JP2020164587A - Odor scavenging laminate adhesive resin composition and package, and packaging structure - Google Patents

Abstract

To provide a novel odor scavenging laminate adhesive resin composition, which has excellent adhesivity and retort heat treatment suitability, and which can scavenge an odorous substance generated after the retort heat treatment; and a package having an odor scavenging property, prepared by using the odor scavenging laminate adhesive resin composition.SOLUTION: The odor scavenging laminate adhesive resin composition comprises a polyester polyol (a) containing a polybasic acid component, a polyisocyanate (b) having a trifunctional or more isocyanate groups, and a hydrogen sulfide scavenging pigment (c), where a proportion of an aromatic polybasic acid in the polybasic acid is 30 mol% to 85 mol%. The odor scavenging laminate adhesive resin composition can be used for pasting films with each other, the films constituting a laminate of a plurality of films including a barrier film and a sealant film.SELECTED DRAWING: None

Description

The present invention relates to an odor trapping laminate adhesive resin composition and a package having odor trapping property, and is excellent in adhesiveness and retort heat treatment suitability, and can capture odorous substances generated after retort heat treatment. The present invention relates to an odor-capturing laminate adhesive resin composition that can be produced, and a packaging body having odor-capturing property produced by using the odor-capturing laminate adhesive resin composition.

Conventionally, a two-component polyester urethane adhesive has been used for laminating a plurality of films constituting a retort food packaging body, and has been widely used.
Among them, when an amino acid compound, particularly a content containing a sulfur-containing amino acid compound, is stored in a package for retort pouch foods and subjected to retort heat treatment, an odor called retort odor is generated, which causes an odor. There is.
Hydrogen sulfide generated by hydrolysis of sulfur-containing amino acid compounds is a major cause of these odors.
Patent Document 1 proposes a deodorizing resin composition containing a thermoplastic resin, a zinc compound as a deodorizing component, a sulfate of aluminum, and a metal oxide. However, since this deodorizing resin composition is used for molded products such as films, sheets, molded containers, and fibers, it is different from the use as the odor trapping laminate adhesive resin composition of the present invention. However, the technical fields are also different. Further, in the present invention, the aromatic polybasic acid in the polybasic acid used for the synthesis of the polyester polyol (a) is set to a specific ratio, whereby the odor trapping laminate adhesive resin composition according to the present invention is used. The cured film is adjusted to a glass transition temperature suitable for catching odors. However, in applications such as Patent Document 1, molding of a deodorizing resin composition occurs when the temperature of the cured film of the cured film of the odor trapping adhesive resin composition according to the present invention is around the glass transition temperature (0 ° C or higher and 30 ° C or lower). The product is too soft to use.
Further, Patent Document 2 proposes a gas barrier laminate in which an adhesion layer, an inorganic vapor deposition layer, a gas barrier layer, and a layer containing a zinc compound are sequentially laminated on one surface of a film base material. However, the layer containing the zinc compound is assumed to be a coating layer, and when the temperature is around the glass transition temperature (0 ° C. or higher and 30 ° C. or lower) of the odor trapping laminate adhesive resin composition according to the present invention, the film and the coating layer are combined. It may not be usable due to problems such as blocking.
Further, in Patent Document 3, an inorganic oxide is blended in an adhesive containing a polyol as a main component, and the inorganic oxide has oxygen absorption such as titanium oxide, zinc oxide, and cerium oxide having oxygen absorbing ability. An adhesive composition has been proposed, and it has been shown that the inorganic oxide blended in the adhesive composition is an inorganic oxide having an oxygen lattice defect by subjecting it to a reduction treatment. However, zinc oxide having an oxygen lattice defect by the reduction treatment is practically impossible to use in the adhesive layer from the viewpoint of stabilization. Further, Patent Document 3 discloses an adhesive composition having an oxygen absorbing ability and a hiding property as a printing ink in an adhesive layer, and the technical field is different from that of the odor capturing of the present invention.

Japanese Unexamined Patent Publication No. 63-175067 Japanese Unexamined Patent Publication No. 2016-221864 Japanese Unexamined Patent Publication No. 2006-131699

An object of the present invention is to provide an odor trapping laminate adhesive resin composition which is excellent in adhesiveness and suitability for retort heat treatment and can capture odorous substances generated after retort heat treatment.
Further, by using the present invention for laminating a plurality of films constituting a package of a retort heat-treated food containing an amino acid compound, particularly a sulfur-containing amino acid compound in the content, hydrogen sulfide generated after the retort heat treatment is captured. The task is to do.
Furthermore, an object of the present invention is to provide an odor trapping laminate adhesive resin composition capable of maintaining its adhesive performance after retort heat treatment.

As a result of diligent studies to solve the above problems, the present inventors have made a polyester polyol (a) containing a polybasic acid component, a polyisocyanate (b) having a trifunctional or higher functional isocyanate group, and hydrogen sulfide. A plurality of films constituting an odor-capturing laminate adhesive resin composition containing a trapping pigment (c) and having an aromatic polybasic acid ratio of 30 mol% or more and 85 mol% or less in the polybasic acid. By using it for bonding to each other, it is excellent in adhesiveness and suitability for retort heat treatment, and odorous substances generated after retort heat treatment can be captured by the odor trapping laminate adhesive resin composition, and further, retort heat treatment. Later, he discovered that the adhesive performance was maintained, and completed the present invention.

The present invention contains a polyester polyol (a) containing a polybasic acid component, a polyisocyanate (b) having a trifunctional or higher functional isocyanate group, and a hydrogen sulfide trapping pigment (c) in the polybasic acid. It is an odor trapping laminate adhesive resin composition characterized in that the ratio of the aromatic polybasic acid of is 30 mol% or more and 85 mol% or less.

Further, the present invention can be carried out as a laminating adhesive used for laminating films constituting a laminated body of a plurality of films including a barrier film and a sealant film.

Further, the present invention can be carried out assuming that the aromatic polybasic acid contains an aromatic polybasic acid in which a carboxyl group is substituted at the meta position of the benzene ring.

Further, the present invention is carried out assuming that the polyisocyanate (b) having a trifunctional or higher functional isocyanate group is a derivative of at least one isocyanate compound selected from the group consisting of hexamethylene diisocyanate, isophorone diisocyanate and xylene diisocyanate. can do.

Further, the present invention can be carried out assuming that the hydrogen sulfide trapping pigment (c) contains zinc oxide.

