JP6935564B1 - Microwave oven gravure ink composition, microwave oven printed matter, laminate, microwave oven printed matter manufacturing method, laminate manufacturing method, packaging bag, lid material and label - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a range-up property which does not generate sparks even when using a microwave oven for business use, a design property having a metallic luster with brightness, and a gravure ink for a microwave oven which can obtain sufficient lamination strength when formed into a laminate. The composition is provided. SOLUTION: An untreated aluminum pigment (A) and a thermoplastic resin (B) are contained, and the thermoplastic resin (B) is an acid-modified vinyl chloride / vinyl acetate copolymer resin (b1) and a polyurethane resin (b2). ), And the solid content weight ratio of the acid-modified vinyl chloride / vinyl acetate copolymer resin (b1) to the polyurethane resin (b2) is (b1) / (b2) = 5/95 to 95/5. The acid value of the acid-modified vinyl chloride / vinyl acetate copolymer resin (b1) is 2 mgKOH / g or more, and the solid content weight ratio of the untreated aluminum pigment (A) to the thermoplastic resin (B) is high. (A) / (B) = 60/40 to 1/99, a gravure ink composition for a microwave oven. [Selection diagram] None

Description

The present invention relates to a gravure ink composition for a microwave oven, a printed matter for a microwave oven, a laminate, a method for producing a printed matter for a microwave oven, a method for producing a laminate, a packaging bag, a lid material, and a label.

Conventionally, flexible packaging products using a plastic film have been used for packaging bags and containers for storing various products such as foods and drinks and detergents. These flexible packaging products are variously designed to increase their commercial value, but they are given a metallic glossy design to enhance the aesthetics and enhance the design by making a difference from the colors of general hues. In some cases, a method of printing an aluminum foil, an aluminum vapor-deposited film, or an ink using an aluminum pigment on a part of the base material has been adopted in order to give a metallic luster.
In recent years, it has become common for frozen foods, retorts, and bento boxes contained in flexible packaging products sold at supermarkets and convenience stores to be heated by a microwave oven. However, since microwaves are used for heating in a microwave oven, if aluminum foil or aluminum vapor deposition film is used for the purpose of giving a metal design to flexible packaging products, sparks due to microwaves reflected on the metal surface will occur, and the packaging material. There was a problem of shrinking. To solve this problem, a packaging material that suppresses sparks when using a microwave oven by printing an aluminum pigment ink has been proposed.

Patent Document 1 describes a plastic film or sheet for packaging in which an ink containing an aluminum pigment is coated on a plastic film or a plastic sheet and is suitable for microwave cooking, and prevents sparks from being generated by microwaves. However, since it is an ink in which aluminum paste is mixed only with urethane resin and solvent, the adhesive force between aluminum and urethane resin, which is a binder, is weak, and the aluminum ink layer becomes a peeling surface due to external force and becomes a laminate. There was a problem that the adhesion was inferior when the plastic was used.

Patent Document 2 describes a packaging material for a microwave oven using a metal scale coated with a curable resin, a metal scale having an aspect ratio of 50 or more, or a non-leaving type metal scale, and has a metallic luster. It is said that a packaging material that has both aesthetic appearance and suppression of sparks when heating a microwave oven can be obtained. However, in the specifically disclosed example of Patent Document 2, it is said that the appearance evaluation of the metallic luster is excellent even in the example outside the scope of the claims, and the aluminum foil has a glossiness of a normal aluminum pigment. It was not possible to obtain a design with a metallic luster with such high brightness.

Further, the plastic film or sheet for packaging of Patent Document 1 and the packaging material described in Patent Document 2 are evaluated by a microwave oven at a household output of 500 to 600 W, and are used in convenience stores and the like. A microwave oven with a high output of 1500 W or more, which is used for commercial purposes, generated sparks and could not be used.

Japanese Unexamined Patent Publication No. 9-226825 Japanese Unexamined Patent Publication No. 2019-51992

Therefore, the present invention provides a microwave oven that does not generate sparks even when used in a commercial microwave oven, has a bright metallic luster design, and has sufficient lamination strength when formed into a laminated body. To provide a gravure ink composition for use.

