink and the film thickness were changed to obtain a light-shielding printed matter PR17.

The whiteness, light-shielding property, and adhesion of the light-shielding printed matter of Examples 6 to 19 and Comparative Examples 7 to 23 were evaluated and shown in Tables 4 and 5.

<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 lightness (L ^* ) value, the better the whiteness. The whiteness was evaluated on a two-point scale: ◯: the lightness (L ^* ) value was 75 or more, and ×: the lightness (L ^{*) value was less than 75.} The whiteness of the light-shielded printed matter containing only the light-shielding ink was not evaluated and is indicated by "-".

<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 ◯: the value of the total light transmittance was less than 2%, and ×: the value of the total light transmittance 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.

[Preparation of laminate]
Takelac A-525 / Takenate A-52 (abbreviation: DL, manufactured by Mitsui Chemicals, Inc.) is coated on the printed layer of the light-shielded 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, instead of printed matter PR2, PR6, PR7, PR8, PR9, PR10, PR11, PR12, PR13, PR14, PR15, PR20, PR21, PR24, PR25, PR26, PR27, PR28, PR29 and PR30, respectively. LAM2, LAM6, LAM7, LAM8, LAM9, LAM10, LAM11, LAM12, LAM13, LAM14, LAM15, LAM20, LAM21, LAM24, LAM25, LAM26, LAM27, LMA28, LAM29 and LAM30 were obtained.

Takelac A-969V / Takenate A-5 (abbreviation: DL, manufactured by Mitsui Chemicals, Inc.) is coated on the printed layer of the light-shielding printed matter PR3 with A-Bar OSP-10 (manufactured by OSG System Products Co., Ltd.). After laminating Tohcello CP GLC (abbreviation: CPP, manufactured by Mitsui Chemicals Tohcello Co., Ltd.), which is a non-stretched polypropylene film having a thickness of 30 μm, aging was performed at 40 ° C. for 24 hours to laminate PR3 / DL / CPP. Body LAM3 was obtained.
Similarly, the printed matter PR3 was replaced with PR18, PR22 and PR23 to obtain laminated bodies LAM18, LAM22 and LAM23.

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 PR4 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 PR4 / DL / EP film. LAM4 was obtained.
Similarly, in place of the light-shielded printed matter PR16 and PR19, laminated bodies LAM16 and LAM19 were obtained, respectively.

Takelac A-620 / Takenate A-65 (abbreviation: DL, manufactured by Mitsui Chemicals, Inc.) is coated on the print layer of the light-shielding printed matter PR5 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 PR5 / DL / EP film. LAM5 was obtained.
Similarly, the printed matter PR5 was replaced with PR17 to obtain a laminated body LAM17.

<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 ◯: the value of the total light transmittance was less than 3%, and ×: the value of the total light transmittance was 3% or more.

According to Tables 4 and 5, it is clear that the light-shielding printed matter of Examples 6 to 14 is excellent in whiteness, light-shielding property, and adhesion. Further, it is clear that the light-shielding printed matter (PR11-12), which is only the light-shielding ink of Examples 16 to 17, is also excellent in light-shielding property and adhesion. Further, it is clear that the light-shielding printed matter of Example 15 in which the printing order of the light-shielding ink and the white ink is reversed is also excellent in whiteness, light-shielding property, and adhesion. In addition, it is clear that the light-shielding property of the laminated body hardly deteriorates even after laminating.
It is clear that the light-shielding printed matter (PR30) in which a white light-shielding layer and a gray-colored layer similar to Patent Document 2 are laminated is inferior in whiteness and impairs cosmeticity. Further, the light-shielding printed matter (PR31), which is an example using the light-shielding gray ink, which is a conventional example, is also inferior in whiteness.
It is clear that the light-shielding printed matter of Comparative Examples 7 to 19 is inferior in any of whiteness, light-shielding property, and adhesion.
It is clear that Comparative Examples 20 to 21, which are only light-shielding inks, are inferior in light-shielding properties.

