JP6935565B1 - Retort gravure ink set, retort printed matter, laminate, retort printed matter manufacturing method, laminate manufacturing method, packaging bag, and lid material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a gravure ink set for retort having retort resistance which can withstand the use of high retort sterilization, design property having high metallic luster and blocking resistance. SOLUTION: The gravure ink contains an untreated aluminum pigment (A) and a thermoplastic resin (B), and the thermoplastic resin is an acid-modified vinyl chloride / vinyl acetate copolymer resin (b1) and a polyurethane resin (b2). ), The curing agent solution contains the isocyanate compound (D) and the solvent (E), and the solid content weight of the thermoplastic resin (B) in the gravure ink and the isocyanate compound (D) in the curing agent solution. The ratio is (B) / (D) = 60/40 to 99/1, and the acid value of the acid-modified vinyl chloride / vinyl acetate copolymer resin (b1) is 2 mgKOH / g or more. A gravure ink set for retort, which is characterized by being a set of ink. [Selection diagram] None

Description

The present invention relates to a gravure ink set for retort, a printed matter for retort, a laminate, a method for producing a printed matter for retort, a method for producing a laminate, a packaging bag, and a lid material.

Retort pouch packaging enables long-term storage at room temperature by filling and sealing the food content in the packaging bag and then heat-sterilizing the microorganisms that cause food spoilage. In recent years, from the viewpoint of long-term storage and convenience of cooking, products such as foods using a large number of retort packages have been displayed on the shelves of mass retailers, and in order to make the products stand out from such a large number of displays. In addition, there was a strong demand for retort packaging with a high metallic luster such as gold and silver.

On the other hand, retort-packed packaging can be stored for a long period of time at room temperature by filling and sealing the food content in the packaging bag and then heat-sterilizing the microorganisms that cause food spoilage. However, heat sterilization of foods at the same time reduces the taste of foods, and the longer the heating time, the more the taste and flavor tend to be reduced. In recent years, the level of demand for taste by consumers has increased, and in order to suppress the reduction of taste, a method called high retort, in which sterilization is performed at a high temperature of 130 ° C. or higher in a short time, has come to be adopted. Packaging materials compatible with high-retort packaging have come to be proposed.

Patent Document 1 describes a liquid ink composition containing a polyurethane resin containing a free carboxyl group, a vinyl chloride vinyl acetate copolymer resin having a hydroxyl group, an organic solvent, and less than 10% by mass of water in the total amount of the composition. Although it is described, it has excellent adhesion to a film, blocking resistance, and retort resistance under high retort conditions, and also has excellent extrusion laminate strength and two-component stability when a curing agent is added. Although it has excellent retort resistance when a pigment such as titanium oxide is used, when Patent Document 1 is applied to an aluminum pigment, the surface of the aluminum pigment reacts with water to generate hydrogen gas, so that it should be used. I couldn't. Further, when a liquid ink composition prepared by draining water from the composition described in Patent Document 1 using an aluminum pigment is printed and then laminated, the retort resistance is inferior and a design that can be called metallic luster is obtained. I couldn't even get it.

Patent Document 2 describes a resin-coated aluminum paste in which fine aluminum powder having a particle diameter of 5 to 20 μm is coated with an acrylic resin, and a high-brightness laminate ink for retort resistance containing a binder resin, and has chemical resistance and a feeling of brightness. It has become an excellent one. However, since it is an aluminum fine particle coated with an acrylic resin, it is not possible to obtain a glossy design like a metal. Further, although it is described that a polyurethane resin and a vinyl chloride vinegar copolymer may be used as the binder, the vinyl chloride / vinyl acetate copolymer having a functional group of a hydroxyl group, which is a specific example, is disclosed. Even if the coalescence (solvine TA5R) was added, the fine aluminum powder was coated with an acrylic resin, so that a design that could be called metallic luster could not be obtained.

In order to obtain a design with metallic luster, we wanted to utilize the metallic luster of aluminum fine powder for printing, but in packaging that requires high retort resistance, the adhesiveness between the aluminum fine powder and the binder resin is poor. It was necessary to treat and insert an acrylic resin or the like that reduces the glossiness between the fine aluminum powder and the binder resin.

JP-A-2010-1932 Japanese Unexamined Patent Publication No. 2010-53193

Therefore, an object of the present invention is to provide a gravure ink set for retort having retort resistance that can withstand the use of high retort sterilization, design property with high metallic luster, and blocking resistance.

