JP6950792B1 - Packaging material with a glittering printing layer and its manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a packaging material which has design property, resistance to a microwave oven and a retort, and can be easily opened by tearing even after heating. SOLUTION: The packaging material has at least a base material, a brilliant printing layer, an adhesive layer and a sealant in order, and the brilliant printing layer contains a brilliant pigment and a urethane resin and is an isocyanate-based curing agent. A packaging material that is crosslinked with and has a weight average molecular weight of the isocyanate-based curing agent of 800 to 6000. [Selection diagram] None

Description

The present invention relates to a packaging material. In particular, the present invention relates to a packaging material having a bright printing layer containing a bright pigment that can be used in a microwave oven and a retort pouch.

The packaging material may be decorated with a metallic tone from the viewpoint of producing a sense of luxury and luxury of the object to be packaged to create an aesthetic appearance. Conventionally, as such a decorative means, a base material on which a metal such as aluminum is vapor-deposited has been used, but in recent years, there have been an increasing number of cases where decoration is performed by a printing layer using an aluminum paste or other bright pigment. rice field.

Further, in recent years, the functionality of packaging materials has been improved, and examples thereof include those having retort resistance and those having microwave resistance. However, even in the case of a laminated packaging material having a printing layer using the above-mentioned bright pigment between the base materials, delamination (floating) in a boil or retort pouch, sparks when placed in a microwave oven, etc. occur. It was pointed out that it would happen. In particular, in the case of microwave oven resistance, it is difficult to use a glitter pigment made of a metal as a raw material for the printing layer of the packaging material, and such a usage pattern is usually avoided.

Therefore, various efforts are being made to avoid the above problems. For example, Patent Document 1 discloses a packaging material containing a printing layer made of an ink for a glittering printing layer using an aluminum paste as a glittering pigment and a urethane resin as a binder resin, and sparks or the like occur in a microwave oven. It is said that there is no such thing. Further, for example, Cited Document 2 describes an invention in which a resin-coated aluminum paste is used to improve retort resistance and laminate strength.

However, microwave oven or retort-resistant heating often causes problems such as not tearing well when opening the packaging material. It is thought that this is due to deterioration of the bright print layer, etc. On the other hand, it is thought that the ease of opening can be improved by reducing the content of the bright pigment in the print layer. It is difficult to satisfy the sex.

Japanese Unexamined Patent Publication No. 2020-33109 Japanese Unexamined Patent Publication No. 2010-053193

An object of the present invention is to provide a packaging material which has design properties, is resistant to microwave ovens and boiled retorts, and can be easily opened by tearing even after heating.

As a result of diligent studies, the inventors have found that the above problems can be solved by using the packaging material of the present invention, and have completed the present invention.

That is, the present invention is a packaging material having at least a base material, a glittering printing layer, an adhesive layer, and a sealant in that order.
The bright printing layer contains a bright pigment and a urethane resin, and is crosslinked with an isocyanate-based curing agent, and the weight average molecular weight of the isocyanate-based curing agent is 800 to 8000.

The present invention also relates to the above-mentioned packaging material, wherein the mass ratio of the urethane resin and the isocyanate-based curing agent is 99: 1 to 60:40.

The present invention also relates to the above-mentioned packaging material in which the molecular weight distribution (Mw / Mn) of the isocyanate-based curing agent is 1.5 to 5.

The present invention also relates to the above-mentioned packaging material, in which the urethane resin contains a constituent unit derived from polyester.

The present invention also relates to the above-mentioned packaging material in which the molecular weight distribution (Mw / Mn) of the urethane resin is 1.5 to 5.

The present invention also relates to the above-mentioned packaging material in which the base material is a polyester base material or a polyamide base material.

The present invention also relates to the above-mentioned packaging material, wherein the bright pigment contains scaly aluminum.

The present invention also relates to the above-mentioned packaging material for microwave ovens or boiled retorts.

Further, the present invention is a method for producing a packaging material having at least a base material, a glittering printing layer, an adhesive layer and a sealant in order.
The bright printing layer includes a step of forming a bright ink containing a bright pigment, a urethane resin, and an isocyanate-based curing agent having a weight average molecular weight of 800 to 8000 on the base material by gravure printing or flexographic printing. , Concerning the manufacturing method of packaging materials.

According to the present invention, it has become possible to provide a packaging material which has design properties, is resistant to microwave ovens and boiled retorts, and can be easily opened by tearing even after heating.

Hereinafter, embodiments of the present invention will be described in detail, but the description of the constituent elements described below is an example (representative example) of the embodiments of the present invention, and the present invention is described as long as the gist of the present invention is not exceeded. Not limited to the content.

Hereinafter, the packaging material of the present invention will be described in detail.
The present invention is a packaging material having at least a base material, a glittering printing layer, an adhesive layer and a sealant in that order, and the printing layer contains a glittering pigment and a urethane resin and is crosslinked with an isocyanate curing agent. This is a packaging material having a weight average molecular weight of the isocyanate-based curing agent of 800 to 8000.
The glittering printing layer may have a decorative aesthetic appearance, and by using a glittering pigment and a urethane resin, the adhesion to a base material or the like is improved, and an isocyanate type having a weight average molecular weight of 800 to 8000 is used. By being crosslinked with a curing agent, the entire packaging material is made resistant and easily torn even after heating in a microwave oven or boil / retort.

In the present specification, the printing layer that does not contain a glittering pigment is referred to as an "ink layer" as opposed to the "brilliant printing layer". The brilliant print layer may be referred to as a "brilliant print layer" or a "brilliant layer", but they have the same meaning.

<Packaging material>
The packaging material of the present invention is a packaging material having a structure in which at least a base material, a glittering printing layer, an adhesive layer and a sealant are laminated from the outer layer side in this order. Specifically, the following laminated structure can be exemplified below in order from the outer layer side (left side). In the configuration display of (1) to (4) below, "/" means the boundary of each layer.
(1) Base material / Bright printing layer / Adhesive layer / Sealant (2) Base material / Bright printing layer / Adhesive layer / Intermediate base material layer / Adhesive layer / Sealant (3) Base material / Bright printing Layer / Ink layer / Adhesive layer / Sealant (4) Base material / Bright print layer / Ink layer / Adhesive layer / Intermediate base material layer / Adhesive layer / Sealant Note that the bright print layer is on the outside (base material side). ) Can be arbitrarily selected as the layer structure to be visible.

<Glittering print layer>
The packaging material of the present invention has a glittering printing layer between the base material and the sealant. The brilliant print layer may be provided on the entire surface of the base material or may be provided on a part of the area of the base material. Further, it may further have an ink layer. Further, the bright printing layer of the packaging material of the present invention contains a urethane resin and a bright pigment, and is crosslinked with an isocyanate-based curing agent having a weight average molecular weight of 800 to 8000.
The thickness of the brilliant print layer is preferably 0.5 to 10 μm, more preferably 0.8 to 7 μm, still more preferably 1. It is 0 to 5 μm.

(Glittering ink)
The brilliant print layer can be formed by printing and applying a brilliant ink. In addition to the above-mentioned bright pigment, the bright ink contains a urethane resin as a binder resin and an isocyanate-based curing agent.

(Glowing pigment)
The glitter pigment preferably contains at least one selected from pearl pigments and metal scales.

(Pearl pigment)
As the pearl pigment, for example, a white pearl pigment, an interference pearl pigment, a colored pearl pigment and the like are preferably mentioned. The pearl pigment is suitable because it tends to improve the microwave oven resistance of the packaging material. In general, the coloring effect of pigments utilizes the phenomenon of light absorption and scattering by pigment particles. On the other hand, pearl pigments have special optical properties that give a deep luster, iridescent color, or metallic feeling like natural pearls by utilizing multiple reflections of light and interference phenomena in a thin film on the pigment surface, for example. It is a pigment.