The present inventors form a printing layer for a microwave oven in which an ink layer for a gravure ink composition for a microwave oven is laminated on at least one surface of a plastic base film with a thickness of 0.1 to 3 μm. The printed matter for a microwave oven, wherein the gravure ink composition for a microwave oven contains an aluminum pigment (A) obtained by an atomizing method and not subjected to a polymerization treatment and a thermoplastic resin (B), and the thermoplastic resin ( B) contains an acid-modified vinyl chloride / vinyl acetate copolymer resin (b1) and a polyurethane resin (b2), and the acid-modified vinyl chloride / vinyl acetate copolymer resin (b1) and the polyurethane resin (b2). ) Has a solid content weight ratio of (b1) / (b2) = 5/95 to 95/5, and the acid-modified vinyl chloride / vinyl acetate copolymer resin (b1) has an acid value of 3 to 30 mgKOH / g. The solid content weight ratio of the unpolymerized aluminum pigment (A) and the thermoplastic resin (B) is (A) / (B) =. It has been found that the above object can be achieved by the printed matter for a microwave oven, which is 60/40 to 1/99, and the present invention has been completed.

That is, in the present invention, (1) a microwave oven printing layer formed by laminating an ink layer with a film thickness of 0.1 to 3 μm on at least one surface of a plastic base film. It is a printed matter for a microwave oven to be formed.
The microwave oven gravure ink composition contains an aluminum pigment (A) obtained by an atomizing method and not polymerized, and a thermoplastic resin (B).
The thermoplastic resin (B) contains an acid-modified vinyl chloride / vinyl acetate copolymer resin (b1) and a polyurethane resin (b2).
The solid content weight ratio of the acid-modified vinyl chloride / vinyl acetate copolymer resin (b1) to the polyurethane resin (b2) is (b1) / (b2) = 5/95 to 95/5.
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 , and the aluminum pigment which has not been polymerized ( A printed matter for a microwave oven, wherein the solid content weight ratio of A) and the thermoplastic resin (B) is (A) / (B) = 60/40 to 1/99.
(2) A laminate characterized in that a sealant layer or a seal layer is laminated on the microwave oven print layer of the microwave oven printed matter according to (1).
(3) The process of preparing the plastic base film and
A printed matter for a microwave oven including a gravure printing step of forming a printing layer for a microwave oven formed by printing a gravure ink composition for a microwave oven with a film thickness of 0.1 to 3 μm on at least one of the plastic base films. It is a manufacturing method of
The microwave oven gravure ink composition contains an aluminum pigment (A) obtained by an atomizing method and not polymerized, and a thermoplastic resin (B).
The thermoplastic resin (B) contains an acid-modified vinyl chloride / vinyl acetate copolymer resin (b1) and a polyurethane resin (b2).
The solid content weight ratio of the acid-modified vinyl chloride / vinyl acetate copolymer resin (b1) to the polyurethane resin (b2) is (b1) / (b2) = 5/95 to 95/5.
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, and the aluminum pigment which has not been polymerized ( A method for producing a printed matter for a microwave oven, wherein the solid content weight ratio of A) and the thermoplastic resin (B) is (A) / (B) = 60/40 to 1/99.
(4) The process of preparing the plastic base film and
A gravure printing step of forming a printing layer for a microwave oven formed by printing a gravure ink composition for a microwave oven 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 or coating process for laminating the seal layer,
It is a manufacturing method of a laminated body containing
The microwave oven gravure ink composition contains an aluminum pigment (A) obtained by an atomizing method and not polymerized, and a thermoplastic resin (B).
The thermoplastic resin (B) contains an acid-modified vinyl chloride / vinyl acetate copolymer resin (b1) and a polyurethane resin (b2).
The solid content weight ratio of the acid-modified vinyl chloride / vinyl acetate copolymer resin (b1) to the polyurethane resin (b2) is (b1) / (b2) = 5/95 to 95/5.
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, and the aluminum pigment which has not been polymerized ( A method for producing a laminate, wherein the solid content weight ratio of A) and the thermoplastic resin (B) is (A) / (B) = 60/40 to 1/99.
(5) In a packaging bag that requires a plastic base film, a microwave oven printing layer having a film thickness of 0.1 to 3 μm, and a sealant layer in this order from the outer layer.
The printing layer for a microwave oven is formed of a gravure ink composition for a microwave oven.
The microwave oven gravure ink composition contains an aluminum pigment (A) obtained by an atomizing method and not polymerized, and a thermoplastic resin (B).
The thermoplastic resin (B) contains an acid-modified vinyl chloride / vinyl acetate copolymer resin (b1) and a polyurethane resin (b2).
The solid content weight ratio of the acid-modified vinyl chloride / vinyl acetate copolymer resin (b1) to the polyurethane resin (b2) is (b1) / (b2) = 5/95 to 95/5.
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, and the aluminum pigment which has not been polymerized ( A packaging bag characterized in that the solid content weight ratio of A) and the thermoplastic resin (B) is (A) / (B) = 60/40 to 1/99.
(6) In the lid material which requires a plastic base film, a printing layer for a microwave oven having a thickness of 0.1 to 3 μm, and a sealant layer in this order from the outer layer, the printing layer for the microwave oven is for a microwave oven. Formed with a gravure ink composition,
The microwave oven gravure ink composition contains an aluminum pigment (A) obtained by an atomizing method and not polymerized, and a thermoplastic resin (B).
The thermoplastic resin (B) contains an acid-modified vinyl chloride / vinyl acetate copolymer resin (b1) and a polyurethane resin (b2).
The solid content weight ratio of the acid-modified vinyl chloride / vinyl acetate copolymer resin (b1) to the polyurethane resin (b2) is (b1) / (b2) = 5/95 to 95/5.
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, and the aluminum pigment which has not been polymerized ( A lid material, wherein the solid content weight ratio of A) and the thermoplastic resin (B) is (A) / (B) = 60/40 to 1/99.
(7) In a label that requires a plastic base film, a microwave oven printing layer having a thickness of 0.1 to 3 μm, and a sealant layer or a seal layer in this order from the outer layer, the microwave oven printing layer is an electron. The gravure ink composition for a microwave oven, which is formed of a gravure ink composition for a microwave oven, contains an aluminum pigment (A) obtained by an atomizing method and not subjected to a polymerization treatment, and a thermoplastic resin (B).
The thermoplastic resin (B) contains an acid-modified vinyl chloride / vinyl acetate copolymer resin (b1) and a polyurethane resin (b2).
The solid content weight ratio of the acid-modified vinyl chloride / vinyl acetate copolymer resin (b1) to the polyurethane resin (b2) is (b1) / (b2) = 5/95 to 95/5.
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, and the aluminum pigment which has not been polymerized ( A label characterized in that the solid content weight ratio of A) and the thermoplastic resin (B) is (A) / (B) = 60/40 to 1/99.
It is about.

