CN116710277A - Container and heating packaging bag - Google Patents
Container and heating packaging bag Download PDFInfo
- Publication number
- CN116710277A CN116710277A CN202180090138.3A CN202180090138A CN116710277A CN 116710277 A CN116710277 A CN 116710277A CN 202180090138 A CN202180090138 A CN 202180090138A CN 116710277 A CN116710277 A CN 116710277A
- Authority
- CN
- China
- Prior art keywords
- layer
- laminate
- electrostatic ink
- adhesive
- container
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000010438 heat treatment Methods 0.000 title claims description 124
- 238000004806 packaging method and process Methods 0.000 title claims description 37
- 239000010410 layer Substances 0.000 claims abstract description 311
- 239000000203 mixture Substances 0.000 claims abstract description 176
- 239000000853 adhesive Substances 0.000 claims abstract description 140
- 230000001070 adhesive effect Effects 0.000 claims abstract description 139
- 238000007789 sealing Methods 0.000 claims abstract description 124
- 239000012790 adhesive layer Substances 0.000 claims abstract description 109
- 150000001875 compounds Chemical class 0.000 claims abstract description 100
- 239000004593 Epoxy Substances 0.000 claims abstract description 95
- 239000000463 material Substances 0.000 claims abstract description 34
- 238000007639 printing Methods 0.000 claims description 73
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- 238000005259 measurement Methods 0.000 description 82
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- 238000007740 vapor deposition Methods 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
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- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 2
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- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
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- 125000003118 aryl group Chemical group 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
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- 230000015556 catabolic process Effects 0.000 description 2
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- 125000005442 diisocyanate group Chemical group 0.000 description 2
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- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
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- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 2
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- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
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Abstract
The present disclosure provides a container comprising a main body having a curved portion, wherein the main body is formed of at least one laminate, the laminate comprises a base material, a primer layer, an adhesive layer, and a sealing layer in this order, and at least a part of a main surface of the primer layer on the sealing layer side has a printed surface made of an electrostatic ink composition, and the adhesive layer comprises at least one of an epoxy compound-containing adhesive composition and a cured product thereof.
Description
Technical Field
The present disclosure relates to a container and a heating package. The present disclosure relates to a container, and more particularly, to a container having a curved portion and formed of at least one laminate.
Background
Containers (e.g., bags) for hermetically storing objects to be packaged such as foods are known. As the container, a package using a film or sheet is often used. Such containers are printed with various information such as decorations, products, brands, and manufacturers. As means for performing such printing, digital printing using an electrostatic ink composition is known. Digital printing uses a digital printer.
For example, patent document 1 proposes that a primer resin is applied to a first flexible substrate such as a PET film to obtain a coated surface, and electrostatic printing is performed on the coated surface using a digital printer (digital printer for packaging and Indigo20000 labels manufactured by HP company), and a crosslinking composition is applied. After a predetermined step is performed in this way, a technique of laminating a first flexible substrate coated with a predetermined component and a second flexible substrate to obtain a laminate (packaging material for containers) has been proposed.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open publication No. 2018-530540
Disclosure of Invention
Problems to be solved by the invention
Since digital printing using an electrostatic ink composition can cope with small lot sizes, a laminate subjected to digital printing is used as a material for various containers. However, the adhesion strength between the electrostatic ink layer formed of the printed portion and the primer layer or the adhesive layer provided by the digital printer is sometimes insufficient, and when an external force is applied, peeling may occur between the electrostatic ink layer and the primer layer or between the electrostatic ink layer and the adhesive layer. In particular, when the laminate is bent and deformed to a large extent, stress generated between the laminates is large, and peeling or the like may occur between the electrostatic ink layer and the primer layer or the adhesive layer. In such a case, for example, there is a possibility that the function as a container is impaired, a misalignment of the printing surface occurs, and it is difficult to recognize the printing information or the like recorded on the printing surface. Although countermeasures are also considered to avoid providing a printing surface on the curved portion, printing on the curved portion is also required to cope with various demands. Therefore, even in the case of having a curved portion, it is useful if the container is a container which does not impair the function as a container and does not impair printed information.
In addition, the adhesion strength between the electrostatic ink layer provided by the digital printer and the adjacent layer may be insufficient. Therefore, when the packaging material produced by the above means is used for a packaging bag on the premise of heat treatment such as boiling and steaming, for example, there is a possibility that the packaging bag will break when heated.
An object of the present disclosure is to provide a container having a printing surface on which printing is performed by a digital printer, and capable of suppressing peeling at an interface between an electrostatic ink layer and a primer layer and an interface between an electrostatic ink layer and an adhesive layer even at a bent portion generated during manufacturing.
Further, an object of the present disclosure is to provide a heating package bag having an electrostatic ink layer obtained by a digital printer and having sufficient resistance to heat treatment.
Means for solving the problems
One embodiment of the present disclosure provides a container including a main body portion having a curved portion, the main body portion being formed of at least one laminate including a base material, a primer layer, an adhesive layer, and a sealing layer in this order, and a printed portion made of an electrostatic ink composition being provided on at least a part of a main surface of the primer layer on the sealing layer side, the adhesive layer including at least one of an epoxy compound-containing adhesive composition and a cured product thereof.
Since the adhesive layer of the container is composed of at least one of the specific adhesive composition and the cured product thereof, a sufficient adhesion state can be maintained even in the bent portion, and peeling at the interface between the electrostatic ink layer and the primer layer and at the interface between the electrostatic ink layer and the adhesive layer is suppressed. Further, since the adhesion state between the layers is maintained even in the bent portion, occurrence of misalignment of the printed portion or the like can be suppressed, and the printed information in the main body portion including the bent portion can be maintained in the initial state where printing is performed. In the use of the container, for example, even when a new bending portion is generated due to bending or the like of the container, the adhesion state between the layers can be maintained, and thus the function (for example, barrier property or the like) as the container can be maintained during the use. Also, bag breakage of the container itself, degradation of printed information, and the like can be suppressed during use.
The curved portion may have the printing portion. Since the main body of the container according to the present disclosure is constituted by the above-described specific laminate, even when the printed portion is located at the curved portion, variations in the printed information can be suppressed.
The epoxy compound may contain a 2-functional alicyclic epoxy compound. Since the epoxy compound is 2-functional, the crosslinking point with the electrostatic ink composition increases, thereby making the main surface (printing surface) of the primer layer more firmly bonded to the adhesive layer.
The adhesive composition may further include a polyol, the polyol may include an aliphatic polyester polyol, and the epoxy compound may include a substance having epoxy groups at both ends. Such an adhesive layer can exhibit high lamination strength even in a high-temperature environment (in particular).
The adhesive composition may further comprise a polyisocyanate, and the polyisocyanate may comprise a xylene diisocyanate derivative. Such polyisocyanates have excellent reactivity with polyols. This improves the curability of the adhesive composition, and can further suppress peeling at the interface between the printed portion (electrostatic ink layer) and the primer layer and at the interface between the printed portion (electrostatic ink layer) and the adhesive layer.
The plug may be further provided to be connected to the main body.
The plug may have a cylindrical outlet, and a flange extending outward from a periphery of a lower end of the outlet.
The main body may be formed of one sheet of the laminate.
The main body may be composed of two laminated bodies serving as side sheets and one laminated body serving as a bottom sheet.
In order to achieve the above object, a heating packaging bag according to one embodiment of the present disclosure is a heating packaging bag comprising a laminate including a base material, a primer layer, an electrostatic ink layer, an adhesive layer, and a sealing layer in this order, wherein the adhesive layer includes at least one of an adhesive composition containing an epoxy compound and a cured product thereof.
The heat resistance and strength of a printed portion formed by printing an electrostatic ink composition with a digital printer tend to deteriorate as compared with the case of using other inks. Therefore, when a laminate having a printed portion (electrostatic ink layer) derived from a conventional electrostatic ink composition is used in a packaging bag for heat treatment, the adhesion in the vicinity of the printed surface is deteriorated, and therefore breakage or the like of the packaging bag may occur. In contrast, according to the above configuration, by curing the adhesive composition containing the epoxy compound, deformation of the laminate due to heating or the like is suppressed, and therefore, the heating bag having sufficient resistance to the heat treatment can be obtained.
The primer layer may include a polyethyleneimine resin. Since the primer layer containing a polyethyleneimine resin is provided, the water resistance is also improved, and particularly, sufficient resistance can be obtained even for heat treatment under an environment where a large amount of moisture exists, such as boiling heat treatment or retort heat treatment.
The outer peripheral portion may include a sealing portion for adhering the sealing layers of the two laminated bodies to each other, and the electrostatic ink layer of the sealing portion may have an ink coating rate of 300% or less. The sealing portion is a region to be bonded by heat such as heat sealing, and therefore the possibility of breakage is higher than other regions. In contrast, by setting the ink coverage ratio of the electrostatic ink layer within the above range, more sufficient resistance of the sealing portion to the heat treatment can be ensured, and a heating package bag having more strong resistance to the heat treatment can be obtained.
The epoxy compound may contain a 2-functional alicyclic epoxy compound. Since such an epoxy compound is 2-functional, crosslinking points with the electrostatic ink composition are increased, thereby making the adhesive layer more firmly bonded to the printed surface of the primer layer.
The adhesive composition may further comprise a polyol, wherein the polyol comprises an aliphatic polyester polyol, and the epoxy compound comprises a substance having epoxy groups at both ends. Such an adhesive layer has high adhesive strength even in a high-temperature environment (in particular). Therefore, even when the heating package is subjected to the heat treatment, breakage of the electrostatic ink composition or breakage of the package can be sufficiently suppressed.
The adhesive composition may further comprise a polyisocyanate, and the polyisocyanate may comprise a xylylene diisocyanate derivative. Such polyisocyanates have excellent reactivity with polyols. This improves the curability of the adhesive composition, and therefore can suppress deformation of the heating bag.
Effects of the invention
According to the present disclosure, it is possible to provide a container having a printing surface on which printing is performed by a digital printer, and capable of suppressing peeling at the interface of an electrostatic ink layer and a primer layer and at the interface of the electrostatic ink layer and an adhesive layer even at a bent portion generated in a manufacturing process.