The white pearl pigment is obtained by covering a scaly base material such as mica, aluminum, and glass with a coating layer made of a colorless high refractive index material such as titanium dioxide, and the thickness of the coating layer is 0.1 to 0. It is relatively small, about 15 μm, and reflects almost all wavelengths of light, so it looks white, silver, or jade. In the interference pearl pigment, the coating layer is a colorless high refractive index material such as titanium dioxide, and the thickness of the coating layer is larger than that of the white pearl pigment, which is more than 0.15 μm. Depending on this thickness, the reflected light and the transmitted light change, and various interference colors are generated. Sometimes called iridescent pearls.
The colored pearl pigment is chromatic and the coating layer is a colored high refractive index material such as ferric oxide, and the periphery of the white pearl pigment is further colored high refractive index material such as ferric oxide or other colored material. There are those coated with a pigment, or those in which a pigment or other colorant is added to the coating layer.

The average particle size of the pearl pigment is preferably 2 to 200 μm, more preferably 3 to 100 μm, and even more preferably 5 to 70 μm. This is because the gloss is good while having microwave oven resistance and retort resistance. The average particle size is a value measured by a laser light scattering method and is a value of D50 (cumulative mass 50% particle size).

The content of the pearl pigment in the brilliant print layer (that is, the content of the pearl pigment in the total brilliant ink solid content) is 15 to 55 in the total mass of the brilliant print layer (in the total brilliant ink solid content). It is preferably by mass, more preferably 20 to 50% by mass, and even more preferably 25 to 45% by mass.

(Metal scales)
Preferable examples of the material of the metal scales include metals and alloys such as aluminum, gold, silver, brass, titanium, chromium, nickel, nickel chromium, and stainless steel. Of these, aluminum scales are preferable.

As the metal scales, non-reefing type metal scales are preferable. The non-leaving type metal scales have a design property because the metal scales are uniformly dispersed in the process of forming the glittering printing layer, and have excellent lamination strength as a packaging material. Therefore, the durability is good even when heated in a microwave oven or a boil / retort. The non-leaving type metal scales are preferably those in which oleic acid, linoleic acid, linolenic acid and other unsaturated fatty acids are adsorbed on the metal surface.

The metal scales are preferably those in which the surface of the metal scales is coated with an acrylic resin. Since the resin-coated metal scales have excellent laminating strength as a packaging material, they have good durability even when heated in a microwave oven or a boil / retort. The resin-coated metal scales can be produced, for example, by the methods described in JP-A-2010-053193 and JP-A-2012-241039.

The average particle size of the metal scales is preferably 3 to 30 μm, more preferably 4 to 25 μm, further preferably 5 to 20 μm, and particularly preferably 8 to 15 μm. .. When the particle size is 3 μm or more, the appearance quality of the printed matter is improved. If it is 80 μm or less, the hiding power of the gravure ink coating film is improved, and the resistance to microwave ovens and retort resistance is also good. The average particle size of the metal particles is measured by a particle size distribution measuring device by light scattering. In the present invention, the particle size obtained by the light scattering method is defined as the average particle size of the D50 value (cumulative mass 50% particle size).

The content of the metal scales in the brilliant print layer (that is, the content of the metal scales in the total amount of the brilliant ink solids) is 15 to 15 in the total mass of the brilliant print layer (in the total amount of the brilliant ink solids). It is preferably 55% by mass, more preferably 20 to 50% by mass, and even more preferably 25 to 45% by mass.

The aspect ratio (average length / average thickness) of the pearl pigment and the bright pigment such as metal scales is preferably 20 or more, and more preferably 30 or more. The aspect ratio of the bright pigment is preferably 400 or less, more preferably 200 or less, and even more preferably 100 or less. This is because the tearability after heating in the microwave oven and after retort is improved.

(Colorant)
The glittering printing layer of the present invention may contain a colorant. Colorants include dyes, pigments and other colorants. Among them, it is preferable to contain a pigment, and the pigment can be used as either an organic pigment or an inorganic pigment. Examples of inorganic pigments include yellow lead, titanium yellow, petals, cadmium red, ultramarine blue, cobalt blue and the like, and examples of organic pigments include soluble azo-based, insoluble azo-based, azo-based, phthalocyanine-based, halogenated phthalocyanine-based pigments. Anthraquinone, Ansanthron, Dianthraquinonyl, Anthrapyrimidine, Perylene, Perinone, Quinacridone, Thioindigo, Dioxazine, Isoindoleinone, Kinoftalone, Azomethinazo, Flavanthron, Diketopyrrolop Pigments such as pyrrolop-based, isoindoline-based, and indanthron-based pigments can be mentioned. In addition, C.I. I. Any pigment indicated by the pigment number can be used.

It is common to use yellow organic pigments at the same time because the glittering print layer becomes golden. Examples of the yellow organic pigment include C.I. I. Among the yellow pigments of Pigment Yellow 1 to 219, a yellow pigment which is an organic compound or an organometallic complex is preferable, and for example, C.I. I. Pigment Yellow 1, C.I. I. Pigment Yellow 3, C.I. I. Pigment Yellow 12, C.I. I. Pigment Yellow 13, C.I. I. Pigment Yellow 14, Pigment Yellow 17, C.I. I. Pigment Yellow 24, C.I. I. Pigment Yellow 42, C.I. I. Pigment Yellow 55, C.I. I. Pigment Yellow 62, C.I. I. Pigment Yellow 65, C.I. I. Pigment Yellow 74, C.I. I. Pigment Yellow 83, C.I. I. Pigment Yellow 86, C.I. I. Pigment Yellow 93, C.I. I. Pigment Yellow 94, C.I. I. Pigment Yellow 95, C.I. I. Pigment Yellow 109, C.I. I. Pigment Yellow 110, C.I. I. Pigment Yellow 117, C.I. I. Pigment Yellow 120, Pigment Yellow 125, C.I. I. Pigment Yellow 128, C.I. I. Pigment Yellow 129, C.I. I. Pigment Yellow 137, C.I. I. Pigment, Yellow 138, C.I. I. Pigment Yellow 139, C.I. I. Pigment Yellow 147, C.I. I. Pigment Yellow 148, C.I. I. Pigment Yellow 150, C.I. I. Pigment Yellow 151, C.I. I. Pigment Yellow 153, C.I. I. Pigment Yellow 154, C.I. I. Pigment Yellow 155, C.I. I. Pigment Yellow 166, C.I. I. Pigment Yellow 168, C.I. I. Pigment Yellow 174, C.I. I. Pigment Yellow 180, C.I. I. Pigment Yellow 185 and C.I. I. Pigment Yellow 213 and the like are preferably mentioned. C. I. It is preferable to use Pigment Yellow 83 or the like.

The content of the colorant is preferably 10 to 70 parts by mass, more preferably 20 to 60 parts by mass, and further preferably 30 to 50 parts by mass with respect to 100 parts by mass of the bright pigment. preferable.

(Urethane resin)
The urethane resin used in the present invention is not limited to the following, but for example, a urethane prepolymer obtained by reacting a polyisocyanate with a polyol is further added with a polyamine (chain extender) and a reaction terminator if necessary. Examples thereof include urethane resin obtained by reaction. The urethane resin may be any resin having a urethane bond, and even if it has a urea bond or the like in addition to the urethane bond, it falls under the concept of the urethane resin. The urethane resin preferably has a constituent unit derived from polyester. In order to obtain a constituent unit derived from polyester, for example, it is achieved when a polyester polyol is used as the above-mentioned polyol.

(Polyisocyanate)
The polyisocyanate preferably contains diisocyanate. Examples of the diisocyanate include aliphatic diisocyanates such as tetramethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate;
Cyclohexane-1,4-diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, lysine diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, methylcyclohexanediisocyanate, m-tetramethyl Alicyclic diisocyanates such as xylylene diisocyanate and diisocyanate obtained by converting the carboxyl group of dimer acid into an isocyanate group;
α, α, α', α'-tetramethylxylylene diisocyanate, 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzylisocyanate , Dimethyldiphenylmethane diisocyanate, tetramethyldiphenylmethane diisocyanate, 1,3-phenylenediocyanate, 1,4-phenylenediocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, o-xylylene diisocyanate and 2,4-tolylene diisocyanate, Examples thereof include aromatic diisocyanates such as 2,6-tolylene diisocyanate. Among these, alicyclic or aromatic aliphatic diisocyanates are preferable, and isophorone diisocyanates, α, α, α', α are particularly preferable from the viewpoint that the reaction is easily controlled and the performance of the obtained urethane resin is well-balanced. '-Tetramethylxylylene diisocyanate is preferred. At least one type of diisocyanate may be used, and two or more types may be used in combination.