The present invention is a microwave oven gravure that can provide a range-up property that does not generate sparks even when used in a commercial microwave oven, a design with a bright metallic luster, and sufficient lamination strength when formed into a laminated body. An ink composition can be provided.

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

The gravure ink composition for a microwave oven of the present invention (hereinafter, also simply referred to as “ink composition”) contains an untreated aluminum pigment (A) and a thermoplastic resin (B), and the thermoplastic resin (B). However, the acid-modified vinyl chloride / vinyl acetate copolymer resin (b1) and the polyurethane resin (b2) are contained, and the acid-modified vinyl chloride / vinyl acetate copolymer resin (b1) and the polyurethane resin (b2) The solid content weight ratio is (b1) / (b2) = 5/95 to 95/5, and the acid value of the acid-modified vinyl chloride / vinyl acetate copolymer resin (b1) is 2 mgKOH / g or more. The solid content weight ratio of the untreated aluminum pigment (A) to the thermoplastic resin (B) is preferably (A) / (B) = 60/40 to 1/99.

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 polyurethane resin (b2), which will be described later, the affinity is improved, and the range-up property and the design property with brightness are improved. , And a printed matter having excellent adhesion 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 range-up property and the laminating strength are improved. 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, 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. 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. 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 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 adsorption ability of the acid-modified vinyl chloride / vinyl acetate copolymer resin to the untreated aluminum pigment is lowered, and the printed matter is printed. Sparks are likely to occur when exposed to microwaves, and if it is larger than 95, the adhesion when formed into a laminated body is lowered.

In the gravure ink composition for a microwave oven 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. When the untreated aluminum pigment (A) is larger than 60, sparks due to microwaves are likely to occur because the resin content is small, and the adhesion is also inferior. I can't get it.

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 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 gravure ink composition for a microwave oven 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 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 printed matter for a microwave oven of the present invention is a printed matter for a microwave oven, wherein the gravure ink composition for a microwave oven is 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. It is preferable to form a layer. The film thickness of the ink layer is more preferably 0.3 to 2 μm. If it is smaller than 0.1 μm, the design is inferior, and if it is larger than 3 μm, the adhesiveness is inferior.