Further, the present invention can be carried out assuming that the glass transition temperature of the adhesive cured film is 0 ° C. or higher and 30 ° C. or lower.

Further, according to the present invention, in a package in which a laminated sheet in which a plurality of films including a barrier film and a sealant film are laminated is used, the sealant film is a content (d) stored in the package. It is characterized in that the sealant film of the innermost layer and the other film are bonded to each other by the odor trapping laminate adhesive resin composition which is arranged in the innermost layer of the laminate sheet which can come into contact with the innermost layer. It is a package having odor trapping properties.
Further, the present invention is a packaging structure comprising the package and the content (d) housed in the package, wherein the content (d) contains a sulfur-containing amino acid compound.

The present invention is a laminate adhesive resin composition used for laminating a plurality of films constituting a package, and comprises a polyester polyol (a) containing a polybasic acid component and a trifunctional or higher functional isocyanate group. Odor-capturing laminate adhesive resin composition containing the polyisocyanate (b) and the hydrogen sulfide trapping pigment (c), and the ratio of aromatic polybasic acid in the polybasic acid is 30 mol% or more and 85 mol% or less. It is a thing. By using the odor-capturing laminate adhesive resin composition according to the present invention for laminating a plurality of films constituting a package, the odor-capturing performance after retort heat treatment is exhibited. The odor trapping performance after a general retort heat treatment is exhibited by providing a film or coating layer using a thermoplastic resin constituting the package as an odor trapping performance layer. On the other hand, in the present invention, the odor trapping laminate adhesive resin composition having the above constitution is used for laminating a plurality of films constituting the package to form an odor trapping laminate adhesive resin. The composition does not come into direct contact with the contents, and the odor-capturing laminate adhesive resin composition can capture odors such as hydrogen sulfide via the sealant film. Further, it is impossible to disperse a plastic film or zinc oxide, which is one of the hydrogen sulfide trapping pigments (c), without increasing the number of layers of a laminate of a plurality of films constituting the package, such as a coating agent. It is possible to selectively use the odor-catching laminating adhesive resin composition having the above-mentioned structure even for a metal foil film, which leads to a reduction in packaging cost.

The present invention captures odors containing at least three of a polyester polyol (a) containing a polybasic acid component, a polyisocyanate (b) having a trifunctional or higher functional isocyanate group, and a hydrogen sulfide trapping pigment (c). It is a sex-laminated adhesive resin composition, and embodiments thereof will be described below.

In the present invention, it is essential to include a polyester polyol (a) containing a polybasic acid component, a polyisocyanate (b) having a trifunctional or higher functional isocyanate group, and a hydrogen sulfide trapping pigment (c). , The compounding form thereof does not matter. However, as a general form, a polyester polyol (a) in which a hydrogen sulfide trapping pigment (c) is dispersed as a main agent (A) and a poly having a trifunctional or higher functional isocyanate group as a curing agent (B). It is preferable to use isocyanate (b).

(About polyester polio (a))
As the polyester polyol (a) included in the present invention, a polyester polyol (a1) or a polyester polyurethane polyol (a2) obtained by extending a urethane chain of a polyester polyol with diisocyanate or the like is used.
The polyester polyol (a) contained in the present invention is obtained, for example, by dehydrating and condensing a polybasic acid and a polyhydric alcohol such as glycol, and has an aromatic such as an aromatic dicarboxylic acid in the total polybasic acid. The blending ratio of the polybasic acid is preferably 30 mol% or more and 85 mol% or less. If the blending ratio of the aromatic polybasic acid in the total polybasic acid is less than 30 mol%, the retort heat treatment suitability is lowered, and the lamination strength after odor capture is lowered. In addition, if the blending ratio of the aromatic polybasic acid in the total polybasic acid exceeds 85 mol%, the film after curing becomes hard, and the odor trapping performance is deteriorated and the appearance of the laminate is deteriorated due to the yuzu skin. cause.
In particular, among aromatic polybasic acids, it is preferable to use an aromatic polybasic acid (particularly an aromatic dicarboxylic acid) in which a carboxyl group is substituted at the meta position of the benzene ring. If only an aromatic polybasic acid in which a carboxyl group is substituted at the para position of the benzene ring is used, the crystallinity of the adhesive may be improved and turbidity may occur. Further, if only an aromatic polybasic acid in which a carboxyl group is substituted at the ortho position of the benzene ring is used, the odor absorption performance may be deteriorated due to a decrease in molecular motion.
From these viewpoints, the blending ratio of the aromatic polybasic acid in which the carboxyl group is substituted at the meta position in the total polybasic acid is preferably 30 mol% or more.

As the aromatic dicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, phthalic anhydride and the like can be used alone or in combination of two or more.

Aliphatic dicarboxylic acid can be used as the polybasic acid. The aliphatic dicarboxylic acids include succinic acid, adipic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassic acid, maleic acid, fumaric acid, itaconic acid and their acid anhydrides, tetrahydrophthalic anhydride and hexahydrophthalic anhydride. An acid, tetrabrom anhydride phthalic acid, tetrachlor phthalic acid anhydride, het acid anhydride, hymic anhydride and the like can be used alone or in combination of two or more.

In addition to aromatic dicarboxylic acids and aliphatic dicarboxylic acids, trimellitic anhydride, pyromellitic anhydride and the like can also be used as polybasic acids, but when these trivalent or higher valent polybasic acids are used, polyester polyol (a1) ) Is easily gelled during synthesis, so a trivalent or higher polybasic acid is preferably added to the total polybasic acid so as to be 30 mol% or less, more preferably 20 mol% or less, and further preferably 10 mol% or less.

Examples of the glycol include ethylene glycol, propylene glycol, diethylene glycol, dipropylene diol, neopentyl glycol, triethylene glycol, tripropylene glycol, tetramethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, 1,3-butanediol, and the like. 1,4-Butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 3-methyl-1,5-pentanediol, The castor oil-modified diol, dimer acid diol, hydride bisphenol A and the like can be used alone or in combination of two or more.

As polyhydric alcohols other than glycol, trihydric alcohols such as glycerin, trimethylolethane, trimethylolpropane, and trishydroxymethylaminomethane, and tetrahydric or higher alcohols such as pentaerythritol and dipentaerythritol can also be used. However, if these trihydric or higher alcohols are used, they are likely to gel during the synthesis of the polyester polyol (a1), so that it is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and further in 100 parts by mass of the total polyhydric alcohol. A trihydric or higher alcohol is preferably added so as to be 10 parts by mass or less.

