TW202237494A - Container and heating packaging bag - Google Patents

Abstract

This container is provided with a body part having a curved section, wherein the body part is configured from at least one laminate, the laminate includes a substrate, a primer layer, an adhesive layer and a sealant layer, in that order, and has a printed surface configured from an electrostatic ink composition in at least part of the sealant layer-side primary surface of the primer layer; the adhesive layer contains an epoxy compound-containing adhesive composition and/or the cured product thereof.

Description

Containers and packaging bags for heating

The disclosure relates to a container and a packaging bag for heating. The container of the present disclosure is particularly related to a container which is composed of at least one laminated body and has a curved portion.

There is known a container (for example: a packaging bag) for sealing and storing food and other packaged objects. As such a container, a package using a thin film or sheet is often used. Various information such as decoration, product, brand, and manufacturer are printed on such a container. As a means for providing such printing, digital printing using electrostatic printing ink compositions is known. Digital printing uses digital printing machines.

For example, in Patent Document 1, it is proposed to apply a primer resin on a first flexible substrate such as a PET film to obtain a coated surface, and to use a digital printing machine (manufactured by HP, Indigo 20000 digital printing machine for labels and packaging) on the coated surface. ) for electrostatic printing and coating of the cross-linked composition. A technique is proposed which obtains a laminate (packaging material for containers) by laminating a first flexible base material coated with a prescribed component and a second flexible base material after performing the prescribed steps in this way. [Prior Art Literature] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. 2018-530478

[Problem to be solved by the invention]

Digital printing using electrostatic printing ink composition can correspond to small batches, so digitally printed laminates are used as materials for various containers. However, the electrostatic printing ink layer formed by the printing part of the digital printing machine may not have sufficient bonding strength with the primer layer or adhesive layer. When an external force is applied, the electrostatic printing ink layer and the primer layer may Delamination occurs between lacquer layers or between electrostatic ink layers and adhesive layers. In particular, when the laminate is bent and its deformation is large, the stress generated between the laminated layers is large, and peeling may occur between the electrostatic ink layer and the primer layer or adhesive layer. In such a situation, for example, the function as a container may be damaged, and the printed surface may be shifted, and it may become difficult to read the printed information written on the printed surface. It is conceivable not to provide a printing surface on the curved portion, but in order to meet various needs, it is required to print on the curved portion as well. Therefore, it would be useful to have a container that does not impair its function as a container and does not impair printed information even if it has a curved portion.

In addition, the electrostatic printing ink layer provided by a digital printing machine may not have sufficient adhesive strength with adjacent layers. Therefore, if the packaging material produced by the above-mentioned means is used in a packaging bag that is premised on heat treatment such as boiling and high-temperature sterilization, for example, the packaging bag may be broken during heating.

One of the objects of the present disclosure is to provide a container that has a printed surface that is printed with a digital printing machine, and at the same time, the curved portion generated during the manufacturing process also inhibits the interface between the electrostatic printing ink layer and the primer layer, and the electrostatic printing surface. Peeling at the interface between the ink layer and the adhesive layer.

Also, one of the objects of the present disclosure is to provide a heating packaging bag which has an electrostatic printing ink layer using a digital printing machine and has sufficient resistance to heat treatment. [Means to solve the problem]

One aspect of the present disclosure is to provide a container having a body portion having a curved portion, wherein the body portion is constituted by at least one laminated body, and the laminated body sequentially includes a base material, a primer layer, and an adhesive layer. , and a sealant layer, having a printing portion made of an electrostatic ink composition on at least a part of the main surface of the primer layer on the side of the sealant layer, and the adhesive layer contains polyol, polyisocyanate, and epoxy resin. At least one of the adhesive composition of the compound and its cured product.

Since the above-mentioned container is composed of at least one of a specific adhesive composition and its hardened product, the adhesive layer can maintain a sufficient adhesive state at the bent portion, and the interface between the electrostatic printing ink layer and the primer layer, and Delamination at the interface between the electrostatic printing ink layer and the adhesive layer. Also, since the bonded state between the layers is maintained in the curved portion, the occurrence of offset in the printed portion, etc. can be suppressed, and the printed information in the body portion including the curved portion can be maintained in an initial state for printing. During the use of the container, for example, even if a new bend is generated due to bending of the container, etc., the bonded state between the layers is maintained, so the function as a container (such as: barrier properties, etc.) can be maintained during use. . Similarly, during the period of use, it is possible to suppress the breakage of the container itself or the deterioration of the printed information.

You may have the said printed part in the said bent part. In the container of the present disclosure, since the body part is constituted by the above-mentioned specific laminate, even if the printing part is located in the curved part, the change of the printed information is suppressed.

The above-mentioned polyol may include aliphatic polyester polyol, and the above-mentioned epoxy compound may include those having epoxy groups at both terminals. Such an adhesive layer can exhibit high lamination strength especially in a high-temperature environment.

The above-mentioned epoxy compound may also contain a bifunctional alicyclic epoxy compound. Since the epoxy compound is difunctional, it can increase the cross-linking point with the electrostatic printing ink composition, and more firmly adhere to the main surface (printing surface) of the primer layer and the adhesive layer. Moreover, when an epoxy compound contains an alicyclic epoxy compound, the reaction with polyisocyanate can be suppressed by the steric barrier of an alicyclic structure. Therefore, it can harden|cure stably, and the adhesiveness of the interface of a printed part and an adhesive agent layer is fully excellent.

The above polyisocyanate may contain xylylene diisocyanate derivatives. Such a polyisocyanate has excellent reactivity with a polyol system. Thereby, the curability of the adhesive composition can be improved, and peeling at the interface between the printed portion (electrostatic ink layer) and the primer layer, and the interface between the printed portion (electrostatic ink layer) and the adhesive layer can be further suppressed .

A mouth plug connected to the above-mentioned body part may be further provided.

The plug may have a cylindrical outflow port and a flange extending outward from the periphery of the lower end of the outflow port.

The above-mentioned body part may be constituted by one sheet of the above-mentioned laminated body.

The body portion may be constituted by two laminates serving as side sheets and one laminate serving as a bottom sheet.

Also, in order to achieve the above object, a heating packaging bag according to an aspect of the present disclosure is a heating bag composed of a laminate having a base material, a primer layer, an electrostatic ink layer, an adhesive layer, and a sealant layer in sequence. In the packaging bag for disposal, the adhesive layer includes at least one of an adhesive composition containing polyol, polyisocyanate, and epoxy compound, and a hardened product thereof.

Printed portions formed by printing an electrostatic ink composition using a digital printing machine tend to be inferior in heat resistance and strength compared to the case of using other inks. Therefore, if a laminate having a printed part (electrostatic ink layer) derived from a conventional electrostatic ink composition is to be applied to a packaging bag for heat treatment, the adhesiveness near the printed surface is poor, so that the packaging bag may be damaged. breakage etc. On the other hand, according to the above configuration, since the deformation of the laminate due to heating or the like is suppressed by hardening the adhesive composition containing the epoxy compound, a heating packaging bag having sufficient resistance to heat treatment is obtained.

The aforementioned primer layer may also contain polyethyleneimine resin. Since the primer layer containing polyethyleneimine resin is provided, water resistance is also improved, and sufficient resistance can be obtained especially for heat treatment in an environment with a large amount of moisture such as boiling heat treatment or high-temperature sterilization heat treatment.

It may be an aspect in which the outer peripheral portion includes a seal portion for bonding the sealant layers of the two laminates together, and the seal portion is an aspect in which the ink coverage of the electrostatic ink layer is 300% or less. Since the sealing part is a region where thermal bonding such as heat sealing is performed, the possibility of damage is higher than other regions. On the other hand, by setting the ink coverage of the electrostatic ink layer within the above-mentioned range, more sufficient resistance to heat treatment can be ensured for the sealing part, and a product having stronger resistance to heat treatment can be obtained. Heater bags.

The said polyol may contain the aliphatic polyester polyol, and the said epoxy compound may include the thing which has an epoxy group at both terminals. Such an adhesive layer has high adhesive strength especially in a high-temperature environment. Therefore, even when the heat treatment is performed on the heating packaging bag, it is possible to sufficiently suppress the breakage of the electrostatic printing ink composition or the damage of the packaging bag.

The said epoxy compound can be set as the aspect which contains the bifunctional alicyclic epoxy compound. Such an epoxy compound, because it is bifunctional, can increase the crosslinking point with the electrostatic printing ink composition, and more firmly adhere to the printing surface of the adhesive layer and the primer layer. Moreover, when an epoxy compound contains an alicyclic epoxy compound, the reaction with polyisocyanate can be suppressed by the steric barrier of an alicyclic structure. Therefore, it can harden|cure stably, and the adhesiveness of the interface of a printing surface and an adhesive agent layer is fully excellent.

The said polyisocyanate can be set as the form which contains a xylylene diisocyanate derivative. Such a polyisocyanate has excellent reactivity with a polyol system. Thereby, the curability of the adhesive composition is improved, and thus deformation of the heating packaging bag can be suppressed. [Effect of Invention]

According to the present disclosure, it is possible to provide a container having a printing surface applied with printing by a digital printing machine, and at the same time, the curved portion generated during the manufacturing process also suppresses the interface between the electrostatic printing ink layer and the primer layer, and the electrostatic printing ink layer Peeling at the interface with the adhesive layer.

According to the present disclosure, there is provided a heating packaging bag having an electrostatic printing ink layer using a digital printing machine and having sufficient resistance to heat treatment.

[Mode for Carrying Out the Invention]

Embodiments of the present disclosure will be described below while referring to the drawings as the case may be. However, the following embodiments are examples for explaining the present disclosure, and are not intended to limit the present disclosure to the following contents. In the description, the same symbols are used for the same elements or elements having the same functions, and overlapping descriptions are omitted as appropriate. In addition, positional relationships such as up, down, left, and right are based on the positional relationships shown in the drawings unless otherwise specified. In addition, the dimensional ratios in the drawings are not limited to the ratios shown in the drawings.

The materials exemplified in this specification can be used alone or in combination of two or more unless otherwise particularly limited. The content of each component in the composition means the total amount of the plurality of substances present in the composition, unless otherwise specified, when there are a plurality of substances corresponding to each component in the composition.

[container] One embodiment of the container is a container having a body portion having a curved portion, wherein the body portion is constituted by at least one laminated body, and the laminated body sequentially includes a base material, a primer layer, an adhesive layer, and a sealant layer, In addition, at least a part of the main surface of the primer layer on the side of the sealant layer has a printed portion made of an electrostatic printing ink composition. The container may be, for example, a packaging bag, a tubular container, a stand-up pouch, and the like. The packaging bag is not limited to being used at normal temperature, and may be a packaging bag exposed to temperature changes such as heating and freezing. The container may also be, for example, a container that is supposed to be further creased in use. In a tubular container or the like, when the packaged object is taken out of the container by pressing and deforming the body portion, new creases may be formed on the body portion. In the case of the container of the present disclosure, even in such a case, the bonded state between the layers is maintained, so the function as a container (for example, barrier property, etc.) can be maintained during use.

Figure 1 shows an example of a container. The container 100 is composed of a sheet of a laminate 300 . The container 100 is a container obtained by first laminating the sealant layers on opposite sides of the approximately rectangular laminated body 300 with a predetermined width to form the sealing portion 101 to form a cylindrical body, and then, Further, on one of the openings of the cylindrical body, sealant layers are bonded to each other with a predetermined width to form a sealing portion 103 . The container 100 has a bent portion 60 and sealing portions 101 and 103 at a body portion 200 . The bent portion 60 is bent so as to follow the side surface of the body portion 200 in order to improve operability when used as a container.

The container 100 shown in FIG. 1 is formed by sealing parts 101, 103 and a non-sealing part (sheet part), and includes a storage part 102 for storing packaged objects (for example, food and beverages, etc.). In this specification, what accommodates the packaged object and seals it is also specifically called a package. In addition, the sealing part 103 at the lower end may be sealed after filling the storage part 102 with the packaged object. The sealing parts 101 and 103 are configured by heat-sealing the sealant layers included in the laminate 300 to each other.

The container 100 may further include a plug connected to the above-mentioned trunk portion 200 . Fig. 2 is a schematic sectional view of an example of a container provided with a plug. 2 shows an example of a container in which a plug 70 is disposed on the unsealed upper end of the container 100, and the sealant layer is heat-sealed to the plug 70 to connect the body 200 of the container 100 with the plug. At this time, the container 100 includes the body part 200 and the plug 70, and by pushing the body part 200, the packaged object can be taken out from the plug. In this specification, such a container is also called a tubular container.

The plug 70 shown in FIG. 2 is shown as an example including a cylindrical outflow port 72 and a flange 74 extending outward from the periphery of the lower end of the outflow port 72 . The spout may have a cylindrical outflow port and a flange extending outward from the periphery of the lower end of the outflow port, and may be, for example, a spout. The position where the plug is provided is not particularly limited. When the mouth bolt is a spout, it can be a so-called central spout or a corner spout.

Another example of the container is shown in FIGS. 3 and 4 . In this container 110, the trunk portion 200 is composed of two laminates 300 serving as side sheets and one laminate 306 serving as a bottom sheet. The container 110 is constructed by bonding the sealant layers of two laminates 300 serving as side sheets and a laminate 306 serving as a bottom sheet to each other. The container 110 has a sealing portion 122 obtained by sticking two laminates 300 serving as side sheets, and a seal portion 122 obtained by sticking a laminate 306 serving as a bottom sheet and two laminates 300 serving as a side sheet. The sealing part 121, and thereby constitute a bag-like form. With such a configuration, the volume of the storage unit 112 can be expanded. The laminated body 306 serving as the bottom sheet has a bent portion 60 generated when the container 110 is manufactured. In addition, in the upper end portion of the container 110 , the released unsealed portion may be sealed after filling the storage portion 112 with the packaged object. The sealing parts 122 and 121 are configured by heat-sealing the sealant layers included in the laminate 300 to each other.

The three laminates constituting the container 110 do not need to have the same layer configuration, and may have different layer configurations, for example.