The present inventors have described the retort printed matter in which the retort gravure ink set is formed by forming a retort printing layer on at least one surface of a plastic base film with a thickness of 0.1 to 3 μm. The gravure ink set for retort is a set of two types of ink , a gravure ink and a curing agent solution used together with the gravure ink.
The gravure ink contains an aluminum pigment (A) obtained by an atomizing method and not polymerized, and a thermoplastic resin (B).
The thermoplastic resin contains an acid-modified vinyl chloride / vinyl acetate copolymer resin (b1) and a polyurethane resin (b2).
The curing agent solution contains an isocyanate compound (D) and a solvent (E).
The solid content weight ratio of the thermoplastic resin (B) in the gravure ink and the isocyanate compound (D) in the curing agent solution is (B) / (D) = 60/40 to 99/1.
The acid-modified vinyl chloride / vinyl acetate copolymer resin (b1) is a carboxyl group-modified vinyl chloride / vinyl acetate copolymer resin having an acid value of 3 to 30 mgKOH / g.
It has been found that the above-mentioned object can be achieved by the printed matter for retort pouch, which is characterized by the above, and the present invention has been completed.

That is, the present invention
(1) The retort gravure ink set is a retort printed matter formed by forming a retort printing layer with a thickness of 0.1 to 3 μm on at least one surface of a plastic base film, and is the retort gravure. The ink set is a set of two types of inks , a gravure ink and a curing agent solution used together with the gravure ink. The gravure ink is obtained by an atomizing method and is not polymerized. The plastic resin (B) is contained, the thermoplastic resin contains an acid-modified vinyl chloride / vinyl acetate copolymer resin (b1), and a polyurethane resin (b2), and the curing agent solution contains an isocyanate compound (D) and a solvent. The solid content weight ratio of the thermoplastic resin (B) in the gravure ink and the isocyanate compound (D) in the curing agent solution containing (E) is (B) / (D) = 60/40 to 99 /. 1. The acid-modified vinyl chloride / vinyl acetate copolymer resin (b1) is a carboxyl group-modified vinyl chloride / vinyl acetate copolymer resin having an acid value of 3 to 30 mgKOH / g . Printed matter for retort ,
(2) A laminate characterized in that a sealant layer is laminated on the retort print layer of the retort printed matter according to (1).
(3) The step of preparing the plastic base film and the gravure ink of the gravure ink set for retort and the curing agent solution are mixed on at least one of the plastic base films and printed with a film thickness of 0.1 to 3 μm. A method for producing a retort printed matter, which comprises a gravure printing step of forming a retort printing layer, wherein the gravure ink is obtained by an atomizing method and is not polymerized with an aluminum pigment (A) and heat. The plastic resin (B) is contained, the thermoplastic resin contains an acid-modified vinyl chloride / vinyl acetate copolymer resin (b1), and a polyurethane resin (b2), and the curing agent solution contains an isocyanate compound (D) and a solvent. The solid content weight ratio of the thermoplastic resin (B) in the gravure ink and the isocyanate compound (D) in the curing agent solution containing (E) is (B) / (D) = 60/40 to 99 /. 1 and
Production of a printed matter for retort, wherein the acid-modified vinyl chloride / vinyl acetate copolymer resin (b1) is a carboxyl group-modified vinyl chloride / vinyl acetate copolymer resin having an acid value of 3 to 30 mgKOH / g. Method,
(4) A step of preparing a plastic base film and a gravure forming a retort printing layer formed by printing a retort gravure ink set with a film thickness of 0.1 to 3 μm on at least one of the plastic base films. A method for producing a laminate including a printing step and a laminating step of laminating a sealant layer. The retort gravure ink set consists of two types of inks, a gravure ink and a curing agent solution used together with the gravure ink. The gravure ink contains an aluminum pigment (A) which has not been polymerized and has not been polymerized, and a thermoplastic resin (B), and the thermoplastic resin has an acid-modified vinyl chloride / vinyl acetate co-weight. The curing agent solution contains the coalesced resin (b1) and the polyurethane resin (b2), contains the isocyanate compound (D) and the solvent (E), and contains the thermoplastic resin (B) and the curing agent solution in the gravure ink. The solid content weight ratio of the isocyanate compound (D) in the resin is (B) / (D) = 60/40 to 99/1, and the acid-modified vinyl chloride / vinyl acetate copolymer resin (b1) is an acid. A method for producing a laminate, which comprises a carboxyl group-modified vinyl chloride / vinyl acetate copolymer resin having a value of 3 to 30 mgKOH / g.
(5) In a packaging bag that requires a plastic base film, a retort printing layer having a thickness of 0.1 to 3 μm, and a sealant layer in this order from the outer layer, the retort printing layer is a retort gravure ink set. The retort gravure ink set is a set of two types of ink, a gravure ink and a curing agent solution used together with the gravure ink, and the gravure ink is obtained by an atomizing method and subjected to a polymerization treatment. The curing agent solution contains an aluminum pigment (A) and a thermoplastic resin (B), and the thermoplastic resin contains an acid-modified vinyl chloride / vinyl acetate copolymer resin (b1) and a polyurethane resin (b2). However, the solid content weight ratio of the thermoplastic resin (B) in the gravure ink and the isocyanate compound (D) in the curing agent solution, which contains the isocyanate compound (D) and the solvent (E), is (B) / ( D) = 60/40 to 99/1, and the acid-modified vinyl chloride / vinyl acetate copolymer resin (b1) is a carboxyl group-modified vinyl chloride / vinyl acetate copolymer resin having an acid value of 3 to 30 mgKOH / g. Is,
The packaging bag, which is characterized by
(6) In a lid material that requires a plastic base film, a retort printing layer having a thickness of 0.1 to 3 μm, and a sealant layer in this order from the outer layer, the retort printing layer is a retort gravure ink. The gravure ink set for retort formed as a set is a set of two types of inks, a gravure ink and a curing agent solution used together with the gravure ink, and the gravure ink is obtained by an atomizing method and subjected to a polymerization treatment. The curing agent contains an aluminum pigment (A) that is not used and a thermoplastic resin (B), and the thermoplastic resin contains an acid-modified vinyl chloride / vinyl acetate copolymer resin (b1) and a polyurethane resin (b2). The solution contains the isocyanate compound (D) and the solvent (E), and the solid content weight ratio of the thermoplastic resin (B) in the gravure ink and the isocyanate compound (D) in the curing agent solution is (B) /. (D) = 60/40 to 99/1, and the acid-modified vinyl chloride / vinyl acetate copolymer resin (b1) is a carboxyl group-modified vinyl chloride / vinyl acetate copolymer having an acid value of 3 to 30 mgKOH / g. Is a resin,
The lid material, which is characterized by
It is about.