Further, the polyester polyol (a1) or the polyester polyurethane polyol (a2) used in the present invention can be used alone or in combination of two or more, and the polyester polyol (a1) and the polyester polyurethane polyol (a2) can be used alone or in combination. The mixture with and may be used as the polyester polyol (a).

The polyester polyol (a) used in the present invention may be a polyester polyurethane polyol (a2) obtained by extending a urethane chain of a polyester polyol with diisocyanate or the like as described above. When extending the urethane chain of the polyester polyol, various urethane chain extenders can be used. As the urethane chain extender, various isocyanate compounds such as known isocyanate compounds and derivatives thereof can be used. Specifically, isocyanate compounds such as xylene diisocyanate, hydrogenated xylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, norbornene diisocyanate, tolylene diisocyanate, hydrogenated tolylene diisocyanate, diphenylmethane diisocyanate, and hydrogenated diphenylmethane diisocyanate, and their trimethylols. Derivatives such as propane adduct, burette, allophanate, and isocyanurate can be used.
The number of functional groups of isocyanate is not particularly limited, but it is preferable to extend the urethane chain mainly with diisocyanate, which is bifunctional, from the viewpoint of coating suitability and adhesive strength.

(About polyisocyanate (b) having trifunctional or higher functional isocyanate groups)
Next, it is essential that the polyisocyanate (b) is an isocyanate compound having a trifunctional or higher functional isocyanate group in its molecular structure. When the odor trapping laminate adhesive resin composition according to the present invention is used for bonding a sealant film in direct contact with the contents to another film in food packaging where odor trapping performance is expected by retort heat treatment. From the viewpoint of hygiene, it is preferable to use an aliphatic isocyanate derivative as the polyisocyanate (b) having a trifunctional or higher functional isocyanate group.
Examples of the type include trimethylolpropane adduct, burette, allophanate, isocyanurate, and the like of aliphatic isocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, xylene diisocyanate, and norbornene diisocyanate. Can be used together.
Further, in the present invention, it is also possible to use a derivative of aromatic isocyanate as the polyisocyanate (b) having a trifunctional or higher functional isocyanate group.
Examples of the type include trimethylolpropane adduct, burette, allophanate, isocyanurate and the like of aromatic isocyanates such as tolylene diisocyanate and diphenylmethane diisocyanate, and can be used alone or in combination of two or more.
Further, as the polyisocyanate (b) having a trifunctional or higher functional isocyanate group, a derivative of an aliphatic isocyanate and a derivative of an aromatic isocyanate can be used in combination as long as the object of the present invention is not impaired.
By blending fine particles such as zinc oxide, it may be difficult to form the three-dimensional network required for film formation. Therefore, in the present invention, three or more functional groups are used for the purpose of suppressing deterioration of film formation. It was assumed that the isocyanate group of the above was contained.

The polyester polyol (a) and the polyisocyanate (b) having a trifunctional or higher functional isocyanate group usually have the polyester polyol (a) as the main agent (A) and the polyisocyanate (b) as the curing agent (B). It is preferable to mix the two immediately before the laminating coating and use it as a two-component curing type. However, it is also possible to react the polyester polyol (a) with the polyisocyanate (b) in advance and use it as a polyester-modified isocyanate curing agent or a one-component adhesive.

(About hydrogen sulfide trapping pigment (c))
The hydrogen sulfide trapping pigment (c) is preferably zinc oxide or a compound containing the same. Commercially available zinc oxide can be used, and examples thereof include zinc oxide pigments (1st, 2nd, and 3rd types), lint-like zinc powder pigments, hexagonal plate-shaped zinc oxide pigments, and active zinc white pigments. .. Among them, from the viewpoint of hygiene used in food packaging, zinc oxide type pigment is particularly preferable. The particle size of the hydrogen sulfide trapping pigment (c) is not particularly limited, but if it exceeds 3.0 μm, it may cause a poor appearance of the laminate. In particular, when the hydrogen sulfide trapping pigment (c) is 0.3 μm or less, which is called fine, or is called ultrafine, which is on the order of nm, the surface area of the hydrogen sulfide trapping pigment (c) increases, and the hydrogen sulfide trapping pigment (c) It is possible to improve the odor trapping performance and the transparency of the adhesive layer. Zinc oxide surface-treated with a surface treatment agent such as silica (silicon dioxide) may be used as the hydrogen sulfide trapping pigment (c).
The particle size in this case is a particle size using an air permeation method, and can be measured using a Leaners air permeation method powder degree measuring device (manufactured by Tokyo Rika Seiki Seisakusho) or the like.
The amount of the hydrogen sulfide trapping pigment (c) added is not particularly limited, and can be adjusted according to the type of contents stored in the package, the amount of odorous substances generated, and the amount of the laminate adhesive applied. However, if the amount of the hydrogen sulfide trapping pigment (c) added exceeds 100 parts by mass with respect to 100 parts by mass of the polyester polio (a), the appearance of the laminate may be poor or the adhesive performance may be deteriorated.
Further, by using a zinc oxide pigment having a high whiteness, it is expected to replace the white ink required for the packaging and reduce the amount of ink used.
Furthermore, by using phosphorus flake zinc powder pigments and hexagonal plate zinc oxide pigments, it is expected to impart gas barrier properties to adhesives, improve barrier properties of barrier films, and suppress defects in film pinholes. Will be done.
In addition to zinc oxide, zinc carbonate or the like can be used as the hydrogen sulfide trapping pigment (c).

The hydrogen sulfide trapping pigment (c) in the present invention is preferably dispersed in the polyester polio (a) in advance. The amount of the hydrogen sulfide trapping pigment (c) added at the time of dispersion is preferably 1 part by mass to 50 parts by mass with respect to 100 parts by mass of the polyester polio (a). More preferably, it is 20 to 40 parts by mass. It is preferable from the viewpoint of dispersibility of the hydrogen sulfide trapping pigment (c) in the polyester polyol (a) and ensuring hydrogen sulfide trapping performance and adhesive performance.
It is possible to disperse in polyisocyanate (b) having a trifunctional or higher functional isocyanate group, but at the time of dispersion, active hydrogen contained in water in the air or water contained in the pigment reacts with the isocyanate group to cause gelation. May cause.
As a dispersion method, a hydrogen sulfide trapping pigment (c) can be dispersed in a polyester polyol (a) or a polyisocyanate (b) having a trifunctional or higher functional isocyanate group using a known disperser. For example, known dispersers include bead mill dispersers, roll mill dispersers, ball mill dispersers, and coreless dispersers.