Claims (7)

An ink layer made of a light-shielding gravure ink composition is laminated on at least one surface of a plastic base film with a thickness of 0.3 to 5 μm, and a white ink layer made of a white ink composition is formed on the ink layer. It is a laminate formed by laminating a printing layer having a thickness of 5 to 10 μm and a sealant layer or a sealing layer on the printing layer.
The light-shielding gravure ink composition contains an oleic acid-treated aluminum pigment (A) having an average particle size of 10 μm or less by an atomizing method, and a thermoplastic resin (B1).
The thermoplastic resin (B1) is an acid value of 2 mg KOH / g or more in which a carboxyl group-modified vinyl chloride-vinyl acetate copolymer resin (b1), viewed contains a polyurethane resin (b2),
The white ink composition contains titanium dioxide (C) and a thermoplastic resin (B2), and the thermoplastic resin (B2) contains a vinyl chloride / vinyl acetate copolymer resin (b3) and a polyurethane resin (b4). , solid content weight ratio of the titanium dioxide (C) and the thermoplastic resin (B2) is a laminate which is a = 60 / 40~90 / 10 (C ) / (B2). A white ink layer made of a white ink composition is laminated on at least one surface of a plastic base film with a thickness of 0.5 to 10 μm, and an ink layer made of a light-shielding gravure ink composition is 0 on the white ink layer. A laminated body formed by laminating a printing layer having a thickness of 3 to 5 μm and a sealant layer or a sealing layer on the printing layer.
The light-shielding gravure ink composition contains an oleic acid-treated aluminum pigment (A) having an average particle size of 10 μm or less by an atomizing method, and a thermoplastic resin (B1).
The thermoplastic resin (B1) contains a carboxyl group-modified vinyl chloride / vinyl acetate copolymer resin (b1) having an acid value of 2 mgKOH / g or more and a polyurethane resin (b2).
The white ink composition contains titanium dioxide (C) and a thermoplastic resin (B2), and the thermoplastic resin (B2) contains a vinyl chloride / vinyl acetate copolymer resin (b3) and a polyurethane resin (b4). , solid content weight ratio of the titanium dioxide (C) and the thermoplastic resin (B2) is a laminate which is a = 60 / 40~90 / 10 (C ) / (B2). The process of preparing the plastic base film and
An ink layer made of a light-shielding gravure ink composition is printed on at least one of the plastic base film with a thickness of 0.3 to 5 μm, and a white ink layer made of a white ink composition is printed on the ink layer with a thickness of 0.5 to 0.5. A gravure printing process that forms a printing layer by printing with a film thickness of 10 μm,
Further, it is a method for manufacturing a laminated body including a laminating step of creating a sealant layer on the printed layer or a coating step of creating a seal layer.
The light-shielding gravure ink composition contains an oleic acid-treated aluminum pigment (A) having an average particle size of 10 μm or less by an atomizing method, and a thermoplastic resin (B1).
The thermoplastic resin (B1) contains a carboxyl group-modified vinyl chloride / vinyl acetate copolymer resin (b1) having an acid value of 2 mgKOH / g or more and a polyurethane resin (b2).
The white ink composition contains titanium dioxide (C) and a thermoplastic resin (B2), and the thermoplastic resin (B2) contains a vinyl chloride / vinyl acetate copolymer resin (b3) and a polyurethane resin (b4). , A method for producing a laminate, wherein the solid content weight ratio of the titanium dioxide (C) and the thermoplastic resin (B2) is (C) / (B2) = 60/40 to 90/10 . The process of preparing the plastic base film and
A white ink layer made of a white ink composition is printed on at least one of the plastic base film with a thickness of 0.5 to 10 μm, and an ink layer made of a light-shielding gravure ink composition is printed on the white ink layer. A gravure printing process that forms a printing layer by printing with a film thickness of 3 to 5 μm,
Further, it is a method for manufacturing a laminated body including a laminating step of creating a sealant layer on the printed layer or a coating step of creating a seal layer.