The containers 100 and 110 can accommodate packaged objects in the non-sealed parts (thin sheet parts) surrounded by the sealed parts 101, 103, 121 and 122, and the further sealed ones are also specifically referred to as packages in this specification. The container may also have an opening means for facilitating opening. The unsealing means may also have: a pair of easy-opening processing parts formed by a V-shaped incision formed by the non-sealed part of the side end or the sealing part 122 of the side end, and a pair of easy-opening processing parts between the pair of easy-opening processing parts becomes the half tangent of the cut orbit. Half tangents can be formed using a laser. The easy-opening processed portion is not limited to a V-shaped cutout, and may be a U-shaped or I-shaped cutout, or may be a group of scars.

The laminate constituting the containers 100 and 110 described above will be described. Fig. 5 is a cross-sectional view schematically showing an example of a laminate. Fig. 5 shows a cross section along the lamination direction (thickness direction) of the laminate. The laminated body 302 has the base material 10, the primer layer 40, the adhesive agent layer 30, and the sealant layer 20 in this order. Each of the substrate 10, the primer layer 40, the adhesive layer 30, and the sealant layer 20 may be in the form of a film. At least a part of the main surface (printed surface) of the primer layer 40 on the sealant layer 20 side may have a printed portion 52 made of an electrostatic printing ink composition. An electrostatic printing ink layer 50 composed of one or more printing parts 52 is provided on the printing surface. In other words, the electrostatic ink layer 50 composed of the printing portion 52 may be provided on at least a part of one main surface of the primer layer 40 close to one main surface of the sealant layer 20 .

The thickness of the laminate 302 may be, for example, 15 to 200 μm, or 18 to 120 μm.

The substrate 10 and the sealant layer 20 may also be flexible substrates. Examples of flexible substrates include: biaxially oriented polypropylene (BOPP), polyethylene terephthalate (PET), oriented polyamide (OPA), non-extended polypropylene (CPP), straight Chain low-density polyethylene (LLDPE), and low-density polyethylene (LDPE), etc.

As the base material 10, for example, a composite film in which a metal foil is laminated on a flexible base material, or a vapor-deposited film in which a metal or the like is vapor-deposited on a flexible base material, or the like may be used. In addition, the above-mentioned metals and the like may be, for example, simple metals such as aluminum or metal oxides such as aluminum oxide. As the base material 10 , a vapor-deposited film (transparent vapor-deposited film) in which aluminum, aluminum oxide, or the like is vapor-deposited on a PET film can be used from the viewpoint of improving gas barrier properties. The thickness of the substrate 10 may be, for example, 7-150 μm, 15-90 μm, or 20-80 μm.

As the sealant layer 20, a CPP film, an LLDPE film, an OPP film, etc. are mentioned, for example. The thickness of the sealant layer 20 may be the same as or different from that of the substrate 10, and may be, for example, 7-150 μm, 15-90 μm, or 20-80 μm.

The primer layer 40 may also contain resin. Examples of resins include polyvinyl alcohol resins, cellulose resins, polyesters, polyamines, polyethyleneimine resins, polyamide resins, polyurethanes, polyacrylic acid polymers, hydroxyl-containing Resins, carboxyl-containing resins, and amine-based polymers, etc. By providing the primer layer 40 on the base material to be printed, printing of the electrostatic printing ink composition using a digital printing machine can be performed smoothly. The coating amount of the resin constituting the primer layer 40 may be, for example, 0.01˜1.5 g/m ² , or 0.05˜1.0 g/m ² .

The laminate 302 includes a printed portion 52 on the main surface (printed surface) of the primer layer 40 opposite to the substrate 10 . An electrostatic ink layer 50 composed of a plurality of printing portions 52 is provided on the printing surface. The electrostatic ink layer 50 is composed of an electrostatic ink composition, and is provided by electrostatic printing using a digital printer. In FIG. 5, a plurality of printing parts 52 may have the same composition, or may have different colors by having different compositions. The printed part 52 may be provided in a manner dispersed on the primer layer 40 , or may be provided in a manner covering the entire surface of the primer layer 40 .

The printing portion 52 in the electrostatic printing ink layer 50 is composed of circular dots of the electrostatic printing ink composition. In other words, even though it appears to be a uniform monochromatic color, there are areas without patterns between halftone dots. The electrostatic printing ink layer 50, when printing the designated area to be printed in a single color, generally separates the circular dots and arranges them. Alternatively, circular dots of the electrostatic printing ink composition of the second color or later may be arranged so as to partially overlap the dots printed in the first color. By changing the size of dots, the shade of the color on the printing surface can be adjusted, and by arranging dots of different colors, the tone of the printing surface can also be adjusted.

The ink coverage of each printing portion 52 constituting the electrostatic ink layer 50 may be 500% or less, for example, 450% or less, or 400% or less. By setting the ink coverage of the printing unit 52 within the above range, the lamination strength of the laminate is further improved, printing can be performed using a plurality of inks, and various printings can be handled. The lower limit of the ink coverage rate of the printing unit 52 is not particularly limited, and may be, for example, 20% or more, 50% or more, 80% or more, or 100% or more. The ink coverage rate of the printing part 52 can be adjusted within the above-mentioned range, and can be, for example, 20-500%, 50-400%, 100-400%, or 100-300%.

In this specification, ink coverage refers to the ratio of dot area per unit area, and is the ink coverage when a designated area to be printed is uniformly printed in a single color. 100%, set the ink coverage rate of the unprinted area to 0%. When printing with inks of a plurality of colors, the ink coverage is calculated for each color of ink, and the total is used as the ink coverage of the target printing portion and electrostatic ink layer. The ink coverage is set by the digital printing machine, and can be adjusted by specifying the desired value in the setting of the ink coverage. As a digital printing machine, "Indigo 20000 digital printing machine for labels and packaging" (product name) etc. manufactured by HP company can be used, for example. In addition, the ink coverage of the electrostatic ink layer in the target laminate can also be confirmed by optical microscope observation of the printed surface of the container or laminate.

In addition, since the printing portion 52 is constituted by circular dots of the electrostatic ink composition, even if the ink coverage rate is 100%, when the surface of the electrostatic ink layer 50 on the sealant layer 20 side is observed with an optical microscope, etc., Then, the main surface of the primer layer 40 can also be confirmed. That is, even if the ink coverage is 100%, the primer layer 40 and the adhesive layer 30 can be directly adhered to. On the other hand, as the ink coverage ratio becomes larger, the ratio of the primer layer 40 in the bonding surface (interface) between the printed portion 52 and the adhesive layer 30 tends to decrease. When using conventional adhesives, if the ink coverage ratio increases, the adhesive force at the interface between the electrostatic printing ink layer and the primer layer, or the interface between the electrostatic printing ink layer and the adhesive layer may decrease, and as a laminate The lamination strength did not play out as expected. On the other hand, in the laminate of the present disclosure, by using the adhesive composition described later, sufficient lamination strength can be exhibited even when the ink coverage is high. In the laminated body of the present disclosure, by using an adhesive composition described later, it is possible to prevent, in particular, expansion of the laminated body 300 during heat treatment, and the like.

The ink coating amount on the main surface (printing surface) of the sealant layer 20 side of the primer layer 40 may be, for example, 0.5 g/m ² or more, 1.0 g/m ² or more, 2.0 g/m ² or more, or 3.0g/ ^m2 or more. When the coating amount of the above-mentioned ink is within the above-mentioned range, it is possible to obtain a colorful printing expression composed of a plurality of colors. The ink coating amount on the main surface of the primer layer 40 on the sealant layer 20 side may be, for example, 8.0 g/m ² or less, or 6.0 g/m ² or less. When the ink coating amount is within the above range, it is possible to more fully suppress the decrease in the adhesive force at the interface between the electrostatic ink layer 50 and the primer layer 40 or the interface between the electrostatic ink layer 50 and the adhesive layer 30 . The coating amount of ink in this specification means the total amount (amount of solid content) of the ink composition used for printing, and in the case of multi-color printing, it means the total value.

Fig. 6 is a cross-sectional view showing another example of the laminate. The laminate 304 of FIG. 6 is different from the laminate 302 of FIG. 5 in that the whole of one side of the primer layer 40 is covered by the electrostatic ink layer 51 (the printing portion 52 covering the entire printing surface). That is, in the laminated body 304 , the coating ratio of the main surface of the primer layer 40 by the electrostatic ink layer 51 is 100 area %. By using the adhesive composition described later, even if it is a structure such as the laminate 304 where it is difficult to ensure a sufficient direct bonding area between the primer layer 40 and the adhesive layer 30 , it has sufficient adhesive strength and suppresses the adhesion of the laminate 304 . delamination etc.

In the laminates 302, 304, the electrostatic ink composition constituting the electrostatic ink layer 50, 51 is an ink composition used for liquid electrophotographic printing, that is, an ink composition used for electrostatic printing, and is printed On substrates such as paper and plastic, or on primer layers. The electrostatic printing ink composition may also contain colorants such as pigments and dyes, and resins. Also, the electrostatic printing ink composition may further contain a carrier fluid or a carrier liquid. The electrostatic printing ink composition may also include, for example, a charge director, a charge adjuvant, a surfactant, a viscosity modifier, an emulsifier, and other additives.

As a coloring agent, a cyan pigment, a magenta pigment, a yellow pigment, a black pigment, etc. are mentioned, for example. From the viewpoint of easiness of digital printing, a resin with a relatively low melting point can be used as the resin. The relatively low melting point may be, for example, 100°C or lower. Examples of the resin include thermoplastic resins such as ethylene acrylic acid copolymers, propylene acrylic acid copolymers, ethylene methacrylic acid copolymers, propylene methacrylic acid copolymers, and ethylene vinyl acetate copolymers. The resin preferably contains at least one of an ethylene acrylic acid copolymer and an ethylene methacrylic acid copolymer.

Examples of the carrier fluid and carrier liquid include hydrocarbons, silicone oils, and vegetable oils. Examples of hydrocarbons include aliphatic hydrocarbons, branched chain aliphatic hydrocarbons, and aromatic hydrocarbons. The electrostatic printing ink composition may be substantially free of carrier fluid and carrier liquid when printed on a substrate. Carrier fluids and carrier liquids, for example, can also be removed by electrophoretic procedures or evaporation in printing. Substantially only the solid content is transferred to the substrate or the primer layer by the above-mentioned removal operation.

The charge director has the function of maintaining a sufficient electrostatic charge on the particles contained in the electrostatic printing ink composition. As the charge director, for example: metal salts of fatty acids, metal salts of sulfosuccinates, metal salts of oxyphosphates, metal salts of alkylbenzenesulfonic acids, metal salts of aromatic carboxylic acids, and ionic compounds such as metal salts of aromatic sulfonic acids; and zwitterionic and nonionic compounds such as polyoxyethylenated alkylamines, lecithin, polyvinylpyrrolidone, and organic acid esters of polyols.

The charge adjuvant has the function of increasing or stabilizing the charge of the particles contained in the electrostatic printing ink composition. Examples of charge adjuvants include barium petroleum sulfonate, calcium petroleum sulfonate, Co naphthenate, Ca naphthenate, Cu naphthenate, Mn naphthenate, naphthenate Ni salt, Zn naphthenate, Fe naphthenate, Ba stearate, Co stearate, Pb stearate, Zn stearate, Al stearate, Cu stearate Salt, Fe stearate, and metal carboxylate, etc.

The electrostatic printing ink layers 50 and 51 may also include a cross-linked product cross-linked by components contained in at least one of the adhesive layer 30 and the primer layer 40 . By including cross-linking substances, the strength of the electrostatic printing ink layer 50, 51 itself can be further improved; and the bonding strength between the printing surface of the primer layer 40 and the electrostatic printing ink layer 50, 51, and the bonding strength between the electrostatic printing ink layer 50, 51 and Adhesive strength of the adhesive layer 30 .

The printed portion 52 of the electrostatic printing ink composition and the adhesive layer 30 are bonded to each other. That is, the printing part 52 becomes the bonding surface with the adhesive layer 30, and the electrostatic printing ink composition and the adhesive composition are in direct contact.

The adhesive composition contains polyol, polyisocyanate, and epoxy compound. These three components (polyol, polyisocyanate, and epoxy compound) can also be cured by at least a part of them reacting with each other to form a cured product. That is, the adhesive composition may also be composed of at least one of an adhesive composition containing polyol, polyisocyanate, and epoxy compound, and its cured product, and the adhesive layer 30 may also be composed of an adhesive composition, its cured product, or a mixture of these. Polyol and polyisocyanate react as the main agent and hardener respectively to produce polyurethane (polyurethane adhesive).

The polyol has two or more hydroxyl groups in one molecule, and may have a number average molecular weight of 400 or more, for example. The number average molecular weight of a polyhydric alcohol may be 10000 or less, for example.

The polyol may contain, for example, at least one selected from the group consisting of polyester polyol and polyether polyol. Among them, from the viewpoint of sufficiently improving the adhesive strength of the adhesive layer 30 in a high-temperature environment, the polyol may include polyester polyol, or may include aliphatic polyester polyol.

Polyester polyols can be obtained, for example, by condensation reactions or transesterification reactions between polyhydric alcohols and polybasic acids, alkyl esters of polybasic acids, anhydrides of polybasic acids, or halides of polybasic acids.

Examples of the polyhydric alcohol include low-molecular-weight diols, low-molecular-weight triols, low-molecular-weight polyols having four or more hydroxyl groups, and the like.

Examples of low molecular weight diols include ethylene glycol, propylene glycol, trimethylene glycol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 1,5- Pentylene glycol, 3-methyl-1,5-pentanediol, 2,2-dimethyl-1,3-propanediol, neopentyl glycol, 1,6-hexanediol, 2,2-diethylene Base-1,3-propanediol, 3,3-dimethylolheptane, and 2-ethyl-2-butyl-1,3-propanediol, etc.