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

The printing layer for a microwave oven preferably has an ink layer formed on at least one surface of a plastic base film. The printing layer for a microwave oven is preferably formed by being coated by a gravure printing method, and can also be coated as a one-point design. The printing layer for a microwave oven may be an ink layer alone formed by laminating with a gravure ink composition for a microwave oven, or may include the ink layer and another ink layer laminated with another gravure ink composition. good. In particular, by forming a printing layer for a microwave oven 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 all solid printing but also gradation printing is 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 printing layer for a microwave oven like 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). It may be configured as an ink layer / DL / other base material), or after forming a printing layer for a microwave oven such as a plastic base material film / another ink layer / ink layer, another base material is dry-laminated or the like. May be laminated (plastic base film / other ink layer / ink layer / DL / other base material).

In the laminate of the present invention, a sealant layer or a seal layer may be laminated on the printing layer for a microwave oven. The sealant layer is preferably a sealant layer obtained by, for example, laminating a laminate having heat-sealing properties or a known sealant film, resin coating by an extrusion laminating method, coating with a heat-sealing agent or a hot-melting agent, or the like. ..

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 printing layer for a microwave oven on the plastic base film is bonded to a known sealant film via an adhesive (dry laminating method, non-solvent laminating method, wet laminating method), or heat-bonded (thermal laminating). Method), resin coating by extrusion laminating (extrusion laminating method, coextrusion laminating method, PE sandwich laminating method) and the like can be preferably used. A laminate can be produced by using these methods alone or in combination.
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.

Resins that can be used for 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 and polypropylene with maleic acid and fumal Examples thereof include acid-modified polyolefin resins modified with an acid, polystyrene resins, and thermoplastic resins such as polybutylene terephthalate resins, and these resins may be one or more laminated.

As the seal layer, as long as the seal strength can be sufficiently ensured, the laminating method is appropriately selected according to the printing substrate, application, configuration, and the like. For example, a heat sealant or hot melt coating can be preferably used. A laminate can be produced by using these methods alone or in combination. 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 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.

Resins that can be used for 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 and polypropylene with maleic acid and fumal Examples thereof include acid-modified polyolefin resins modified with an acid, polystyrene resins, and thermoplastic resins such as polybutylene terephthalate resins, and these resins may be one or more laminated.

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 emulsion, urethane emulsion, ethylene-vinyl alcohol emulsion, polyethylene emulsion, polypropylene emulsion, and ethylene vinyl acetate emulsion. Can be mentioned.

In addition to the printing layer for microwave ovens, the sealant layer or the sealing layer, the laminate of the present invention has rigidity, waist, gas barrier property, fragrance retention, moisture resistance, pinhole resistance, deadhole property, and light shielding property. An intermediate layer may be laminated to impart or enhance performance such as linear cutability. When the intermediate layer is provided, it is not always necessary to provide the printing layer for a microwave oven on the plastic base film, and the printing layer for a microwave oven may be provided on the intermediate layer.

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

When an adhesive is used in the dry laminating method, non-solvent laminating method, wet laminating method, extrusion laminating method, etc., a commercially available adhesive may be used. Examples thereof include epoxy-based, polyester-based, polyethyleneimine-based, polybutadiene-based, water-based urethane-based, isocyanate-based, organic titanium-based, starch-based water-soluble adhesives, and water-based adhesives such as vinyl acetate emulsions. As a method of applying the adhesive for 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 preservation, retort, agriculture, civil engineering, fishery, automobile interior / exterior, marine products, daily necessities, building material interior / exterior, housing equipment, medical / medical. It is preferably used for equipment, autoclave, pharmaceutical, home appliances, furniture, stationery / office supplies, sales promotion, commercial, electrical and electronic industry, and industrial materials. Above all, it is more preferable to be used for packaging.

The method for producing a printed matter for a microwave oven of the present invention comprises a step of preparing a plastic base film and a gravure ink composition for a microwave having a thickness of 0.1 to 3 μm on at least one of the plastic base films. It is preferable to include a gravure printing step of forming a printed layer formed by printing. The film thickness of the print layer is more preferably 0.3 to 2 μm. If it is smaller than 0.1 μm, the brightness is lowered and the design is inferior. If it is larger than 3 μm, the adhesion is poor.

The method for producing a printed matter for a microwave oven may be a single printing layer obtained by printing the gravure ink composition for a microwave oven, but the printing layer and another printing layer obtained by printing another gravure ink composition may be used. The gravure printing step of forming may be included, and it is more preferable that the gravure printing step is formed by using a multicolor gravure printing machine.