According to the present disclosure, a heating package having an electrostatic ink layer using a digital printer and having sufficient resistance to heat treatment can be provided.
Drawings
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 having a plug.
Fig. 3 is a perspective view showing other examples of the container.
Fig. 4 is an end view along the IV-IV line 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 the package bag.
Fig. 8 is a plan view showing another example of the package bag.
Fig. 9 is a reference diagram showing the peeling inhibition performance evaluation results of the examples.
Fig. 10 is a reference diagram showing the peeling inhibition performance evaluation results of the examples.
Fig. 11 is a reference diagram showing the peeling inhibition performance evaluation results of the examples.
Fig. 12 is a diagram illustrating the shape of the seal portion of the package according to the embodiment and the comparative example.
Detailed Description
Embodiments of the present disclosure will be described below with reference to the drawings, as appropriate. However, the following embodiments are examples for illustrating the present disclosure, and are not intended to limit the present disclosure to the following. In the description, the same elements or elements having the same functions are denoted by the same reference numerals, and overlapping description is omitted as occasion demands. If not specifically described, the positional relationship between the upper, lower, left, right, etc. is based on the positional relationship shown in the drawings. Further, the dimensional ratios of the drawings are not limited to the ratios shown.
If not specifically stated, the materials exemplified in the present specification may be used singly or in combination of 1 or 2 or more. In the case where a plurality of substances corresponding to the respective components in the composition are present, unless otherwise specified, the content of the respective components in the composition means the total amount of the plurality of substances present in the composition.
[ Container ]
One embodiment of the container is a container provided with a main body portion having a curved portion, wherein the main body portion is formed of at least one laminate, the laminate includes a base material, a primer layer, an adhesive layer, and a sealing layer in this order, and a printing portion made of an electrostatic ink composition is provided on at least a part of a main surface of the primer layer on the sealing layer side. The container may be, for example, a packaging bag, a tube container, a stand-up pouch (standing pouch), or the like. The package is not limited to use at normal temperature, and may be one that is exposed to temperature changes such as heating and freezing. The container may for example be a container which is envisaged to be further creased in use. In a tube container or the like, when the body is pressed to deform the body so as to take out the packaged article from the container, a new crease can be formed in the body. In the case of the container of the present disclosure, the adhesion state between the layers can be maintained even in this case, and thus the function (for example, barrier property and the like) as a container can be maintained during use.
Fig. 1 shows an example of a container. The container 100 is formed of a sheet of the laminate 300. The container 100 is a container obtained by: first, the sealing layers on opposite sides of the generally rectangular laminate 300 are adhered to each other at a predetermined width to form a sealing portion 101, to thereby form a cylindrical body, and then, the sealing layers are adhered to each other at a predetermined width to form a sealing portion 103 at one opening of the cylindrical body. The main body 200 of the container 100 has a curved portion 60 and sealing portions 101, 103. The bent portion 60 is formed by bending the sealing portion 101 along the side surface of the main body 200 in order to improve operability and the like when used as a container.
The container 100 shown in fig. 1 includes a housing portion 102 formed of seal portions 101 and 103 and a non-seal portion (sheet portion) and housing a packaged object (for example, a beverage, a food, or the like). In this specification, an object that accommodates a packaged object and is sealed is particularly referred to as a package. The sealing portion 103 at the lower end may be sealed after the container 102 is filled with the packaged material. The sealing portions 101 and 103 are formed by heat-sealing the sealing layers of the laminate 300.
The container 100 may further include a plug connected to the main body 200. Fig. 2 is a schematic cross-sectional view showing an example of a container with a plug. Fig. 2 shows an example of a container in which a plug 70 is disposed at an unsealed upper end portion of the container 100, and a seal layer is heat-sealed to the plug 70 to connect the main body 200 of the container 100 to the plug. In this case, the container 100 includes the body 200 and the plug 70, and the packaged material can be removed from the plug by pressing the body 200. In this specification, such a container is also referred to as a tube container.
The plug 70 shown in fig. 2 is shown as an example composed of a cylindrical outlet 72 and a flange 74 extending outward from the periphery of the lower end of the outlet 72. The plug may have a cylindrical outlet and a flange extending outward from the periphery of the lower end of the outlet, and may be a spout (spout) or the like. The position where the plug is provided is not particularly limited. In the case of the plug being a mouthpiece, this may be a so-called central mouthpiece or a horn mouthpiece.
Fig. 3 and 4 show other examples of containers. The main body 200 of the container 110 is composed of a two-piece laminate 300 serving as a side sheet and a one-piece laminate 306 serving as a bottom sheet. The container 110 is configured by adhering sealing layers of a two-sheet laminate 300 serving as a side sheet and a one-sheet laminate 306 serving as a bottom sheet to each other. The container 110 has: a sealing portion 122 formed by adhering two laminated bodies 300, which are side sheets, to each other; the sealing portion 121 formed by bonding the laminate 306 serving as the bottom sheet and the two laminates 300 serving as the side sheets is formed into a bag shape. With such a configuration, the volume of the housing 102 can be enlarged. Laminate 306, which is a bottom sheet, has curved portion 60 that is produced when container 110 is manufactured. The open non-sealing portion may be sealed at the upper end portion of the container 110 after the packaged material is filled in the accommodating portion 112. The sealing portions 122 and 121 are formed by heat-sealing the sealing layers included in the laminate 300.
The three-sheet laminate constituting the container 110 does not have to have the same layer structure, and may have different layer structures, for example.
The containers 100 and 110 can accommodate the packaged material in a non-sealing portion (sheet portion) surrounded by the sealing portions 101, 121, and 122, and in this specification, the container that is further sealed is referred to as a package. The container may further include an unsealing mechanism for facilitating unsealing. The unsealing mechanism comprises: a pair of easy-to-open processed portions formed by V-shaped cuts formed in the non-sealing portion of the side end portion or the sealing portion 122 of the side end portion, and a half-cut line as a tearing rail between the pair of easy-to-open processed portions. The half-cut line may be formed using a laser. The easy-to-open processing portion is not limited to the V-shaped slit, and may be a U-shaped slit, an I-shaped slit, or the like, or may be a score line (score lines).
A laminate constituting the above-described containers 100 and 110 will be described. Fig. 5 is a cross-sectional view schematically showing an example of the laminate. Fig. 5 shows a cross section along the lamination direction (thickness direction) of the laminate. Laminate 302 has substrate 10, primer layer 40, adhesive layer 30, and sealing layer 20 in this order. The substrate 10, the primer layer 40, the adhesive layer 30, and the sealing layer 20 may each have a film-like shape. The primer layer 40 may have a printed portion 52 made of an electrostatic ink composition on at least a part of the main surface (printed surface) on the sealing layer 20 side. An electrostatic ink layer 50 composed of 1 or 2 or more printing portions 52 is provided on the printing surface. In other words, the electrostatic ink layer 50 formed of the printed portion 52 may be provided on at least a portion of one main surface of the pair of main surfaces of the primer layer 40, which is close to the sealing 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 sealing layer 20 may be flexible substrates. Examples of the flexible substrate include: biaxially oriented polypropylene (BOPP), polyethylene terephthalate (PET), oriented Polyamide (OPA), unstretched polypropylene (CPP), linear Low Density Polyethylene (LLDPE), low Density Polyethylene (LDPE), and the like.
As the substrate 10, for example, a composite film obtained by adhering a metal foil to a flexible substrate, a vapor-deposited film obtained by vapor-depositing a metal or the like on a flexible substrate, or the like may be used. The metal may be, for example, a metal simple substance such as aluminum or a metal oxide such as aluminum oxide. From the viewpoint of improving the gas barrier properties, a vapor deposited film (transparent vapor deposited film) obtained by vapor deposition of aluminum, aluminum oxide, or the like on a PET film may be used as the base material 10. The thickness of the substrate 10 may be, for example, 7 to 150. Mu.m, 15 to 90. Mu.m, or 20 to 80. Mu.m.
Examples of the sealing layer 20 include a CPP film, an LLDPE film, and an OPP film. The thickness of the sealing layer 20 may be the same as or different from the thickness of the substrate 10, and may be, for example, 7 to 150 μm, 15 to 90 μm, or 20 to 80 μm.
Primer layer 40 may comprise a resin. Examples of the resin include: polyvinyl alcohol resins, cellulose resins, polyesters, polyamines, polyethyleneimine resins, polyamide resins, polyurethanes, polyacrylic acid polymer hydroxyl-containing resins, carboxyl-containing resins, amine-based polymers, and the like. By providing the primer layer 40 on the substrate to be printed, printing of the electrostatic ink composition using the digital printer can be performed smoothly. The resin constituting the primer layer 40 may be applied in an amount of, for example, 0.01 to 1.5g/m 2 Or 0.05 to 1.0g/m 2 。
Laminate 302 includes printed portion 52 on the main surface (printing surface) of primer layer 40 opposite substrate 10. An electrostatic ink layer 50 including 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, the plurality of printing portions 52 may have the same composition, or may have different colors by having different compositions from each other. The printed portion 52 may be provided so as to be spread on the primer layer 40, or may be provided so as to cover the entire one surface of the primer layer 40.
The printed portion 52 in the electrostatic ink layer 50 is constituted by circular dots of the electrostatic ink composition. In other words, even though the single color looks the same, there is a region of plain color between dots. In the case of printing a predetermined area to be printed with a single color, the electrostatic ink layer 50 is generally constituted by disposing circular dots so as to be separated from each other; when printing with 2 or more colors, circular dots of the electrostatic ink composition of the 2 nd color or later are arranged so as to overlap each other between the dots printed in the 1 st color or with the dots printed in the 1 st color. The shade of the color on the printing surface can be adjusted by changing the size of the dots. By configuring the dots of different colors, the tone of the printing surface can be adjusted.
The ink coverage rate of each printed 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 ratio of the printing portion 52 in the above range, the laminate is excellent in lamination strength, and printing using a plurality of inks is possible, so that a plurality of types of printing can be handled. The lower limit of the ink coverage rate of the printing unit 52 is not particularly limited, and may be 20% or more, 50% or more, 80% or more, or 100% or more, for example. The ink coverage rate of the printing portion 52 may be adjusted within the above range, and may be, for example, 20 to 500%, 50 to 400%, 100 to 400%, or 100 to 300%.