Examples of low molecular weight triols include glycerol, 2-methyl-2-hydroxymethyl-1,3-propanediol, 2,4-dihydroxy-3-hydroxymethylpentane, 1,2 ,6-hexanetriol, trimethylolethane, trimethylolpropane, 2-methyl-2-hydroxymethyl-1,3-propanediol, 2,4-dihydroxy-3-(hydroxymethyl ) pentane, and 2,2-bis(hydroxymethyl)-3-butanol, etc.

Examples of low-molecular-weight polyhydric alcohols having four or more hydroxyl groups include tetramethylolmethane, neopentylthritol, diperythritol, D-sorbitol, xylitol, and D-mannitol. , and D-hexyl alcohol, etc.

As an alkyl ester of a polybasic acid, the methyl ester of a polybasic acid, the ethyl ester of a polybasic acid, etc. are mentioned, for example. As an acid anhydride of a polybasic acid, the acid anhydride derived from a polybasic acid is mentioned, for example. As the anhydride of polybasic acid, more specifically, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, 2-alkyl (12 to 18 carbon atoms) succinic anhydride, tetrahydrophthalic anhydride, Anhydride, and trimellitic anhydride, etc.

As the acid halide of the polybasic acid, for example, an acid halide derived from the above-mentioned alkyl ester of the polybasic acid or an acid anhydride of the polybasic acid, and the like are exemplified. As an acid halide of a polybasic acid, more specifically, oxalyl dichloride, adipyl dichloride, sebacyl dichloride, etc. are mentioned.

As polyether polyol, polyalkylene oxide etc. are mentioned, for example. The polyether polyol may be, for example, one obtained by addition-reacting alkylene oxides such as ethylene oxide and/or propylene oxide using a low-molecular-weight polyol as an initiator. More specifically, polyether polyols include polyethylene glycol, polypropylene glycol, polyethylene-polypropylene glycol (random or block copolymer), and the like. Further examples of the polyether polyol include polytetramethylene ether glycol obtained by ring-opening polymerization of tetrahydrofuran and the like.

Polyisocyanate has two or more isocyanate groups in one molecule. Examples of the polyisocyanate include polyisocyanate monomers, polyisocyanate derivatives, and isocyanate group-terminated prepolymers. The adhesive composition may also contain a plurality of different types of polyisocyanates. The molar ratio (NCO/OH) of the isocyanate group contained in polyisocyanate with respect to the hydroxyl group of a polyol can be 0.5-10, for example. Such an adhesive composition can form a cured product having high adhesive strength and excellent flexibility.

As a polyisocyanate monomer, aliphatic polyisocyanate, aromatic polyisocyanate, araliphatic polyisocyanate, and alicyclic polyisocyanate etc. are mentioned, for example.

Examples of aliphatic polyisocyanates include trimethylene diisocyanate, 1,2-propylidene diisocyanate, butylene diisocyanate (tetramethylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate), 1,5-pentamethylene diisocyanate (PDI), hexamethylene diisocyanate (HDI), 2,4,4 - Trimethylhexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate methyl caproate, etc.

Examples of the araliphatic polyisocyanate include xylylene diisocyanate derivatives. Examples of xylylene diisocyanate derivatives include xylylene diisocyanate (1,3-xylylene diisocyanate or 1,4-xylylene diisocyanate) (XDI), tetra Methylxylylene diisocyanate (1,3-tetramethylxylylene diisocyanate, or 1,4-tetramethylxylylene diisocyanate) (TMXDI), ω,ω'-diisocyanate- 1,4-diethylbenzene, xylylene diisocyanate obtained by reacting xylylene diisocyanate with trimethylolpropane, etc.

From the viewpoint of improving the reactivity with the main ingredient (e.g., polyol), the content of the xylylene diisocyanate derivative relative to the entire polyisocyanate can be, for example, 10% by mass or more, 20% by mass or more, 30% by mass or more, or 40% by mass or more. Reactivity can be further improved by making content of the xylylene diisocyanate derivative 30 mass % or more with respect to the whole polyisocyanate.

Examples of alicyclic polyisocyanates include 1,3-cyclopentane diisocyanate, 1,3-cyclopentene diisocyanate, cyclohexane diisocyanate (1,4-cyclohexane diisocyanate, 1, 3-cyclohexane diisocyanate), 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate) (IPDI), methylcyclohexane diisocyanate ( Methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate), norbornane diisocyanate (NBDI), etc.

二

三酮(oxadiazine-trione)改質物、碳二亞胺改質物、脲二酮(uretdione)改質物、及脲酮亞胺(uretonimine)改質物等。Examples of polyisocyanate derivatives include polymers of the above-mentioned polyisocyanate monomers, allophanate-modified products, polyol-modified products, and polyol-modified products produced by the reaction of monomers and alcohols. Substances, biuret modified substances, urea modified substances,

two

Triketone (oxadiazine-trione) modified substance, carbodiimide modified substance, uretdione (uretdione) modified substance, uretonimine (uretonimine) modified substance, etc.

The isocyanate group-terminated prepolymer is a urethane prepolymer having at least two isocyanate groups at molecular terminals. The isocyanate group-terminated prepolymer can be obtained by subjecting at least one selected from the group consisting of polyisocyanate monomers, polyisocyanate derivatives, and isocyanate group-terminated prepolymers to a polyol for urethane reaction. In this case, the molar ratio (NCO/OH) of the isocyanate group contained in the polyisocyanate to the hydroxyl group of the polyol may be, for example, 0.5 or more, 0.6 or more, 0.8 or more, 1 or more, or 1.5 or more. The above molar ratio (NCO/OH) may be 10 or less, 5 or less, 4 or less, or 3 or less. Examples of the numerical range of the molar ratio (NCO/OH) include, for example, 0.5-10, 0.5-5, 0.8-4, and 0.6-3.

The epoxy compound may be a compound having one or two or more epoxy groups in one molecule. From the viewpoint of further improving the adhesive strength of the adhesive layer 30 in a high-temperature environment, it may have epoxy groups at both ends. As the epoxy compound, for example: glycidyl ether type epoxy compound, glycidylamine type epoxy compound, glycidyl ester type epoxy compound, and alicyclic epoxy compound (cyclic aliphatic epoxy compounds), etc.

The molecular weight of the epoxy compound may be, for example, 500 or less, 450 or less, or 400 or less. When the molecular weight of the epoxy compound is within the above range, the epoxy compound can fully penetrate into the electrostatic printing ink composition constituting the electrostatic printing ink layer. The lower limit of the molecular weight of an epoxy compound may be 98 or more, for example.

Examples of the alicyclic epoxy compound include epoxycyclohexylmethyl epoxycyclohexanecarboxylate and bis(epoxycyclohexyl adipate).

Examples of monofunctional alicyclic epoxy compounds having one epoxy group in one molecule include 3,4 epoxycyclohexylmethyl methacrylate and 1,2-epoxy-4-ethylene Cyclohexane etc. Examples of bifunctional epoxy compounds having two epoxy groups in one molecule include 3',4'-epoxycyclohexylmethyl 3,4 epoxycyclohexanecarboxylate, adipate bis (3,4-epoxycyclohexyl methyl ester), and 4-vinylcyclohexene dioxide, etc. Also, as an epoxy compound having one or more epoxy groups in one molecule, 1 of 2,2-bis(hydroxymethyl)-1-butanol represented by the following general formula (I) can be mentioned. , 2-epoxy-4-(2-oxiranyl) cyclohexane adduct.

In the above general formula (I), n may be an integer of 1-4.

The epoxy compound is preferably an alicyclic epoxy compound containing bifunctionality. Since it is bifunctional, it increases the crosslinking points with the electrostatic printing ink composition and primer resin and accelerates the hardening reaction of the adhesive, making it easy to harden. Moreover, since it is an alicyclic form, the reaction with polyisocyanate can be suppressed by steric hindrance. Therefore, it can harden|cure stably, and the adhesiveness of the interface of the printed part 52 and the adhesive agent layer 30 is fully excellent.

From the viewpoint of both high adhesive strength and excellent shear inhibition, the content of the epoxy compound in the adhesive composition relative to 100 parts by mass of the polyol can be, for example, 3 to 25 parts by mass, 6-25 mass parts, or 8-20 mass parts. When the content of the epoxy compound is too large, the excellent shearing inhibition tends to be impaired. That is, when the adhesive layer 30 is formed, the adhesive surface may deviate or the adhesive composition may overflow. When the compounding quantity of an epoxy compound becomes too small, there exists a tendency for the adhesive strength on the high temperature hot water treatment condition to fall.

From the viewpoint of sufficiently improving the sealing strength and the adhesive strength under high-temperature hot water treatment conditions, the content of polyisocyanate in the adhesive composition may be, for example, 10 to 50 parts by mass relative to 100 parts by mass of polyol , 15 to 35 parts by mass, or 20 to 30 parts by mass.

The molar ratio of the epoxy group contained in an epoxy compound with respect to the isocyanate group contained in a polyisocyanate can be 0.5-10, 1.5-9, or 2.0-6.5, for example. Thereby, a more sufficient high adhesive strength can be maintained under the condition of high-temperature hot water treatment.

The adhesive composition constituting the adhesive layer 30 may contain optional components such as additives in addition to the above-mentioned components. Examples of additives include antioxidants, ultraviolet absorbers, light stabilizers, fillers, silane coupling agents, epoxy resins, catalysts, coatability improvers, leveling agents, nucleating agents, slip agents , release agent, defoamer, plasticizer, surfactant, pigment, dye, organic microparticle, inorganic microparticle, antifungal agent, and flame retardant, etc. The adhesive composition may contain solvents such as organic solvents.

The adhesive composition is followed by printing the printing portion 52 and the sealant layer 20 of the electrostatic printing ink composition. Any layer may be provided between the adhesive layer 30 and the sealant layer 20 . The laminates 302 and 304 may further have a barrier layer or the like between the adhesive layer 30 and the sealant layer 20 , for example. At this time, the adhesive composition is used to bond the printing part 52 and any layer (for example, a barrier layer, etc.). The adhesive composition is formed by the reaction of polyol and polyisocyanate to form a urethane bond, which functions as an adhesive. Also in the presence of the epoxy compound, the formation of the urethane bond proceeds smoothly, so that the printed portion 52 and the sealant layer 20 or an arbitrary layer can be bonded with sufficiently high bonding strength.

The adhesive composition may also have the function of crosslinking the electrostatic ink composition forming the electrostatic ink layer 50, 51 while forming urethane bonds. Thereby, the bonding strength of the printing surface and the sealant layer 20 or an arbitrary layer can be further improved.

When the coverage ratio of the electrostatic ink layer 50 to the main surface (printing surface) of the primer layer 40 becomes higher, or when the ink coverage ratio in the printing part 52 (electrostatic ink layers 50, 51) becomes higher, generally There is a tendency for the adhesive force between the electrostatic printing ink layers 50, 51 and the adhesive layer 30 to decrease, but in the case of the above-mentioned adhesive composition, sufficient adhesive strength can be exhibited. Also, when the coverage ratio of the electrostatic ink layer 50 to the main surface of the primer layer 40 or the ink coverage ratio in the printing part 52 (electrostatic ink layer 50, 51) becomes high, the The content of the epoxy compound contained in the adhesive composition can make the epoxy compound fully penetrate into the electrostatic printing ink layer 50, 51 composed of the electrostatic printing ink composition, and can further suppress the reduction of the adhesive strength. The impregnated epoxy compound has the effect of increasing the strength of the xerographic ink composition (the xerographic ink layer 50, 51) by crosslinking the xerographic ink composition. Therefore, even when the ink coverage rate in the printing portion 52 is high, and heat treatment such as high-temperature sterilization heat treatment is applied, the decrease in adhesive strength can be sufficiently suppressed.

The adhesive composition can maintain high adhesive strength even after heat treatment, and on the other hand, it is also excellent in pot life. Therefore, workability such as coating and lamination processing when bonding the printed surface and the base material is also excellent. The adhesive composition may contain polyol and polyisocyanate which form urethane, and an epoxy compound, and at least a part of them becomes a cured product to form an adhesive layer. This reduces the number of layers constituting the laminated body 300 compared to the case where the adhesive layer and the epoxy coating layer consisting only of polyurethane are provided separately. Therefore, for example, when a laminate is produced by roll-to-roll (roll to roll), it is possible to suppress the meandering of the cured roll and the occurrence of wrinkles due to blocking (blocking), etc. In addition, the curing step after coating can be reduced, and the efficiency of production can be improved.

Laminates 302, 304 in which the electrostatic printing ink layers 50, 51 on the printing surface are in direct contact with the adhesive layer 30, and components such as epoxy compounds and/or polyisocyanates contained in the adhesive composition fully penetrate into the electrostatic printing ink layer. 50, 51 middle. Thereby, the electrostatic ink composition constituting the electrostatic ink layer 50, 51 can be cross-linked, and the strength of the electrostatic ink composition (electrostatic ink layer 50, 51) can be improved. Also, the bonding strength between layers can be improved. Also, as shown in Fig. 5, even if the printing surface includes a non-patterned part (transparent part) without the electrostatic printing ink layer 50, the adhesiveness can be eliminated because the epoxy compound is contained in the adhesive layer. . On the other hand, if an epoxy coating layer is provided separately from the adhesive layer 30, if there is a non-patterned part on the printing surface, the epoxy compound will become excessive near the non-patterned part, and stickiness will easily occur. sex. In this way, the laminated body 300 can adhere to the printed surface including the non-patterned portion where the printed portion 52 is not formed with high adhesive strength, while eliminating the adhesiveness.