(Polyol)
As the polyol, polyester polyol, polyether polyol, polycarbonate polyol, polyolefin polyol and the like can also be used. The urethane resin preferably has a constituent unit derived from a polyester polyol. In this case, it is preferable that the total mass of the urethane resin is 50% by mass or more (main component).

The polyol used in the present invention preferably has a number average molecular weight of 500 to 10,000. Here, the number average molecular weight used for the polyol is calculated from the hydroxyl value, and the hydroxyl value is calculated by esterifying or acetylating the hydroxyl groups in the resin and back-dripping the remaining acid with an alkali in 1 g of the resin. The amount of hydroxyl groups is a value converted into the number of mg of potassium hydroxide, which is a value performed according to JIS K0070. When the number average molecular weight of the polyol is 10,000 or less, the blocking resistance to the plastic film is excellent. Further, when the number average molecular weight of the polyol is 500 or more, the urethane resin film is excellent in flexibility and adhesion to a plastic film. For the above reasons, the number average molecular weight is more preferably 1,000 to 5,000.

The polyol is preferably a diol. The diol refers to a compound having two hydroxyl groups in one molecule. Examples of the diol include polyols such as polyester diol, polyether diol, polycarbonate, and polybutadiene glycol. At least one type of diol may be used, and two or more types may be used in combination.

(Polyester polyol)
The polyester polyol is preferably a polyester diol, and the polyester diol is preferably a polyester diol which is a condensate of a diol and a dicarboxylic acid.
Examples of the polyester diol include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol, and 1,8-octane. Diol, 1,9-nonanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-methyl-1,3-propanediol, 3,3,5-trimethylpentanediol, 2,4-diethyl -1,5-pentanediol, 1,12-octadecanediol, 1,2-alkanediol, 1,3-alkanediol, 1-monoglyceride, 2-monoglyceride, 1-monoglycerin ether, 2-monoglycerin ether, dimer Preferable examples include diol and hydrogenated dimer diol. Polyester polyols can be used alone or in admixture of two or more. It is preferably a polyester diol which is a condensate of a diol containing a branched diol and a dicarboxylic acid. Further, it may be a polyester diol obtained by ring-opening reaction of a cyclic ester (lactone or the like).
Examples of the dicarboxylic acid include adipic acid, phthalic anhydride, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, succinic acid, oxalic acid, malonic acid, pimelic acid, azelaic acid, sebacic acid, suberic acid, glutaric acid, 1 , 4-Cyclohexyldicarboxylic acid, dimer acid, hydrogenated dimer acid and the like are preferably mentioned, and among them, adipic acid, succinic acid, sebacic acid and the like are preferable.
Further, as a raw material of the polyester polyol, a polyol having 3 or more hydroxyl groups and a polyvalent carboxylic acid having 3 or more carboxyl groups can be used in combination.

Among these, as a preferable specific example, those containing a polyester-derived structural unit composed of adipic acid, succinic acid, sebacic acid and other dibasic acids and a diol having a branched structure are preferable. This is because the adhesion to the plastic base material and the solubility of the ink composition can be improved. The diol having a branched structure is preferably a diol having a structure in which at least one hydrogen of the alkylene glycol is substituted with an alkyl group, and the diol having a branched structure is, for example, 1,2-propanediol. 1,3-Butanediol, 2-methyl-1,3-propanediol, neopentyldiol, 1,4-pentanediol, 3-methyl-1,5-pentanediol, 2,5-hexanediol, 2-methyl -1,4-Pentanediol, 2,4-diethyl-1,5-pentanediol, 2-butyl-2-ethyl-1,3-propanediol, 2-methyl-1,8-octanediol, 2,2 , 4-trimethyl-1,3-pentanediol, 2,2,4-trimethyl-1,6-hexanediol and the like are preferably mentioned. Of these, at least one selected from 1,2-propanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, and 2-butyl-2-ethyl-1,3-propanediol is preferable, and 1 , 2-Propanediol and / or polyester polyols containing 3-methyl-1,5-pentanediol are still preferred.

(Polyether polyol)
Preferred examples of the polyether polyol are polymers or copolymers such as methylene oxide, ethylene oxide, propylene oxide and tetrahydrofuran. These can be used alone or in combination of two or more. More specifically, it preferably contains polyethylene glycol, polypropylene glycol, polytrimethylene glycol, polytetramethylene glycol and a copolymer composed of any of these, and may include polyethylene glycol, polypropylene glycol and polytetramethylene glycol. It is still preferable.

(Polyamine)
The chain extender is preferably a polyamine. Examples of the polyamine include, but are not limited to, ethylenediamine, propylenediamine, hexamethylenediamine, isophoronediamine, dicyclohexylmethane-4,4'-diamine, dimerdiamine obtained by converting the carboxyl group of dimer acid into an amino group, and the like. Diamines are preferred. These can be used alone or in combination of two or more.
Amino acids can also be used for chain extension. The amino acid refers to a compound having both an amino group and an acidic functional group in one molecule, and preferred examples thereof include glutamine, asparagine, lysine, diaminopropionic acid, ornithine, diaminobenzoic acid and diaminobenzenesulfonic acid. Since the acidic group has a high probability of not reacting with the isocyanate group in the process of synthesizing the urethane resin, the acid value can be maintained in the urethane resin.

As the reaction terminator, monoalcohol or monoamine is preferably used in the case of a urethane resin that can be produced only by the urethanization step, and monoamine is used in the case of a urethane resin that is produced by performing a urea conversion reaction step in addition to the urethanization step. Is preferable.
The monoalcohol is preferably a substituted or unsubstituted alcohol, and preferred examples include methanol, ethanol, n-propanol, isopropyl alcohol, 1-butanol, and the like. As the monoamine, substituted or unsubstituted monoamine is preferable, and n-butylamine, n-dibutylamine, octylamine, diethylamine, monoethanolamine, monopropanolamine, diethanolamine, dipropanolamine and the like are preferably mentioned. Further, as the reaction terminator, the compounds listed as the chain extender can also be used, and at least one kind may be used, and two or more kinds may be used in combination.

In the production of a urethane prepolymer having an isocyanate group at the terminal obtained by reacting a polyisocyanate with a polyol, the molar equivalent ratio of NCO of polyisocyanate to OH of polyol (molar equivalent of NCO of polyisocyanate / molar of OH of polyol compound). The equivalent amount) is preferably 1.3 to 3 and more preferably 1.5 to 2.

The urethane resin preferably has an active hydrogen group having a hydroxyl value and / or an amine value. This is to obtain a reaction site with a curing agent described later. The hydroxyl value is preferably 0.5 to 30 mgKOH / g, more preferably 1 to 20 mgKOH / g, and even more preferably 2 to 15 mgKOH / g. When it has an amine value, it is preferably 0.1 to 15 mgKOH / g, and more preferably 1 to 12 mgKOH / g. On the other hand, the acid value of the urethane resin is preferably 5 mgKOH / g or less, and more preferably 3 mgKOH / g or less. This is because the acid value is poorly reactive with the isocyanate-based curing agents described below.

The weight average molecular weight of the urethane resin is preferably 5,000 to 100,000, more preferably 5,000 to 80,000, and even more preferably 10,000 to 60,000. This is because the bright print layer becomes a strong film by cross-linking with a curing agent described later, and can withstand heating in a microwave oven or a retort.
The weight average molecular weight of the present invention and the molecular weight distribution (Mw / Mn) described later can be measured by a gel permeation chromatography (GPC) method. As an example, use Water2690 (manufactured by Waters) as a GPC apparatus, PLgel, 5 μm as a column of HLC-8220 (manufactured by Tosoh Co., Ltd.), MIXED-D (manufactured by Polymer Laboratories), TSKgelSuperAW series (manufactured by Tosoh Co., Ltd.), or the like. Can be done. Tetrahydrofuran, 1,2,4-trichlorobenzene, N, N-dimethylformamide (with 0.01N-lithium bromide added) and the like can be used as the developing solvent, and the flow rate is 0.5 to 1.5 ml / min. It is preferable to have. An RI detector or the like can be used for detection, and the sample injection concentration can be measured under conditions such as 0.5 to 1.5 milligrams / milliliter and the injection amount is 0.1 to 1.0 microliters. The weight average molecular weight can be obtained as a polystyrene-equivalent value.