The method for producing a laminate of the present invention may include a step of laminating a sealant layer or a coating step of laminating a seal layer after a gravure printing step according to a method for producing a printed matter for a microwave oven.
Examples of the step of laminating 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 laminating the sealant layer. May be a process such as coating with a heat sealant or a hot melt agent.
In addition to the printing layer, the sealant layer or the sealing layer, performances 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 are imparted or enhanced. It may include the step of laminating the intermediate layer for this purpose.

The packaging bag of the present invention requires a plastic base film, a microwave oven printing layer, and a sealant layer in this order from the outer layer, and the microwave oven printing layer is formed of the microwave oven gravure ink composition. It is preferable to have.

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 a microwave oven, and a sealant layer, and it is preferable that the printing layer for a microwave oven is formed of the gravure ink composition for a microwave oven. .. The form of the lid material may be any of well-known forms such as a cover, a lid, and a cap.

Further, it is preferable that the container is in close contact with the container to form a closed container. Adhesion to the container may be carried out manually, or a machine such as an automatic sealing device may be used. These may be appropriately selected depending on the type, form and size, quantity, sealed container, equipment, environment, etc. of the food, and may be attached or adhered with a heat seal (heat pressure seal), a surface seal, an adhesive, or the like. It may be done by a method using such as.
It is more preferable that the container is a bottomed cylindrical container. In this case, the lid material preferably covers the opening of the bottomed cylindrical 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 requires a plastic base film, a printing layer for a microwave oven, a sealant layer or a sealing layer, and the printing layer for a microwave oven is formed of the gravure ink composition for a microwave oven. Is preferable.
Further, a label can be obtained by laminating an adhesive layer or an adhesive layer on a plastic base film or another base material on the other side on which the printing layer for a microwave oven is formed, and further laminating a release layer. As long as the adhesive layer or adhesive layer adheres to the release layer with a plastic base film or other base material such as a rubber-based adhesive material or an acrylic resin-based adhesive material, and the release layer can be easily peeled off. Either may be used. The release layer may be a polyethylene film, a polyester film, or paper (release paper).

The gravure ink composition for a microwave oven 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 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 it with a diluting solvent. The viscosity in this case is preferably 10 to 40 seconds at 25 ° C. If it is less than 10 seconds, it is easy to swim, and if it is longer than 40 seconds, the transferability at the time of printing is deteriorated.

The diluting solvent may be any one as long as it can be used by adjusting the viscosity of the ink composition, and examples thereof include organic solvents, and commercially available ones can also be used, and there is no particular limitation. Commercially available products include TA52 solvent (alcohol-based solvent), PU533 solvent (toluene-based), 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) (all of which are manufactured by Tokyo Ink Co., Ltd.) and the like.

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.

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]
Carboxyl-modified vinyl chloride / vinyl acetate copolymer resin (solvine M5, acid value 5.9 mgKOH / g, manufactured by Nisshin Kagaku Kogyo Co., Ltd.) 20 parts, methyl ethyl ketone (MEK) 80 parts, put in a beaker, 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.

[Untreated aluminum pigment]
Using 100 g of raw 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 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 untreated aluminum pigment in the aluminum paste was a non-leaving type and had a solid content of 70%.

[Making ink for microwave oven]
(Example 1)
Carboxy-modified vinyl chloride / vinyl acetate copolymer resin CL1 25 parts, polyurethane resin (solid content 30%, manufactured by Tokyo Ink Co., Ltd.) 30 parts, aluminum paste A1 (untreated aluminum pigment 70%) 5 parts, propyl acetate 40 parts were charged in a beaker and stirred at 600 rpm for 30 minutes to obtain 100 parts of the microwave ink G1 of Example 1.

(Examples 2 to 6, Comparative Examples 1 to 6 and Comparative Example 8)
Similarly, the microwave oven inks G2 to G12 and G14 of Examples 2 to 6, Comparative Examples 1 to 6 and Comparative Example 8 were prepared according to the formulations shown in Tables 1 and 2.

(Comparative Example 7)
Carboxyl modified vinyl chloride / vinyl acetate copolymer resin CL1 25 parts, polyurethane resin (solid content 30%, manufactured by Tokyo Ink Co., Ltd.) 30 parts, aluminum paste A2 (resin coated aluminum pigment 44%: BP-280PA, Toyo (Manufactured by Aluminum Co., Ltd.) 5 parts and 40 parts of propyl acetate were placed in a beaker and stirred at 600 rpm for 30 minutes to obtain 100 parts of the microwave ink G13 of Comparative Example 7.