The laminated bodies 302, 304 are as described above, can sufficiently ensure the adhesive strength between the electrostatic printing ink layer 50, 51 and the base material 10, the primer layer 40, and the adhesive agent layer 30, so it can constitute a kind of container. 60 also inhibits peeling between the xerographic ink layers 50 , 51 and the substrate 10 , primer layer 40 , and adhesive layer 30 . In such a container, the bonded state between the layers is also maintained at the bent portion 60, so the occurrence of deviation of the printed surface, etc. can be suppressed, and the printed information in the body portion 200 including the bent portion 60 can be maintained in an initial state for printing. . During the use of the container, for example, even if a new bending part is generated due to bending of the container, etc., the bonding state between the layers is maintained, so the function of the container (such as: barrier properties, etc.) can be maintained during the period of use. maintain. Similarly, during the period of use, it is possible to suppress the breakage of the container itself or the deterioration of the printed information. In addition, such a container, even if the curved portion has a printed surface, suppresses the occurrence of peeling between laminated layers, so the information written on the printed surface can be read, and it is useful as a container for food and hygiene products that emphasize appearance. However, the usage is not limited to these. For example, after high-temperature hot water treatment and high-temperature sterilization heat treatment, the adhesive strength and sealing strength are also excellent, so it can also be used as a material for constituting high-temperature sterilization containers, microwave oven compatible containers, and boiling containers.

In the laminated body of a modification, you may have the primer layer 40 on the opposing surface of the base material 10 and the sealant layer 20, respectively. Furthermore, between the base material 10 and the sealant layer 20, from the viewpoint of improving the gas barrier properties and water vapor barrier properties of the laminates 302 and 304, between the base material 10 and the primer layer 40, and /or At least one of a metal layer such as aluminum foil and a resin layer such as a nylon film is provided between the sealant layer 20 and the adhesive layer 30 .

Specific examples of the layer structure of the laminate are illustrated below. In each illustration, the left end corresponds to the substrate 10 , and the right end corresponds to the sealant layer 20 , which means that the layers are stacked sequentially from left to right. In addition, the first adhesive layer is the adhesive layer 30 , and the second adhesive layer and the third adhesive layer may be conventional adhesive layers.

(1) Transparent evaporated PET film/primer layer/electrostatic ink layer/1st adhesive layer/nylon layer/2nd adhesive layer/CPP film (non-stretched polypropylene film) (2) PET film/primer layer/electrostatic ink layer/first adhesive layer/aluminum layer/second adhesive layer/nylon layer/third adhesive layer/CPP film (non-stretched polypropylene film) (3) PET film/primer layer/electrostatic ink layer/first adhesive layer/nylon layer/second adhesive layer/CPP film (non-stretched polypropylene film) (4) PET film/primer layer/electrostatic ink layer/1st adhesive layer/aluminum layer/2nd adhesive layer/polyethylene film

In each of the above specific examples, any layer may be provided at any position between the first adhesive layer and the sealant layer 20 . (1) and (2) can be applied as laminates for high temperature sterilization, (3) can be used as laminates for microwave ovens, (4) can be used as nutritional supplements or face masks. mask) layered body. However, the use is not limited to the above.

The above-mentioned laminate can be prepared, for example, by the following method. One embodiment of the manufacturing method of the laminate will be described below. One example of a method of manufacturing a laminate is to manufacture the laminate 302 shown in FIG. 5 . It has: the step of first forming the primer layer 40 on one surface of the film-like substrate 10, the step of printing the electrostatic printing ink composition on the primer layer 40 to form the electrostatic printing ink layer 50 composed of the printing part 52, and The surface of the electrostatic printing ink layer 50 and the sealant layer 20 is subjected to the bonding step using the above-mentioned specific adhesive composition.

The primer layer 40 may also be formed on one surface of the substrate 10 by flexographic printing, gravure printing, or the like. The primer layer 40 can also cross-link the resin material by a cross-linking agent. Crosslinking can also be performed by irradiation with ultraviolet light, heating, ionizing radiation such as electron beams, and non-ionizing radiation such as microwave radiation.

Printing of the electrostatic printing ink composition can be performed by electrostatic printing using a digital printing machine.

The bonding of the electrostatic printing ink layer 50 and one side of the sealant layer 20 using the adhesive composition can be performed by lamination. Lamination can be performed using arbitrary devices. The epoxy compound and/or polyisocyanate contained in the adhesive composition can penetrate into the electrostatic printing ink composition and the primer layer 40 constituting the electrostatic printing ink layer 50, and can be combined with the electrostatic printing ink composition and the primer layer 40. Containing components undergo a cross-linking reaction. Thereby, the strength of the electrostatic printing ink layer 50 can be improved, and at the same time, the laminated body 300 in which the interface of each layer is fully bonded can be obtained. At the time of lamination, at least a part of the adhesive composition can be cured to become a cured product. In this manner, a laminate 302 including the base material 10 , the primer layer 40 , the electrostatic ink layer 50 , the adhesive layer 30 , and the sealant layer 20 in this order can be manufactured. The laminated body 304 and the laminated body of the modified example can also be manufactured in the same manner as the laminated body 302 .

The laminates 302 and 304 manufactured in this manner have the configurations, properties and shapes described in the above embodiments. The content of the description of the laminated bodies 302, 304 and their modified examples can also be applied to the description of the embodiment of the above-mentioned manufacturing method.

[Packaging bags for heating] Fig. 7 is a plan view showing an example of a packaging bag 120 (packaging bag for heating) according to an embodiment. As shown in FIG. 7 , the packaging bag 120 is composed of a laminated body 300 sequentially having a base material, a primer layer, an electrostatic ink layer, an adhesive layer, and a sealant layer. The structure of the laminated body 300 will be described later. The packaging bag 120 may be, for example, a sealed bag in a state where packaged objects such as food and beverages are stored. The packaging bag 120 may or may not have a curved portion.

Moreover, the packaging bag 120 is a packaging bag for heating. The packaging bag for heating is a packaging bag in which the heat treatment is performed on the assumption that the object to be packaged is stored. Heat treatment includes "high temperature sterilization heat treatment", "boiling heat treatment", and "microwave heat treatment". The high-temperature sterilization heat treatment is, for example, a treatment in which the content is filled and a heat of 100° C. or higher is applied under pressure and heating. For example, a steam method or the like can be used. In addition, the boiling heat treatment is a treatment in which the packaging bag is heated in heated water (hot water), and the heating is performed under conditions up to 100°C. In addition, the microwave heating treatment is a heating treatment using a so-called microwave oven, and is a treatment in which water molecules are vibrated and rotated by electromagnetic waves (microwaves), thereby exothermic substances containing moisture. Most of the treatments are performed for the purpose of sterilization of packaging bags or packaged objects.

The packaging bag 120 is constructed by bonding the sealant layers of a pair of laminated bodies 300 together. The packaging bag 120 includes a seal portion 101 that bonds (seals) the peripheries of a pair of film-shaped substantially rectangular laminates 300 , and a storage portion 124 formed between the pair of laminates 300 by the seal portion 101 . . The sealing portion 101 forms a pair of side end portions, lower end portions, and upper end portions of the rectangular packaging bag 120 . In this way, the packaging bag 120 forms the sealing part 101 by the entire periphery of each of the respective peripheries of a pair of laminated bodies 300 in a state in which sealant layers are overlapped in plan view. In the storage part 124, for example, to-be-packed goods (for example: food and beverages) can be accommodated. In addition, in the following embodiments, the packaged object is housed and sealed may be particularly referred to as the package 400 . In addition, the sealing portion 101 at the lower end portion may be sealed after filling the storage portion 124 with the object to be packaged. The sealing portion 101 is configured by heat-sealing the sealant layers included in the laminate 300 .

In addition, the laminated bodies 300 constituting a pair of packaging bags 120 do not need to have the same layer configuration. For example, a pair of laminated bodies may have different layer configurations.

The packaging bag 120 may include an opening means 140 for facilitating opening. The opening means 140 has a pair of easy-opening processing parts 144 formed by V-shaped incisions formed on the sealing part 101 at the side end, and a half-tangent line of a track between the pair of easy-opening processing parts 144. 141. The half cut line 141 can be formed by using laser, for example. The easy-opening processed portion 144 is not limited to a V-shaped cutout, and may be a U-shaped or I-shaped cutout, or may be a group of scars.

The procedure for manufacturing the packaging bag 120 and the packaging body 400 using the laminated body 300 will be described below. A laminated body 300 formed into a pair of predetermined shapes is prepared. The sealant layers provided on one surface of each laminated body 300 are made to face each other, and the sealant layers are bonded to each other. At this time, the sealing part 101 is formed for a pair of side end parts and the lower end part (or upper end part), whereby the sealing part 101 is formed in a state where three of the four sides are closed, and an unsealed part is formed inside it. As a result, a packaging bag 130 in which only the upper end (or only the lower end) is unsealed as shown in FIG. 8 is obtained.

Next, from the upper end portion (or lower end portion) in the unsealed state, the packaged object is filled into the storage portion 132 of the packaging bag 130 . Thereafter, the sealant layers of the laminate 300 are adhered to each other at the upper end (or lower end) of the unsealed state, and the sealed portion 101 is formed at the upper end (or lower end). As a result, the package 400 including the packaging bag 120 and the packaged objects stored therein can be manufactured.

The above-mentioned packaging bag 120 is a packaging bag that can be used when it is assumed that heat treatment as the packaging body 400 is performed in a state where the object to be packaged is accommodated as described above. If the above-mentioned heat treatment is used, since the packaging bag 120 itself is heated, resistance to heat is required. Also, in any heat treatment, since water molecules exist around in a high-temperature environment, water resistance at high temperatures is required. In addition, since the packaging bag 120 is heat-treated in a state in which the contents are stored, it is considered that the sealing portion 101 is particularly easily affected by the heat treatment. In response to these requirements, the packaging bag 120 is configured by combining specific materials to form each layer constituting the laminate 300, thereby improving the water resistance and heat resistance of the laminate. Moreover, as the packaging bag 120, by making a part of the composition of the laminated body 300 in the sealing part 101 satisfy specific conditions, damage to the packaging bag 120 in the sealing part 101 can be prevented particularly during heat treatment.

Next, for the laminate 300 constituting the packaging bag 120 described above, the laminates 302 and 304 described as the constituent materials of the above-mentioned container can be used, and unless otherwise specified, the description can be applied. For example, materials and the like constituting each layer may be those exemplified when describing the corresponding layers in the description of the container described above.

The primer layer 40 may also contain resin. When the packaging bag 120 is used for heating, the resin preferably contains polyethyleneimine resin. Also, the primer layer 40 may further include, for example, polyvinyl alcohol resin, cellulose resin, polyester, polyamine, polyamide resin, polyurethane, Resins such as polyacrylic acid polymers, hydroxyl-containing resins, carboxyl-containing resins, and amine-based polymers. By providing the primer layer 40 made of polyethyleneimine resin on the base material to be printed, the laminate 300 having improved water resistance and suitable for heat treatment can be manufactured. The content of the polyethyleneimine resin in the primer layer 40 may be 80% by mass or more, may be 90% by mass or more, or may be 97% by mass or more. The coating amount of the resin constituting the primer layer 40 may be, for example, 0.01˜1.5 g/m ² , or 0.05˜1.0 g/m ² .

The laminated body 300 is equipped with the printing part 52 on the one main surface (printed surface) close to the sealant layer 20 among the pair of main surfaces of the primer layer 40. As shown in FIG. The printing surface is provided with an electrostatic printing ink layer 50 . The electrostatic ink layer 50 is composed of an electrostatic ink composition, and is provided by electrostatic printing using a digital printer. In FIG. 5, a plurality of printing parts 52 may have the same composition, or may have different colors by having different compositions. The electrostatic ink layer 50 can be constituted by the printing part 52 provided in a manner dispersed on the primer layer 40, or can be formed by the printing part 52 provided in a manner covering the entire surface of the primer layer 40. to form.

When the packaging bag 120 is used for heating, the ink coverage of each printing portion 52 constituting the electrostatic ink layer 50, 51 may be 100-400%. By setting the ink coverage of the printing portion 52 within the above range, the laminate has excellent lamination strength, and printing can be performed using a plurality of inks, and various printings can be handled.

The laminated body 300 ( 302 , 304 ) can sufficiently secure the adhesive strength between the electrostatic ink layers 50 , 51 and the substrate 10 , the primer layer 40 , and the adhesive layer 30 as described above. Therefore, when the laminate 300 is used as a heating packaging bag and subjected to heat treatment, peeling between the electrostatic ink layers 50 and 51 and the base material 10, the primer layer 40, and the adhesive layer 30 can be suppressed.

A specific example of the layer structure of the laminate when the packaging bag 120 is used for heating will be illustrated below. In each illustration, the left end corresponds to the substrate 10 , and the right end corresponds to the sealant layer 20 , which means that the layers are stacked sequentially from left to right. In addition, the first adhesive layer is the adhesive layer 30 , and the second adhesive layer and the third adhesive layer may be conventional adhesive layers.

(5) Transparent evaporated PET film/primer layer/electrostatic ink layer/1st adhesive layer/nylon layer/2nd adhesive layer/CPP film (non-stretched polypropylene film) (6) PET film/primer layer/electrostatic ink layer/first adhesive layer/aluminum layer/second adhesive layer/nylon layer/third adhesive layer/CPP film (non-stretched polypropylene film) (7) Nylon layer/primer layer/electrostatic ink layer/first adhesive layer/LLDPE (linear low density polyethylene) film (8) PET film/primer layer/electrostatic ink layer/1st adhesive layer/nylon layer/2nd adhesive layer/CPP film

In each of the above specific examples, any layer may be provided at any position between the first adhesive layer and the sealant layer 20 . The above (5) and (6) can be mainly used for packaging bags assumed to be subjected to high-temperature sterilization heat treatment, (7) can be mainly used for packaging bags assumed to be subjected to boiling heat treatment, and (8) can be mainly used for packaging bags assumed to be subjected to microwave heating treatment bags. However, the use is not limited to the above.

The above-mentioned laminate can be produced by the same manufacturing method as that of the above-mentioned laminate as a constituent material of the container.

[effect] As described in the above-mentioned embodiment, the packaging bag 120 (heating packaging bag) of this embodiment is formed by sequentially laminating the laminate 300 of the substrate 10, the primer layer 40, the adhesive layer 30, and the sealant layer 20. constitute. In addition, the adhesive layer 30 includes at least one of an adhesive composition containing a polyol, a polyisocyanate, and an epoxy compound, and a cured product of the adhesive composition. Moreover, from a viewpoint of improving water resistance, the primer layer 40 may contain polyethyleneimine resin.