In the present specification, the ink coverage (ink coverage) represents the ratio of dot area per unit area, and is a value in which the ink coverage in a region that is not printed is set to 0% when a predetermined region to be printed is uniformly printed in a single color, as 100%. When printing with inks of a plurality of colors, the ink coverage rate can be calculated for each color of ink, and the ink coverage rates of the target printing portion and the electrostatic ink layer can be summed up. The ink coverage rate is set by a digital printer, and the ink coverage rate can be adjusted by specifying a desired value in the setting. As the digital printer, for example, "Indigo20000 label manufactured by HP company, a digital printer for packaging" (product name), and the like can be used. The ink coverage rate of the electrostatic ink layer in the laminate to be subjected to the inspection may be checked by observing the printed surface of the container or laminate with an optical microscope.
Since the printing portion 52 is formed of circular dots of the electrostatic ink composition, even when the ink coverage is 100%, the main surface of the primer layer 40 can be confirmed when the surface of the electrostatic ink layer 50 on the sealing layer 20 side is observed by an optical microscope or the like. That is, even if the ink coverage is 100%, the primer layer 40 and the adhesive layer 30 can be directly bonded. On the other hand, as the value of the ink coverage becomes larger, the proportion of primer layer 40 at the adhesion surface (interface) of printed portion 52 and adhesive layer 30 tends to be smaller. In the case of using a conventional adhesive, when the ink coverage increases, the adhesion at the interface between the electrostatic ink layer and the primer layer or at the interface between the electrostatic ink layer and the adhesive layer may be reduced, and the lamination strength as a laminate may not be exhibited to the desired extent. On the other hand, in the laminate according to the present disclosure, by using the adhesive composition described later, sufficient lamination strength can be exhibited even when the ink coverage becomes large. In the laminate according to the present disclosure, the use of the adhesive composition described later can prevent, in particular, expansion or the like of the laminate 300 during the heating process.
The ink application amount on the main surface (printing surface) of the primer layer 40 on the sealing layer 20 side may be, for example, 0.5g/m 2 Above, 1.0g/m 2 Above, 2.0g/m 2 Above or 3.0g/m 2 The above. By setting the ink application amount within the above range, a multicolor printed display composed of a plurality of colors can be obtained. The ink application amount on the main surface of the primer layer 40 on the sealing layer 20 side may be 8.0g/m, for example 2 Below or 6.0g/m 2 The following is given. By setting the ink application amount within the above range, the decrease in adhesion 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 can be sufficiently suppressed. The ink application amount in the present specification means the total amount (solid content) of the ink composition used for printing, and in the case of multicolor printing, the total value thereof.
Fig. 6 is a cross-sectional view showing another example of the laminate. In the laminate 304 of fig. 6, the whole of one surface of the primer layer 40 is covered with the electrostatic ink layer 51 (the printed portion 52 formed on the whole of the printed surface), which is different from the laminate 302 of fig. 5. That is, in the laminate 304, the coating ratio of the electrostatic ink layer 51 to the main surface of the primer layer 40 is 100 area%. By using the adhesive composition described later, even in a structure such as the laminate 304 in which it is difficult to sufficiently secure the direct adhesion area between the primer layer 40 and the adhesive layer 30, sufficient adhesion strength is provided, and interlayer peeling and the like of the laminate 304 are suppressed.
In the laminated bodies 302 and 304, the electrostatic ink composition constituting the electrostatic ink layers 50 and 51 is an ink composition used for liquid electrophotographic printing, that is, electrostatic printing, and is printed on a substrate such as paper or plastic, or a primer layer. The electrostatic ink composition may contain a colorant such as a pigment and a dye, and a resin. In addition, the electrostatic ink composition may further comprise a carrier fluid or carrier liquid. The electrostatic ink composition may also contain, for example, charge directors (charge directors), charge adjuvants (charge adjuvants), surfactants, viscosity modifiers, emulsifiers, and other additives.
Examples of the colorant include cyan pigment, magenta pigment, yellow pigment, and black pigment. From the viewpoint of ease of digital printing, a resin having a low melting point may be used as the resin. The lower melting point may be, for example, 100 ℃ or lower. Examples of the resin include: thermoplastic resins such as ethylene acrylic acid copolymer, ethylene methacrylic acid copolymer, propylene methacrylic acid copolymer, and ethylene vinyl acetate copolymer. The resin preferably comprises 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, vegetable oils, and the like. Examples of the hydrocarbon include aliphatic hydrocarbons, branched aliphatic hydrocarbons, and aromatic hydrocarbons. In the case of printing the electrostatic ink composition on a substrate, the carrier fluid and carrier liquid may be substantially absent. For example, the carrier fluid and carrier liquid may be removed by an electrophoretic process in printing or evaporation. By the above-described removal operation, substantially only the solid component is transferred onto the substrate or primer layer.
The charge director has the function of maintaining a sufficient electrostatic charge on the particles contained in the electrostatic ink composition. Examples of the charge director include: a metal salt of a fatty acid, a metal salt of sulfosuccinic acid, a metal salt of oxyphosphoric acid, a metal salt of alkylbenzenesulfonic acid, a metal salt of aromatic carboxylic acid, a metal salt of aromatic sulfonic acid, or a plasma compound; and zwitterionic and nonionic compounds such as polyoxyethylated alkylamines, lecithins, polyvinylpyrrolidone, and organic acid esters of polyhydric alcohols.
The charge adjuvant has an effect of increasing or stabilizing the charge of particles contained in the electrostatic ink composition. Examples of the charge adjuvant include: barium sulfonate, calcium sulfonate, cobalt naphthenate, calcium naphthenate, copper naphthenate, manganese naphthenate, nickel naphthenate, zinc naphthenate, iron naphthenate, barium stearate, cobalt stearate, pb stearate, zinc stearate, al stearate, cu stearate, iron stearate, metal carboxylates, and the like.
The electrostatic ink layers 50, 51 may include a crosslinked product obtained by crosslinking components contained in at least one of the adhesive layer 30 and the primer layer 40. By including the crosslinked product, the strength of the electrostatic ink layers 50 and 51 themselves, the adhesion strength between the printed surface of the primer layer 40 and the electrostatic ink layer 50, and the adhesion strength between the electrostatic ink layer 50 and the adhesive layer 30 can be further improved.
The printed portion 52 of the electrostatic ink composition and the adhesive layer 30 are adhered to each other. That is, the printed portion 52 forms an adhesion surface with the adhesive layer 30, and the electrostatic ink composition is in direct contact with the adhesive composition.
The adhesive composition contains an epoxy compound. The epoxy compound reacts with the components constituting the electrostatic ink composition, the adhesive layer, and the primer layer to be cured, whereby the adhesive layer and the printed surface of the primer layer can be firmly bonded. The epoxy compound itself may be cured to form a cured product. The adhesive composition may further contain at least one selected from the group consisting of a polyol and a polyisocyanate, may further contain a polyol, may further contain a polyisocyanate, and may further contain a polyol and a polyisocyanate. The adhesive composition may contain a polyol, a polyisocyanate, and an epoxy compound. These three components (polyol, polyisocyanate, and epoxy compound) can be at least partially reacted with each other to be cured into a cured product. That is, the adhesive composition may be composed of at least one of an adhesive composition including a polyol, a polyisocyanate, and an epoxy compound, and a cured product thereof, and the adhesive layer 30 may be composed of an adhesive composition, a cured product thereof, or a mixture thereof. The polyol and polyisocyanate react as a main agent and a curing agent, respectively, to produce polyurethane (polyurethane adhesive).
The epoxy compound may be a compound having 1 or 2 or more epoxy groups in 1 molecule. From the viewpoint of further improving the adhesive strength of the adhesive layer 30 under a high-temperature environment, epoxy groups may be present at both ends. Examples of the epoxy compound include a glycidyl ether type epoxy compound, a glycidyl amine type epoxy compound, a glycidyl ester type epoxy compound, and an alicyclic epoxy compound (cyclic aliphatic epoxy compound).
The epoxy compound in the adhesive composition may penetrate into layers adjacent to the adhesive layer (e.g., primer layer, electrostatic ink layer, sealing layer, etc.). By such penetration, adhesion between the layers after curing of the epoxy compound can be further improved. In this case, the primer layer, the electrostatic ink layer, and the sealing layer contain at least one of an epoxy compound and a cured product thereof (epoxy resin or the like). The molecular weight of the epoxy compound may be, for example, 500 or less, 450 or less, or 400 or less. By making the molecular weight of the epoxy compound within the above range, the epoxy compound can be made to penetrate more sufficiently into the electrostatic ink composition constituting the electrostatic ink layer. The lower limit of the molecular weight of the epoxy compound may be, for example, 98 or more.
Examples of the alicyclic epoxy compound include: epoxycyclohexylmethyl-epoxycyclohexane carboxylate, bis (epoxycyclohexyl) adipate, and the like.
Examples of the 1-functional alicyclic epoxy compound having 1 epoxy group in 1 molecule include 3, 4-epoxycyclohexylmethyl methacrylate and 1, 2-epoxy-4-vinylcyclohexane. Examples of the 2-functional epoxy compound having 2 epoxy groups in 1 molecule include 3',4' -epoxycyclohexylmethyl-3, 4 epoxycyclohexane carboxylate, bis (3, 4-epoxycyclohexylmethyl) adipate, and 4-vinylcyclohexene dioxide. Further, examples of the epoxy compound having 1 or more epoxy groups in 1 molecule include 1, 2-epoxy-4- (2-oxiranyl) cyclohexane adducts of 2, 2-bis (hydroxymethyl) -1-butanol represented by the following general formula (I).
[ chemical formula 1]
In the above general formula (I), n may be an integer of 1 to 4.