[Making printed matter for microwave ovens]
Attach the engraving helio plate (compressed stylus 130 °, 70 L / cm) to the gravure calibrator GRAVO-PROOF (product number: CM-W, manufactured by Nissho Gravure Co., Ltd.), and dilute the microwave ink G1 with a diluting solvent (MEK 40). 40 parts of propyl acetate, 20 parts of isopropyl alcohol) After adjusting the viscosity to 17 seconds in 3, printing was performed on a PET film (E-5102, 12 μ, manufactured by Toyobo Co., Ltd.) with a film thickness of 1.1 μm to obtain a printed matter PR1 for a microwave oven. Similarly, as shown in Table 3, the ink for microwave oven and the film thickness were changed to obtain printed matter PR5, PR6, PR7, PR8, PR9, and PR12 for microwave oven, respectively.

Further, the film base material is replaced with Pyrene P-2161 (abbreviation: OPP, manufactured by Toyobo Co., Ltd.), which is a stretched polypropylene film having a thickness of 20 μm, and a microwave oven ink G2 is printed with a film thickness of 1.0 mm to print printed matter PR2. Obtained. Similarly, as shown in Table 3, the ink for microwave oven and the film thickness were changed to obtain printed matter PR13 and PR14 for microwave oven, respectively.

Similarly, the film substrate is replaced with Barrierox 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. Printing was performed to obtain a printed matter PR3. Similarly, as shown in Table 3, the ink for microwave oven and the film thickness were changed to obtain printed matter PR10 and PR15 for microwave oven, respectively.

Similarly, the film substrate was replaced with Bonnil RX (abbreviation: nylon, manufactured by Kohjin Film & Chemicals Co., Ltd.), which is a nylon film having a thickness of 15 μm, and microwave oven ink G4 was printed with a film thickness of 2.3 mm. A printed matter PR4 for a microwave oven was obtained. Similarly, as shown in Table 3, the ink for the microwave oven and the film thickness were changed to obtain the printed matter PR11 for the microwave oven.

[Preparation of laminate]
Takelac A-525 / Takenate A-52 (abbreviation: DL, manufactured by Mitsui Chemicals, Inc.) is coated on the print layer of printed matter PR1 for microwave ovens by A-Bar OSP-10 (manufactured by OSG System Products Co., Ltd.). Then, the 15 μm-thick nylon film emblem ONMB-RT (manufactured by Unitika Ltd.) was bonded, and similarly, the 60 μm-thick CPP Trefan NO ZK93KM (manufactured by Toray Film Processing Co., Ltd.) was bonded. After that, aging was carried out at 50 ° C. for 72 hours to obtain a laminated product LAM1. Similarly, instead of the printed matter PR5-9 and PR12 for the microwave oven, laminated bodies LAM5-9 and LAM12 were obtained, respectively.

Takelac A-969V / Takenate A-5 (abbreviation: DL, manufactured by Mitsui Chemicals, Inc.) is applied on the print layer of the printed matter PR2 for microwave ovens with A-Bar OSP-10 (manufactured by OSG System Products Co., Ltd.). After laminating Tosero CP GLC (abbreviation: CPP, manufactured by Mitsui Chemicals Tohcello Co., Ltd.), which is a non-stretched polypropylene film with a thickness of 30 μm, aging was performed at 40 ° C. for 24 hours to obtain a laminated LAM2. rice field. Similarly, instead of the printed matter PR13 and PR14 for the microwave oven, laminated bodies LAM13 and LAM14 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 printed matter PR3 for microwave ovens. Then, the 15 μm-thick nylon film emblem ONMB-RT (manufactured by Unitika Ltd.) is bonded, and similarly, the 60 μm-thick Trefan NO ZK93KM (manufactured by Toray Film Processing Co., Ltd.) is bonded, and then 50. Aging was carried out at ° C. for 72 hours to obtain a laminated product LAM3. Similarly, instead of the printed matter PR10 and PR15 for the microwave oven, laminated bodies LAM10 and LAM15 were obtained, respectively.

Takelac A-620 / Takenate A-65 (abbreviation: DL, manufactured by Mitsui Chemicals, Inc.) is coated on the print layer of the printed matter PR4 for microwave ovens with A-Bar OSP-10 (manufactured by OSG System Products Co., Ltd.). After laminating CMPS008C (abbreviation: EP film, manufactured by Mitsui Chemicals Tohcello Co., Ltd.), which is a co-pressing film having a thickness of 30 μm, aging was performed at 35 ° C. for 48 hours to obtain a laminated product LAM4. Similarly, instead of the printed matter PR11 for a microwave oven, laminated bodies LAM11 were obtained.