(About the content (d) containing a sulfur-containing amino acid compound)
The odor trapping laminate adhesive resin composition according to the present invention is used, for example, for laminating a sealant film that can come into contact with the content (d) contained in a package to be subjected to retort heat treatment and another film. And contains a sulfur-containing amino acid compound as the content (d). Examples of the sulfur-containing amino acid compound include methionine, cysteine, homocysteine, taurine and the like, and are contained in all foods. Examples of foods containing sulfur-containing amino acid compounds include seafood such as bonito, sardines, shirasu, and autumn sword fish, beans such as sesame, soybeans, and kinako, and vegetables such as nira, onion, and onions. Examples include retort curry, oden, mapo tofu, and bonito boiled in miso. When a sulfur-containing amino acid compound is hydrolyzed, odorous gases such as hydrogen sulfide and mercaptan are generated. Hydrogen sulfide may be preferred as a boiled egg scent when it is very dilute, but when the concentration exceeds a certain level, it is disliked as an unpleasant rotten egg odor and causes food odor and harshness.
By using the odor trapping laminate adhesive resin composition according to the present invention for laminating a plurality of films constituting a package to be subjected to retort heat treatment, sulfide contained in the odor trapping laminate adhesive resin composition The hydrogen trapping pigment (c) traps odorous gases such as hydrogen sulfide and mercaptan generated after the retort heat treatment to suppress the retort odor.

Further, the odor trapping laminate adhesive resin composition in the present invention is also expected to be used for industrial applications. Hydrogen sulfide reacts with silver and copper, which are widely used in all electronic devices, and metal corrosion progresses. Further, the sulfide-based solid electrolyte material used for the lithium ion battery generates hydrogen sulfide when it comes into contact with the atmosphere. As a means of suppressing the generation of these metal corrosions and hydrogen sulfide, it is expected that the hydrogen sulfide trapping function of the odor trapping laminate adhesive resin composition according to the present invention will be utilized.
At that time, the form of use is not particularly limited, and examples include a package using the odor trapping laminate adhesive resin composition of the present invention, a sheet shape such as a back sheet of a solar cell, and a cup lid material. Be done.

(About glass transition temperature)
The glass transition temperature of the cured film of the odor trapping laminate adhesive resin composition in the present invention is preferably 0 ° C. or higher and 30 ° C. or lower. If the glass transition temperature is less than 0 ° C., it may not be able to withstand the heat during the retort heat treatment and may cause delamination. Further, when the glass transition temperature exceeds 30 ° C., the cured film is too hard, so that sufficient odor trapping performance may not be exhibited. If the cured film is hard, transfer of the vapor-deposited layer in the film to be adhered may occur, and the types of films that can be used are limited. Therefore, the temperature is preferably 25 ° C. or lower. On the other hand, from the viewpoint of preventing the occurrence of delamination, the temperature is preferably 4 ° C. or higher, more preferably 8 ° C. or higher. The adjustment of the glass transition temperature is preferably adjusted by adjusting the blending ratio of the aromatic polybasic acid in the polybasic acid used for the synthesis of the polyester polyol (a). It is also possible to adjust the glass transition temperature of the cured film by increasing or decreasing the ratio of the polyisocyanate (b) having a trifunctional or higher functional isocyanate group in the odor trapping laminate adhesive resin composition in the present invention. When the ratio of the polyisocyanate (b) having a trifunctional or higher functional isocyanate group in the odor trapping laminate adhesive resin composition in the present invention is increased, the rubber elastic coefficient of the cured film decreases, resulting in a so-called hard and brittle film. It ends up. In this case, it may cause delamination during the retort heat treatment. The ratio of the polyisocyanate (b) having a trifunctional or higher functional isocyanate group in the odor trapping laminate adhesive resin composition in the present invention has a trifunctional or higher functional isocyanate group to the OH component of the polyester polyol (a). The ratio of the NCO component of the polyisocyanate (b) preferably has an NCO / OH in the range of 1.5 to 3.0. Generally, the above NCO / OH in the polyester urethane adhesive is preferably in the range of 1.0 to 2.0, but in the present invention, hydrogen sulfide is added by incorporating the hydrogen sulfide trapping pigment (c). Since there is a high possibility that the isocyanate group is absorbed by the trapping pigment (c) and the isocyanate group is inactivated, the NCO / OH is preferably in the range of 1.5 to 3.0.
The glass transition temperature can be measured using a rigid pendulum type physical property tester.

It is preferable to use a silane coupling agent for the odor trapping adhesive resin composition of the present invention. The types include γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and γ. -Aminopropyltrimethoxysilane, γ- (2- (aminoethylamino) propyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N-( β-Aminoethyl) -γ-aminopropyldimethoxymethylsilane, N-ethyl-4-amino-3,3-dimethylbutyldimethoxymethylsilane, N-ethyl-4-amino-3,3-dimethylbutyltrimethoxysilane, Examples include N-butyl-3-amino-2-methylpropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, and ethoxy derivatives thereof, and one selected from these groups. Alternatively, two or more types can be used.

In the odor-capturing laminate adhesive resin composition of the present invention, a pigment that captures odorous substances other than hydrogen sulfide and mercaptan can be used as long as the function of the present invention is not impaired. Examples of the type include a physical adsorbent such as silica, activated carbon, and zeolite, and a type in which an odorous substance other than hydrogen sulfide or mercaptan is chemically reacted with an amino group, an epoxy group, or the like to capture the substance.
Specifically, as physical adsorbents, silver-based inorganic antibacterial agent Zeomic (manufactured by Sinanen Zeomic Co., Ltd.), zeolite-based deodorant Dashlight (manufactured by Sinanen Zeomic Co., Ltd.), Skull HK (manufactured by Antibacterial Research Institute Co., Ltd.), Examples of the chemical reaction capture type include Chemcatch H-6000HS (manufactured by Otsuka Chemical Co., Ltd.), Chemcatch T-6900 (manufactured by Otsuka Chemical Co., Ltd.), and one or more selected from these groups. It can be used.

Further, the odor-catching laminate adhesive resin composition of the present invention contains various kinds of tackifiers, reaction accelerators, leveling agents, ultraviolet absorbers, defoamers, etc., as long as the object of the present invention is not impaired. Additives, coloring pigments, and extender pigments can also be added.