The epoxy compound preferably comprises a 2-functional alicyclic epoxy compound. Being 2-functional, the crosslinking points with the electrostatic ink composition and the primer resin are increased to promote the curing reaction of the adhesive, thereby facilitating curing. In addition, in the case where the adhesive composition further contains a polyisocyanate, the epoxy compound is alicyclic, and thus the reaction with the polyisocyanate can be suppressed by the steric hindrance effect. Therefore, the adhesive agent can be stably cured, and the adhesion of the interface between the printed portion 52 and the adhesive layer 30 is sufficiently excellent.
The polyol has 2 or more hydroxyl groups in one molecule, and has a number average molecular weight of 400 or more, for example. The number average molecular weight of the polyol 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, the polyol may contain a polyester polyol or an aliphatic polyester polyol from the viewpoint of sufficiently improving the adhesive strength of the adhesive layer 30 in a high-temperature environment.
The polyester polyol can be obtained, for example, by a condensation reaction or transesterification reaction of a polyhydric alcohol with a polybasic acid, an alkyl ester of a polybasic acid, an acid anhydride of a polybasic acid, or an acyl halide of a polybasic acid.
Examples of the polyol include low molecular weight diols, low molecular weight triols, and low molecular weight polyols having 4 or more hydroxyl groups.
Examples of the low molecular weight diol include: ethylene glycol, propylene glycol, trimethylene glycol, 1, 4-butanediol, 1, 3-butanediol, 1, 2-butanediol, 1, 5-pentanediol, 3-methyl-1, 5-pentanediol, 2-dimethyl-1, 3-propanediol, neopentyl glycol, 1, 6-hexanediol, 2-diethyl-1, 3-propanediol, 3-dimethylolheptane, and 2-ethyl-2-butyl-1, 3-propanediol, and the like.
Examples of the low molecular weight triol 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, 2-bis (hydroxymethyl) -3-butanol, and the like.
Examples of the low molecular weight polyol having 4 or more hydroxyl groups include: tetramethylolmethane, pentaerythritol, dipentaerythritol, D-sorbitol, xylitol, D-mannitol (D-mannite), and the like.
Examples of the alkyl ester of the polybasic acid include methyl ester of the polybasic acid and ethyl ester of the polybasic acid. The acid anhydride of the polybasic acid may be, for example, an acid anhydride derived from the polybasic acid. More specifically, examples of the acid anhydride of the polybasic acid include oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, 2-alkyl (having 12 to 18 carbon atoms) succinic anhydride, tetrahydrophthalic anhydride, and trimellitic anhydride.
Examples of the acid halide of the polybasic acid include acid halides derived from alkyl esters of the polybasic acid or acid anhydrides of the polybasic acid. More specifically, examples of the acyl halide of the polybasic acid include oxalic acid dichloride, adipic acid dichloride, and sebacic acid dichloride.
Examples of the polyether polyol include polyalkylene oxides. For example, the polyether polyol can be obtained by subjecting an alkylene oxide such as ethylene oxide and/or propylene oxide to an addition reaction using a low molecular weight polyol as an initiator. More specifically, the polyether polyol includes polyethylene glycol, polypropylene glycol, polyethylene glycol polypropylene glycol (random or block copolymer), and the like. Further, as the polyether polyol, polytetramethylene ether glycol obtained by ring-opening polymerization of tetrahydrofuran or the like can be mentioned.
The polyisocyanate has 2 or more isocyanate groups in one molecule. Examples of the polyisocyanate include polyisocyanate monomers, polyisocyanate derivatives, and isocyanate-terminated prepolymers. The adhesive composition may contain a plurality of polyisocyanates different from each other. The molar ratio (NCO/OH) of isocyanate groups contained in the polyisocyanate to hydroxyl groups of the polyol may be, for example, 0.5 to 10. Such an adhesive composition can form a cured product having high adhesive strength and excellent flexibility.
Examples of the polyisocyanate monomer include aliphatic polyisocyanates, aromatic polyisocyanates, araliphatic polyisocyanates, and alicyclic polyisocyanates.
Examples of the aliphatic polyisocyanate include: trimethylene diisocyanate, 1, 2-propylene 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-trimethylhexamethylene diisocyanate, 2, 4-trimethylhexamethylene diisocyanate, methyl 2, 6-diisocyanate caproate, and the like.
Examples of the aromatic aliphatic polyisocyanate include xylene diisocyanate derivatives. Examples of the xylene diisocyanate derivative include: xylene diisocyanate (1, 3-xylene diisocyanate, or 1, 4-Xylene Diisocyanate) (XDI), tetramethylxylene diisocyanate (1, 3-tetramethylxylene diisocyanate, or 1, 4-tetramethylxylene diisocyanate) (TMXDI), ω' -diisocyanato-1, 4-diethylbenzene, and polyol modifications of xylene diisocyanate obtained by reacting xylene diisocyanate with trimethylolpropane, and the like.
The content of the xylylene diisocyanate derivative relative to the whole polyisocyanate may be, for example, 10 mass% or more, 20 mass% or more, 30 mass% or more, or 40 mass% or more from the viewpoint of improving the reactivity with the main agent (for example, polyol). The reactivity can be further improved by setting the content of the xylylene diisocyanate derivative to 30 mass% or more relative to the whole polyisocyanate.
Examples of the alicyclic polyisocyanate include: 1, 3-cyclopentane diisocyanate, 1, 3-cyclopentene diisocyanate, cyclohexane diisocyanate (1, 4-cyclohexane diisocyanate, 1, 3-cyclohexane diisocyanate), 3-isocyanatomethyl-3, 5-trimethylcyclohexyl isocyanate (isophorone diisocyanate) (IPDI), methylcyclohexane diisocyanate (methyl-2, 4-cyclohexane diisocyanate, methyl-2, 6-cyclohexane diisocyanate), norbornane diisocyanate (NBDI), and the like.
Examples of the polyisocyanate derivative include: the above-mentioned polymers of polyisocyanate monomers, allophanate modified products, polyol modified products produced by reacting monomers with alcohols, biuret modified products, urea modified products, oxadiazinetrione modified products, carbodiimide modified products, uretdione modified products, uretonimine modified products, and the like.
The isocyanate group-terminated prepolymer is a urethane prepolymer having at least 2 isocyanate groups at the molecular terminals. The isocyanate-terminated prepolymer can be obtained by subjecting at least one selected from the group consisting of a polyisocyanate monomer, a polyisocyanate derivative, and an isocyanate-terminated prepolymer to a urethanization reaction with a polyol. In this case, the molar ratio (NCO/OH) of isocyanate groups contained in the polyisocyanate to hydroxyl groups 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 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 0.5 to 10, 0.5 to 5, 0.8 to 4, and 0.6 to 3.
The content of the epoxy compound in the adhesive composition may be, for example, 3 to 25 parts by mass, 6 to 25 parts by mass, or 8 to 20 parts by mass relative to 100 parts by mass of the polyol from the viewpoint of having both high adhesive strength and excellent shear inhibiting ability. When the content of the epoxy compound is too large, the excellent shear suppression force tends to be impaired. That is, there is a case where the adhesive surface is displaced or the adhesive composition flows out when the adhesive layer 30 is formed. When the compounding amount of the epoxy compound is too small, the adhesive strength under the high-temperature hot water treatment condition tends to be lowered.
The content of the polyisocyanate in the adhesive composition may be, for example, 10 to 50 parts by mass, 15 to 35 parts by mass, or 20 to 30 parts by mass, based on 100 parts by mass of the polyol, from the viewpoint of sufficiently improving the seal strength and the adhesive strength under the high-temperature water treatment condition.
The molar ratio of the epoxy groups contained in the epoxy compound to the isocyanate groups contained in the polyisocyanate may be, for example, 0.5 to 10, 1.5 to 9, or 2.0 to 6.5. Thus, a sufficiently high adhesive strength can be maintained under high-temperature hot water treatment conditions.
In addition to the above components, the adhesive composition constituting the adhesive layer 30 may contain any component such as an additive. Examples of the additive include: antioxidants, ultraviolet absorbers, light stabilizers, fillers, silane coupling agents, epoxy resins, catalysts, coatability improvers, leveling agents, nucleating agents, lubricants, antiblocking agents, defoamers, plasticizers, surfactants, pigments, dyes, organic microparticles, inorganic microparticles, mold inhibitors, flame retardants, and the like. The adhesive composition may contain a solvent such as an organic solvent.
The adhesive composition adheres the printed portion 52 printed with the electrostatic ink composition to the sealing layer 20. Any layer may be provided between the adhesive layer 30 and the sealing layer 20. The laminated bodies 302 and 304 may further have a barrier layer or the like between the adhesive layer 30 and the sealing layer 20, for example. In this case, the adhesive composition adheres the printed portion 52 to an arbitrary layer (e.g., a barrier layer or the like). In the case where the adhesive composition contains a polyol and a polyisocyanate, a urethane bond is formed by the reaction of the polyol and the polyisocyanate, thereby more fully functioning as an adhesive. The urethane bond formation proceeds smoothly even in the coexistence of the epoxy compound, so that the printed portion 52 and the sealing layer 20 or any layer can be bonded together with a more sufficiently high bonding strength.
The adhesive composition may have a function of forming urethane bonds and a function of crosslinking the electrostatic ink composition forming the electrostatic ink layers 50, 51. This can further improve the adhesion strength between the printed surface and the sealing layer 20 or any layer.
When the coating ratio of the electrostatic ink layer 50 to the main surface (printed surface) of the primer layer 40 is high or when the ink coating ratio of the printed portion 52 (electrostatic ink layers 50, 51) is high, the adhesion between the electrostatic ink layer 50 and the adhesive layer 30 tends to be low in general, but in the case of the adhesive composition, sufficient adhesive strength can be exhibited. When the coating ratio of the electrostatic ink layer 50 to the main surface of the primer layer 40 or the ink coating ratio of the printed portion 52 (electrostatic ink layers 50 and 51) is increased, the epoxy compound contained in the adhesive composition is increased accordingly, whereby the epoxy compound can sufficiently penetrate into the electrostatic ink layers 50 and 51 composed of the electrostatic ink composition, and the decrease in the adhesive strength can be further suppressed. The permeated epoxy compound has an effect of improving the strength of the electrostatic ink composition (electrostatic ink layers 50, 51) by crosslinking the electrostatic ink composition. Therefore, even when the ink coverage rate of the printing portion 52 is high and a heating treatment such as a retort heat treatment is performed, the decrease in the adhesive strength can be sufficiently suppressed.