The microwave oven printed matter of Examples 1 to 6 and Comparative Examples 1 to 8 were evaluated for range-up property, adhesion, design property, and laminate strength, and are shown in Table 3.

<Range up>
A sample cut into a 10 cm × 10 cm printed matter for a microwave oven is placed in a microwave oven (product number: HMN-18B, manufactured by HOSHIZAKI Corporation, high frequency output: 1800 W, round plate: 200 mm) and heated for 2 minutes. evaluated. For the evaluation, the heat was evaluated by visually observing the surface condition and feeling when the sample after the microwave oven was taken out from the microwave oven. These operations were repeated 10 times with 10 panelists. The total score was calculated with 1 point being the one with no change in the surface condition and no temperature rise due to microwaves, and 0 point being the one where the printed matter was warm after heating or the printed matter sparked during heating. The evaluation was made on a two-point scale: ◯: total score was 90 points or more, and ×: total score was less than 90 points.

<Adhesion>
Using the printed matter for a microwave oven, a cellophane tape (18 mm, manufactured by Nichiban Co., Ltd.) was attached to the sample surface, and when the cellophane tape was peeled off, the degree of attachment to the cellophane tape on the printed surface was visually observed. It was 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.

<Design>
The design was evaluated by observing using a sample after range-up under a standard light source (model: Macbeth judgeII, manufactured by X-Rite). Ten panelists evaluated and calculated the total score, with 1 point having a metallic luster design and 0 point having no metallic luster design.
The evaluation was made on a two-point scale of 〇: total score of 7 or more and ×: less than 7.

<Laminate strength>
Each laminate is made into a strip with a width of 15 mm to form a test piece, and five of these test pieces are prepared and T-shaped peeled and pulled by a universal tensile tester (RTE-1210, manufactured by Orientec Co., Ltd.). The tensile strength of each test piece was measured 5 times at a speed of 300 mm / min, and the average value was calculated. The same test was performed on the laminated matter (blank test piece) of the printed matter that was not printed, and the average value was calculated. The laminate strength was evaluated in two stages: ◯: the laminate strength was 80% or more with respect to the average value of the blank test piece, and ×: the average load was less than 80% with respect to the average value of the blank test piece. ..

According to Table 3, the printed matter for microwave oven (PR1 to 8) and the laminate (LAM1 to 6) using the ink for microwave oven of Examples 1 to 6 have range-up property, design property, adhesion, and laminate strength. It is clear that it is excellent.
The printed matter (PR7) and the laminate (LAM7) for a microwave oven using the ink for a microwave oven of Comparative Example 1 similar to Patent Document 1 are inferior in all of range-up property, design property, adhesion, and laminate strength. Is clear.
It is clear that the printed matter for a microwave oven (PR13) and the laminate (LAM13) using the ink for a microwave oven of Comparative Example 7 similar to Patent Document 2 are inferior in design.
The printed matter for microwave oven (PR8-12) and the laminate (LAM8-12) using the ink for microwave oven of Comparative Examples 2 to 6 have either range-up property, adhesion, lamination strength, or design property. It is clear that it is inferior.
Further, it is clear that the printed matter for microwave oven (PR14, PR15) and the laminated body (LAM14, LAM15) whose film thickness is out of the range are inferior in any of range-up property, design property, adhesion, and lamination strength. be.

Claims (7)