Examples of the tackifier include paraffin wax, polyethylene wax, rosin, rosing lycerin ester, terpene, alkylphenol and the like, and one or more selected from these groups can be used.

Reaction accelerators include metal catalysts such as dibutyltin dilaurate, dibutyltin diacetate, dioctyltin dilaurate, dibutyltin dimarate, tetrabutyl titanate, and tetraisopropyl titanate, and 1,8-diazabicyclo (5,4,0) -7. Tertiary amines such as −undecene, 1,5-diazabicyclo (4,5,0) -5-nonen, 6-dibutylamino-1,8-diazabicyclo (5,4,0) -7-undesene, and triethanolamine Examples thereof include reactive tertiary amines such as amines, and one or more selected from these groups can be used.

Leveling agents include acrylic polymers, modified silicones, and acetylenediols, UV absorbers include benzotriazoles, hydroxyphenyltriazines, and hindered amines, and defoamers include organic polyethers and surfactants. Examples thereof include activators and inorganic silicone compounds, and one or more selected from these groups can be used.

Coloring pigments include organic pigments such as anthraquinone, diketopyrrolopyrrole, perylene maroon, carbon black, dioxazine, perylene, benzimidazolone, isoindolinone, isoindolin, phthalocyanine, and indanslen, yellow iron oxide, and red. Inorganic pigments such as iron oxide, azomethine copper complex, titanium oxide, and silicon oxide can be mentioned, and the extender pigments include barium sulfate, calcium carbonate, barium sulfate, barium carbonate, calcium carbonate, magnesium oxide, magnesium carbonate, and magnesium hydroxide. , Barium titanate, calcium hydroxide, calcium sulfite, calcium sulfate, calcium oxide, calcium silicate, titanium oxide, silica, zeolite, talc and other inorganic pigments, one or two selected from these groups. It can be used more than seeds.

(About application amount)
The coating amount of the adhesive resin composition of the present invention is about ² to 5 g / m ² , preferably about 3 to 5 g / m ² . If the coating amount is less than 2 g / m ² , sufficient odor trapping performance may not be obtained. In addition, if it exceeds 5 g / m ² , it may be disadvantageous in terms of economy.

(About number average molecular weight)
The number average molecular weight of the polyester polio (a) in the present invention is preferably in the range of 5,000 to 50,000, and when it exceeds 50,000, the viscosity of the obtained odor trapping laminate adhesive resin composition becomes high. It becomes expensive, and the problem that the amount of the diluting solvent used at the time of coating increases and the problem that the coating suitability deteriorates occur. On the other hand, when the number average molecular weight is less than 5,000, the molecular weight is low, which may cause a decrease in heat resistance during the retort heat treatment.
The number average molecular weight of the polyester polyol (a) in the present invention is a polystyrene-equivalent value obtained by gel permeation chromatography (GPC). For example, the measurement conditions of the following examples are that the temperature of the column (KF-805L × 2 manufactured by Showa Denko KK) is 35 ° C., the eluent is tetrahydrofuran (THF), the flow velocity is 1.0 ml / min, and the detection is RI. It was performed with a detector (differential refractometer) and the sample concentration was 0.3% by mass.

(About laminateable film)
The laminating film according to the present invention is not particularly limited, and can be used when laminating films having the same or different sticking surfaces selected from plastic materials, metal materials, and inorganic materials. More specifically, a plastic film such as polyethylene terephthalate, polyamide typified by nylon, polyethylene, polypropylene, a vapor-deposited film obtained by depositing aluminum, silica, alumina or the like on a plastic film as a base material, a polyvinyl alcohol film, or poly. Examples thereof include organic barrier films such as vinylidene chloride film and ethylene vinyl alcohol copolymer film, and metal films such as metal foils such as aluminum foils, copper foils and stainless steel foils. Odor trapping laminate adhesive resin composition according to the present invention. The thing can be used when adhering these various films to each other.
Among these, the sealant film includes a film having a relatively low heat melting temperature (for example, a non-stretched polypropylene (CPP) film, a linear low-density polyethylene (LLDPE, linear polyethylene) film), and a biaxially stretched polypropylene having heat-sealing properties. (OPP) film, polyethylene terephthalate (PET) film, etc.), and examples of the barrier film include a vapor-deposited film, an organic barrier film, and a metal film.
The plastic film may be stretched or unstretched.

(How to use)
The specific method of use in the odor-capturing laminate adhesive resin composition of the present invention is not particularly limited, but for example, non-solvent type lamination used after heating to an appropriate viscosity and blending the main agent and the curing agent. Examples thereof include a method and a dry lamination method in which a compound adhesive is diluted and adjusted to an appropriate coating viscosity with a solvent. As the solvent used in the dry lamination method, a solvent that does not contain a hydroxyl group or an amino group that reacts with an isocyanate group is used, and specific examples thereof include ethyl acetate and methyl ethyl ketone.
The odor-catching laminate adhesive resin composition according to the present invention exhibits an odor-capturing performance of capturing odorous substances generated after retort heat treatment when used for laminating films constituting a package of retort food. However, its use is not limited to packaging, and can be used for various purposes as a laminate adhesive, for example, bonding a plurality of films constituting a back sheet of a solar cell to each other. ..

(About laminated sheet and packaging)
The package according to the present invention is produced by using a laminated sheet. For example, a package produced by making a bag of a laminated sheet or a lid for covering an opening of a tray or a cup-shaped plastic container. A laminated sheet as a material can be mentioned.
The laminated sheet is formed by laminating a plurality of films including the above-mentioned barrier film and sealant film, and the sealant film is arranged in the innermost layer of the laminated sheet. Here, the innermost layer of the laminated sheet means a layer that can come into contact with the contents (d) stored in the package in the package manufactured by bag-making the laminated sheet, and in the laminated sheet itself. , Corresponds to the surface layer of the laminated sheet.
The laminated sheet may have an appropriate layer structure of two or more layers, such as being formed by laminating a barrier film, a plastic film, and a sealant film.
The odor trapping adhesive resin composition according to the present invention is used for laminating a sealant film that can come into contact with the content (d) and a film to be laminated on the sealant film among a plurality of films constituting the laminate sheet. That is the most effective in terms of odor capture. However, for example, in the case of a laminated sheet having a layer structure of three or more layers including a barrier film and a sealant film, various known adhesives are used for bonding the sealant film and the film to be laminated on the sealant film, and other than the sealant film. The odor-capturing laminate adhesive resin composition according to the present invention may be used for bonding the films to each other, and the odor-capturing laminate adhesive resin composition according to the present invention may be used for bonding all the films constituting the laminate sheet. You may use the thing. Examples of the film other than the sealant film include the above-mentioned plastic film, barrier film, organic barrier film, and metal film excluding the sealant film.
When the laminated sheet is used for a package for retort foods, ONY / CPP, ONY / LLDPE, PET / CPP, ONY / LLDPE, PET / ONY / CPP can be exemplified when the laminated sheet has a transparent structure. , VMPET / ONY / CPP can be exemplified in the case of a transparent vapor deposition configuration, and PET / ALM / CPP, PET / ALM / ONY / CPP, PET / ONY / ALM / CPP can be exemplified in the case of an ALM configuration. ..
The thickness of each of the plurality of films constituting the laminated sheet is not particularly limited, and may be appropriately set according to the use and function of the laminated sheet or the package.