The adhesive composition can maintain high adhesive strength even after heat treatment, and is excellent in pot life. Therefore, the workability such as coating and lamination processing at the time of bonding the printed surface and the substrate is also excellent. The adhesive composition may contain an epoxy compound, a urethane-forming polyol and a polyisocyanate, and an epoxy compound, and at least a part of them may be cured to form an adhesive layer. This can reduce the number of layers constituting the laminate 300, compared with the case where the adhesive layer containing only polyurethane and the epoxy coating layer are provided separately. Therefore, for example, when a laminate is produced by roll-to-roll, meandering of the aged rolls, wrinkles due to sticking, and the like can be suppressed. In addition, the aging process after coating can be reduced, and the manufacturing efficiency can be improved.
In the laminated bodies 302 and 304 in which the electrostatic ink layers 50 and 51 on the printing surface are in direct contact with the adhesive layer 30, the epoxy compound (an epoxy compound and/or a polyisocyanate, etc., as the case may be) contained in the adhesive composition sufficiently penetrates the electrostatic ink layers 50 and 51. Thus, the electrostatic ink composition constituting the electrostatic ink layers 50 and 51 can be crosslinked, and the strength of the electrostatic ink composition (electrostatic ink layers 50 and 51) can be improved. In addition, the bonding strength between the layers can be improved. In addition, as shown in fig. 5, even when the plain portion (transparent portion) without the electrostatic ink layer 50 is included in the printed surface, the epoxy compound is included in the adhesive layer, and thus, the printed surface can be made non-tacky. On the other hand, when the epoxy coating layer is provided separately from the adhesive layer 30, if the printed surface includes a plain portion, the epoxy compound in the vicinity of the plain portion becomes excessive and tackiness tends to occur. In this way, the laminate 300 can adhere the printed surface including the plain portion where the printed portion 52 is not formed with high adhesive strength, and can be made non-tacky.
As described above, the laminated bodies 302 and 304 can sufficiently secure the adhesive strength between the electrostatic ink layers 50 and 51 and the substrate 10, the primer layer 40, and the adhesive layer 30, and thus can constitute a container in which peeling between the electrostatic ink layers 50 and 51 and the substrate 10, the primer layer 40, and the adhesive layer 30 is suppressed even in the bent portion 60. In such a container, since the adhesion state between the layers is maintained in the bending portion 60, occurrence of misalignment of the printing surface or the like is suppressed, and the printing information in the main body portion 200 including the bending portion 60 can be maintained in the initial state in which printing is performed. Even when a bending portion is newly generated due to bending or the like of the container during use of the container, for example, the adhesion state between the layers can be maintained, and thus the function (for example, barrier property or the like) as the container can be maintained during use. Also, during use, bag breakage of the container itself, degradation of printed information, and the like can be suppressed. In addition, in such a container, even when the curved portion has a printed surface, the occurrence of peeling between layers or the like can be suppressed, and therefore information described on the printed surface can be recognized, which is advantageous as a container for foods and beverages, sanitary products, and the like in which appearance is important. However, the use is not limited to these. For example, since the adhesive strength and the seal strength are excellent even after the high-temperature hot water treatment and the retort heat treatment, the material can be used as a material constituting a container for retort, a container for a microwave oven, and a container for boiling.
In the laminate according to the modification, the primer layer 40 may be provided on the surface of the substrate 10 facing the sealing layer 20. In addition, from the viewpoint of improving the gas barrier properties and the water vapor barrier properties of the laminates 302 and 304, at least one of a metal layer such as aluminum foil and a resin layer such as nylon film may be provided between the substrate 10 and the primer layer 40 and/or between the sealing layer 20 and the adhesive layer 30 between the substrate 10 and the sealing layer 20.
A specific example of the layer structure of the laminate is illustrated below. In each example, it means that the left end corresponds to the base material 10, the right end corresponds to the sealing layer 20, and the layers are laminated in this order from left to right. In addition, the 1 st adhesive layer is the adhesive layer 30, and the 2 nd and 3 rd adhesive layers may be conventional adhesive layers.
(1) Transparent vapor deposition PET film/primer layer/electrostatic ink layer/1 st adhesive layer/nylon layer/2 nd adhesive layer/CPP film (unstretched polypropylene film)
(2) PET film/primer layer/electrostatic ink layer/1 st adhesive layer/aluminum layer/2 nd adhesive layer/nylon layer/3 rd adhesive layer/CPP film (unstretched Polypropylene film)
(3) PET film/primer layer/electrostatic ink layer/1 st adhesive layer/nylon layer/2 nd adhesive layer/CPP film (unstretched Polypropylene film)
(4) PET film/primer layer/electrostatic ink layer/2 nd adhesive layer/aluminum layer/2 nd adhesive layer/polyethylene film
In the above specific examples, an arbitrary layer may be provided at an arbitrary position between the first adhesive layer and the sealing layer 20. (1) and (2) are suitable for use as a laminate for cooking, (3) for use as a laminate for a microwave oven, and (4) for use as a laminate for packaging bags containing a supplement or a mask. However, the application is not limited to the above.
The laminate described above can be produced, for example, by the following method. An embodiment of a method for producing a laminate will be described below. In one example of a method for manufacturing a laminate, a laminate 302 shown in fig. 5 is manufactured. First, the method includes: a step of forming a primer layer 40 on one surface of the film-like substrate 10; a step of forming an electrostatic ink layer 50 composed of a printing portion 52 by printing the electrostatic ink composition on the primer layer 40; and adhering the electrostatic ink layer 50 to one surface of the sealing layer 20 using the specific adhesive composition.
The primer layer 40 may be formed on one side of the substrate 10 by flexographic printing, gravure printing, or the like. The primer layer 40 may be formed by crosslinking a resin raw material with a crosslinking agent. Crosslinking may be performed by ultraviolet light, heating, irradiation of ionizing radiation such as electron beam, or non-ionizing radiation such as microwave radiation.
Printing of the electrostatic ink composition can be performed by electrostatic printing using a digital printer.
Bonding of the electrostatic ink layer 50 to one surface of the sealing layer 20 using the adhesive composition may be performed by lamination. Lamination may be performed using any device. The epoxy compound (epoxy compound and/or polyisocyanate, as the case may be) contained in the adhesive composition may penetrate into the electrostatic ink composition and primer layer 40 constituting the electrostatic ink layer 50, and undergo a crosslinking reaction with the components contained in the electrostatic ink composition and primer layer 40. This can improve the strength of the electrostatic ink layer 50 and can provide a laminate 300 in which the interfaces of the layers are sufficiently bonded. At least a portion of the adhesive composition may be cured to become a cured product upon lamination. In this way, the laminate 302 including the base material 10, the primer layer 40, the electrostatic ink layer 50, the adhesive layer 30, and the sealing layer 20 in this order can be manufactured. Laminate 304 and the laminate according to the modification may be produced in the same manner as laminate 302.
The laminated bodies 302 and 304 thus manufactured have the structure and properties described in these embodiments. The description of the modification of the laminates 302 and 304 is also applicable to the description of the embodiment of the manufacturing method.
[ heating packaging bag ]
Fig. 7 is a plan view showing an example of the package bag 120 (heating package bag) according to one embodiment. As shown in fig. 7, the package bag 120 is composed of a laminate 300 having a base material, a primer layer, an electrostatic ink layer, an adhesive layer, and a sealing layer in this order. The structure of the laminate 300 will be described later. The packaging bag 120 may be a bag sealed in a state where packaged objects such as beverage and food are accommodated therein. The package 120 may or may not have a curved portion.
The package 120 is a heating package. The heating package is a package which is supposed to be subjected to a heating process in a state where a packaged material is contained. The heat treatment includes "cooking heat treatment", "boiling heat treatment", and "microwave heat treatment", etc. The retort heat treatment is, for example, a treatment in which heating is performed under pressure with the contents filled therein and with heat of 100 ℃ or higher applied thereto, and for example, steam or the like can be used. The boiling heat treatment is a treatment of heating the package in heated water (hot water) and heating the package up to 100 ℃. The microwave heating treatment is a heating treatment using a so-called microwave oven, and is a treatment of vibrating and rotating water molecules by electromagnetic waves (microwaves) to generate heat from a substance containing moisture. These treatments are all treatments for sterilizing the packaging bag or the packaged article.
The package bag 120 is formed by adhering sealing layers of a pair of laminates 300 to each other. The packaging bag 120 includes: a sealing portion 101 formed by adhering (sealing) peripheral edges of a pair of film-shaped, substantially rectangular laminates 300, and a housing portion 124 formed between the pair of laminates 300 by the sealing portion 101. The sealing portion 101 is formed at a pair of side ends, a lower end, and an upper end of the rectangular package bag 120. Thus, the sealing portion 101 is formed around the entire periphery of each of the pair of laminated bodies 300 in which the sealing layers of the package bag 120 overlap with each other in a plan view. For example, a packaged object (e.g., a beverage or food) may be accommodated in the accommodation portion 124. In the following embodiments, an article to be packaged and sealed is sometimes referred to as a package 400. The sealing portion 101 at the lower end may be sealed after the container 124 is filled with the packaged material. The sealing portion 101 is formed by heat-sealing the sealing layers included in the laminate 300.
The pair of laminated bodies 300 constituting the package bag 120 need not have the same layer configuration, and for example, the pair of laminated bodies may have different layer configurations.
The package bag 120 may further include an opening mechanism 140 for facilitating opening. The unsealing mechanism 140 includes: a pair of easy-to-open processed portions 144 formed by V-shaped cuts formed in the seal portion 101 at the side end portions, and a half-cut line 141 as a tearing rail between the pair of easy-to-open processed portions 144. The half-cut line 141 may be formed using, for example, a laser. The easy-open processing portion 144 is not limited to the V-shaped slit, and may be a U-shaped slit, an I-shaped slit, or the like, or may be a score line (score lines).