The molecular weight distribution (Mw / Mn) of the urethane resin is preferably 1.5 to 5, more preferably 2 to 4, and even more preferably 2.2 to 3.5. Mw represents a weight average molecular weight, and Mn represents a number average molecular weight. When Mw / Mn is in the above range, the cohesive force and adhesive force are strengthened by cross-linking with the isocyanate-based curing agent described below, and sufficient resistance is exhibited in a microwave oven, boil and retort, and easy tearing property is exhibited. It is thought that. In addition, Mw, Mn and Mw / Mn can be obtained by gel permeation chromatography (GPC) as described above.

In order to keep the molecular weight distribution (Mw / Mn) of urethane resin within the above range, selection of urethane synthetic raw material in urethane resin synthesis, solid content mass ratio, dropping rate of reactive raw material such as polyisocyanate in synthetic reaction, stirring speed The molecular weight distribution (Mw / Mn) can be kept within the range by appropriately setting the shape of the stirring blade and the reaction temperature. When the chain extension reaction is further carried out, it is particularly effective to set the dropping rate and the temperature range control when reacting the polyamine and the urethane prepolymer to a constant width in order to set the molecular weight distribution within a predetermined range. Controlling the reaction temperature is important, and it is preferable to control the temperature between 50 and 130 ° C. in the synthesis of the urethane prepolymer, and control the temperature in the range of 10 to 50 ° C. when reacting the polyamine and the urethane prepolymer. preferable.
It is also effective to set the charging ratio of the reaction raw materials to an appropriate ratio in order to keep the molecular weight distribution within a predetermined range. The charging ratio includes, for example, the NCO / OH ratio, which is the ratio of the hydroxyl groups of polyol and hydroxyic acid, and the isocyanate group of polyisocyanate, and is the ratio of the amino group of polyamine to the isocyanate group of urethane prepolymer. , Amino group / NCO ratio and the like. Further, in order to control the molecular weight distribution, it is preferable to use a polymerization terminator (also referred to as a reaction terminator) for the purpose of preventing an excessive polymerization reaction. Preferable examples of the polymerization inhibitor include monoalcohols and monoamines.

(Isocyanate-based curing agent)
In the packaging material of the present invention, an isocyanate-based curing agent is used in order to improve the resistance to microwave ovens and retorts and the subsequent tearability. If the urethane resin has a hydroxyl group, amino group or other active hydrogen group, it is crosslinked with the active hydrogen group, and if the urethane resin does not have the active hydrogen group, it is self-crosslinked with only an isocyanate-based curing agent. Laminate strength, easy tearability, etc. are improved. The urethane resin preferably has a hydroxyl group, an amino group or other active hydrogen group.

The weight average molecular weight of the isocyanate-based curing agent conventionally used in packaging materials is as small as less than 600, and in most cases, it is a low molecular weight compound. However, in this case, although there is no problem if it is simply used as a packaging material, when a pearl pigment or a metal scale is contained as a pigment component, the cohesive force is insufficient and the characteristics are not satisfied. In addition, there is a concern that the low molecular weight compound may migrate to the base material, the ink layer, and the adhesive layer.

Hereinafter, preferred embodiments of the isocyanate-based curing agent are shown. The weight average molecular weight of the isocyanate-based curing agent needs to be 800 to 8000, preferably 900 to 6000, and even more preferably 1000 to 4000. The molecular weight distribution (Mw / Mn) of the isocyanate-based curing agent is preferably 1.5 to 5, more preferably 2 to 5, and even more preferably 2 to 4. When the weight average molecular weight and Mw / Mn are in the above range, the cohesive force and the adhesive force are strengthened by the action with the urethane resin, and the microwave oven, boil and retort show sufficient resistance and are easily torn. Is thought to be expressed.

As the isocyanate-based curing agent, a polyisocyanate containing an adduct-type polyisocyanate (adduct-type), a biuret-type polyisocyanate (biuret-type), an isocyanurate-type polyisocyanate (isocyanurate-type), or the like is preferable. The bodies and isocyanurates are, for example, adducts obtained from the reaction of trimethylolpropane and other polyols with diisocyanates, biuret bodies obtained by dimerizing diisocyanates and connecting them with biuret bonds, and isocyanates obtained from cyclic trimerization reactions of diisocyanates. Nurate form and the like can be mentioned. As the diisocyanate, the above-mentioned diisocyanate may be arbitrarily selected and used. Among them, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hydrogenated diphenylmethane diisocyanate (hydrogenated MDI), hexamethylene diisocyanate (HDI). , Isophorone diisocyanate, xylylene diisocyanate (XDI), hydrogenated xylylene diisocyanate (hydrogenated XDI) and the like are preferably mentioned. Adduct-type polyisocyanate, biuret-type polyisocyanate, and isocyanurate-type polyisocyanate may be used in combination, or may be used in combination with other polyisocyanates.

In order to keep the weight average molecular weight and molecular weight distribution (Mw / Mn) of the isocyanate-based curing agent within the above ranges, selection of diisocyanate, polyol, etc. in the synthesis of the isocyanate-based curing agent, the solid content mass ratio, polyisocyanate in the synthesis reaction, etc. The dropping speed of the reactive raw material, the stirring speed, the shape of the stirring blade, and the reaction temperature can be appropriately set within the range. It should be noted that it is effective to set the molecular weight distribution within a predetermined range by setting the dropping rate and the temperature range control when reacting the polyamine and the polyisocyanate to a constant width.
Further, it is effective to set the preparation ratio of the reaction raw material to an appropriate ratio so that the molecular weight distribution is within a predetermined range. The charging ratio includes, for example, the NCO / OH ratio, which is the ratio of the isocyanate group of the polyol and the polyisocyanate, and the amino group / NCO ratio, which is the ratio of the amino group of the polyamine and the isocyanate group of the polyisocyanate. Can be mentioned. Control of the reaction temperature is important, and it is preferable to control the temperature between 50 and 130 ° C. in the synthesis using the polyol and the polyisocyanate, and control the temperature in the range of 10 to 50 ° C. when reacting the polyamine and the polyisocyanate. Is preferable. The solid content is also important, and the solid content during the reaction is preferably 40 to 80% by mass. The reaction solvent is also important, and it is preferable to use ethyl acetate, normal propyl acetate or other ester-based organic solvents.

The mass ratio of the urethane resin to the isocyanate-based curing agent (urethane resin: isocyanate-based curing agent) is preferably 99: 1 to 60:40, preferably 98: 2 to 65:35. It is still more preferable that it is 95: 5 to 70:30. When the combined resin described below is used in addition to the urethane resin, the mass ratio of the total amount of the urethane resin and the combined resin and the isocyanate-based curing agent is preferably 99: 1 to 60:40. , 95: 5 to 70:30 is still preferable. This is because it is considered that the effects of cross-linking and adhesion to the base material are improved in the above range, sufficient resistance is exhibited in a microwave oven and boiled retort, and easy tearing property is exhibited.

<Combination resin>
It is preferable that the glitter ink forming the glitter print layer has a combined resin together with the urethane resin. The preferred embodiment of the combined resin is shown below.
For example, polyolefin resins such as polyethylene resins and chlorinated polypropylene resins, poly (meth) acrylic resins, polyvinyl chloride resins, polyvinyl acetate resins, vinyl chloride-vinyl acetate copolymers, polystyrene resins, Styrene-butadiene copolymer, vinylidene fluoride resin, polyvinyl alcohol resin, polyvinyl acetal resin, polyvinyl butyral resin, polybutadiene resin, polyester resin, polyamide resin, alkyd resin, epoxy resin, unsaturated Fibers such as polyester resin, heat-curable poly (meth) acrylic resin, melamine resin, urea resin, phenol resin, xylene resin, maleic acid resin, nitrocellulose, ethylcellulose, acetylbutylcellulose, ethyloxyethylcellulose, etc. Examples thereof include elementary resins, rubber resins such as chloride rubber and cyclized rubber, petroleum resins, and natural resins such as rosin and casein.
Among them, at least one selected from vinyl chloride copolymer resin, cellulosic resin and rosin resin is preferable. It is still more preferable that it is a vinyl chloride copolymer resin.