When the package according to the present invention is produced by bag-making, the bag-making method is not particularly limited, and various bag-making methods can be used to produce the package. For example, two laminated sheets may be laminated so that the sealant films face each other, and heat-sealed on all sides to prepare a package. The two laminated seals and folds constituting the front part and the back part may be formed. A standing pouch-shaped package may be produced by arranging the sealant film so as to form the inside of the package and heat-sealing on all sides using the laminated sheet constituting the bottom portion. Further, one laminated seal may be folded in half so that the sealant film is on the inside, and heat-sealed on three sides to prepare a package.

The present invention will be described in more detail with reference to the following Examples and Comparative Examples, but the present invention is not limited to these Examples.

(Synthesis Example 1 of Polyester Polioll (a1))
Ethylene glycol (50.0 g), neopentyl glycol (160.0 g), 1,6-hexanediol (190.0 g), isophthalic acid (190.0 g), in a flask equipped with a nitrogen introduction tube, a stirrer, a rectification tower, and a condenser. 326.0 g), terephthalic acid (100.0 g), and sebacic acid (174.0 g) were added and dehydrated and condensed at an internal temperature of 180 to 200 ° C. with stirring. After confirming that the acid value was 15 mgKOH / g and further advancing the dehydration reaction at 200 to 240 ° C. while blowing nitrogen, after confirming that the acid value was 2 mgKOH / g or less, the internal pressure was adjusted to 15 Torr. The reaction was continued under reduced pressure, and after confirming that the acid value was 0.1 mgKOH / g or less, the reaction was terminated, and the solid content was adjusted to 60% with ethyl acetate. The obtained polyester polyol had a number average molecular weight of 8,000, which was designated as polyester polio (a1-1).

(Synthesis Example 2 of Polyester Polioll (a1))
Ethylene glycol (50.0 g), neopentyl glycol (160.0 g), 1,6-hexanediol (190.0 g), isophthalic acid (190.0 g), in a flask equipped with a nitrogen introduction tube, a stirrer, a rectification tower, and a condenser. 400.0 g), sebacic acid (160.0 g), and adipic acid (40.0 g) were added, and the mixture was dehydrated and condensed at an internal temperature of 180 to 200 ° C. with stirring. After confirming that the acid value was 15 mgKOH / g and further advancing the dehydration reaction at 200 to 240 ° C. while blowing nitrogen, after confirming that the acid value was 2 mgKOH / g or less, the internal pressure was increased to 15 Torr. The reaction was continued under reduced pressure, and after confirming that the acid value was 0.1 mgKOH / g or less, the reaction was terminated, and KBM-403 (γ-glycidoxypropyltrimethoxysilane manufactured by Shinetsu Silicone Co., Ltd.) was added. After blending 2.7 g, the solid content was adjusted to 60% with ethyl acetate. Further, after cooling to 60 ° C., dibutyltin dilaurate (0.1 g) was added, and the mixture was stirred for 10 minutes. The solid content was adjusted to 60% with the obtained ethyl acetate. The obtained polyester polyol had a number average molecular weight of 8,000, and this was designated as polyester polio (a1-2).

(Synthesis Example 3 of Polyester Polioll (a1))
Ethylene glycol (176.0 g), neopentyl glycol (151.0 g), 3-methyl-1,5-pentanediol (139.0 g) in a flask equipped with a nitrogen introduction tube, a stirrer, a rectification tower, and a condenser. , 1,6-Hexanediol (139.0 g), isophthalic acid (337.0 g), and sebacic acid (346.0 g) were added and dehydrated and condensed at an internal temperature of 180 to 200 ° C. with stirring. After confirming that the acid value was 15 mgKOH / g and further advancing the dehydration reaction at 200 to 240 ° C. while blowing nitrogen, after confirming that the acid value was 2 mgKOH / g or less, the internal pressure was adjusted to 15 Torr. The reaction was continued under reduced pressure, and after confirming that the acid value was 0.1 mgKOH / g or less, the reaction was terminated, and the solid content was adjusted to 70% with ethyl acetate. The obtained polyester polyol had a number average molecular weight of 10,000, and this was designated as polyester polio (a1-3).

(Synthesis Example 1 of Polyester Polyurethane Polyester (a2))
Further, the obtained polyester polyol (a1-3) (500.0 g) and xylene diisocyanate (Takenate 500: manufactured by Mitsui Chemicals, Inc.) (16.2 g) were charged and heated under reflux for 6 hours to extend the urethane chain. It was. The infrared absorption spectrum of the product in the flask was measured, and after confirming that the absorption of the isocyanate group of 2270 cm- ¹ had disappeared, the reaction was terminated and KBM-403 (γ- of Shinetsu Silicone Co., Ltd.) was terminated. After adding 2.7 g of glycidoxypropyltrimethoxysilane), the mixture was further cooled to 60 ° C., dibutyltin dilaurate (0.1 g) was added, and the mixture was stirred for 10 minutes. The obtained product was adjusted to a solid content of 60% with ethyl acetate. The obtained polyester polyurethane polyol had a number average molecular weight of 12,000, and this was designated as the polyester polyurethane polyol (a2).