The steps for producing the package bag 120 and the package 400 using the laminate 300 will be described below. A pair of laminated bodies 300 shaped into a predetermined shape are prepared. The sealing layers provided on one surface of each laminate 300 are opposed to each other, and the sealing layers are bonded to each other. At this time, the sealing portion 101 is formed with respect to the pair of side end portions and the lower end portion (or the upper end portion), whereby the sealing portion 101 in a state where three sides among four sides are closed is formed, and a non-sealing portion is formed inside thereof. As a result, the package bag 130 shown in fig. 8 in which only the upper end portion (or only the lower end portion) is not sealed is obtained.
Next, the inside of the accommodating portion 132 of the package bag 130 is filled with the packaged material from the upper end (or lower end) in the unsealed state. Then, the sealing layers of the laminated body 300 are bonded to each other at the upper end (or lower end) in the unsealed state, thereby forming the sealing portion 101 at the upper end (or lower end). As a result, the package 400 including the package bag 120 and the packaged object accommodated therein can be manufactured.
As described above, the above-described package bag 120 is a package bag that can be used when the package body 400 is subjected to heat treatment assuming a state in which the packaged material is contained. According to the above-described heat treatment, the package bag 120 itself is heated, and thus, resistance to heat is required. In addition, since water molecules are present around the periphery in a high-temperature environment in any heating treatment, water resistance at a high temperature is required. Further, in the package bag 120, since the heat treatment is performed in a state where the content is contained, it is considered that the sealing portion 101 is particularly susceptible to the heat treatment. In response to these demands, the packaging bag 120 is configured by combining specific materials to form the layers constituting the laminate 300, thereby improving the water resistance and heat resistance as a laminate. Further, as the package bag 120, by making a part of the constitution of the laminate 300 in the sealing portion 101 satisfy a specific condition, in particular, breakage of the package bag 120 in the sealing portion 101 at the time of heat treatment can be prevented.
Next, the laminate 300 constituting the package bag 120 may be the laminates 302 and 304 described as the constituent materials of the container, and the description thereof may be applied unless otherwise specified. For example, materials and the like constituting the respective layers may be those exemplified when the corresponding layers are described in the description of the container. Hereinafter, the laminate body 302 will be described by way of example using the laminate body 300.
Primer layer 40 may comprise a resin. In the case where the package 120 is used for heating, the resin preferably contains a polyethyleneimine resin. In addition to the polyethyleneimine resin, the primer layer 40 may further contain, for example, a polyvinyl alcohol resin, a cellulose-based resin, a polyester, a polyamine, a polyamide resin, a polyurethane, a hydroxyl-containing resin of a polyacrylic acid polymer, a carboxyl-containing resin, an amine-based polymer, or the like. By providing a substrate to be printed withBy placing the primer layer 40 containing a polyethyleneimine resin, the water resistance is improved, and a laminate 302 suitable for heat treatment can be produced. The content of the polyethyleneimine resin in the primer layer 40 may be 80 mass% or more, 90 mass% or more, or 97 mass% or more. The resin constituting the primer layer 40 may be applied in an amount of, for example, 0.01 to 1.5g/m 2 Or 0.05 to 1.0g/m 2 。
Laminate 302 includes printed portion 52 on one main surface (printed surface) of primer layer 40, which is adjacent to sealing layer 20. An electrostatic ink layer 50 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, the plurality of printing portions 52 may have the same composition, or may have different colors by having different compositions from each other. The electrostatic ink layer 50 may be constituted by printed portions 52 provided so as to be spread on the primer layer 40, or may be constituted by printed portions 52 provided so as to cover the entire one surface of the primer layer 40.
When the package bag 120 is used for heating, the ink coverage rate of each printed portion 52 constituting the electrostatic ink layer 50 may be 100 to 400%. By setting the ink coverage ratio of the printing unit 52 in the above range, the laminate has excellent lamination strength, and can be printed with a plurality of inks, and can also cope with a plurality of types of printing.
As described above, the laminate 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. Therefore, when the laminate 300 is used as a heating package for 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.
In the case where the package bag 120 is used for heating, a specific example of the layer structure of the laminate is illustrated below. In each example, it means that the left end corresponds to the base material 10, the right end corresponds to the sealing layer 20, and the layers are laminated in this order from left to right. In addition, the 1 st adhesive layer is the adhesive layer 30, and the 2 nd adhesive layer and the 3 rd adhesive layer may be conventional adhesive layers.
(5) Transparent vapor deposition PET film/primer layer/electrostatic ink layer/1 st adhesive layer/nylon layer/2 nd adhesive layer/CPP film (unstretched polypropylene film)
(6) PET film/primer layer/electrostatic ink layer/1 st adhesive layer/aluminum layer/2 nd adhesive layer/nylon layer/3 rd adhesive layer/CPP film (unstretched Polypropylene film)
(7) Nylon layer/primer layer/electrostatic ink layer/1 st adhesive layer/LLDPE (linear low density polyethylene) film
(8) PET film/primer layer/electrostatic ink layer/1 st adhesive layer/nylon layer/2 nd adhesive layer/CPP film
In the above specific examples, an arbitrary layer may be provided at an arbitrary position between the first adhesive layer and the sealing layer 20. The above (5) and (6) are assumed to be packaging bags mainly used for the boiling heat treatment, (7) are assumed to be packaging bags mainly used for the boiling heat treatment, and (8) are assumed to be packaging bags mainly used for the microwave heat treatment. However, the application is not limited to the above.
The laminate can be produced by the same production method as the laminate as the constituent material of the container.
[ Effect ]
As described in the above embodiment, the packaging bag 120 (heating packaging bag) according to the present embodiment is constituted by the laminate 300 in which the base material 10, the primer layer 40, the adhesive layer 30, and the sealing layer 20 are laminated in this order. In addition, the adhesive layer 30 contains at least one of an adhesive composition containing an epoxy compound and a cured product of the adhesive composition. In addition, the primer layer 40 may contain a polyethyleneimine resin from the viewpoint of improving water resistance.
The heat resistance and strength of the electrostatic ink composition using the digital printer tend to deteriorate as compared with other inks. Therefore, when the laminate having the electrostatic ink layer derived from the electrostatic ink composition is applied to a packaging bag for heat treatment, breakage of the packaging bag or the like may occur. In contrast, according to the above configuration, by curing the adhesive composition containing the epoxy compound, deformation of the laminate due to heating or the like can be suppressed, and therefore, a heating package bag having sufficient resistance to heat treatment can be obtained. In addition, when the primer layer containing a polyethyleneimine resin is provided, the water resistance is also improved, and particularly, more sufficient resistance can be obtained even for heat treatment under an environment where a large amount of moisture exists, such as boiling heat treatment or retort heat treatment.
The packaging bag 120 (heating packaging bag) includes a sealing portion 101 that bonds the sealing layers 20 of the 2-sheet laminate 300 to each other at the outer peripheral portion. In the sealing portion 101, the ink coating rate of the electrostatic ink layer 50 may be 300% or less. Since the sealing portion 101 is a region to be bonded by heat such as heat sealing, the possibility of breakage is higher than in other regions. In contrast, by setting the ink coverage ratio of the electrostatic ink layer within the above range, a more sufficient resistance to the heat treatment can be ensured even for the sealing portion, and a heating package having a stronger resistance to the heat treatment can be obtained.
The epoxy compound may be one in which the epoxy compound contains a 2-functional alicyclic epoxy compound. Such epoxy compounds, being 2-functional, increase the cross-linking points with the electrostatic ink composition and firmly adhere to the printing surface.
The adhesive composition may further contain a polyol, wherein the polyol contains an aliphatic polyester polyol, and the epoxy compound contains a substance having epoxy groups at both ends. Such an adhesive layer 30 has high adhesive strength even in a high-temperature environment (in particular). Therefore, when the laminate 300 is assembled to produce a package, breakage of the electrostatic ink composition or breakage of the package can be sufficiently suppressed.
The adhesive composition may further comprise a polyisocyanate, and the polyisocyanate may comprise a xylylene diisocyanate derivative. Such polyisocyanates have excellent reactivity with polyols. This improves the curability of the adhesive composition, and therefore can suppress deformation of the laminate 300 and the packaging bag.
The laminate 300 (302, 304) and the packaging bag thus produced have the constitution and properties as described in the embodiments. The description of the laminated body 300, the packaging bag, and the modified examples thereof also apply to the description of the embodiment of the manufacturing method described above.
Although the above description has been given of several embodiments, the description of the common configuration can be applied to each other. In addition, the present disclosure is not limited by any of the above embodiments.
Examples
The present disclosure will be described in more detail with reference to examples, comparative examples, and reference examples, but the present disclosure is not limited to the following examples.
Example I-1
[ production of laminate ]
As a base material, an alumina vapor deposited PET film (trade name: GLARH12, thickness: 12 μm, manufactured by letter press Co., ltd.) was prepared. A water-based primer resin (a resin containing polyethyleneimine, manufactured by Michelman corporation, trade name: DP 050) was applied to the alumina plating surface, thereby forming a primer layer. So that the coating amount of the aqueous polyethyleneimine is 0.10 to 0.18g/m 2 Is coated in the manner of (3).
A digital printer (digital printer for packaging and Indigo20000 labels manufactured by HP corporation) was used to perform predetermined printing on the surface of the primer layer. As the electrostatic ink composition, an electrostatic ink composition (HP Indigo ElectroInk) containing a thermoplastic resin containing a copolymer of ethylene acrylic acid and ethylene methacrylic acid is used. As the colors of the electrostatic ink compositions, yellow (Y), magenta (M), and cyan (C) were used as shown in table 1. A plurality of samples having different colors and ink coverage rates of the electrostatic ink composition were prepared. The ink coverage is shown in table 1. The ink coverage rate was adjusted by the setting of the digital printer. The total ink coating ratio was 200%.