The light-shielding gravure ink composition contains an oleic acid-treated aluminum pigment (A) having an average particle size of 10 μm or less by an atomizing method, and a thermoplastic resin (B1).
The thermoplastic resin (B1) contains a carboxyl group-modified vinyl chloride / vinyl acetate copolymer resin (b1) having an acid value of 2 mgKOH / g or more and a polyurethane resin (b2).
The white ink composition contains titanium dioxide (C) and a thermoplastic resin (B2), and the thermoplastic resin (B2) contains a vinyl chloride / vinyl acetate copolymer resin (b3) and a polyurethane resin (b4). , solid content weight ratio of the titanium dioxide (C) and the thermoplastic resin (B2) the production of the laminate you wherein the Ru (C) / (B2) = 60 / 40~90 / 10 der Method . In a packaging bag that requires a plastic base film, a white ink layer, an ink layer, and a sealant layer or a seal layer in order from the outer layer.
The white ink layer has a film thickness of 0.5 to 10 μm and
The titanium dioxide (C) and the thermoplastic resin (B2) are contained, and the thermoplastic resin (B2) contains a vinyl chloride / vinyl acetate copolymer resin (b3) and a polyurethane resin (b4), and the titanium dioxide (C) is contained. And the thermoplastic resin (B2) are formed of a white ink composition having a solid content weight ratio of (C) / (B2) = 60/40 to 90/10.
The ink layer has a film thickness of 0.3 to 5 μm and
It contains an oleic acid-treated aluminum pigment (A) having an average particle size of 10 μm or less by an atomizing method, and a thermoplastic resin (B1).
The thermoplastic resin (B1) is a light-shielding gravure ink composition containing a carboxyl group-modified vinyl chloride / vinyl acetate copolymer resin (b1) having an acid value of 2 mgKOH / g or more and a polyurethane resin (b2). A packaging bag characterized by being formed. In order from the outer layer, in the lid material which requires the plastic base film, the white ink layer, the ink layer, and the sealant layer or the seal layer.
The white ink layer has a film thickness of 0.5 to 10 μm and
The titanium dioxide (C) and the thermoplastic resin (B2) are contained, and the thermoplastic resin (B2) contains a vinyl chloride / vinyl acetate copolymer resin (b3) and a polyurethane resin (b4), and the titanium dioxide (C) is contained. And the thermoplastic resin (B2) are formed of a white ink composition having a solid content weight ratio of (C) / (B2) = 60/40 to 90/10.
The ink layer has a film thickness of 0.3 to 5 μm and
It contains an oleic acid-treated aluminum pigment (A) having an average particle size of 10 μm or less by an atomizing method, and a thermoplastic resin (B1).
The thermoplastic resin (B1) is a light-shielding gravure ink composition containing a carboxyl group-modified vinyl chloride / vinyl acetate copolymer resin (b1) having an acid value of 2 mgKOH / g or more and a polyurethane resin (b2). A lid material characterized by being formed . In a label that requires a plastic base film, a white ink layer, an ink layer, and a sealant layer or a seal layer in order from the outer layer,
The white ink layer has a film thickness of 0.5 to 10 μm and
The titanium dioxide (C) and the thermoplastic resin (B2) are contained, and the thermoplastic resin (B2) contains a vinyl chloride / vinyl acetate copolymer resin (b3) and a polyurethane resin (b4), and the titanium dioxide (C) is contained. And the thermoplastic resin (B2) are formed of a white ink composition having a solid content weight ratio of (C) / (B2) = 60/40 to 90/10.
The ink layer has a film thickness of 0.3 to 5 μm and
It contains an oleic acid-treated aluminum pigment (A) having an average particle size of 10 μm or less by an atomizing method, and a thermoplastic resin (B1).
The thermoplastic resin (B1) is a light-shielding gravure ink composition containing a carboxyl group-modified vinyl chloride / vinyl acetate copolymer resin (b1) having an acid value of 2 mgKOH / g or more and a polyurethane resin (b2). A label characterized by being formed .