According to the present invention, it is possible to provide a gravure ink set for retort having retort resistance that can withstand the use of high retort sterilization, design property with high metallic luster, and blocking resistance.

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 retort gravure ink set of the present invention (hereinafter, also simply referred to as "ink set") is a retort gravure ink set containing a gravure ink and a curing agent solution used together with the gravure ink, and is the gravure ink. Contains an untreated aluminum pigment (A) and a thermoplastic resin (B), and the thermoplastic resin contains an acid-modified vinyl chloride / vinyl acetate copolymer resin (b1) and a polyurethane resin (b2) and is cured. The agent solution contains the isocyanate compound (D) and the solvent (E), and the solid content weight ratio of the thermoplastic resin (B) in the gravure ink and the isocyanate compound (D) in the curing agent solution is (B). / (D) = 60/40 to 99/1, and the acid value of the acid-modified vinyl chloride / vinyl acetate copolymer resin (b1) is 2 mgKOH / g or more, which is a set of two types of inks.

The gravure ink and the curing agent solution are produced as different liquids, and are mixed and used when producing a printed matter. The compositions contained in the gravure ink and the curing agent solution are described below.

[Gravure ink]
The untreated aluminum pigment (A) contained in the gravure ink preferably has an average thickness of 0.01 to 1.0 μm, more preferably 0.05 to 0.7 μm. Generally, the untreated aluminum pigment has a scaly shape, is represented by a thickness and a particle size, and the thickness is obtained by a method of directly observing with an electron microscope. The average thickness referred to here was measured with respect to the thickness of 10 particles and used as the average value. If the average thickness exceeds 1.0 μm, the brightness is inferior and the metallic luster may not be exhibited. If the average thickness is less than 0.01 μm, the production of the untreated aluminum pigment itself is difficult and expensive.

The untreated aluminum pigment (A) preferably has an average particle size larger than 1 to 100 μm, and more preferably an average particle size of 3 to 80 μm. The particle size is the average particle size of the longest diameter of the scale shape, 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.

For the purpose of suppressing the reaction with water, acid, and alkali, there is a type in which the surface of the aluminum pigment is polymerized with an acrylic resin or the like. However, the untreated aluminum pigment (A) of the present invention is polymerized with an acrylic resin or the like. Use untreated aluminum pigments that do not. By including the untreated aluminum pigment in combination with the acid-modified vinyl chloride / vinyl acetate copolymer resin (b1) and the isocyanate compound (D) described later, the affinity is improved and the design has a metallic luster. , A printed matter having excellent retort resistance can be obtained.

The thermoplastic resin (B) 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. Within the above range, the retort resistance becomes good, and a design having a metallic luster can be obtained. 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, capric acid, pelargonic acid, and capric 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 and the like. Be done. Of these, (maleic anhydride) maleic anhydride is more preferable.

Such carboxyl group-modified vinyl chloride / vinyl acetate copolymer resins are commercially available, and are commercially available. ), 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 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 mass ratio of (b1) / (b2) = 5/95 to 95/5. .. It is more preferable that (b1) / (b2) = 10/90 to 85/5. When the ratio of the acid-modified vinyl chloride / vinyl acetate copolymer resin (b1) is less than 5, the brightness is lowered and the design of the metallic luster is inferior, and when it is larger than 95, when the curing agent solution is added. , May gel.

The thermoplastic resin (B) 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 An allylate resin, a polyether ether ketone resin, and the like are preferable. These resins may be one kind or two or more kinds.