An adhesive composition having a solid content of 36.5 mass% was prepared by blending an aliphatic polyester polyol (trade name: TAKELAC A626, hereinafter also referred to as "(A)") as a main agent, a polyisocyanate (trade name: TAKENATE A, hereinafter also referred to as "(B)") as a curing agent, 3',4' -epoxycyclohexylmethyl-3, 4 epoxycyclohexane carboxylate (hereinafter also referred to as "C") as an epoxy compound, and ethyl acetate as a solvent. The structure of the epoxy compound is shown in the following formula (1). The ratio of the mass references of the components (mass references) is (a): (B): (C) =8:1:0.28.
The adhesive composition prepared as described above was applied on the printed surface on which the electrostatic ink composition was printed using a dry lamination apparatus, thereby forming an adhesive layer. The coating amount of the adhesive composition was set to 4.0g/m 2 。
[ chemical formula 2]
The nylon film and the unstretched polypropylene film were bonded together using a commercially available adhesive to prepare a laminate film. Using the dry lamination apparatus, the nylon film and the adhesive layer were bonded together so that the adhesive layer on the base material faced the nylon film of the laminated film, thereby obtaining a laminate. The curing time (aging) was set at 40℃for 2 days.
Comparative example I-1
A laminate was produced in the same manner as in example I-1, except that the epoxy compound ((C) component) was not blended in the preparation of the adhesive composition.
< evaluation of peeling inhibition Property of laminate >
The laminates prepared in example I-1 and comparative example I-1 were each evaluated for peeling inhibition performance upon heating. Specifically, the laminate was folded in half to form a bent portion, and a sample fixed with a clip was used as an evaluation sample, and the evaluation sample was heated at the heating temperature shown in table 1 for 45 minutes, and the state of the bent portion of the heated evaluation sample was observed by an optical microscope. The evaluation was performed according to the following criteria. The results are shown in Table 1.
A: no peeling was observed.
B: slight voids were confirmed between the stacks.
C: delamination was observed between the stacks.
TABLE 1
As shown in table 1, it can be confirmed that: in the laminate of example I-1, a sufficient peel inhibiting performance can be exhibited even in the bent portion by using a predetermined adhesive composition. In the laminate of comparative example I-1, it is presumed that the resin component of the electrostatic ink layer was melted and peeled off. In comparative example I-1, it was confirmed that: this tendency becomes remarkable as the heating temperature increases. On the other hand, in the laminate of example I-1, it was confirmed that: a sufficient peeling inhibition performance is maintained even when heated. The laminate of example I-1 is expected to have a sufficient peeling inhibiting effect even when the resin component is not heated (for example, at room temperature) during curing.
< evaluation of peeling inhibition Property of laminate 2>
The peeling inhibition performance was evaluated at the time of heating in the same manner as the above-described "1 for the peeling inhibition performance of a laminate" except that the heating temperature and the heating time were changed for each of the laminates prepared in example I-1 and comparative example I-1. The results are shown in Table 2.
TABLE 2
/>
As shown in table 2, the same tendency as the above-described "1 of evaluation of peeling inhibition performance of the laminate" was confirmed even when the heating temperature and the heating time were changed. As shown in the results of the laminate of example I-1, it was confirmed that: the container according to the present disclosure has sufficient resistance to a retort heat treatment at 120 ℃ or higher (for example, a heat and pressure sterilization treatment at 120 ℃ for 30 minutes).
< heat seal test of bent portion: evaluation of Peel inhibition Performance 3-
Next, the influence of sealing in a state where the bent portion was provided was evaluated. 3 sheets of the laminate prepared in example I-1 and comparative example I-1 were prepared, respectively, and a stand-up pouch (container having the same constitution as the container shown in FIG. 3 and FIG. 4) composed of 3 sheets of the same laminate was prepared. Specifically, a sheet material serving as a back sheet was folded in half between two laminated bodies serving as side sheets, and the laminated bodies were subjected to a pressure of 0.2MPa using a thermal tilt tester, and were subjected to a treatment at the temperature shown in table 3 for 1 second, thereby sealing the laminated bodies. When the laminate to be the bottom sheet portion of the stand-up pouch is folded into a mountain shape, the laminate is disposed so that the sealing layer side is positioned inside the container. As a thermal tilt tester, "HG-100" (product name) manufactured by Toyo Seiki Kagaku Co., ltd. After the preparation, the cross section of the bottom sheet portion including the stand-up pouch was observed by an optical microscope. The evaluation criteria were the same as those of the above-mentioned "1 of the evaluation of the peeling inhibition performance of the laminate". The results are shown in Table 3. For reference, FIG. 9 shows the appearance of the bent portion of the laminate of the base sheets of example I-1 and comparative example I-1 before sealing and after sealing at 210 ℃.
TABLE 3
As shown in table 3, it can be confirmed that: even in the heating treatment in a state where pressure is applied such that the sealing layers are adhered to each other, peeling is sufficiently suppressed in the laminate prepared in example I-1.
< heat seal test of bent portion: evaluation of Peel inhibition Performance 4-
The heat seal test with the "bent portion" described above was performed by changing the pressure condition applied at the time of sealing or the time at the time of sealing: evaluation of peel inhibition performance 3 "the same evaluation. The results are shown in tables 4 and 5 and fig. 10 and 11.
TABLE 4
TABLE 5
As shown in table 4, table 5, fig. 10, and fig. 11, it can be confirmed that: in the case of the laminate of example I-1, peeling can be sufficiently suppressed even under heat-sealing conditions under the general sealing conditions in the case of producing a container by sealing the laminate.
From the results of the above-described example I-1 and comparative example I-1, it was confirmed that: by using the adhesive composition containing an epoxy compound, the peeling-inhibiting effect between the layers constituting the laminate can be sufficiently exhibited. As a main factor of such a peeling inhibiting effect, it is considered that improvement in strength of the electrostatic ink composition and improvement in adhesion strength between layers are contributing. Hereinafter, for reference, examples of the adhesive composition after adjustment are shown.
Reference example I-1
[ production of laminate ]
Except that (a): (B): (C) A laminate was produced in the same manner as in example I-1, except that the mass-based blending ratio of each component in the adhesive composition was changed as shown in table 5. The laminate thus obtained was measured for lamination strength by the method described below. The results are shown in Table 6.
< evaluation of laminate Strength of laminate >
For the laminate prepared in reference example I-1, the lamination strength was measured according to JIS K6854-1:1999. Specifically, the prepared laminate was first cut into 15mm wide as a measurement sample. After delamination of the end of the measurement sample, the sample was subjected to angle: 90 °, stretching speed: the peel strength between layers of the laminate was measured using a tensile tester at 300 mm/min and room temperature. The peel strength was a lamination strength at normal temperature (20 ℃). The measurement results are shown in Table 6.
Reference example I-2
A2-liquid adhesive was prepared in which a 1 st liquid composed of an aliphatic polyester polyol (A) (trade name: TALELACA626, manufactured by Mitsui chemical Co., ltd.) and a 2 nd liquid composed of a polyisocyanate (B) (trade name: TAKENATEA50, manufactured by Mitsui chemical Co., ltd.) and an epoxy compound (C) were respectively contained in a container. The 1 st liquid and the 2 nd liquid were mixed to prepare the adhesive compositions shown in table 6. A laminate was produced in the same manner as in reference example I-1 except that the adhesive composition was used, and the adhesive strength was measured. The measurement results are shown in Table 6.
Comparative example I-2
A laminate was produced in the same manner as in reference example I-1 except that the epoxy compound (C) was not blended in the preparation of the adhesive composition, and the adhesive strength was measured. The measurement results are shown in Table 6.
Comparative example I-3
A laminate was produced in the same manner as in reference example I-1 except that the epoxy compound of formula (1) was applied to the surface on which the electrostatic ink composition was printed to provide an epoxy coating layer, and the adhesive composition of comparative example I-2 was applied to the epoxy coating layer. The coating amount of the epoxy coating was set to be 0.53 parts by mass in the formulation shown in table 5. The measurement results are shown in FIG. 6.
TABLE 6
The column [ (B)/(A) ] x 100 of Table 6 shows the blending amount (parts by mass) of the polyisocyanate with respect to 100 parts by mass of the aliphatic polyester polyol. The column [ (C)/(A) ] x 100 of Table 6 shows the amount of the epoxy compound blended (parts by mass) with respect to 100 parts by mass of the aliphatic polyester polyol. The column "epoxy group/isocyanate group" in Table 6 indicates the molar ratio of the epoxy group contained in the epoxy compound (C) to the isocyanate group contained in the polyisocyanate (B).
As shown in table 6, it can be confirmed that: the adhesive strength of the laminate of reference examples I-1 to I-2, in which the adhesive layer containing an epoxy compound was bonded to the printed surface, was higher than that of the laminate of comparative example I-2, in which the adhesive layer containing no epoxy compound was bonded to the printed surface. In comparative example I-3, although a high adhesive strength was obtained, the number of steps was increased because an epoxy coating layer was formed in addition to the adhesive layer. Curing (aging) of the epoxy coating takes 2 days and productivity is lowered.
In the laminate of comparative example I-2, peeling occurred near the interface of the electrostatic ink layer and the primer layer. In the laminate of comparative example I-3, the electrostatic ink layer was broken by coagulation. On the other hand, in the laminates of reference examples I-1 to I-2, sufficient lamination strength was exhibited, and further, peeling at the interface between the electrostatic ink layer and the adhesive layer and cohesive failure of the electrostatic ink layer were not found to occur under load. This indicates that the cohesive force of the electrostatic ink layer is improved. In reference examples I-1 to I-2, the molar ratio of the isocyanate groups contained in the polyisocyanate (B) to the hydroxyl groups of the aliphatic polyester polyol (a) was in the range of 0.5 to 10.
Next, the laminate of reference example I-1 and comparative example I-3 was measured for hot water lamination strength and seal strength in addition to lamination strength. In the measurement, a sample having a total of 500% of ink coverage and a sample having a total of 200% of ink coverage were used. The details of the measurement procedure are as follows.
[ measurement of Hot Water lamination Strength ]
The laminate of reference example I-1 and comparative example I-3 was cut into 15mm wide pieces to obtain measurement samples. After the interlayer peeling of the end portion of the measurement sample, the peel strength was measured by using a tensile tester in a state immersed in hot water at 90 ℃. Namely, the peeling angle: free, stretching speed: 300 mm/min. The peel strength is shown in table 7 as hot water lamination strength.