The gravure ink composition for a microwave oven is a printed matter for a microwave oven, which forms a printed matter for a microwave oven formed by laminating an ink layer with a film thickness of 0.1 to 3 μm on at least one surface of a plastic base film. hand,
The microwave oven gravure ink composition contains an aluminum pigment (A) obtained by an atomizing method and not polymerized, and a thermoplastic resin (B).
The thermoplastic resin (B) contains an acid-modified vinyl chloride / vinyl acetate copolymer resin (b1) and a polyurethane resin (b2).
The solid content weight ratio of the acid-modified vinyl chloride / vinyl acetate copolymer resin (b1) to the polyurethane resin (b2) is (b1) / (b2) = 5/95 to 95/5.
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 , and the aluminum pigment which has not been polymerized ( A printed matter for a microwave oven, wherein the solid content weight ratio of A) and the thermoplastic resin (B) is (A) / (B) = 60/40 to 1/99. A laminate characterized by laminating a sealant layer or a seal layer on the microwave oven print layer of the printed matter for a microwave oven according to claim 1. The process of preparing the plastic base film and
A printed matter for a microwave oven including a gravure printing step of forming a printing layer for a microwave oven formed by printing a gravure ink composition for a microwave oven with a film thickness of 0.1 to 3 μm on at least one of the plastic base films. It is a manufacturing method of
The microwave oven gravure ink composition contains an aluminum pigment (A) obtained by an atomizing method and not polymerized, and a thermoplastic resin (B).
The thermoplastic resin (B) contains an acid-modified vinyl chloride / vinyl acetate copolymer resin (b1) and a polyurethane resin (b2).
The solid content weight ratio of the acid-modified vinyl chloride / vinyl acetate copolymer resin (b1) to the polyurethane resin (b2) is (b1) / (b2) = 5/95 to 95/5.
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, and the aluminum pigment which has not been polymerized ( A method for producing a printed matter for a microwave oven, wherein the solid content weight ratio of A) and the thermoplastic resin (B) is (A) / (B) = 60/40 to 1/99. The process of preparing the plastic base film and
A gravure printing step of forming a printing layer for a microwave oven formed by printing a gravure ink composition for a microwave oven 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 or coating process for laminating the seal layer,
It is a manufacturing method of a laminated body containing
The microwave oven gravure ink composition contains an aluminum pigment (A) obtained by an atomizing method and not polymerized, and a thermoplastic resin (B).
The thermoplastic resin (B) contains an acid-modified vinyl chloride / vinyl acetate copolymer resin (b1) and a polyurethane resin (b2).
The solid content weight ratio of the acid-modified vinyl chloride / vinyl acetate copolymer resin (b1) to the polyurethane resin (b2) is (b1) / (b2) = 5/95 to 95/5.
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, and the aluminum pigment which has not been polymerized ( A method for producing a laminate, wherein the solid content weight ratio of A) and the thermoplastic resin (B) is (A) / (B) = 60/40 to 1/99. In a packaging bag that requires a plastic base film, a microwave oven printing layer having a film thickness of 0.1 to 3 μm, and a sealant layer in this order from the outer layer.
The printing layer for a microwave oven is formed of a gravure ink composition for a microwave oven.
The microwave oven gravure ink composition contains an aluminum pigment (A) obtained by an atomizing method and not polymerized, and a thermoplastic resin (B).
The thermoplastic resin (B) contains an acid-modified vinyl chloride / vinyl acetate copolymer resin (b1) and a polyurethane resin (b2).
The solid content weight ratio of the acid-modified vinyl chloride / vinyl acetate copolymer resin (b1) to the polyurethane resin (b2) is (b1) / (b2) = 5/95 to 95/5.
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, and the aluminum pigment which has not been polymerized ( A packaging bag characterized in that the solid content weight ratio of A) and the thermoplastic resin (B) is (A) / (B) = 60/40 to 1/99. In order from the outer layer, in a lid material that requires a plastic base film, a printing layer for a microwave oven having a thickness of 0.1 to 3 μm, and a sealant layer, the printing layer for a microwave oven has a gravure ink composition for a microwave oven. Formed of things,
The microwave oven gravure ink composition contains an aluminum pigment (A) obtained by an atomizing method and not polymerized, and a thermoplastic resin (B).
The thermoplastic resin (B) contains an acid-modified vinyl chloride / vinyl acetate copolymer resin (b1) and a polyurethane resin (b2).
The solid content weight ratio of the acid-modified vinyl chloride / vinyl acetate copolymer resin (b1) to the polyurethane resin (b2) is (b1) / (b2) = 5/95 to 95/5.
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, and the aluminum pigment which has not been polymerized ( A lid material characterized in that the solid content weight ratio of A) and the thermoplastic resin (B) is (A) / (B) = 60/40 to 1/99. In a label that requires a plastic base film, a microwave oven printing layer having a thickness of 0.1 to 3 μm, and a sealant layer or a sealing layer in this order from the outer layer, the microwave oven printing layer is a microwave oven gravure. Formed with an ink composition
The microwave oven gravure ink composition contains an aluminum pigment (A) obtained by an atomizing method and not polymerized, and a thermoplastic resin (B).
The thermoplastic resin (B) contains an acid-modified vinyl chloride / vinyl acetate copolymer resin (b1) and a polyurethane resin (b2).
The solid content weight ratio of the acid-modified vinyl chloride / vinyl acetate copolymer resin (b1) to the polyurethane resin (b2) is (b1) / (b2) = 5/95 to 95/5.
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, and the aluminum pigment which has not been polymerized ( A label characterized in that the solid content weight ratio of A) and the thermoplastic resin (B) is (A) / (B) = 60/40 to 1/99.