The vinyl chloride copolymer resin is preferably a vinyl chloride-vinyl acetate copolymer resin, a vinyl chloride-acrylic copolymer resin, or the like. The weight average molecular weight of the vinyl chloride copolymer resin is preferably 5,000 to 100,000, more preferably 5,000 to 50,000. The content of the structural unit derived from the vinyl acetate monomer in 100% by mass of the solid content of the vinyl chloride copolymer resin is preferably 70 to 95% by mass. The glass transition temperature is preferably 50 ° C to 90 ° C. The vinyl chloride copolymer resin preferably has a hydroxyl group, and the hydroxyl value is preferably 10 to 200 mgKOH / g. This is because the reactivity with the isocyanate-based curing agent is improved, and the hydroxyl group is preferably derived from a hydroxyl group derived from a vinyl alcohol unit or an acrylic monomer having a hydroxyl group.

The mass ratio (urethane resin: combined resin) of the urethane resin to the vinyl chloride copolymer resin and other combined resins is preferably 95: 5 to 30:70, and preferably 90: 10 to 40:60. More preferred. This is because the adhesion to the base material, the physical characteristics of the coating film, the lamination strength, and the like are improved.

(Organic solvent)
The brilliant ink may contain an organic solvent, water or other medium. If it is an organic solvent, it is not limited, but if it is an organic solvent, toluene or other aromatic organic solvent, methyl ethyl ketone or other ketone organic solvent, ethyl acetate, normal propyl acetate or other ester organic solvent, ethanol, isopropanol, normal propanol or other Alcoholic organic solvents and the like are preferable. Water may be contained, and when an organic solvent is used as the main medium, it is preferably contained in an amount of 10% by mass or less.

(Additive)
Bright inks, as required, include, for example, light stabilizers such as fillers, stabilizers, plasticizers, antioxidants, UV absorbers, dispersants, thickeners, desiccants, lubricants, and antistatic agents. Any additive such as an inhibitor and a cross-linking agent can be added.

(Ink layer)
The ink layer refers to a printing layer formed from the above-mentioned printing ink that does not have a glittering pigment, and conventional screen inks, gravure inks, flexo inks, inkjet inks, offset inks, and other printing inks are preferable. For example, JP-A-2005-298618, JP-A-2006-299136, JP-A-2009-249388, JP-A-2013-127038, JP-A-2017-19991, JP-A-2006-131844, The printing inks described in JP-A-2013-40248, JP-A-2007-231148, JP-A-2006-257302 and the like can be preferably used. However, it is not limited to these. Of these, the use of gravure ink, flexo ink, and inkjet ink is preferable, and the use of gravure ink and / or flexo ink is still preferable.

<Base material>
The base material is preferably a plastic film, which plays a role as a base material on the outer layer side of the packaging material, and is composed of a material having light transmission so that the brilliant printing layer can be visually recognized from the outside.
Specifically, polyethylene (PE) -based and polypropylene (PP) -based polyolefin resins, cyclic polyolefin resins, polystyrene resins, acrylonitrile-styrene copolymer (AS) resins, and acrylonitrile-butadiene-styrene copolymers. (ABS) resin, poly (meth) acrylic resin, polycarbonate resin, polyvinyl alcohol resin, ethylene-vinyl alcohol copolymer (EVOH), ethylene-vinyl ester copolymer saponified product, polyethylene terephthalate (PET) and poly Polyester resins such as butylene terephthalate (PBT) and polyethylene naphthalate (PEN), polyamide resins such as various nylons (Ny), polyurethane resins, acetal resins, cellulose resins, polyvinylidene chloride resins (PVDC), etc. Can be mentioned. The base material may be uniaxially stretched or biaxially stretched. Further, it may be a composite film in which two or more of the above resin films are laminated. Further, it may be in a form in which a metal oxide such as silica or alumina is vapor-deposited.

The base material preferably has excellent heat resistance from the viewpoint of heating in a microwave oven and retort treatment. As the resin constituting the base material having excellent heat resistance, a polyester resin and / or a polyamide resin or the like is suitable.
Specific examples of the base material having excellent heat resistance include a single polyester film, a single polyamide film such as nylon, and a composite film containing one or more polyester films and polyamide films. Examples of the composite film include PET / Ny / PET and a coextruded stretched film having a composition of PET / Ny from the outer layer side. Further, as the composite film, it is also preferable to combine one or more of polyester film and polyamide film with one or more of ethylene-vinyl alcohol copolymer film and polyvinylidene chloride film.

The thickness of the base material is not particularly limited and can be appropriately set depending on the intended use of the packaging material, but is usually preferably about 5 to 50 μm, more preferably 10 to 30 μm.

As for the base material, the total light transmittance of JIS K7361-1: 1997 is preferably 85% or more, and more preferably 90% or more. Further, the base material preferably has a haze of JISK7136: 2000 of 1.5% or less, more preferably 1.0% or less, and further preferably 0.5% or less.

<Formation of brilliant print layer and ink layer>
As a method for forming the brilliant printing layer and the ink layer, a printing method such as screen printing, offset printing, flexo printing, dry offset printing, gravure printing, and inkjet printing is performed on the base material using the brilliant ink or the like. Can be more preferably formed. Of these, gravure printing or flexographic printing is still preferable.

<Gravure printing>
(Gravure version)
The gravure plate is a metal cylinder, and recesses are made for each color by engraving or corrosion / laser. There are no restrictions on the use of engraving and laser, and it can be set arbitrarily according to the pattern. As the number of lines, those of 100 to 300 lines are appropriately used, and the larger the number of lines, the finer the printing is possible. The thickness of the print layer is preferably 0.1 μm to 100 μm.
(Gravure printing machine)
In a gravure printing machine, one printing unit includes the above gravure plate and a doctor blade. There are many printing units, and printing units corresponding to organic solvent-based printing inks and pattern inks can be set, and each unit has an oven drying unit. Printing is performed by rotary printing, which is a take-up printing method. The type of plate and the type of doctor blade are appropriately selected, and the one according to the specifications can be selected.

<Flexographic printing>
(Flexographic version)
Examples of the plate used for flexographic printing include a photosensitive resin plate that utilizes ultraviolet curing by a UV light source and an elastomer material plate that uses a direct laser engraving method. Regardless of the method of forming the image portion of the flexographic plate, a plate having a screening line number of 75 lpi or more is used. Any sleeve or cushion tape can be used to attach the plate.
(Flexographic printing machine)
Flexographic printing machines include CI type multicolor flexographic printing machines, unit type multicolor flexographic printing machines, etc., and the ink supply method can be a chamber method or a two-roll method, and an appropriate printing machine can be used. can.

(Gas barrier layer)
The gas barrier layer can be provided between the base material and the sealant, if necessary. The gas barrier layer plays a role of blocking the permeation of oxygen, water vapor, etc. between the object to be packaged by the packaging material and the external environment of the packaging material. In addition, it may also be provided with a light-shielding property that blocks the transmission of visible light, ultraviolet rays, and the like. The gas barrier layer may be composed of only one layer or may be composed of a plurality of layers of two or more layers.

Examples of the gas barrier layer (deposited film) include silicon (Si), aluminum (Al), magnesium (Mg), calcium (Ca), potassium (K), tin (Sn), sodium (Na), and boron (. A vapor-deposited film formed of an inorganic substance such as B), titanium (Ti), lead (Pb), zirconium (Zr), yttrium (Y) or an oxide thereof is suitable. Among these, when the packaging material is for a microwave oven, inorganic oxides such as silicon oxide, aluminum oxide, and magnesium oxide are preferable.
Examples of the method for forming the vapor deposition film include vacuum vapor deposition, sputtering, physical vapor deposition (PVD) such as ion plating, chemical vapor deposition (CVD) such as plasma chemical vapor deposition, thermochemical vapor deposition, and photochemical vapor deposition. Law etc. can be mentioned.

The film thickness of the thin-film deposition film varies depending on the forming material, the required gas barrier performance, and the like, but is usually preferably about 5 to 200 nm, more preferably 5 to 150 nm, and further preferably 10 to 100 nm. In the case of an inorganic oxide such as a silicon oxide or an aluminum oxide, it is preferably about 5 to 100 nm, more preferably 5 to 50 nm, and further preferably 10 to 30 nm.