Electrostatic printing ink compositions used in digital printing machines tend to be inferior in heat resistance and strength compared to other printing inks. Therefore, if the laminate having the electrostatic ink layer derived from the electrostatic ink composition is to be applied to a packaging bag for heat treatment, the packaging bag may be damaged or the like. On the other hand, according to the above configuration, the deformation of the laminate due to heating or the like can be suppressed by hardening the adhesive composition containing the epoxy compound, so a heating packaging bag having sufficient resistance to heat treatment can be obtained. . In addition, when the primer layer containing polyethyleneimine resin is included, the water resistance is also improved, and more sufficient resistance can be obtained especially for heat treatment in an environment with a lot of moisture such as boiling heat treatment or high-temperature sterilization heat treatment.

Moreover, the packaging bag 120 (packaging bag for heating) includes the sealing part 101 which connects the sealant layer 20 of the laminated body 300 of 2 sheets in the outer peripheral part. In addition, in the sealing part 101, the ink coverage rate of the electrostatic ink layer 50, 51 may be 300% or less. Since the sealing part 101 is a region where thermal bonding such as heat sealing is performed, the possibility of damage is higher than other regions. On the other hand, by setting the ink coverage ratio of the electrostatic printing ink layer within the above-mentioned range, more sufficient resistance to heat treatment can be ensured for the sealing part, and heating with stronger resistance to heat treatment can be obtained. Use a bag.

Moreover, the polyol may contain the aliphatic polyester polyol, and the thing which has an epoxy group at both terminals may be included in an epoxy compound. Such an adhesive layer 30 has high adhesive strength especially in a high-temperature environment. Therefore, when the laminated body 300 is combined to form a packaging bag, it is possible to sufficiently suppress the breakage of the electrostatic printing ink composition or the damage of the packaging bag.

An aspect in which the epoxy compound includes a bifunctional alicyclic epoxy compound may be used. Such an epoxy compound, since it is bifunctional, increases the crosslinking points with the electrostatic printing ink composition, and strongly adheres to the printing surface. Moreover, since it is an alicyclic form, the reaction with polyisocyanate can be suppressed by steric hindrance. Therefore, it can harden|cure stably, and the adhesiveness of the interface of a printing surface and an adhesive agent layer is fully excellent.

An aspect in which the polyisocyanate includes a xylylene diisocyanate derivative may be used. Such a polyisocyanate has excellent reactivity with a polyol system. Thereby, the curability of the adhesive composition is improved, and thus deformation of the laminate 300 and the packaging bag can be suppressed.

The laminated body 300 (302, 304) and packaging bag manufactured in this way have the structure and property shape demonstrated in these embodiments. The description of the laminated body 300, the packaging bag, and the modified examples thereof can also be applied to the description of the above-mentioned embodiment of the manufacturing method.

As mentioned above, although some embodiment was demonstrated, about the common structure, mutual description is applicable. In addition, this indication is not limited at all by the said embodiment. [Example]

Although the contents of the present disclosure will be described in more detail with reference to Examples, Comparative Examples, and Reference Examples, the present disclosure is not limited to the following Examples.

(Example I-1) [Preparation of a laminate] As a base material, an alumina-deposited PET film (manufactured by Toppan Printing Co., Ltd., trade name: GLARH12, thickness: 12 μm) was prepared. A water-based primer resin (resin containing polyethyleneimine, manufactured by Michelman, trade name: DP050) was applied to the alumina vapor-deposited surface to form a primer layer. Coating is performed so that the coating amount of the aqueous polyethyleneimine becomes 0.10 to 0.18 g/m ² .

A predetermined printing was performed on the surface of the primer layer using a digital printer (manufactured by HP, Indigo 20000 digital printer for labels and packaging). As the electrostatic printing ink composition, an electrostatic printing ink composition (HP Indigo ElectroInk) containing a thermoplastic resin containing a copolymer of ethylene acrylic acid and ethylene methacrylic acid was used. As the colors of the electrostatic printing ink composition, yellow (Y), magenta (M) and cyan (C) are used. The coverage of each ink is adjusted by the settings of the above-mentioned digital printing machine. The total ink coverage rate is 200%.

Aliphatic polyester polyol (manufactured by Mitsui Chemicals Co., Ltd., trade name: TAKELAC A626, hereinafter also referred to as "(A)") as the main agent, polyisocyanate (Mitsui Chemicals Co., Ltd. Manufactured by the company, trade name: TAKENATE A50, hereinafter also referred to as "(B)"), 3',4'-epoxycyclohexylmethyl 3,4 epoxycyclohexanecarboxylate as an epoxy compound (hereinafter There is also a case called "C"), and ethyl acetate as a solvent to prepare an adhesive composition with a solid content concentration of 36.5% by mass. The structure of this epoxy compound is shown in the following formula (1). The blending ratio (mass standard) of the mass basis of each component is set to (A):(B):(C)=8:1:0.28.

On the printing surface on which the electrostatic printing ink composition was printed, the adhesive composition prepared as described above was applied using a dry laminator to form an adhesive layer. The coating amount of the adhesive composition was set to 4.0 g/m ² .

The nylon film and the non-stretched polypropylene film were laminated with a commercially available adhesive to produce a laminated film. Using the above-mentioned dry lamination device, the adhesive layer on the base material and the nylon film of the above-mentioned laminated film face each other, and the nylon film and the adhesive layer are laminated to obtain a laminated body. The curing time (aging) was set at 40° C. for 2 days.

(Comparative Example I-1) A laminate was prepared in the same manner as in Example I-1 except that the epoxy compound ((C) component) was not blended when preparing the adhesive composition.

<Evaluation of Peeling Inhibition Performance of Laminate Part 1> For the laminates prepared in Example I-1 and Comparative Example I-1, the evaluation of peeling inhibition performance during heating was performed. Specifically, the laminate was folded in half to form a bent portion, and it was fixed with clips as an evaluation sample, and the evaluation sample was heated at the heating temperature listed in Table 1 for 45 minutes, and the heated sample was observed by an optical microscope. The evaluation was performed using the condition of the bent portion of the sample. Evaluation was performed by the following criteria. The results are shown in Table 1. A: Peeling was not observed. B: Slight voids were observed between laminated layers. C: Peeling was observed between laminates.

[Table 1] Heating temperature [°C] Heating time [minutes] Evaluation (peeling inhibition performance) Example I-1 100 45 A 110 45 A 120 45 A Comparative Example I-1 100 45 B 110 45 C 120 45 C

As shown in Table 1, in the laminated body of Example I-1, it was confirmed that by using the specified adhesive composition, sufficient detachment suppression performance was exhibited also at the bent portion. In the laminate of Comparative Example I-1, it is presumed that the resin component of the electrostatic printing ink layer melted and peeled off. In addition, in Comparative Example I-1, it was confirmed that this tendency becomes conspicuous as the heating temperature rises. On the other hand, in the laminated body of Example I-1, it was confirmed that sufficient peeling suppression performance was maintained even when heated. In the laminated body of Example I-1, the same sufficient detachment inhibitory effect can be expected even when the resin component is cured without heat (for example, at room temperature).

<Evaluation of Peeling Inhibition Performance of Laminate Part 2> For the laminates prepared in Example I-1 and Comparative Example I-1, respectively, the heating temperature and heating time were changed, and heating was performed in the same manner as in the above-mentioned "evaluation of peeling inhibition performance of laminates 1". Evaluation of the peeling inhibition performance during the test. The results are shown in Table 2.

[Table 2] Heating temperature [°C] Heating time [minutes] Evaluation (peeling inhibition performance) Example I-1 115 30 A 121 30 A 125 30 A Comparative Example I-1 115 30 C 121 30 C 125 30 C

As shown in Table 2, even when the heating temperature and heating time were changed, the same tendency as in the above-mentioned "evaluation of peeling inhibition performance of laminated body 1" was confirmed. As shown by the results of the laminated body of Example I-1, if it is the container disclosed in the present disclosure, it is confirmed that it is sufficient for high-temperature sterilization heat treatment (for example: 120°C, 30 minutes of heat and pressure sterilization treatment) at 120°C or higher. patience.

<Heat-sealing test of bent portion: evaluation of peeling inhibition performance part 3> Next, the influence due to sealing in the state where the bent portion was provided was evaluated. Prepare 3 laminates prepared in Example I-1 and Comparative Example 1-1 respectively, and prepare a stand-up pouch consisting of 3 identical laminates (with the same structure as the container shown in Fig. 3 and Fig. 4). container). Specifically, the sheet to be the bottom sheet was folded in half and arranged between the two laminates to be the side sheets, and a pressure of 0.2 MPa was applied to the laminate for 1 second using a thermal gradient testing machine, and the values shown in Table 3 were measured. Temperature treatment, sealing. In addition, when the laminated body serving as the bottom sheet portion of the stand-up pouch is folded into a mountain shape, it is arranged so that the side of the sealant layer becomes the inner side of the container. As a thermal gradient tester, "HG-100" (product name) manufactured by Toyo Seiki Seisakusho Co., Ltd. was used. After the preparation, the section of the bottom sheet portion including the stand-up pouch was observed with an optical microscope. The evaluation criteria used the same criteria as in the above-mentioned "Evaluation 1 of the peeling suppression performance of the laminate". The results are shown in Table 3. Also, for reference, FIG. 9 shows the appearance of the curved portion of the laminate serving as the bottom sheet of Example I-1 and Comparative Example I-1 before sealing and after sealing at 210°C.

[table 3] Sealing temperature [°C] Evaluation (peeling inhibition performance during heat sealing) Example I-1 190 A 200 A 210 A Comparative Example I-1 190 B 200 C 210 C

As shown in Table 3, it was confirmed that peeling was sufficiently suppressed in the laminate prepared in Example I-1 even in heat treatment such as in a state where the sealant layers were bonded together and pressure was applied.

<Heat-sealing test of bent portion: evaluation of peeling inhibition performance part 4> The pressure conditions applied at the time of sealing or the time of sealing were changed, and the same evaluation as the above-mentioned "Heat-sealing test of bent portion: evaluation of peeling inhibition performance part 3" was performed. The results are shown in Table 4 and Table 5, and Fig. 10 and Fig. 11 .

[Table 4] Sealing conditions Evaluation (peeling inhibition performance during heat sealing) Sealing temperature [°C] Applied pressure [MPa] Sealing time [seconds] Example I-1 200 0.2 1 A 200 0.3 1 A 200 0.4 1 A Comparative Example I-1 200 0.2 1 C 200 0.3 1 C 200 0.4 1 C

[table 5] Sealing conditions Evaluation (peeling inhibition performance during heat sealing) Sealing temperature [°C] Applied pressure [MPa] Sealing time [seconds] Example I-1 200 0.2 0.2 A 200 0.2 0.5 A 200 0.2 1 A Comparative Example I-1 200 0.2 0.2 B 200 0.2 0.5 C 200 0.2 1 C

As shown in Table 4 and Table 5, and Fig. 10 and Fig. 11, if it is the laminated body of Example I-1, under the general sealing conditions when the container is manufactured by sealing the laminated body, it is confirmed that Peeling is sufficiently suppressed even under heat-sealing conditions.

From the results of Example I-1 and Comparative Example I-1 above, it was confirmed that by using the adhesive composition containing polyol, polyisocyanate, and epoxy compound, the delamination between the layers constituting the laminate can be sufficiently suppressed Effect. As the main cause of such peeling suppression effect, it is considered that the improvement of the strength of the electrostatic printing ink composition and the improvement of the adhesion strength between the layers contribute. For reference only, the following shows an example of adjusting the composition of the adhesive composition.

(Reference Example I-1) [Making of laminated body] The blending ratio (A):(B):(C) of the mass basis of each component in the adhesive composition was changed as shown in Table 6, except that it was performed in the same manner as in Example I-1 to make a laminate body. Moreover, lamination strength (adhesion strength) was measured by the method mentioned later about the obtained laminated body. The results are shown in Table 6.

<Evaluation of adhesive strength of laminate> For the laminate prepared in Reference Example I-1, the adhesion strength was measured according to the description in JIS K 6854-1:1999. Specifically, first, the prepared laminate was cut into a width of 15 mm and used as a measurement sample. After peeling the interlayer at the end of the measurement sample, the peel strength between the layers of the laminate was measured using a tensile tester under the conditions of angle: 90°, tensile speed: 300 mm/min, and room temperature. Let this peel strength be the adhesive strength in normal temperature (20 degreeC). The measurement results are shown in Table 6.

(Reference Example I-2) Prepare the first solution containing aliphatic polyester polyol (A) (manufactured by Mitsui Chemicals Co., Ltd., trade name: TAKELAC A626), and polyisocyanate (B) (manufactured by Mitsui Chemicals Co., Ltd., trade name: TAKENATE A50). ) and the second liquid of the epoxy compound (C) are respectively accommodated in a two-component type adhesive in a container. The first liquid and the second liquid were mixed to prepare the blended adhesive composition shown in Table 6. Except using this adhesive composition, it carried out similarly to Reference Example I-1, the laminated body was produced, and the measurement of the adhesive strength was performed. The measurement results are shown in Table 6.

(Comparative Example 1-2) When preparing the adhesive composition, except that the epoxy compound (C) was not blended, a laminate was produced in the same manner as in Reference Example I-1, and the adhesive strength was measured. The measurement results are shown in Table 6.

(Comparative Example 1-3) For the printing surface printed with the electrostatic printing ink composition, the epoxy compound of formula (1) is coated to form an epoxy coating layer, and the adhesive composition of Comparative Example 1-2 is coated on this epoxy coating layer, in addition In the same manner as in Reference Example I-1, a laminate was produced, and the bonding strength was measured. The coating amount of the epoxy coating layer was set to an amount corresponding to 0.53 parts by mass in the blend shown in Table 6. The measurement results are shown in Table 6.