(Synthesis Example 4 of Polyester Polyester (a1))
Ethylene glycol (70.0 g), neopentyl glycol (140.0 g), 1,6-hexanediol (190.0 g), isophthalic acid (70.0 g), isophthalic acid (70.0 g), in a flask equipped with a nitrogen introduction tube, a stirrer, a rectification tower, and a condenser. 300.0 g) and terephthalic acid (300.0 g) were added, and the mixture was dehydrated and condensed at an internal temperature of 180 to 200 ° C. with stirring. After confirming that the acid value was 15 mgKOH / g and further advancing the dehydration reaction at 200 to 240 ° C. while blowing nitrogen, after confirming that the acid value was 2 mgKOH / g or less, the internal pressure was increased to 15 Torr. The reaction was continued under reduced pressure, and after confirming that the acid value was 0.1 mgKOH / g or less, the reaction was terminated, and KBM-403 (γ-glycidoxypropyltrimethoxysilane manufactured by Shinetsu Silicone Co., Ltd.) was added. After blending 2.7 g, the solid content was adjusted to 60% with ethyl acetate. Further, after cooling to 60 ° C., dibutyltin dilaurate (0.1 g) was added, and the mixture was stirred for 10 minutes. The obtained polyester polyol had a number average molecular weight of 23,000, and this was designated as a polyester polyol (a1-4).

(Synthesis Example 5 of Polyester Polyester (a1))
Ethylene glycol (80.0 g), neopentyl glycol (300.0 g), isophthalic acid (150.0 g), sebacic acid (470.0 g) in a flask equipped with a nitrogen introduction tube, a stirrer, a rectification column, and a condenser. Was added, and the mixture was dehydrated and condensed at an internal temperature of 180 to 200 ° C. with stirring. After confirming that the acid value was 15 mgKOH / g and further advancing the dehydration reaction at 200 to 240 ° C. while blowing nitrogen, after confirming that the acid value was 2 mgKOH / g or less, the internal pressure was increased to 15 Torr. The reaction was continued under reduced pressure, and after confirming that the acid value was 0.1 mgKOH / g or less, the reaction was terminated, and KBM-403 (γ-glycidoxypropyltrimethoxysilane manufactured by Shinetsu Silicone Co., Ltd.) was added. After blending 2.7 g, the solid content was adjusted to 60% with ethyl acetate. Further, after cooling to 60 ° C., dibutyltin dilaurate (0.1 g) was added, and the mixture was stirred for 10 minutes. The obtained polyester polyol had a number average molecular weight of 23,000, and this was designated as a polyester polyol (a1-5).

(Dispersion of hydrogen sulfide trapping pigment (c) in polyester polyol (a))
230 g of 1.5 mm zirconia beads are packed in a 225 ml glass bottle, and based on the formulation table in Table 1, polyester polyol (a1-1 to a1-5) or polyester polyurethane polyol (a2) (56.0 g), Ethyl acetate (35.6 g) and hydrogen sulfide trapping pigment (c) (8.4 g) were added, dispersed with a paint shaker for 2 hours, beads were removed with a filter paper, and a dispersion was collected. As the hydrogen sulfide trapping pigment (c), zinc oxide 1 type (average particle size of 0.60 μm manufactured by Sakai Chemical Co., Ltd.) or fine zinc oxide (average particle size of 0.29 μm manufactured by Sakai Chemical Co., Ltd.) was used. The unit of each substance in the compounding ratio shown in Table 1 is a mass part.

(Example of application of odor trapping adhesive)
RU-77T (Rock Paint polyester adhesive main agent solid content 60%) 10.0 g, H-7 (Rock Paint aliphatic isocyanate curing agent solid content 60%) 1.0 g, ethyl acetate is used as a diluent. After adjusting the solid content to 25%, a transparent vapor-deposited polyethylene terephthalate film (Mitsubishi Chemical Co., Ltd. Tech Barrier V 12 μm) was coated with a bar coater so that the dry coating amount was 4.0 g / m ² . After volatilizing ethyl acetate with a hand dryer, a nylon film (ONBC-RT 15 μm manufactured by Unitika Ltd.) was attached.
Next, based on the formulation table in Table 1, the main agent (A) and the curing agent (B) in which the hydrogen sulfide trapping pigment (c) is dispersed are each blended, and ethyl acetate is used as a diluent to obtain a solid content of 25. The odor-capturing laminate adhesive resin compositions of Examples 1 to 6 and Comparative Examples 1 to 3 were prepared. Each odor trapping laminate adhesive resin composition is applied to the film surface of the nylon film bonded to the transparent vapor-deposited polypropylene terephthalate film with a bar coater so that the dry coating amount is 4.0 g / m ^2. After volatilizing ethyl acetate with a hand dryer, a non-axially stretched polypropylene (CPP) film (ZK207 60 μm manufactured by Toray Film Processing Co., Ltd.) was attached and nipped on a hot plate at 60 ° C. 6. A laminated sheet using the odor-capturing laminate adhesive resin composition of Comparative Examples 1 to 3 was obtained. The obtained laminated sheet was cured in an atmosphere of 40 ° C. for 5 days. As the curing agent (B), H-7 (aliphatic isocyanate curing agent solid content 60% manufactured by Rock Paint Co., Ltd.) was used.

(About laminate strength)
For the laminated sheet after curing, a test piece having a width of 15 mm was prepared, and a tensile tester was used to prepare a test piece having a width of 50 mm / min. The lamination strength between the nylon film and the CPP film was measured by T-type peeling at the pulling speed of.
Regarding the laminating strength of the laminated sheet, those having a strength of 5.0 N / 15 mm or more were accepted, and those having a strength of less than 5.0 N / 15 mm were rejected. The measurement result was the lamination strength before the retort heat treatment.
Further, the two laminated sheets that had been cured were laminated so that the film surfaces of the CPP film faced each other, and heat-sealed on three sides to prepare a pouch for retort pouch. After injecting 30 ml of 0.03% L-cysteine solution as the content (d) into the retort pouch, the opening was heat-sealed to obtain the content (d) sealed in the retort pouch (inner size 10 ×). 10 cm) was subjected to retort heat treatment at 121 ° C. for 60 minutes using a retort food autoclave (small sterilizer) manufactured by Tommy Kogyo Co., Ltd. A test piece with a width of 15 mm was cut out from the pouch for retort pouch after the retort heat treatment, and the laminate strength was measured under the same conditions as the measurement of the laminate strength before the retort heat treatment, and the measurement result was obtained by laminating after the retort heat treatment. It was made strong. The ratio of the strength of the laminate after the retort heat treatment to the strength of the laminate before the retort heat treatment was defined as the strength retention rate, and the strength retention rate of 50% or more was regarded as acceptable, and less than 50% was regarded as rejected.
Table 2 shows the lamination strength (unit: N / 15 mm) before and after the retort heat treatment and the evaluation results of the strength maintenance rate (◯: pass, ×: fail).
In Comparative Example 2, when the retort pouch after the retort heat treatment was visually confirmed, delamination was confirmed between the nylon film and the CPP film, so the lamination strength was not measured.