In the gravure ink constituting the gravure ink set of the present invention, the untreated aluminum pigment (A) and the thermoplastic resin (B) have a solid content mass ratio of (A) / (B) = 60/40 to 1. It is preferably / 99, and more preferably (A) / (B) = 55/45 to 10/90. If (A) is larger than 60, the adhesion to the film substrate of the gravure ink set is inferior because the resin content is small, and if it is smaller than 1, the brightness is lowered due to the small pigment content and metallic luster cannot be obtained. ..
The solid content in the gravure ink 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.

As the gravure ink, 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 or more.
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 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 particular, when a yellow organic pigment is contained, a gold-like hue is obtained, and a high-class feeling can be imparted.

The curing agent solution constituting the gravure ink set of the present invention preferably contains an isocyanate compound (D) and a solvent (E). Examples of the isocyanate compound include tolylene diisocyanate, aromatic diisocyanates such as 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, and 4,4'-. Aliphatic diisocyanates such as dicyclohexyldiisocyanate and pentane-1,5-diisocyanate (stavioPDI) and modified products such as trimethylolpropane trimerics, isocyanurates, bullets and allophanates thereof can be used, 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 Co., Ltd.) ), Mytec Y260A (manufactured by Mitsubishi Chemical Co., Ltd.), Coronate Isocyanate HX, Coronate Isocyanate HL, Coronate Isocyanate L (manufactured by Toso Co., Ltd.), Desmodur N75MPA / X (manufactured by Bayer), LG Hardener C (Tokyo Ink (Tokyo Inc.) Co., Ltd.) and the like can be exemplified. Of these, aliphatic diisocyanates are more preferable.

When the isocyanate compound (D) is mixed with the gravure ink at the time of printing, it reacts with the amino group and / or the hydroxyl group of the polyurethane resin (C) in the gravure ink and is cured, so that the retort resistance is improved.

The concentration of the isocyanate compound (D) is such that the solid content weight ratio of the thermoplastic resin (B) in the gravure ink and the isocyanate compound (D) in the curing agent solution is (B) / (D) = 60/40. It is preferably contained in an amount of about 99/1, and more preferably (B) / (D) = 62/38 to 95/5. If (B) is larger than 99, the retort resistance is inferior, and if (B) is smaller than 60, blocking may occur when the printed matter is wound into a roll in the printing process.

Examples of the solvent (E) 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 and ethanol. Alcohol-based solvents such as isopropyl alcohol, normal propyl alcohol, 1-butanol, 2-butanol, isobutanol, tert-butanol, ethyl acetate, n-propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, acetate Ester solvents such as tert-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 ether-based solvents such as glycol 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. , 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, propylene glycol monoethyl ether acetate and the like. 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.

In the retort printed matter of the present invention, the retort gravure ink set forms a retort printed layer formed by laminating an ink layer with a thickness of 0.1 to 3 μm on at least one surface of a plastic base film. Is preferable. The film thickness of the ink layer is more preferably 0.3 to 2 μm. If it is smaller than 0.1 μm, the brightness is lowered and a metallic luster design cannot be obtained. If it is larger than 3 μm, blocking is likely to occur, and the retort resistance and design are also inferior.

The plastic base film is preferably at least one selected from the plastic film or sheet and a laminate thereof. For example, a polyester film such as polyethylene terephthalate (PET), polyethylene naphthalate, or polybutylene terephthalate, a polyamide film or a barrier polyamide film having a barrier layer in the middle, a PET film or a polyamide film provided with a vapor-deposited layer such as alumina or silica. Examples thereof include a transparent vapor-deposited polyester film or a transparent vapor-deposited polyamide film, various coating films coated with a polyvinylidene chloride resin, a polyvinyl alcohol resin, a polyacrylic acid resin, and the like. These may be one kind or two or more kinds 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, 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 retort printing layer is preferably formed by laminating an ink layer on at least one surface of a plastic base film. The retort printing 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 printing layer for retort may be an ink layer alone formed by laminating with a gravure ink composition for retort, or may include the ink layer and another ink layer laminated with another gravure ink set. In particular, by laminating a printing layer for retort pouch on a printing layer of a yellow organic pigment, a design having a gold-like metallic luster can be obtained. Further, since it is formed by coating by a gravure printing method, not only full solid printing but also gradation printing and partial printing are possible. Depending on the final packaging mode, these ink layers may change the arrangement position of the printing base material for forming these printing layers, and the forming order of these ink layers and other ink layers may change. .. That is, for example, after forming a retort printing layer such as a plastic base film / ink layer / other ink layer, another base material is laminated by dry laminating or the like (plastic base film / ink layer / other ink). It may be configured as a layer / DL / other base material), or a print layer for retort is formed such as a plastic base material film / another ink layer / ink layer (or a plurality of layers such as an ink layer / another ink layer). After that, another base material may be laminated (plastic base film / other ink layer / ink layer / (other ink layer or the like /) DL / other base material) by dry laminating or the like.