<Intermediate base material layer>
The packaging material of the present invention may have an intermediate base material layer between the glitter printing layer and the sealant. The intermediate base material layer is a layer provided as needed for the purpose of improving the strength of the packaging material and improving the processability. Examples of the constituent material of the intermediate base material layer include a plastic film-like base material. As the base material, the same base material as the above-mentioned base material can be used. In consideration of heating in a microwave oven and retort treatment, the intermediate base material layer preferably has excellent heat resistance in order to increase the heat resistance of the packaging material. A polyester base material, a polyamide base material, or the like is preferably used.

<Adhesive layer>
In the packaging material, each constituent layer is laminated via an adhesive layer from the viewpoint of improving the bonding strength between the layers. The adhesive layer can be formed by a method using a known dry laminating adhesive.
Examples of the dry laminating adhesive include polyvinyl acetate adhesives, polyacrylic acid ester adhesives, cyanoacrylate adhesives, ethylene copolymer adhesives, cellulose adhesives, polyester adhesives, and polyamide adhesives. Adhesives, polyimide adhesives, amino resin adhesives such as urea resin and melamine resin, phenol resin adhesives, epoxy adhesives, polyurethane adhesives (for example, cured products of polyols and isocyanate compounds), reactions Examples thereof include mold (meth) acrylic acid-based adhesives, rubber-based adhesives made of chloroprene rubber, nitrile rubber, styrene-butadiene rubber, etc., silicone-based adhesives, alkali metal silicates, inorganic adhesives made of low-melting point glass, and the like.
The adhesive is formed by applying it to a printing layer, sealant or intermediate substrate layer and then bonded to each layer, substrate or sealant. The coating film thickness is preferably 0.5 to 5 μm, and more preferably 1 to 4 μm.

<Sealant>
The sealant has a role of protecting the packaged object by having the inner layer side surface come into direct contact with the packaged object. In order to make the packaging material into a bag shape, it is preferable that the innermost layer of the sealant has a heat-sealing property. Examples of the material constituting the sealant include low density polyethylene (LDPE), linear low density polyethylene (LLDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), ethylene-vinyl acetate copolymer, and propylene. Examples thereof include polyolefin-based resins such as homopolymers and ethylene-propylene copolymers, and one or more of these resins can be used. The sealant may be composed of a single layer or two or more layers. The sealant is preferably a non-stretched film made of the above-mentioned resin in order to suppress shrinkage during heat sealing.

From the viewpoint of heating in a microwave oven or a retort, the sealant is preferably composed of a resin having excellent heat resistance, specifically, a propylene resin such as polypropylene or an ethylene-propylene copolymer. And HDPE are preferred.

The thickness of the sealant is not particularly limited and is appropriately set according to the use of the packaging material, the type and properties of the object to be packaged, and the like, but is usually preferably 10 to 200 μm. Further, in the case of a pouch (particularly a retort pouch), the thickness of the sealant is preferably 20 to 150 μm, more preferably 30 to 100 μm.

(Manufacturing method of packaging material)
The packaging material of the present invention is a method for producing a packaging material having at least a base material, a brilliant printing layer, an adhesive layer and a sealant, and the brilliant printing layer has a brilliant pigment, a urethane resin and a weight average molecular weight. The step includes a step of forming by gravure printing or flexographic printing on the substrate by brilliant ink containing an isocyanate-based curing agent of 800 to 8000. Further, if necessary, an ink layer may be arbitrarily formed on the brilliant print layer to form a print layer to improve the design. The adhesive layer may be formed by being applied onto the printed layer, or may be formed by being applied to a sealant.
A preferred embodiment is, for example, a mode in which an adhesive is applied and formed on the printing layer, and then a sealant is bonded. When the packaging material further has an intermediate base material layer, the embodiment includes a step of temporarily adhering the printing layer and the intermediate base material layer with an adhesive, and further adhering the intermediate base material layer and the sealant. preferable. The configuration is arbitrary and is not particularly limited.
The packaging material thus obtained is cut into a predetermined size, and the edge portions are heat-sealed so that the sealants are put together with each other to form a bag. The temperature of the heat seal is preferably 50 to 250 ° C, and more preferably 80 to 180 ° C. The heat seal pressure may be a condition such as 1 to 5 kg / cm ^2. One piece of packaging material may be bent to heat-seal the edge, or two or more pieces of packaging material may be heat-sealed. Further, the bag made of the packaging material may be one in which all the openings are heat-sealed after the contents are wrapped.

(Boyle retort)
Normally, packaging materials such as pouches are subjected to high-temperature heating (pressurization) treatment for the purpose of sterilizing after sealing the contents in advance in order to extend the expiration date, and this is called retort. The heating time required for bacteria to die decreases logarithmically as the temperature rises. On the other hand, boil sterilization is a method of sterilizing food by putting it in hot water after packaging it, which is a so-called water bath. The general method is to put the food in a basket, soak the food in a hot water tank at a fixed temperature, and take it out after a certain period of time. It means that it can be processed. Retort is generally performed at 120-130 ° C and boil is around 100 ° C. Therefore, if the packaging material has heat resistance in retort, it also has resistance in boiling.

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, parts and% in the present invention represent parts by mass and% by mass.

(Hydroxy group value)
Obtained according to JIS K0070.
(Acid value)
Obtained according to JIS K0070.
(Amine value)
The amine value was determined according to the following method according to JIS K0070 with the same amount of potassium hydroxide as the equivalent of hydrochloric acid required to neutralize the amino group contained in 1 g of the resin.
The sample was precisely weighed in an amount of 0.5 to 2 g (sample solid content: Sg). To the precisely weighed sample, 50 mL of a mixed solution of methanol / methyl ethyl ketone = 60/40 (mass ratio) was added and dissolved. Bromophenol blue was added to the obtained solution as an indicator, and the obtained solution was titrated with a 0.2 mol / L ethanolic hydrochloric acid solution (titer: f). With the point where the color of the solution changed from green to yellow as the end point, the amine titer was determined by the following (Equation 2) using the titration amount (AmL) at this time.
(Formula 2) Amine value = (A × f × 0.2 × 56.108) / S [mgKOH / g]

(Weight average molecular weight Mw, number average molecular weight Mn and molecular weight distribution Mw / Mn)
The weight average molecular weight Mw, the number average molecular weight Mn, and the molecular weight distribution Mw / Mn are measured by measuring the molecular weight distribution using a GPC (gel permeation chromatography) device (HLC-8220 manufactured by Tosoh Corporation), and polystyrene is used as a standard material. It was calculated as the converted molecular weight. The measurement conditions are shown below.
Column: The following columns were connected in series and used.
TSKgelSuperAW2500 manufactured by Tosoh Corporation
TSKgelSuperAW3000 manufactured by Tosoh Corporation
TSKgelSuperAW4000 manufactured by Tosoh Corporation
Tosoh Co., Ltd. TSK gelland color SuperAWH
Detector: RI (Differential Refractometer)
Measurement conditions: Column temperature 40 ° C
Eluent: Tetrahydrofuran Flow rate: 1.0 mL / min

[Synthesis Example 1] (Synthesis of Urethane Resin 1)
It is a condensate of 3-methyl-1,5-pentanediol (hereinafter, "MPD") and adipic acid (hereinafter, "AA") having a number average molecular weight of 2000 in a reaction vessel with stirring wings under a nitrogen gas atmosphere. 90 parts of polyester polyol (polypoly P-2010 manufactured by Kuraray Co., Ltd.), 10 parts of polypropylene glycol (hereinafter "PPG") having a number average molecular weight of 2000, and 1 part of 1,3-propanediol (hereinafter "1,3-PD"). .5 parts, 31 parts of isophorone diisocyanate (hereinafter “IPDI”), and 33.1 parts of propyl acetate were reacted under a nitrogen stream at 80 ° C. and a stirring speed of 150 rpm for 5 hours to obtain a solvent solution of terminal isocyanate urethane prepolymer. .. Then, in another reaction vessel with stirring wings, 11 parts of isophorone diamine (hereinafter “IPDA”), 1.5 parts of iminobispropylamine (hereinafter “IBPA”), and 0.8 parts of 2-ethanolamine (hereinafter “2EtAm”). 307.1 parts of a mixed solvent of propyl acetate / isopropanol (hereinafter “IPA”) = 60/40 was rapidly stirred at a stirring speed of 180 rpm and held at 40 ° C. to obtain a terminal isocyanate prepolymer solution. Was added dropwise at 40 ° C. over 60 minutes and then reacted at 80 ° C. for 1 hour. After completion of the reaction, the solid content was adjusted to 30% by mass with a mixed solvent of propyl acetate / IPA to obtain one solution of urethane resin.