(About glass transition temperature)
Odor trapping of the cured laminated sheet Laminate adhesive The adhesive layer made of the resin composition and the nylon film interface are peeled off, and the peeled adhesive layer is placed up in a dull steel plate shape to form a rigid body. The glass transition temperature was measured using a pendulum type physical property tester (RPT-3000W manufactured by A & D Co., Ltd.). As the measurement conditions, the frame FRB-100 and the edge FRP020 were used, and the measurement interval was 10 seconds, the adsorption time was 1 second, and the temperature rising rate was 2.8 ° C./min. The temperature was raised from −20 ° C. to 100 ° C., and the inflection point of the obtained logarithmic decrement was adopted as the glass transition temperature. The glass transition temperature adopted is shown in Table 3 together with the ratio of the aromatic polybasic acid in the polybasic acid used for the synthesis of the polyester polyol (a1) or the polyester polyurethane polyol (a2).

(About hydrogen sulfide capture performance)
After injecting 30 ml of 0.03% L-cysteine solution as the content (d) into the retort pouch prepared by the above method, the opening was heat-sealed and the content (d) obtained was sealed. The retort pouch (inner size 10 × 10 cm) was heat-treated at 121 ° C. for 60 minutes using a retort food autoclave (small sterilizer) manufactured by Tommy Kogyo Co., Ltd. Hydrogen sulfide in the retort pouch after the retort heat treatment was collected, and hydrogen sulfide was quantified using a sulfide pack test by the methylene blue color change method manufactured by Kyoritsu Institute of Physical and Chemical Research Co., Ltd. A hydrogen sulfide concentration of less than 0.5 ppm was considered acceptable, and a hydrogen sulfide concentration of 0.5 ppm or higher was rejected. Table 4 shows the concentration of hydrogen sulfide after the retort heat treatment and the evaluation results (◯: pass, ×: fail). In addition, as the concentration "before retort heat treatment", calculation of hydrogen sulfide assuming that all the sulfur contained in 30 ml of the 0.03% L-cysteine solution sealed as the content was hydrolyzed to hydrogen sulfide. The concentrations are also shown in Table 4.
In Comparative Example 2, when the retort pouch after the retort heat treatment was visually confirmed, delamination was confirmed between the nylon film and the CPP film, so hydrogen sulfide was not quantified.

As a result of the above, it was confirmed that the odor-catching laminate adhesive composition according to each of the above examples has excellent adhesiveness and suitability for retort heat treatment, and can capture odorous substances generated after the retort heat treatment. Specifically, in Examples 1 to 6, hydrogen sulfide generated after the retort heat treatment is captured by the zinc oxide particles which are the hydrogen sulfide trapping pigment (c) contained in the odor trapping laminate adhesive composition and heated. Since the strength retention rate of the laminate strength between the nylon film and the CPP film before and after the treatment is 50% or more, the odor-capturing laminate adhesive composition according to the present invention has sufficient adhesiveness, retort heat treatment suitability, and odor. It was confirmed that it has a capture performance.
On the other hand, in Comparative Example 1 in which the blending ratio of the aromatic polybasic acid in the polybasic acid used for the synthesis of the polyester polyol (a) was 100 mol%, and Comparative Example 3 in which the hydrogen sulfide trapping pigment (c) was not contained, In Comparative Example 2, the odor trapping performance was lower than that of Examples 1-6, and the blending ratio of the aromatic polybasic acid in the polybasic acid used for the synthesis of the polyester polyol (a) was less than 30 mol%. Delamination was confirmed between the nylon film and the CPP film, and it was confirmed that the retort heat treatment suitability was lowered. Further, in Comparative Example 1, it was confirmed that the strength retention rate was less than 50% and the suitability for retort heat treatment was low.
As described above, by adjusting the blending ratio of the aromatic polybasic acid in the polybasic acid used for the synthesis of the polyester polyol (a) to the range of 30 mol% or more and 85 mol% or less, the adhesive cured film can catch the odor. It is advantageous in that it can be adjusted to a suitable glass transition temperature, and it is possible to achieve both sufficient adhesiveness, suitability for retort heat treatment, and odor trapping performance.

Claims (8)

It contains a polyester polyol (a) containing a polybasic acid component, a polyisocyanate (b) having a trifunctional or higher functional isocyanate group, and a hydrogen sulfide trapping pigment (c).
An odor trapping laminate adhesive resin composition, wherein the ratio of the aromatic polybasic acid in the polybasic acid is 30 mol% or more and 85 mol% or less. The odor-capturing laminate adhesive resin composition according to claim 1, which is a laminate adhesive used for laminating films constituting a laminate of a plurality of films including a barrier film and a sealant film. .. The odor trapping laminate adhesive resin composition according to claim 1 or 2, wherein the aromatic polybasic acid contains an aromatic polybasic acid in which a carboxyl group is substituted at the meta position of the benzene ring. Claims 1 to 1, wherein the polyisocyanate (b) having a trifunctional or higher functional isocyanate group is a derivative of at least one isocyanate compound selected from the group consisting of hexamethylene diisocyanate, isophorone diisocyanate, and xylene diisocyanate. The odor trapping laminate adhesive resin composition according to any one of 3. The odor trapping laminate adhesive resin composition according to any one of claims 1 to 4, wherein the hydrogen sulfide trapping pigment (c) contains zinc oxide. The odor-capturing laminated adhesive resin composition according to any one of claims 1 to 5, wherein the glass transition temperature of the adhesive cured film is 0 ° C. or higher and 30 ° C. or lower. In a packaging body in which a laminated sheet in which a plurality of films including a barrier film and a sealant film are laminated is used.
The sealant film is arranged on the innermost layer of the laminated sheet which can come into contact with the content (d) stored in the package.
The odor trapping property according to any one of claims 1 to 6, wherein the sealant film of the innermost layer and the other film are bonded to each other by the odor trapping adhesive resin composition. The package provided. A packaging structure comprising the package according to claim 7 and the content (d) housed in the package, wherein the content (d) contains a sulfur-containing amino acid compound.