In the laminate of the present invention, a sealant layer formed by dry lamination may be laminated on the print layer for retort pouch. Examples of the sealant layer include a laminated body having heat-sealing properties and a layer laminated by laminating known sealant films.

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 retort printing layer on the plastic base film is bonded to a known sealant film via an adhesive by a dry laminating method.
The thickness of the sealant layer is not particularly limited, but is preferably 2 to 200 μm for the sealant film.

As the sealant film, for example, one type or two or more types of polyolefin films such as polyethylene, polypropylene, and copolymers thereof may be laminated.

In addition to the retort printing layer and the sealant layer, the laminate of the present invention has rigidity, waist, gas barrier property, fragrance retention, moisture resistance, pinhole resistance, dead hole property, light shielding property, linear cut property, etc. An intermediate layer may be laminated to impart or enhance the performance of the above. When the intermediate layer is provided, it is not always necessary to apply the retort printing layer to the plastic base film, and the retort printing 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 polyethylene terephthalate (PET), polyester film, ethylene-vinyl alcohol, alcohol-based film, polyamide film or barrier polyamide film with a barrier layer in the middle, PET film or polyamide film with alumina or silica. Examples thereof include a transparent vapor-deposited polyester film or a transparent vapor-deposited polyamide film provided with the vapor-deposited layer of the above, various coating films coated with polyvinylidene chloride resin, polyvinyl alcohol resin, polyacrylic acid resin and the like, and a co-extruded film of PET and nylon. 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.

The adhesive used in the dry laminating method may be a commercially available adhesive, and examples thereof include a two-component urethane resin adhesive. As a method of applying the adhesive for laminating 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 laminate of the present invention is used for packaging, food storage, microwave oven, agriculture, civil engineering, fishery, automobile interior / exterior, marine, daily necessities, building material interior / exterior, housing equipment, medical / medical / It is preferably used for medical equipment, pharmaceuticals, home appliances, furniture, stationery / office supplies, sales promotion, commercial use, electrical and electronic industrial use, industrial material use, and the like.

The method for producing a printed matter for retort of the present invention is a step of preparing a plastic base film and printing the gravure ink set for retort on at least one of the plastic base films with a thickness of 0.1 to 3 μm. It is preferable to include a gravure printing step of forming a printed layer. The film thickness of the print layer is more preferably 0.3 to 2 μm. If it is smaller than 0.1 μm, metallic luster cannot be obtained because the brightness is lowered, and if it is larger than 3 μm, the retort resistance and blocking resistance may be inferior.

The method for producing the printed matter for retort may be a single print layer obtained by printing the gravure ink set for retort, but gravure printing for creating another print layer formed by printing the print layer and another gravure ink set. The process may be included, and it is more preferable that the product is produced by a gravure printing process using a multicolor gravure printing machine.

The laminate of the present invention may include a step of laminating a sealant layer after a gravure printing step according to a method for producing a printed matter for retort. The step of laminating the sealant layer may be, for example, a step of laminating a laminate having heat-sealing property or a known sealant film.
In addition to the printing layer and the sealant layer, for imparting or enhancing performance such as rigidity, waist, gas barrier property, aroma retention property, moisture proof property, pinhole resistance, dead hole property, light shielding property, and linear cut property. The step of laminating the intermediate layer may be included.

The packaging bag of the present invention requires a plastic base film, a printing layer for retort, and a sealant layer in this order from the outer layer, and it is preferable that the printing layer for retort is formed by the gravure ink set for retort. ..

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 requires a plastic base film, a printing layer for retort, and a sealant layer, and it is preferable that the printing layer for retort is formed by the gravure ink set for retort. The form of the lid material may be any of well-known forms such as a cover, a lid, and a cap.

In the gravure ink set for retort, the solid content weight ratio of the thermoplastic resin (B) in the gravure ink and the isocyanate compound (D) in the curing agent solution is preferably (B) / (D) = 60/40 to. It is adjusted to be 99/1, and more preferably 62/38 to 95/5.