(Urethane resin 1)
Amine value: 6.5 mgKOH / g
Hydroxy group value: 5.0 mgKOH / g
Acid value: 0.1 mgKOH / g
Glass transition temperature: -40 ° C
Weight average molecular weight: 50,000
Mw / Mn: 2.7

[Synthesis Example 2] (Synthesis of Urethane Resin 2)
90 parts of polyester polyol (polyol P-2010 manufactured by Kuraray Co., Ltd.), 10 parts of PPG, 1.5 parts of 1,3-PD, which is a condensate of MPD and AA, in a reaction vessel with stirring wings under a nitrogen gas atmosphere. 31 parts of IPDI and 33.1 parts of propyl acetate were reacted under a nitrogen stream at 50 ° C. and a stirring speed of 50 rpm for 8 hours to obtain a solvent solution of terminal isocyanate urethane prepolymer. Next, 11 parts of IPDA, 1.5 parts of IBPA, 0.8 parts of 2EtAm, 307.1 parts of a mixed solvent of propyl acetate / IPA) = 60/40 were stirred at a stirring speed of 80 rpm and held at 80 ° C. to obtain the obtained product. The terminal isocyanate prepolymer solution was added dropwise at 80 ° C. over 60 minutes and then reacted at 80 ° C. for 1 hour. After completion of the reaction, the solid content was adjusted to 30% by mass with a mixed solvent of propyl acetate / IPA to obtain a urethane resin 2 solution.

(Urethane resin 2)
Amine value: 6.0 mgKOH / g
Hydroxy group value: 5.0 mgKOH / g
Acid value: 0.1 mgKOH / g
Glass transition temperature: -40 ° C
Weight average molecular weight: 60,000
Mw / Mn: 5.6

[Synthesis Example 3] (Synthesis of Urethane Resin 3)
In a reaction vessel with stirring wings under a nitrogen gas atmosphere, 100 parts of polypropylene glycol having a number average molecular weight of 2000, 1.5 parts of 1,3-PD, 31 parts of IPDI, and 33.1 parts of propyl acetate are stirred under a nitrogen stream at 80 ° C. The reaction was carried out at a speed of 150 rpm for 5 hours to obtain a solvent solution of the terminal isocyanate urethane prepolymer. Next, in another reaction vessel with a stirring blade, 11 parts of IPDA, 1.5 parts of IBPA, 0.8 parts of 2EtAm, and 307.1 parts of a mixed solvent of propyl acetate / IPA = 60/40 were rapidly stirred at a stirring speed of 180 rpm. The mixture was kept at 40 ° C., the obtained terminal isocyanate prepolymer solution was added dropwise at 40 ° C. over 60 minutes, and then the reaction was carried out at 80 ° C. for 1 hour. After completion of the reaction, the solid content was adjusted to 30% by mass with a mixed solvent of propyl acetate / IPA to obtain one solution of urethane resin.

(Urethane resin 3)
Amine value: 6.0 mgKOH / g
Hydroxy group value: 5.0 mgKOH / g
Acid value: 0.1 mgKOH / g
Glass transition temperature: -70 ° C
Weight average molecular weight: 45,000
Mw / Mn: 2.6

[Synthesis Example 4] (Synthesis of Curing Agent 1)
Stirring 15 parts of trimethylolpropane, 60.3 parts of toluene-2,4-diisocyanate and 32.3 parts of pre-dehydrated ethyl acetate in a reaction vessel with stirring blades under a nitrogen gas atmosphere at 50 ° C. and 150 rpm. The reaction was carried out at a rate of 3 hours to obtain a curing agent 1 having a solid content of 70% by mass.
(Hardener 1 (Adduct type))
Weight average molecular weight: 1200
Mw / Mn: 2.5

[Synthesis Example 5] (Synthesis of Curing Agent 2)
Stirring 15 parts of trimethylolpropane, 29.8 parts of toluene-2,4-diisocyanate and 99.3 parts of pre-dehydrated ethyl acetate in a reaction vessel with stirring blades under a nitrogen gas atmosphere at 50 ° C. and 150 rpm. The reaction was carried out at a rate of 3 hours to obtain a curing agent 2 having a solid content of 70% by mass.
(Hardener 2 (Adduct type))
Weight average molecular weight: 2500
Mw / Mn: 3.3

[Synthesis Example 6] (Synthesis of Curing Agent 3)
In a nitrogen gas atmosphere, in a reaction vessel with stirring blades, 15 parts of ditrimethylolpropane, 39.7 parts of toluene-2,4-diisocyanate and 23.4 parts of ethyl acetate were reacted at 100 ° C. and 100 rpm for 3 hours. A curing agent 3 having a solid content of 70% by mass was obtained.
(Hardener 3 (Adduct type))
Weight average molecular weight: 3500
Mw / Mn: 5.5

[Example 1] (Preparation of packaging material 1)
The following brilliant ink S1 is gravure-printed on the entire surface of the gas barrier layer of a 12 μm-thick plastic film (silica-deposited polyethylene terephthalate film Mitsubishi Chemical Co., Ltd. Tech Barrier VX), dried, and brilliant with a dry film thickness of 1.5 μm. A sex print layer was formed. Next, a white ink (Rioalpha R631 white manufactured by Toyo Ink Co., Ltd.) was gravure-printed on the entire surface of the glittering printing layer and dried to form a white printing layer having a dry film thickness of 1.5 μm. Next, a urethane-based adhesive (TM-250HV / CAT-RT86L-60 manufactured by Toyo Morton Co., Ltd.) was applied onto the white printing layer and dried to form a first adhesive layer having a thickness of 2.5 μm. The first adhesive layer and the intermediate base material layer (stretched nylon (Ny), thickness 15 μm) were dry-laminated.
Next, a urethane adhesive (TM-250HV / CAT-RT86L-60 manufactured by Toyo Morton Co., Ltd.) was applied and dried on the sealant (CPP, unstretched polypropylene, thickness 70 μm), and an adhesive layer having a thickness of 2.5 μm was applied. Was formed. Next, the sealant having the second adhesive layer formed was dry-laminated on the surface of the intermediate base material layer to obtain the packaging material 1 of Example 1.
From the outer layer side, the packaging material 1 of Example 1 includes a silica-deposited base material, a printing layer (brilliant printing layer, a white printing layer), a first adhesive layer, an intermediate base material layer, a second adhesive layer, and the like. It has a sealant in this order.