[Table 6] Reference Example I-1 Reference example I-2 Comparative Example I-2 Comparative Example I-3 Blending of Adhesive Composition Blending ratio [parts by mass] Aliphatic polyester polyol (A) 8 8 8 8 Polyisocyanate (B) 1 1.5 1 1 Epoxy compound (C) 1.6 1.5 0 0 [(B)/(A)]×100 12.5 18.8 12.5 12.5 [(C)/(A)]×100 20.0 18.8 0.0 0.0 Epoxy / Isocyanate 4.8 3.0 0 0 Ink coverage total Bonding strength [N/15mm] Y100%+W200% 300% 3.0 3.1 1.1 3.2 M100%+W200% 300% 2.9 2.7 0.5 3.6 C100%+W200% 300% 2.6 2.4 0.8 3.8 K100%+W200% 300% 2.5 2.5 0.8 3.4 W200% 200% 2.7 2.9 1.2 3.3 C100%+M100%+Y100%+W200% 500% 2.9 2.9 0.6 2.5 C100%+M100%+W200% 400% 2.8 3.0 0.4 2.6 C100%+Y100%+W200% 400% 3.5 3.2 0.8 2.7 M100%+Y100%+W200% 400% 3.2 3.4 0.8 2.6

The compounding quantity (mass part) of the polyisocyanate with respect to 100 mass parts of aliphatic polyester polyols is shown in the column of [(B)/(A)]x100 of Table 6. The compounding quantity (mass part) of the epoxy compound with respect to 100 mass parts of aliphatic polyester polyols is shown in the column of [(C)/(A)]x100 of Table 6. In the column of "epoxy group/isocyanate group" of Table 6, the molar ratio of the epoxy group contained in an epoxy compound (C) with respect to the isocyanate group contained in a polyisocyanate (B) is shown.

As shown in Table 6, it was confirmed that the laminates of Reference Examples I-1 to I-2, in which an adhesive layer containing an epoxy compound was bonded to the printed surface, compared to laminates in which an adhesive layer containing no epoxy compound was bonded to the printed surface. The laminated body of Comparative Example I-2 was adhered to, and the subsequent strength became higher. In addition, in Comparative Example I-3, relatively high adhesive strength was obtained, but since an epoxy coating layer was also formed in addition to the adhesive layer, the number of steps increased. It takes 2 days to harden (cure) the epoxy coating layer, and productivity falls.

The laminate of Comparative Example I-2 peeled off near the interface between the electrostatic ink layer and the primer layer. In the laminate of Comparative Example I-3, the electrostatic printing ink layer system was cohesively broken. On the other hand, the laminates of Reference Examples I-1 to I-2 exhibited sufficient adhesive strength, and when a load was barely applied, they peeled off at the interface between the electrostatic printing ink layer and the adhesive layer, and the electrostatic printing ink layer was not visible. cohesive failure. This implies that the cohesion of the electrostatic printing ink layer is improved. Moreover, the molar ratio of the isocyanate group contained in the polyisocyanate (B) in reference example I-1-I-2 with respect to the hydroxyl group of an aliphatic polyester polyol (A) exists in the range of 0.5-10.

Next, for the laminates of Reference Example I-1 and Comparative Example I-3, in addition to the bonding strength, hot water bonding strength and sealing strength were also measured. The measurement is based on the sum of ink coverage rate of 500% and 200%. The details of the measurement procedure are as follows.

[Measurement of Hot Water Bonding Strength] The laminates of Reference Example I-1 and Comparative Example I-3 were each cut to a width of 15 mm to obtain samples for measurement. After peeling off the interlayer at the end of the sample for measurement, the peeling strength was measured using a tensile tester while being immersed in hot water at 90°C. That is, the peeling angle: free, and the stretching speed: 300 mm/min. This peel strength is shown in Table 7 as hot water adhesion strength.

[Measurement of sealing strength (before heat treatment)] Using the pair of laminates of Reference Example I-1, non-stretched polypropylene films were laminated and heat-sealed to form a sealed portion. Thereby, the non-stretched polypropylene films were thermally welded to each other, and a measurement sample having a width of 15 mm was prepared. According to JIS K 7127:1999, the sealing strength in the sealing part of the prepared measurement sample was measured. The measurement system measures the peeling strength between heat seals using a tensile tester under the conditions of peeling angle: 90°, tensile speed: 300 mm/min, and normal temperature (20° C.). Let this peel strength be the sealing strength "before heat treatment". The measurement results are shown in Table 7. Using the laminate of Comparative Example I-3, the same measurement sample was prepared and the same measurement was performed. The measurement results are shown in Table 7.

[Determination of sealing strength (after boiling)] Heat the measurement sample prepared in the above "Measurement of sealing strength (before heat treatment)" in water at 100°C for 30 minutes. Thereafter, the sealing strength was measured by the same procedure as in the above-mentioned "measurement of sealing strength (before heat treatment)". The measurement results are shown in the column of "after boiling" in Table 7.

[Measurement of sealing strength after high temperature sterilization (120°C)] The high-temperature sterilization heat treatment (120°C x 30 minutes) was performed on the measurement sample prepared in the above-mentioned "measurement of sealing strength (before heat treatment)". Peel strength was measured in the same manner as "measurement of sealing strength (before heat treatment)" using a tensile tester. The measurement results are shown in the column of "120°C x 30 minutes" in Table 7.

[Measurement of sealing strength after high temperature sterilization (130°C)] The high-temperature sterilization heat treatment (130° C.×30 minutes) was performed on the measurement sample prepared in the above-mentioned “measurement of sealing strength (before heat treatment)”. Using a tensile tester, the peel strength was measured in the same manner as in "Measurement of sealing strength (without heat treatment)". The measurement results are shown in the column of "130°C x 30 minutes" in Table 7.

[Table 7] Reference Example I-1 Comparative Example I-3 Ink coverage 200% 500% 200% 500% Hot water adhesion strength [N/15mm] 90°C 1.0 1.1 <0.1 <0.1 Seal strength Before heat treatment 53.0 53.0 51.0 52.0 after boiling 44.0 51.0 22.0 35.0 120℃×30 minutes 55.0 54.0 52.0 53.0 130℃×30 minutes 52.0 54.0 53.0 54.0

As shown in Table 7, the hot water bonding strength was significantly higher in Reference Example I-1 than in Comparative Example I-3. Also, it was confirmed that the seal strength of Reference Example I-1 was superior to that of Comparative Example I-3. In particular, the sealing strength of Reference Example I-1 was sufficiently high even after boiling, but the sealing strength of Comparative Example I-3 decreased significantly after boiling. In the laminate of Comparative Example I-3, when heated in the presence of moisture, it was confirmed that the bonding strength and sealing strength were greatly reduced.

(Example II-1) [Preparation of a laminate] A nylon film (thickness: 15 μm) was prepared as a base material. A water-based primer resin (resin containing polyethyleneimine, manufactured by Michelman, trade name: DP050) was coated on one of the main surfaces of the nylon film to form a primer layer. Coating is performed so that the coating amount of the aqueous polyethyleneimine becomes 0.10 to 0.18 g/m ² .

A predetermined printing was performed on the surface of the primer layer using a digital printer (manufactured by HP, Indigo 20000 digital printer for labels and packaging). As the electrostatic printing ink composition, an electrostatic printing ink composition (HP Indigo ElectroInk) containing a thermoplastic resin containing a copolymer of ethylene acrylic acid and ethylene methacrylic acid was used. As the colors of the electrostatic printing ink composition, as shown in Table 8, white (W) and cyan (C) were used. Several samples with different color and ink coverage of the electrostatic printing ink composition were prepared. Ink coverage is set as shown in Table 8. The coverage of each ink is adjusted by the settings of the above-mentioned digital printing machine. As shown in Table 8, the total ink coverage ratio was 100 to 300%.

Aliphatic polyester polyol (manufactured by Mitsui Chemicals Co., Ltd., trade name: TAKELAC A626, hereinafter also referred to as "(A)") as the main agent, polyisocyanate (Mitsui Chemicals Co., Ltd. Manufactured by the company, trade name: TAKENATE A50, hereinafter also referred to as "(B)"), 3',4'-epoxycyclohexylmethyl 3,4 epoxycyclohexanecarboxylate as an epoxy compound (hereinafter There is also a case called "C"), and ethyl acetate as a solvent to prepare an adhesive composition with a solid content concentration of 36.5% by mass. The structure of this epoxy compound is shown in the following formula (1). The blending ratio (mass standard) of the mass basis of each component is set to (A):(B):(C)=8:1:0.28.

On the printing surface on which the electrostatic printing ink composition was printed, the adhesive composition prepared as described above was applied using a dry laminator to form an adhesive layer. The coating amount of the adhesive composition was set to 4.0 g/m ² .

An LLDPE film (manufactured by FUTAMURA CHEMICAL, trade name: XMTN, thickness: 60 μm) was prepared, and the adhesive layer on the substrate was bonded to the LLDPE film using the above-mentioned dry laminator to obtain a laminate. The curing time (aging) was set at 40° C. for 2 days.

(Embodiment II-2, II-3) Except for changing the color and ink coverage of the electrostatic printing ink composition as described in Table 8, a laminate was prepared in the same manner as in Example II-1.

(Comparative Examples II-1 to II-3) A laminate was prepared in the same manner as in Examples II-1 to II-3 except that the epoxy compound ((C) component) was not blended when preparing the adhesive composition.

[Creation of packaging body] For each of the above-mentioned Examples II-1 to II-3 and Comparative Examples II-1 to II-3, two rectangular laminates of 150 mm×200 mm were prepared. At this time, the laminated system of Example II-1 and Comparative Example II-1 was prepared without coating the electrostatic printing ink composition on the outer peripheral part with a width of 10 mm, and Examples II-2 to II-3 and Comparative Examples II-2 to II The layered system of -3 is prepared to apply the electrostatic printing ink composition also on the outer periphery. The two laminated bodies are stacked with the main surfaces on the LLDPE film side facing each other, and a pair of end portions along the long side direction and one end portion along the short side direction are bonded together by heat sealing. Three of the four sides around the laminated body form the sealing portion. FIG. 12 shows the main surface of the laminated body 310 . First, by the initial heat sealing, the sealing portion 111 is formed on three sides of the laminated body 310, and a packaging bag in a state of being closed on three sides is produced. The width T (see FIG. 12 ) of the sealing portion 111 at this time was set to 10 mm. The sealing portion 114 is formed by bonding two laminates together by heat sealing on the side where the sealing portion 111 is not formed. Also for the sealing portion 114, the width T was set to 10 mm. That is, when using the laminates of Example II-1 and Comparative Example II-1, a packaging bag was prepared in which the seal portions 111 and 114 were in a state where no electrostatic printing ink composition was printed on the laminate.

In addition, 500 ml of water was introduced as the content in the packaging bag until the sealing portion 114 was completely sealed to seal the inside. Thereby, the packages of Examples II-1 to II-3 and Comparative Examples II-1 to II-3 were produced. As mentioned above, 500 ml of water was filled inside the package.

＜Evaluation of bonding strength (before boiling)＞ The adhesive strength was measured for the packages of Examples II-1 to II-3 and Comparative Examples II-1 to II-3 according to the description in JIS K 6854-1:1999. Specifically, first, the laminates of Examples II-1 to II-3 and Comparative Examples II-1 to II-3 before being filled with water were cut into a width of 15 mm, and replaced with the prepared examples II-1 to II-3 and the packages of Comparative Examples II-1 to II-3 were used as measurement samples. After peeling the interlayer at the end of the measurement sample, the peel strength between the layers of the laminate was measured using a tensile tester under the conditions of angle: 90°, tensile speed: 300 mm/min, and room temperature. Let this peel strength be the adhesive strength in normal temperature (20 degreeC). The measurement results are shown in Table 8.

＜Evaluation of bonding strength (after boiling)＞ Each of the packages of Examples II-1 to II-3 and Comparative Examples II-1 to II-3 was heated in water at 90° C. for 30 minutes (boiling heat treatment). Thereafter, a part of the package was cut out in the same procedure as the above-mentioned <evaluation of adhesion strength (before boiling)>, and the adhesion strength was measured. The measurement results are shown in Table 8.

[Table 8] Ink type Ink coverage rate[%] before boiling after boiling Bonding strength [N/15mm] exam preparation Bonding strength [N/15mm] exam preparation Example II-1 - - 8.5 Peel between Nylon/LLDPE 7.2 Peel between Nylon/LLDPE Example II-2 W 100 3.7 Cohesive failure of electrostatic printing ink layer 5.3 Cohesive failure of electrostatic printing ink layer Example II-3 C.W 300 2.2 〃 3.7 〃 Comparative Example II-1 - - 6.5 〃 7.0 〃 Comparative Example II-2 W 100 2.3 〃 3.2 〃 Comparative Example II-3 C.W 300 0.9 〃 1.4 〃

From the above results, it was confirmed that compared with the case where there was no electrostatic ink layer (Example II-1, Comparative Example II-1), the adhesion strength decreased due to the presence of the electrostatic ink layer, and it was confirmed that if the ink was covered The rate becomes larger, then the intensity decreases. In particular, when the ink coverage rate becomes 300%, it is confirmed that in Comparative Example II-3, the adhesion strength to the package (laminated body) becomes 2 or less before boiling and after boiling, which is unacceptable. Possibility of use as packaging bags for heat treatment. In addition, in all except Example II-1, the adhesion strength after boiling became large. This is presumed to be due to the progress of the reaction of the isocyanate as a curing agent contained in the adhesive composition during boiling.

＜Evaluation of sealing strength (before boiling)＞ For the packages of Examples II-1 to II-3 and Comparative Examples II-1 to II-3 respectively, before filling with water (before the sealing part 114 is completely sealed and the inside is sealed), the package containing The seal portion was cut out to prepare a measurement sample with a width of 15 mm. According to JIS K 7127:1999, the sealing strength in the sealing part of the prepared measurement sample was measured. The measurement system measures the peeling strength between heat seals using a tensile testing machine under the conditions of peeling angle: 90°, tensile speed: 300 mm/min, and normal temperature (20° C.). Let this peel strength be the sealing strength "before heat treatment". The measurement results are shown in Table 9.