The gravure ink set for retort 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.) Then, 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 gravure ink 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. 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, henschel 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 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. 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 curing agent solution can be produced by a known method by uniformly dissolving or dispersing an isocyanate compound, 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, henschel 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 curing agent solution 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 diluting solvent in the curing agent solution may be any one as long as it can be used by adjusting the viscosity of the curing agent solution, and examples thereof include organic solvents, and commercially available ones can also be used, and there is no particular limitation. Commercially available products include PU533 solvent (toluene-containing solvent), PU515 solvent (non-toluene solvent), SL9155 solvent (non-toluene solvent), SL9164 solvent (non-ketone solvent), SL9170 solvent (non-ketone solvent) (above, All of them are 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 vinyl chloride / vinyl acetate copolymer resin]
Put 20 parts of carboxyl group-modified vinyl chloride / vinyl acetate copolymer resin (solvine M5, acid value 5.9 mgKOH / g, manufactured by Nisshin Chemical Industry Co., Ltd.) and 80 parts of methyl ethyl ketone (MEK) in a beaker at 600 rpm. The mixture was stirred for 30 minutes to obtain 100 parts of a carboxyl-modified vinyl chloride / vinyl acetate copolymer resin CL1 having a solid content of 20%. Similarly, using a carboxyl-modified vinyl chloride / vinyl acetate copolymer resin (Kanevinyl T5DA, acid value 6.5 mgKOH / g, manufactured by Kaneka Co., Ltd.), both carboxyl group-modified vinyl chloride and vinyl acetate having a solid content of 20% are used. 20% solid content using polymer resin CL2, a hydroxyl group-containing vinyl chloride / vinyl acetate copolymer resin with a solid content of 20% (hydroxyl value 98 mgKOH / g, acid value 0 mgKOH / g, manufactured by Nissin Chemical Industry Co., Ltd.) CL3 and a non-modified vinyl chloride / vinyl acetate copolymer resin (solvine CL, acid value 0 mgKOH / g, manufactured by Nisshin Kagaku Kogyo Co., Ltd.) were used to obtain CL4 having a solid content of 20%.

[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 atomization method as raw materials, 3. Together with 5 kg of 2φ bearing balls, they were charged into a ball mill and pulverized to obtain a slurry.
After completion of pulverization, the slurry was sieved to 37 μm to remove coarse particles, and then excess solvent was removed by a filter press to obtain a cake having a solid content of 90%. The obtained cake was transferred into a vertical mixer, mineral spirit was added, and the mixture was stirred for 15 minutes to obtain an aluminum paste A1 containing an untreated aluminum pigment. The aluminum pigment contained in the composition was a non-leaving type and had a solid content of 70%.

[Gravure ink]
Gravure ink set 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 70%) 5 parts, acetic acid 40 parts of propyl was placed in a beaker and mixed and stirred at 600 rpm for 30 minutes to prepare gravure ink g1, and then the curing agent solution S1 (LG curing agent C, isocyanate compound, solvent: ethyl acetate, solid content 50%, Tokyo 5 parts of Ink Co., Ltd.) were placed in a beaker, stirred, and dispersed for 10 minutes to obtain 105 parts of a gravure ink set G1.

(Examples 2 to 5 and Comparative Examples 2 to 8)
Similarly, the gravure ink sets G2 to G5 and G7 to G13 of Examples 2 to 5 and Comparative Examples 2 to 8 were prepared according to the formulations shown in Tables 1 and 2. In Comparative Example 8, a polyurethane resin PU2 having a free carboxyl group (product name: UR-1400, acid-modified polyurethane resin manufactured by Toyobo Co., Ltd., solid content 30%) was used as the polyurethane resin.

(Comparative Example 1)
Carboxyl modified vinyl chloride / vinyl acetate copolymer resin CL1 35 parts, polyurethane resin PU1 25 parts, aluminum paste A2 (resin coated aluminum pigment 44%: BP-280PA, manufactured by Toyo Aluminum Co., Ltd.) 13 parts, propyl acetate 27 parts Was charged into a beaker and stirred at 600 rpm for 30 minutes to prepare gravure ink g6, and then 5 parts of a curing agent solution S1 (LG curing agent C) was charged into a beaker and stirred for 10 minutes to disperse the gravure. 105 parts of ink set G6 was obtained.

[Preparation of printed matter for retort pouch]
Attach the engraving helio plate (compress stylus 130 °, 70 L / m) to GRAVO-PROOF (product number: CM-W, manufactured by Nissho Gravure Co., Ltd.), and dilute the gravure ink set G1 with a diluting solvent (MEK 40 parts, acetic acid). With 40 parts of propyl and 20 parts of IPA), Zahn Cup No. After adjusting the viscosity to 17 seconds in No. 3, printing was performed on a PET film (E-5102, manufactured by Toyobo Co., Ltd.) having a thickness of 12 μm with a film thickness of 1.2 μm to obtain a printed matter PR1 for retort pouch. Similarly, as shown in Table 3, the gravure ink set and the film thickness were changed to obtain PR2-3, PR6-7, and PR9-13 for retort printed matter, respectively.

Further, the film base material was replaced with Barrier Rocks 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. Got Similarly, as shown in Table 3, the retort ink set and the film thickness were changed to obtain retort printed matter PR5 and PR8, respectively.

[Preparation of laminate]
Takelac A-525 / Takenate A-52 (abbreviation: DL, manufactured by Mitsui Chemicals, Inc.) is coated on the print layer of the printed matter PR1 for retort with A-Bar OSP-10 (manufactured by OSG System Products Co., Ltd.). After laminating the nylon film emblem ONMB-RT (manufactured by Unitika Ltd.) with a thickness of 15 μm, and similarly, the CPP Trefan NO ZK93KM (manufactured by Toray Film Processing Co., Ltd.) with a thickness of 60 μm. , Aged at 50 ° C. for 72 hours to obtain a laminated product LAM1. Similarly, instead of the printed matter PR2-3, PR6-7, and PR9-13 for retort pouch, laminated bodies LAM2-3, LAM6-7, and LAM9-13 were obtained, respectively.