<Glittering ink S1>
15 parts by mass of composition containing metal scales and mineral spirit (12 parts by mass of solid content)
(The content of metal scales is 80% by mass)
(Metal scales: non-leaving type aluminum scales on which oleic acid is adsorbed on the surface, average particle size 10 μm, average thickness 0.07 μm)
13 parts by mass of yellow organic pigment (CI Pigment Yellow 83 average particle size: 150 nm)
-Inorganic fine particles 1 part by mass (silica particles, average primary particle size: 20 nm)
-Binder resin 50 parts by mass (solid content 15 parts by mass)
(Urethane resin 1 above)
-Organic solvent 78 parts by mass (mixed solvent of propylene glycol monomethyl ether, normal propyl acetate, ethyl acetate, isopropanol)
・ Isocyanate-based curing agent 3 parts by mass (solid content 2.1 parts by mass)
(The above curing agent 1)

[Examples 2 to 12] (Preparation of packaging materials 2 to 12)
Packaging materials 2 to 12 of Examples 2 to 12 were obtained in the same manner as in Example 1 except that the raw materials shown in Table 1 and the brilliant ink having a blending ratio were used. In Table 1, the abbreviations represent the following.
-White pearl pigment: mica coated with titanium oxide Average particle size 12 μm Solid content 100% by mass
-TLA-100: Isocyanurate-type isocyanate-based curing agent manufactured by Asahi Kasei Corporation Weight average molecular weight: 1300 Mw / Mn: 2.4 Solid content 70% by mass
-E402-80B: Isocyanate-based curing agent manufactured by Asahi Kasei Corporation Weight average molecular weight: 4000 Mw / Mn: 3.4 Solid content 70% by mass
-D-178NL: Isocyanate-based curing agent manufactured by Mitsui Chemicals, Inc. Weight average molecular weight: 600 Solid content 70% by mass

[Comparative Examples 1 to 4] (Preparation of packaging materials 15 to 18)
Packaging materials 15 to 18 of Comparative Examples 1 to 4 were obtained in the same manner as in Example 1 except that the raw materials shown in Table 1 and the bright ink having a blending ratio were used. In Table 1, the abbreviations represent the following.
-White pigment: Titanium oxide CR-90 manufactured by Ishihara Sangyo Co., Ltd. Solid content 100% by mass

(Measurement and evaluation)
The following measurements and evaluations were performed on the packaging materials of Examples and Comparative Examples. The results are shown in Table 1.

<Design>
Under the illumination of a three-wavelength fluorescent lamp, the packaging materials of Examples and Comparative Examples were observed from a direction slightly deviated from the specular reflection direction of the fluorescent lamp, and the aesthetic appearance due to gloss was evaluated.
You can feel a high level of metallic luster, and you can feel a metallic luster with 4 points that are extremely aesthetically pleasing based on the metallic luster and 2 points that cannot be said to be either. What is a high level metallic luster? Twenty subjects evaluated the score with one point that could not be said, and calculated the average score.
<Evaluation criteria>
A: Average score is 3.5 or more and B: Average score is more than 3 and less than 3.5 C: Average score is more than 2.5 and less than 3 D: Average score is less than 2.5

<Microwave oven resistance>
For the packaging materials obtained in the above Examples and Comparative Examples, the contents were heated in a microwave oven at 600 W for 3 minutes as a 1: 1: 1 soup (ketchup: vinegar: water = mass ratio 1: 1: 1). The appearance was evaluated.
A: No change was seen in the appearance. (Good)
B: There was no change in the appearance, but there was some deformation. (Slightly good)
C: Only one laminate float was seen on the exterior. (Practical)
D: Multiple laminate floats were seen on the exterior. (Defective)
The evaluations that are practical are A, B, and C.
In all of the above packaging materials, expansion due to water vapor was observed during the heating process of the microwave oven, but no sparks or perforation phenomenon was observed.

<Retort resistance>
The packaging materials obtained in the above Examples and Comparative Examples were retort-treated at 120 ° C. for 30 minutes with the contents as a 1: 1: 1 soup (ketchup: vinegar: water = mass ratio 1: 1: 1). The change in appearance was visually evaluated according to the following criteria.
A: No change was seen in the appearance. (Good)
B: There was no change in the appearance, but there was some deformation. (Slightly good)
C: Only one laminate float was seen on the exterior. (Practical)
D: Multiple laminate floats were seen on the exterior. (Defective)
The evaluations that are practical are A, B, and C.

<Easy tearing>
The packaging materials obtained in the above Examples and Comparative Examples were subjected to the above microwave oven test, and then samples were prepared according to JIS K7128-1: 1998 and evaluated by the resistance when torn by the Intesco 2.01 universal tensile tester. bottom.
[Evaluation criteria]
A: Less than 1.5N (good)
B: 1.5N or more and less than 2.0N (slightly good)
C: 2.0N or more and less than 2.5N (practical)
D: 2.5N or more (defective)
The evaluations that are practical are A, B, and C.

[Example 13] (Preparation of packaging material 13)
The above-mentioned glitter ink S1 was gravure-printed on the entire surface of the gas barrier layer of a plastic film (silica vapor-deposited polyamide (nylon) film Mitsubishi Chemical Co., Ltd.) with a thickness of 12 μm and dried to obtain a dry film thickness of 1.5 μm. A glittering print layer was formed. Next, a white ink (Rioalpha R631 white manufactured by Toyo Ink Co., Ltd.) was gravure-printed on the entire surface of the glittering printing layer and dried to form a white printing layer having a dry film thickness of 1.5 μm. Next, an adhesive (TM-250HV / CAT-RT86L-60 manufactured by Toyo Morton Co., Ltd.) is applied onto the white printing layer and dried to form a urethane-based adhesive layer having a thickness of 2.5 μm, and the adhesive layer is formed. On top of the sealant (CPP, unstretched polypropylene, thickness 70 μm) was dry-laminated to obtain the packaging material 13 of Example 13.
The packaging material 13 has a silica-deposited base material, a printing layer (bright printing layer, a white printing layer), an adhesive layer, and a sealant in this order from the outer layer side. When this packaging material was evaluated in the same manner as in the above Examples, it was found that the design property was A, the microwave oven resistance was A, the retort resistance was B, and the tear resistance was A.

[Example 14] (Preparation of packaging material 14)
The above-mentioned glitter ink S10 is gravure-printed on the entire surface of the gas barrier layer of a plastic film (silica vapor-deposited polyamide (nylon) film Mitsubishi Chemical Co., Ltd.) with a thickness of 12 μm and dried to obtain a dry film thickness of 1.5 μm. A glittering print layer was formed. Next, a white ink (Rioalpha R631 white manufactured by Toyo Ink Co., Ltd.) was gravure-printed on the entire surface of the glittering printing layer and dried to form a white printing layer having a dry film thickness of 1.5 μm. Next, an adhesive (TM-250HV / CAT-RT86L-60 manufactured by Toyo Morton Co., Ltd.) is applied onto the white printing layer and dried to form a urethane-based adhesive layer having a thickness of 2.5 μm, and the adhesive layer is formed. On top of the sealant (CPP, unstretched polypropylene, thickness 70 μm) was dry-laminated to obtain the packaging material 14 of Example 14.
The packaging material 14 has a silica-deposited base material, a printing layer (bright printing layer, a white printing layer), an adhesive layer, and a sealant in this order from the outer layer side. When this packaging material was evaluated in the same manner as in the above Examples, it was found that the design property was A, the microwave oven resistance was A, the retort resistance was B, and the tear resistance was A.

From the above, it was found that the packaging material of the present invention is excellent in microwave oven resistance and retort resistance, and has easy tearing property even after the heating. It should be noted that the result is that the isocyanate-based curing agent does not have a predetermined weight average molecular weight, or is inferior in easy tearing property when it does not have a curing agent, and lacks designability when it does not have a bright pigment. ..

Claims (9)

A packaging material having at least a base material, a glittering printing layer, an adhesive layer, and a sealant in that order.
A packaging material in which the brilliant printing layer contains a brilliant pigment and a urethane resin and is crosslinked with an isocyanate-based curing agent, and the weight average molecular weight of the isocyanate-based curing agent is 800 to 8000. The packaging material according to claim 1, wherein the mass ratio of the urethane resin to the isocyanate-based curing agent is 99: 1 to 60:40. The packaging material according to claim 1 or 2, wherein the isocyanate-based curing agent has a molecular weight distribution (Mw / Mn) of 1.5 to 5. The packaging material according to any one of claims 1 to 3, wherein the urethane resin contains a constituent unit derived from polyester. The packaging material according to any one of claims 1 to 4, wherein the urethane resin has a molecular weight distribution (Mw / Mn) of 1.5 to 5. The packaging material according to any one of claims 1 to 5, wherein the base material is a polyester base material or a polyamide base material. The packaging material according to any one of claims 1 to 6, wherein the bright pigment contains scaly aluminum. The packaging material according to any one of claims 1 to 7, which is for a microwave oven or a boiled retort. A method for producing a packaging material having at least a base material, a glittering printing layer, an adhesive layer, and a sealant in that order.
The bright printing layer includes a step of forming a bright ink containing a bright pigment, a urethane resin, and an isocyanate-based curing agent having a weight average molecular weight of 800 to 8000 on the base material by gravure printing or flexographic printing. , Manufacturing method of packaging material.