＜Evaluation of sealing strength (after boiling)＞ Each of the packages of Examples II-1 to II-3 and Comparative Examples II-1 to II-3 was heated in water at 90° C. for 30 minutes (boiling heat treatment). After that, the package was opened, and the water filled inside was removed, and then the sealing strength was measured in the same procedure as in the above-mentioned "evaluation of sealing strength (before boiling)". The measurement results are shown in Table 9.

In addition, "Film Break" in Table 9 indicates that the measurement was completed in a state where the film was broken. Also, "triangular peeling" means a state where peeling occurs between layers in at least one of a pair of laminates. In addition, "edge break (edge break)" means the state which breaks at the boundary part of a heat-sealed part and the inside of a bag.

[Table 9] Ink coverage rate[%] before boiling after boiling Sealing Strength[N/15mm] exam preparation Sealing Strength[N/15mm] exam preparation Example II-1 - 59.0 film break 55.0 film break Example II-2 100 54.0 triangle stripping 53.7 cracked edge Example II-3 300 52.8 〃 54.0 〃 Comparative Example II-1 - 56.0 film break 54.3 film break Comparative Example II-2 100 36.1 triangle stripping 47.8 cracked edge Comparative Example II-3 300 31.1 〃 29.3 triangle stripping

From the above results, it was confirmed that the seal strength decreased due to the presence of the electrostatic ink layer compared to the case where there was no electrostatic ink layer (Example II-1, Comparative Example II-1), and it was confirmed that if the ink was coated The larger the rate, the lower the sealing strength. Regarding Comparative Examples II-2 and II-3, it was confirmed that the sealing strength in at least one of before boiling and after boiling was 40 N/15 mm or less, so there was a possibility that it could not be used as a packaging bag for heat treatment.

＜Aerated boiling test＞ For each of the above-mentioned Examples II-1 to II-3 and Comparative Examples II-1 to II-3, prepare two rectangular laminates of 150mm x 200mm, and make them in the same way as the above-mentioned packaging. Packages for gas boiling test.

In addition, before the sealing part 114 is completely sealed and the inside is sealed, 300ml of water is introduced as the contents of the packaging bag, and then 100ml of air is further filled. This point is used for the adhesive strength and sealing strength tests. The packaging is different. In this way, the packages for the gas boiling test of Examples II-1 to II-3 and Comparative Examples II-1 to II-3 were produced. As mentioned above, 300ml of water and 100ml of air were filled inside the package.

Three packages of the aforementioned Examples II-1 to II-3 and Comparative Examples II-1 to II-3 were respectively prepared, and each was heated in 100° C. water for 60 minutes. The surface of the heated package was visually observed, and the presence or absence of floating of the printed surface due to the electrostatic printing ink composition on the surface of the laminate was observed. The measurement results are shown in Table 10.

[Table 10] Ink coverage rate[%] Number of packages confirmed to be floating (N=3) Example II-1 - 0 Example II-2 100 0 Example II-3 300 0 Comparative Example II-1 - 0 Comparative Example II-2 100 2 Comparative Example II-3 300 3

From the results of the above-mentioned Examples and Comparative Examples, it was confirmed that the adhesive composition containing polyol, polyisocyanate, and epoxy compound has resistance to heat treatment. As the main cause of the improvement of the resistance to such heat treatment, it is considered that the improvement of the strength of the electrostatic printing ink composition and the improvement of the adhesion strength between the layers contribute. In order to verify these enhancement effects, the following experiments were carried out.

(Reference Example II-1) [Production of adhesive composition and laminate] As a base material, a polyethylene terephthalate film (PET film, thickness: 12 μm) was prepared. One side of the PET film was coated with the same water-based primer resin as in Example II-1 to form a primer layer. The coating amount of water-based polyethyleneimine was also the same as in Example II-1.

Using the digital printing machine used in Example II-1, the primer layer was printed on the surface as specified. As the electrostatic printing ink composition, an electrostatic printing ink composition (HP Indigo ElectroInk) containing a thermoplastic resin containing a copolymer of ethylene acrylic acid and ethylene methacrylic acid was used. As the colors of the electrostatic printing ink composition, as shown in Table 11, white (W), yellow (Y), magenta (M), cyan (C), and black (K) were used. Several samples with different color and ink coverage of the electrostatic printing ink composition were prepared. The ink coverage ratios of the respective colors and their totals are set as shown in Table 11. As shown in Table 11, the total ink coverage rate is 200-500%.

The same adhesive composition as in Example II-1 was prepared, and the adhesive composition was applied to the printing surface by the same procedure as in Example II-1 to form an adhesive layer. The coating amount of the adhesive composition was set to 4.0 g/m ² .

A laminated film comprising an aluminum foil (manufactured by Toyo Aluminum Co., Ltd., thickness: 7 μm), a nylon film, and a non-stretched polypropylene film in this order was prepared. Using the same dry lamination device as in Example II-1, the adhesive layer on the base material and the aluminum foil of the laminated film face each other, and the aluminum foil and the adhesive layer were bonded together to obtain a laminate. The curing time (aging) was set at 40° C. for 2 days.

[Measurement of adhesive strength (room temperature)] According to JIS K 6854-1:1999, the adhesive strength of the manufactured laminate was measured. Specifically, the produced laminate was cut into a width of 15 mm, and used as a measurement sample. After peeling the interlayer at the end of the measurement sample, the peel strength between the layers of the laminate was measured using a tensile tester under the conditions of angle: 90°, tensile speed: 300 mm/min, and room temperature. Let this peel strength be the adhesive strength in normal temperature (20 degreeC). The measurement results are shown in Table 11.

(Reference example II-2 to II-6) Except that the blending of the adhesive composition was changed as shown in Table 11 and Table 12, a laminate was produced in the same manner as in Reference Example II-1, and the adhesive strength was measured. The measurement results are shown in Table 11 and Table 12.

(Reference Example II-7) Prepare the first solution containing aliphatic polyester polyol (A) (manufactured by Mitsui Chemicals Co., Ltd., trade name: TAKELAC A626), and polyisocyanate (B) (manufactured by Mitsui Chemicals Co., Ltd., trade name: TAKENATE A50). ) and the second liquid of the epoxy compound (C) are respectively accommodated in a two-component type adhesive in a container. The first liquid and the second liquid were mixed to prepare the blended adhesive composition shown in Table 12. Except using this adhesive composition, it carried out similarly to Reference Example II-1, the laminated body was produced, and the measurement of the adhesive strength was performed. The measurement results are shown in Table 12.

(Comparative Example II-4) Except not mixing the epoxy compound (C) when preparing the adhesive composition, it carried out similarly to Reference Example II-1, the laminated body was produced, and the measurement of the adhesive strength was performed. The measurement results are shown in Table 12.

(Comparative Example II-5) For the printing surface printed with the electrostatic printing ink composition, the epoxy compound of formula (1) is coated to form an epoxy coating layer, and the adhesive composition of Comparative Example II-4 is coated on this epoxy coating layer, in addition In the same manner as in Reference Example II-1, a laminate was produced, and the adhesive strength was measured. The coating amount of the epoxy coating layer was an amount corresponding to 0.53 parts by mass in the blend shown in Table 11. The measurement results are shown in Table 12.

[Table 11] Reference Example II-1 Reference Example II-2 Reference Example II-3 Reference Example II-4 Reference Example II-5 Blending of Adhesive Composition Blending ratio [parts by mass] Aliphatic polyester polyol (A) 8 8 8 8 8 Polyisocyanate (B) 1 1 1 1 1 Epoxy compound (C) 0.28 0.58 0.78 1.2 1.6 [(B)/(A)]×100 12.5 12.5 12.5 12.5 12.5 [(C)/(A)]×100 3.5 7.3 9.8 15.0 20.0 Epoxy / Isocyanate 0.8 1.8 2.4 3.6 4.8 Ink coverage total Bonding strength [N/15mm] Y100%+W200% 300% 1.2 1.6 1.8 2.7 3.0 M100%+W200% 300% 0.8 1.0 1.2 1.8 2.9 C100%+W200% 300% 1.3 1.5 1.6 2.8 2.6 K100%+W200% 300% 0.8 1.2 1.3 2.5 2.5 W200% 200% 1.7 1.8 2.6 2.5 2.7 C100%+M100%+Y100%+W200% 500% 0.6 1.4 1.2 1.8 2.9 C100%+M100%+W200% 400% 0.7 1.0 1.0 1.6 2.8 C100%+Y100%+W200% 400% 1.2 1.2 1.4 2.3 3.5 M100%+Y100%+W200% 400% 1.2 1.4 1.6 2.5 3.2

[Table 12] Reference Example II-6 Reference Example II-7 Comparative Example II-4 Comparative Example II-5 Blending of Adhesive Composition Blending ratio [parts by mass] Aliphatic polyester polyol (A) 8 8 8 8 Polyisocyanate (B) 1 1.5 1 1 Epoxy compound (C) 2.0 1.5 0 0 [(B)/(A)]×100 12.5 18.8 12.5 12.5 [(C)/(A)]×100 25.0 18.8 0.0 0.0 Epoxy / Isocyanate 6.1 3.0 0 0 Ink coverage total Bonding strength [N/15mm] Y100%+W200% 300% 2.5 3.1 1.1 3.2 M100%+W200% 300% 1.8 2.7 0.5 3.6 C100%+W200% 300% 2.5 2.4 0.8 3.8 K100%+W200% 300% 2.5 2.5 0.8 3.4 W200% 200% 2.5 2.9 1.2 3.3 C100%+M100%+Y100%+W200% 500% 3.0 2.9 0.6 2.5 C100%+M100%+W200% 400% 2.9 3.0 0.4 2.6 C100%+Y100%+W200% 400% 3.6 3.2 0.8 2.7 M100%+Y100%+W200% 400% 3.2 3.4 0.7 2.6

The compounding quantity (parts by mass) of the polyisocyanate with respect to 100 parts by mass of aliphatic polyester polyols is shown in the column of [(B)/(A)]*100 of Table 11 and Table 12. In the column of [(C)/(A)]×100 of Table 11 and Table 12, the compounding quantity (mass part) of the epoxy compound with respect to 100 mass parts of aliphatic polyester polyols is shown. In the column of "epoxy group/isocyanate group" of Table 11 and Table 12, the molar ratio of the epoxy group contained in an epoxy compound (C) with respect to the isocyanate group contained in a polyisocyanate (B) is shown.

As shown in Table 11 and Table 12, it was confirmed that the laminates of Reference Examples II-1 to II-7 in which an adhesive layer containing an epoxy compound was bonded to the printed surface were more effective than the adhesive layer containing no epoxy compound. The laminate of Comparative Example II-4 in which the layer was bonded to the printed surface had higher bond strength. In addition, in Comparative Example II-5, relatively high adhesive strength was obtained, but since an epoxy coating layer was also formed in addition to the adhesive layer, the number of steps increased. It takes 2 days to harden (cure) the epoxy coating layer, and productivity falls.

The laminate of Comparative Example II-4 peeled off near the interface between the electrostatic ink layer and the primer layer. In the laminate of Comparative Example II-5, the electrostatic printing ink layer was cohesively broken. On the other hand, the laminates of Reference Examples II-1 to II-7 peeled off at the interface between the electrostatic ink layer and the adhesive layer, and cohesive failure of the electrostatic ink layer was not observed. This implies that the cohesion of the electrostatic printing ink layer is improved. Moreover, the molar ratio of the isocyanate group contained in the polyisocyanate (B) in reference example II-1-II-7 with respect to the hydroxyl group of an aliphatic polyester polyol (A) exists in the range of 0.5-10.

Next, the adhesive strength, hot water adhesive strength, and sealing strength of the laminates of Reference Example II-5 and Comparative Example II-5 were measured. The measurement is based on the sum of ink coverage rate of 500% and 200%. The details of the measurement procedure are as follows.

[Measurement of Hot Water Bonding Strength] The laminates of Reference Example II-5 and Comparative Example II-5 were each cut to a width of 15 mm to obtain samples for measurement. After peeling off the interlayer at the end of the sample for measurement, the peeling strength was measured using a tensile tester while being immersed in hot water at 90°C. That is, the peeling angle: free, and the stretching speed: 300 mm/min. This peel strength is shown in Table 13 as hot water adhesion strength.

[Measurement of sealing strength (before heat treatment)] Using the pair of laminates of Reference Example II-5, non-stretched polypropylene films were stacked and heat-sealed to form a sealed portion. Thereby, the non-stretched polypropylene films were thermally welded to each other, and a measurement sample having a width of 15 mm was prepared. According to JIS K 7127:1999, the sealing strength in the sealing part of the prepared measurement sample was measured. The measurement system measures the peeling strength between heat seals using a tensile testing machine under the conditions of peeling angle: 90°, tensile speed: 300 mm/min, and normal temperature (20° C.). Let this peel strength be the sealing strength "before heat treatment". The measurement results are shown in Table 13. Also, using the laminate of Comparative Example II-5, the same measurement sample was prepared and the same measurement was performed. The measurement results are shown in Table 13.

[Determination of sealing strength (after boiling)] Heat the measurement sample prepared in the above "Measurement of sealing strength (before heat treatment)" in water at 100°C for 30 minutes. Thereafter, the sealing strength was measured by the same procedure as in the above-mentioned "measurement of sealing strength (without heat treatment)". The measurement results are shown in the column of "after boiling" in Table 13.

[Measurement of sealing strength after high temperature sterilization (120°C)] The high-temperature sterilization heat treatment (120°C x 30 minutes) was performed on the measurement sample prepared in the above-mentioned "measurement of sealing strength (before heat treatment)". Peel strength was measured in the same manner as "measurement of sealing strength (before heat treatment)" using a tensile tester. The measurement results are shown in the column of "120°C x 30 minutes" in Table 13.

[Measurement of sealing strength after high temperature sterilization (130°C)] The high-temperature sterilization heat treatment (130° C.×30 minutes) was performed on the measurement sample prepared in the above-mentioned “measurement of sealing strength (before heat treatment)”. Using a tensile tester, the peel strength was measured in the same manner as in "Measurement of sealing strength (without heat treatment)". The measurement results are shown in the column of "130°C x 30 minutes" in Table 13.