Dick dry LX-760 / KP-70 (abbreviation: DL, manufactured by DIC Co., Ltd.) is coated with A-Bar OSP-10 (manufactured by OSG System Products Co., Ltd.) on the print PR4 for retort. , 15 μm thick nylon film emblem ONMB-RT (manufactured by Unitika Ltd.) is bonded, and similarly, 60 μm thick Trefan NO ZK93KM (manufactured by Toray Film Processing Co., Ltd.) is bonded, and then 50 ° C. Aging was carried out for 72 hours to obtain a laminated body LAM4. Then, instead of the printed matter PR5 and PR8, laminated bodies LAM5 and LAM8 were obtained, respectively.

<Retort resistance>
Two of each laminate were ^{adhered by heat sealing under the conditions of 3 kgf / cm 2} , 180 ° C. and 1 second to obtain a 15 cm × 10 cm packaging bag having an opening. This packaging bag was filled with a mixture of salad oil / ketchup / vinegar = 1/1/1 as the content, and then the opening was sealed by heat sealing in the same manner as the above conditions to prepare a packaging bag. This packaging bag was retorted at 135 ° C. for 30 minutes by a hot water shower method, and the appearance of the packaging bag was visually observed and evaluated. The appearance of the packaging bag was evaluated for any floating due to peeling of the printing layer.
The evaluation was made on a two-point scale: 〇: no change at all, ×: floating was observed.

<Blocking resistance>
Two printed matter for retort is cut into a size of 3 cm × 3 cm, the printed surface and the non-printed surface are overlapped, and ^{a load of 5 N / cm 2} is applied at 50 ° C. for 24 hours, and then the printed surface and the non-printed surface are printed. The ink peeling state when the overlapped portions of the surfaces were peeled off was confirmed, and the ink peeling and peeling resistance at that time were evaluated.
The evaluation was made in two stages: ◯: peeling without resistance and no ink peeling, and ×: high resistance at the time of peeling and ink peeling was observed.

<Design>
Whether the sample of the above-mentioned retort resistance evaluation test has a design in which metallic luster is recognized with respect to the surface state of the laminates of Examples and Comparative Examples under a standard light source (model: Macbeth judgeII, manufactured by X-Rite). evaluated. Ten panelists evaluated and calculated the total score, with 1 point having metallic luster and 0 point having no metallic luster. The evaluation was made on a two-point scale of 〇: total score of 7 or more and ×: less than 7.

According to Table 3, it is clear that the printed matter for retort using the gravure ink sets of Examples 1 to 5 is excellent in retort resistance, blocking resistance, and design property.
The laminate LAM6 of Comparative Example 1 using the gravure ink g6 using the resin-coated aluminum pigment and the gravure ink set G6 of the curing agent solution S1 similar to Patent Document 2 is inferior in both retort resistance and design. It is clear.
Further, it is clear that the laminate LAM13 of Comparative Example 8 using the gravure ink g13 using the polyurethane resin having a free carboxyl group and the hydroxyl group-containing vinyl chloride / vinyl acetate copolymer resin is inferior in both retort resistance and design. Is.
Further, the laminated body LAM7 using the gravure ink g7 using the hydroxyl group-containing vinyl chloride / vinyl acetate copolymer resin CL3 and the gravure ink set G7 of the curing agent solution S1 of Comparative Example 2 has both retort resistance and design properties. It is clear that it is inferior.
Further, the laminated body LAM10 using the gravure ink g10 using the unmodified vinyl chloride / vinyl acetate copolymer resin CL4 and the gravure ink set G10 of the curing agent solution S1 of Comparative Example 5 has retort resistance and design. It is clear that both sexes are inferior.
The retort printed matter (PR8, PR9) and the laminate (LAM8, LAM9) using the gravure ink sets (G8, G9) of Comparative Examples 3 to 4 are inferior in any of the retort resistance, blocking resistance, and design property. It is clear.
Further, the retort printed matter (PR11, PR12) and the laminate (LAM11, LAM12) of Comparative Examples 6 to 7, whose film thickness is out of the range, are inferior in any of the retort resistance, blocking resistance, and design property. Is clear.

Claims (6)

The retort gravure ink set is a retort printed matter in which a retort printing layer is formed on at least one surface of a plastic base film with a thickness of 0.1 to 3 μm, and the retort gravure ink set is , A set of two types of ink , a gravure ink and a curing agent solution used together with the gravure ink.
The gravure ink contains an aluminum pigment (A) obtained by an atomizing method and not polymerized, and a thermoplastic resin (B).
The thermoplastic resin contains an acid-modified vinyl chloride / vinyl acetate copolymer resin (b1) and a polyurethane resin (b2).
The curing agent solution contains an isocyanate compound (D) and a solvent (E).
The solid content weight ratio of the thermoplastic resin (B) in the gravure ink and the isocyanate compound (D) in the curing agent solution is (B) / (D) = 60/40 to 99/1.
The acid-modified vinyl chloride / vinyl acetate copolymer resin (b1) is a carboxyl group-modified vinyl chloride / vinyl acetate copolymer resin having an acid value of 3 to 30 mgKOH / g.
Printed matter for retort pouches . A laminate according to claim 1 , wherein a sealant layer is laminated on the retort print layer of the printed matter for retort. The process of preparing the plastic base film and
A gravure printing step of mixing a gravure ink of a gravure ink set for retort and a curing agent solution on at least one of the plastic base films and printing with a thickness of 0.1 to 3 μm to form a printed layer for retort. A method for producing printed matter for retort , including
The gravure ink contains an aluminum pigment (A) obtained by an atomizing method and not polymerized, and a thermoplastic resin (B).
The thermoplastic resin contains an acid-modified vinyl chloride / vinyl acetate copolymer resin (b1) and a polyurethane resin (b2).
The curing agent solution contains an isocyanate compound (D) and a solvent (E).
The solid content weight ratio of the thermoplastic resin (B) in the gravure ink and the isocyanate compound (D) in the curing agent solution is (B) / (D) = 60/40 to 99/1.
The acid-modified vinyl chloride / vinyl acetate copolymer resin (b1) is a carboxyl group-modified vinyl chloride / vinyl acetate copolymer resin having an acid value of 3 to 30 mgKOH / g.
A method for manufacturing a printed matter for retort pouch. The process of preparing the plastic base film and
A gravure printing step of forming a retort printing layer formed by printing a retort gravure ink set with a film thickness of 0.1 to 3 μm on at least one of the plastic base films.
Laminating process for laminating the sealant layer and
It is a manufacturing method of a laminated body containing
The gravure ink set for retort is a set of two types of ink, a gravure ink and a curing agent solution used together with the gravure ink.
The gravure ink contains an aluminum pigment (A) obtained by an atomizing method and not polymerized, and a thermoplastic resin (B).
The thermoplastic resin contains an acid-modified vinyl chloride / vinyl acetate copolymer resin (b1) and a polyurethane resin (b2).
The curing agent solution contains an isocyanate compound (D) and a solvent (E).
The solid content weight ratio of the thermoplastic resin (B) in the gravure ink and the isocyanate compound (D) in the curing agent solution is (B) / (D) = 60/40 to 99/1.
The acid-modified vinyl chloride / vinyl acetate copolymer resin (b1) is a carboxyl group-modified vinyl chloride / vinyl acetate copolymer resin having an acid value of 3 to 30 mgKOH / g.
A method for manufacturing a laminated body, which is characterized in that. In a packaging bag that requires a plastic base film, a printing layer for retort having a thickness of 0.1 to 3 μm, and a sealant layer in this order from the outer layer, the printing layer for retort is formed by a gravure ink set for retort. It is,
The gravure ink set for retort is a set of two types of ink, a gravure ink and a curing agent solution used together with the gravure ink.
The gravure ink contains an aluminum pigment (A) obtained by an atomizing method and not polymerized, and a thermoplastic resin (B).
The thermoplastic resin contains an acid-modified vinyl chloride / vinyl acetate copolymer resin (b1) and a polyurethane resin (b2).
The curing agent solution contains an isocyanate compound (D) and a solvent (E).
The solid content weight ratio of the thermoplastic resin (B) in the gravure ink and the isocyanate compound (D) in the curing agent solution is (B) / (D) = 60/40 to 99/1.
The acid-modified vinyl chloride / vinyl acetate copolymer resin (b1) is a carboxyl group-modified vinyl chloride / vinyl acetate copolymer resin having an acid value of 3 to 30 mgKOH / g.
A packaging bag characterized by that.
In the lid material that requires a plastic base film, a printing layer for retort having a thickness of 0.1 to 3 μm, and a sealant layer in order from the outer layer, the printing layer for retort is a gravure ink set for retort. Formed,
The gravure ink set for retort is a set of two types of ink, a gravure ink and a curing agent solution used together with the gravure ink.
The gravure ink contains an aluminum pigment (A) obtained by an atomizing method and not polymerized, and a thermoplastic resin (B).
The thermoplastic resin contains an acid-modified vinyl chloride / vinyl acetate copolymer resin (b1) and a polyurethane resin (b2).
The curing agent solution contains an isocyanate compound (D) and a solvent (E).
The solid content weight ratio of the thermoplastic resin (B) in the gravure ink and the isocyanate compound (D) in the curing agent solution is (B) / (D) = 60/40 to 99/1.
The acid-modified vinyl chloride / vinyl acetate copolymer resin (b1) is a carboxyl group-modified vinyl chloride / vinyl acetate copolymer resin having an acid value of 3 to 30 mgKOH / g.
A lid material characterized by that.