[Table 13] Reference Example II-5 Comparative Example II-5 Ink coverage 200% 500% 200% 500% Hot water adhesion strength [N/15mm] 90°C 1.0 1.1 <0.1 <0.1 Seal strength Before heat treatment 53.0 53.0 51.0 52.0 after boiling 44.0 51.0 22.0 35.0 120℃×30 minutes 55.0 54.0 52.0 53.0 130℃×30 minutes 52.0 54.0 53.0 54.0

As shown in Table 13, the hot water bonding strength was significantly higher in Reference Example II-5 than in Comparative Example II-5. Also, it was confirmed that the seal strength of Reference Example II-5 was superior to that of Comparative Example II-5. In particular, the sealing strength of Reference Example II-5 was sufficiently high even after boiling, but the sealing strength of Comparative Example II-5 was greatly reduced after boiling. In the laminate of Comparative Example II-5, when heated in the presence of moisture, it was confirmed that the bonding strength and sealing strength were greatly reduced.

(Reference Example II-8) [Production of adhesive composition and laminate] As a base material, a polyethylene terephthalate film (PET film, thickness: 12 μm) was prepared. One side of the PET film was coated with the same water-based primer resin as in Example II-1 to form a primer layer. The coating amount of water-based polyethyleneimine was also the same as in Example II-1.

Using the digital printing machine used in Example II-1, the primer layer was printed on the surface as specified. As the colors of the electrostatic printing ink composition, white (W), yellow (Y), magenta (M), and cyan (C) are used. As the ink coverage rate, W200% and C100%+M100%+Y100%+W200% were prepared. In Table 14, the former is referred to as "ink coverage (1)", and the latter is referred to as "ink coverage (2)". In this manner, two types of samples having different ink coverage ratios of electrostatic ink compositions were prepared.

Example II-1 and the adhesive composition were prepared, and the adhesive composition was applied to the printing surface in the same procedure as in Example II-1 to form an adhesive layer. The coating amount of the adhesive composition was set to 4.0 g/m ² .

The laminated film used in Example II-1 (a laminated film obtained by bonding a nylon film and a non-stretched polypropylene film with a commercially available adhesive) was carried out in the same manner as in Example II-1, and bonded to the base Adhesive layer of the material to obtain a laminate. Curing time (curing) is set at 40° C.×2 days.

The sealing strength (before heat treatment) and sealing strength (after boiling) of the laminate obtained in this way were measured. The measurement results are shown in Table 14. Moreover, adhesive strength (before heat treatment) and heat adhesive strength (120 degreeC) were measured by the following procedure.

Using the pair of laminates in Reference Example II-8, non-stretched polypropylene films were laminated and heat-sealed to produce a three-sided bag having a seal. Water is enclosed in this three-sided bag. Thereafter, a high-temperature sterilization heat treatment (120° C.×30 minutes) was performed using a high-temperature sterilization treatment device (manufactured by Hisaka Seisakusho). After high-temperature sterilization heat treatment, cut to 15mm wide, take a sample of the sealing part, and measure the interlayer strength between the electrostatic printing ink layer and the layer contacting the electrostatic printing ink layer. The measured peel strength is shown in the column of "thermal bonding strength (120 degreeC)" of Table 14. In addition, Table 14 also shows the adhesive strength before the high-temperature sterilization heat treatment.

(Reference example II-9 to II-12) When preparing an adhesive composition, except having changed the compounding quantity of polyisocyanate (B) as shown in Table 14, it carried out similarly to Reference Example II-8, and produced the laminated body. The produced laminate was evaluated in the same manner as in Reference Example II-8. The evaluation results are shown in Table 14.

(Comparative Example II-6) A laminate was produced in the same manner as in Comparative Example II-4, except that a manual laminator was used to laminate the printing surface on which the electrostatic ink composition was printed, without using a dry laminator. The color and ink coverage of the electrostatic printing ink composition are set as shown in Table 14. The produced laminate was evaluated in the same manner as in Reference Example II-8. The evaluation results are shown in Table 14.

[Table 14] Reference Example II-8 Reference Example II-9 Reference Example II-10 Reference Example II-11 Reference Example II-12 Comparative Example II-6 Blending of Adhesive Composition Blending ratio [parts by mass] Aliphatic polyester polyol (A) 8 8 8 8 8 8 Polyisocyanate (B) 1.0 1.2 1.5 2.0 3.0 1.0 Epoxy compound (C) 1.6 1.6 1.6 1.6 1.6 0.0 [(B)/(A)]×100 12.5 15.0 18.8 25.0 37.5 12.5 [(C)/(A)]×100 20.0 20.0 20.0 20.0 20.0 0.0 Epoxy / Isocyanate 4.8 4.0 3.2 2.4 1.6 0.0 Bonding strength (before heat treatment) Ink coverage (1) 0.4 0.3 0.4 0.5 0.5 0.3 [N/15mm] Ink coverage (2) 0.2 0.5 0.5 0.8 0.6 0.1 Thermal bonding strength (120°C) Ink coverage (1) 0.2 0.1 0.2 0.9 0.2 0.0 [N/15mm] Ink coverage (2) 0.2 0.1 0.3 0.5 0.3 0.0 Seal strength (before heat treatment) Ink coverage (1) 41.0 42.0 45.0 47.0 46.0 30.0 [N/15mm] Ink coverage (2) 43.0 42.0 46.0 49.0 48.0 31.0 Seal strength (after boiling) Ink coverage (1) 38.0 40.0 42.0 44.0 45.0 26.0 [N/15mm] Ink coverage (2) 40.0 39.0 45.0 47.0 42.0 24.0

As shown in Table 14, in each reference example, it was confirmed that high adhesive strength and sealing strength were obtained even under heating conditions. Also, it was confirmed that by adjusting the blending ratio of polyisocyanate (B) to aliphatic polyester polyol (A), thermal bonding strength (120°C) and sealing strength (before heat treatment and boiling Rear). On the other hand, in Comparative Example II-6 in which the epoxy compound (C) was not used, it was confirmed that the adhesive strength and the sealing strength were greatly reduced when exposed to high-temperature hot water treatment conditions. Moreover, the molar ratio of the isocyanate group contained in the polyisocyanate (B) in reference example II-8-II-12 with respect to the hydroxyl group contained in aliphatic polyester polyol (A) exists in the range of 0.5-10.

(Reference example II-13 to II-17) 3 of aliphatic polyester polyol (A1) (manufactured by Mitsui Chemicals, Inc., TAKELAC A525), polyisocyanate (B1) (manufactured by Mitsui Chemicals, Inc., TAKENATE A52), and an epoxy compound (C) are blended. , 3',4'-epoxycyclohexylmethyl 4-epoxycyclohexanecarboxylate to prepare an adhesive composition. The blending ratio is set as shown in Table 15. Except using such an adhesive composition, it carried out similarly to Reference Examples II-8-II-12 respectively, and produced the laminated body, and evaluated it. The evaluation results are shown in Table 15.

(Comparative Example II-7) Blend aliphatic polyester polyol (A1) (Mitsui Chemicals Co., Ltd., TAKELAC A525) and polyisocyanate (B1) (Mitsui Chemicals Co., Ltd., TAKENATE A52) as polyols to prepare an adhesive composition . The blending ratio is set as shown in Table 15. Except using such an adhesive composition, it carried out similarly to the comparative example II-4, produced the laminated body, and evaluated it. The evaluation results are shown in Table 15.

[Table 15] Reference Example II-13 Reference Example II-14 Reference Example II-15 Reference Example II-16 Reference Example II-17 Comparative Example II-7 Blending of Adhesive Composition Blending ratio [parts by mass] Aliphatic polyester polyol (A) 9.0 9.0 9.0 9.0 9.0 9.0 Polyisocyanate (B) 1.0 1.0 1.8 2.0 3.0 1.0 Epoxy compound (C) 1.7 1.7 1.7 1.7 1.7 0.0 [(B)/(A)]×100 11.1 11.1 20.0 22.2 33.3 11.1 [(C)/(A)]×100 18.9 18.9 18.9 18.9 18.9 0.0 Epoxy / Isocyanate 8.4 8.4 4.7 4.2 2.8 0.0 Bonding strength (before heat treatment) Ink coverage (1) 0.3 0.3 0.3 0.4 0.6 0.2 [N/15mm] Ink coverage (2) 0.2 0.3 0.5 0.4 0.5 0.1 Thermal bonding strength (120°C) Ink coverage (1) 0.2 0.1 0.3 0.2 0.3 0.0 [N/15mm] Ink coverage (2) 0.3 0.2 0.2 0.3 0.4 0.0 Seal strength (before heat treatment) Ink coverage (1) 40.0 43.0 42.0 43.0 46.0 30.0 [N/15mm] Ink coverage (2) 39.0 40.0 39.0 40.0 47.0 32.0 Seal strength (after boiling) Ink coverage (1) 35.0 41.0 41.0 38.0 42.0 26.0 [N/15mm] Ink coverage (2) 36.0 40.0 40.0 39.0 44.0 24.0

As shown in Table 15, even when the combination of the aliphatic polyester polyol and the polyisocyanate was changed, it was confirmed that high adhesive strength and sealing strength were obtained in each reference example. Also, it was confirmed that by adjusting the blending ratio of the polyisocyanate (B1) to the aliphatic polyester polyol (A1), the thermal bonding strength (120° C.) and the sealing strength (without heat treatment and boiling) can be sufficiently improved. Rear). On the other hand, in Comparative Example II-7 in which the epoxy compound (C) was not used, it was confirmed that the adhesive strength and the sealing strength were greatly reduced when exposed to high-temperature hot water treatment conditions. Moreover, the molar ratio of the isocyanate group contained in polyisocyanate (B1) in reference example II-13-II-17 with respect to the hydroxyl group contained in aliphatic polyester polyol (A1) exists in the range of 0.5-10. [Possibility of industrial use]

According to the present disclosure, it is possible to provide a container having a printing surface applied with printing by a digital printing machine, and at the same time, the curved portion generated during the manufacturing process also suppresses the interface between the electrostatic printing ink layer and the primer layer, and the electrostatic printing ink layer Peeling at the interface with the adhesive layer.

According to the present disclosure, it is possible to provide a packaging bag having an electrostatic printing ink layer using a digital printing machine while having sufficient resistance to heat treatment.

10: Substrate 20: Sealant layer 30: Adhesive layer 40: primer layer 50,51: electrostatic printing ink layer 52: Printing department 60: bending part 70: Mouth plug 72: outflow port 74: Flange 100,110: container 101,103,111,114,121,122: sealing part 102,112,124,132: storage department 120,130: Packaging bags 140: means of unsealing 141: half tangent 144:Easy-opening processing department 200: carcass 300, 302, 304, 306, 310: Laminates 400: package body

Fig. 1 is a perspective view showing an example of a container. Fig. 2 is a schematic cross-sectional view showing an example of a container provided with a stopper. Fig. 3 is a perspective view showing another example of the container. Fig. 4 is an end view along line IV-IV of Fig. 3 . Fig. 5 is a cross-sectional view showing an example of a laminate. Fig. 6 is a cross-sectional view showing another example of the laminate. Fig. 7 is a plan view showing an example of a packaging bag. Fig. 8 is a plan view showing another example of the packaging bag. FIG. 9 is a reference graph showing the results of evaluation of peeling inhibition performance in Examples. FIG. 10 is a reference graph showing the results of evaluation of peeling inhibition performance in Examples. FIG. 11 is a reference graph showing the results of evaluation of peeling inhibition performance in Examples. Fig. 12 is a diagram illustrating the shape of the sealing portion of the package of the example and the comparative example.

none.

Claims (15)

A container having a body portion having a curved portion, The carcass is composed of at least one laminated body, The laminate sequentially includes a base material, a primer layer, an adhesive layer, and a sealant layer, and at least a part of the main surface of the primer layer on the sealant layer side has a printing portion composed of an electrostatic printing ink composition , And the adhesive layer includes at least one of an adhesive composition containing polyol, polyisocyanate, and epoxy compound, and a hardened product thereof. The container according to claim 1, which has the printed portion at the curved portion. The container according to claim 1 or 2, wherein the polyol includes aliphatic polyester polyol, and the epoxy compound includes epoxy groups at both ends. The container according to any one of claims 1 to 3, wherein the epoxy compound comprises a bifunctional alicyclic epoxy compound. The container according to any one of claims 1 to 4, wherein the polyisocyanate comprises xylylene diisocyanate derivatives. The container according to any one of claims 1 to 5, further comprising a mouth plug connected to the body. The container according to claim 6, wherein the plug has a cylindrical outlet and a flange extending outward from the periphery of the lower end of the outlet. The container according to any one of claims 1 to 7, wherein the body part is constituted by one sheet of the laminated body. The container according to any one of claims 1 to 8, wherein the body portion is composed of two laminates serving as side sheets and one laminate serving as a bottom sheet. A packaging bag for heating, which is a packaging bag for heat treatment composed of a laminate sequentially comprising a base material, a primer layer, an electrostatic printing ink layer, an adhesive layer, and a sealant layer, the adhesive layer containing At least one of the adhesive composition of polyol, polyisocyanate and epoxy compound and its cured product. The heating packaging bag according to claim 10, wherein the primer layer contains polyethyleneimine resin. The heating packaging bag according to claim 10 or 11, which includes a sealing portion for bonding the sealant layers of the two laminates to each other on the outer peripheral portion, The sealing part is that the ink coverage rate of the electrostatic ink layer is 300% or less. The packaging bag according to any one of claims 10 to 12, wherein the polyol includes aliphatic polyester polyol, and the epoxy compound includes those having epoxy groups at both ends. The heating packaging bag according to any one of claims 10 to 13, wherein the epoxy compound comprises a bifunctional alicyclic epoxy compound. The heating packaging bag according to any one of claims 10 to 14, wherein the polyisocyanate comprises a xylylene diisocyanate derivative.

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