[ measurement of seal Strength (before Heat treatment) ]
Using the pair of laminated bodies of reference example I-1, heat sealing was performed in such a manner that the unstretched polypropylene films were overlapped with each other, thereby forming a sealed portion. Thus, the unstretched polypropylene films were heat-welded to each other to prepare a measurement sample having a width of 15 mm. The seal strength of the seal portion of the measurement sample thus prepared was measured in accordance with JIS K7127:1999. In this measurement, a tensile tester was used at a peeling angle: 90 °, stretching speed: the peel strength between heat seals was measured at room temperature (20 ℃ C.) at 300 mm/min. The peel strength was used as the seal strength before heat treatment. The measurement results are shown in Table 7. The same measurement sample was prepared using the laminate of comparative example I-3, and the same measurement was performed. The measurement results are shown in Table 7.
[ measurement of seal Strength (after boiling) ]
The measurement sample prepared in the above "measurement of seal strength (before heat treatment)" was heated in water at 100℃for 30 minutes. Then, the seal strength was measured by the same procedure as the above-mentioned "measurement of seal strength (before heat treatment)". The measurement results are shown in the column "after boiling" of Table 7.
[ measurement of seal Strength after steaming (120 ℃ C.) ]
The measurement sample prepared in the above "measurement of seal strength (before heat treatment)" was subjected to a retort heat treatment (120 ℃ C..times.30 minutes). The peel strength was measured by a tensile tester in the same manner as "measurement of seal strength (before heat treatment)". The measurement results are shown in column "120 ℃ C..times.30 minutes" of Table 7.
[ measurement of seal Strength after cooking (130 ℃ C.) ]
The measurement sample prepared in the above "measurement of seal strength (before heat treatment)" was subjected to a retort heat treatment (130 ℃ C..times.30 minutes). The peel strength was measured by a tensile tester in the same manner as "measurement of seal strength (no heat treatment)". The measurement results are shown in column "130 ℃ C..times.30 minutes" of Table 7.
TABLE 7
As shown in Table 7, the hot water lamination strength of reference example I-1 was significantly higher than that of comparative example I-3. In addition, it was confirmed that the seal strength of reference example I-1 was also superior to that of comparative example I-3. In particular, the seal strength of reference example I-1 was sufficiently high even after boiling, whereas the seal strength of comparative example I-3 was greatly lowered after boiling. It can be confirmed that: the laminate of comparative example I-3 was significantly reduced in both lamination strength and seal strength when heated in the presence of moisture.
Example II-1
[ production of laminate ]
As a substrate, a nylon film (thickness: 15 μm) was prepared. A primer layer was formed by applying a water-based primer resin (a resin containing polyethyleneimine, manufactured by Michelman corporation, trade name: DP 050) to one main surface of the nylon film. So that the coating amount of the aqueous polyethyleneimine is 0.10 to 0.18g/m 2 Is coated in the manner of (3).
A digital printer (digital printer for packaging and Indigo20000 labels manufactured by HP corporation) was used to perform predetermined printing on the surface of the primer layer. As the electrostatic ink composition, an electrostatic ink composition (HP Indigo ElectroInk) containing a thermoplastic resin containing a copolymer of ethylene acrylic acid and ethylene methacrylic acid is used. As the colors of the electrostatic ink compositions, as shown in table 8, white (W) and cyan (C) were used. A plurality of samples having different colors and ink coverage rates of the electrostatic ink composition were prepared. The ink coverage is shown in table 8. The ink coverage rate was adjusted by the setting of the digital printer. As shown in table 8, the total ink coverage was 100 to 300%.
An adhesive composition having a solid content of 36.5 mass% was prepared by blending an aliphatic polyester polyol (trade name: TAKELAC A626, hereinafter also referred to as "component (A)") as a main agent, a polyisocyanate (trade name: TAKENATE A, hereinafter also referred to as "component (B)") as a curing agent, 3',4' -epoxycyclohexylmethyl-3, 4 epoxycyclohexane carboxylate (hereinafter also referred to as "component (C)") as an epoxy compound, and ethyl acetate as a solvent. The structure of the epoxy compound is shown in the following formula (1). The ratio of the mass references of the components (mass references) is (a): (B): (C) =8:1:0.28.
The adhesive composition prepared as described above was applied on the printed surface on which the electrostatic ink composition was printed using a dry lamination apparatus, thereby forming an adhesive layer. The coating amount of the adhesive composition was set to 4.0g/m 2 。
[ chemical formula 3]
LLDPE films (FUTAMURA CHEMICAL CO., manufactured by LTD., trade name: XMTN, thickness: 60 μm) were prepared, and an adhesive layer on a substrate was bonded to the LLDPE films using the dry lamination apparatus, to obtain a laminate. The curing time (aging) was set at 40℃for 2 days.
Examples II-2 and II-3
A laminate was produced in the same manner as in example II-1, except that the color and ink coverage of the electrostatic ink composition were changed as shown in table 8.
(comparative examples II-1 to II-3)
Laminates were produced in the same manner as in examples II-1 to II-3, except that the epoxy compound ((C) component) was not blended in the preparation of the adhesive composition.
[ production of packaging body ]
For each of examples II-1 to II-3 and comparative examples II-1 to II-3, two rectangular laminates of 150 mm. Times.200 mm were prepared. At this time, the laminate of example II-1 and comparative example II-1 prepared a laminate in which the electrostatic ink composition was not applied to the outer peripheral portion having a width of 10mm, and the laminate of example II-2 to II-3 and comparative examples II-2 to II-3 prepared a laminate in which the electrostatic ink composition was also applied to the outer peripheral portion. The two laminated bodies are overlapped with the main surfaces of the LLDPE film side facing each other, and heat-sealed, so that a pair of end portions in the longitudinal direction and one end portion in the width direction are bonded to each other, whereby a seal portion is formed on three sides among four sides around the laminated body. In fig. 12, a main surface of the laminate 310 is shown. First, the seal portions 111 are formed on three sides of the laminate 310 by the first heat sealing, and a package bag in which three sides are closed is produced. The width T (see fig. 12) of the sealing portion 111 at this time is set to 10mm. The sealing portion 114 is formed by heat-sealing and bonding 2 sheets of laminated body to the side where the sealing portion 111 is not formed. The width T of the sealing portion 114 is also set to 10mm. That is, when the laminate of example II-1 and comparative example II-1 is used, a package bag is prepared in which the electrostatic ink composition is not printed in the laminate in the sealing portions 111 and 114.
Before the sealing portion 114 is completely sealed to bring the inside into a sealed state, 500ml of water is introduced as the content in the package bag. Packages according to examples II-1 to II-3 and comparative examples II-1 to II-3 were produced. As described above, 500ml of water was filled in the package.
< evaluation of lamination Strength (before boiling >
The package bodies according to examples II-1 to II-3 and comparative examples II-1 to II-3 were measured for lamination strength according to JIS K6854-1:1999. Specifically, first, instead of the prepared packages of examples II-1 to II-3 and comparative examples II-1 to II-3, the laminates of examples II-1 to II-3 and comparative examples II-1 to II-3 before filling with water were cut into 15mm widths as measurement samples. After the interlayer of the end of the measurement sample was peeled off, the sample was subjected to a tensile tester at an angle: 90 °, stretching speed: the peel strength between layers of the laminate was measured at room temperature at 300 mm/min. The peel strength was used as the lamination strength at room temperature (20 ℃). The measurement results are shown in Table 8.
< evaluation of lamination Strength (after boiling)
The packages of examples II-1 to II-3 and comparative examples II-1 to II-3 were heated in water at 90℃for 30 minutes (retort heat treatment). Then, a part of the package was cut out by the same procedure as the above-described < evaluation of lamination strength (before boiling) > to measure lamination strength. The measurement results are shown in Table 8.
TABLE 8
From the above results, it was confirmed that the lamination strength was decreased due to the presence of the electrostatic ink layer, compared with the case where the electrostatic ink layer was not present (example II-1, comparative example II-1), and that the lamination strength was decreased as the ink coverage rate was increased. In particular, when the ink coating ratio reached 300%, it was confirmed that in both cases before and after boiling, the lamination strength in the package (laminate) was 2 or less, and the use as a packaging bag for heat treatment was not possible in comparative example II-3. In all of examples II-1 to II-3 and comparative examples II-1 to II-3, the laminate strength after boiling was increased. It is presumed that this is caused by the reaction of isocyanate as a curing agent contained in the adhesive composition at the time of boiling.
< evaluation of seal Strength (before boiling >
For each of the packages of examples II-1 to II-3 and comparative examples II-1 to II-3, a measurement sample having a width of 15mm was produced by cutting the package so as to include a sealing portion before filling with water (before completely sealing the sealing portion 114 to seal the interior). The seal strength of the seal portion of the measurement sample thus prepared was measured in accordance with JIS K7127:1999. In the measurement, a tensile tester was used, and the tensile tester was used at a peeling angle: 90 °, stretching speed: the peel strength between heat seals was measured at room temperature (20 ℃ C.) at 300 mm/min. The peel strength was used as the seal strength before heat treatment. The measurement results are shown in Table 9.
< evaluation of seal 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℃for 30 minutes (boiling heat treatment). Then, the package was opened, and after removing the water filled in the package, the seal strength was measured by the same procedure as the above-mentioned "evaluation of seal strength (before boiling)". The measurement results are shown in Table 9.
In table 9, "membrane rupture" means ending the measurement in a state of membrane rupture. The "triangular peeling" refers to a state in which at least one of the pair of laminated bodies is peeled off between the layers. The "cut edge" refers to a state in which breakage occurs at the boundary portion between the heat-sealed portion and the inside of the bag.
TABLE 9
From the above results, it was confirmed that the seal strength was decreased due to the presence of the electrostatic ink layer, compared with the case where the electrostatic ink layer was not present (example II-1, comparative example II-1), and that the seal strength was decreased as the ink coverage rate was increased. As for comparative examples II-2 and II-3, it was confirmed that the seal strength was 40N/15mm or less in at least one of before and after boiling, and therefore, the use of the packaging bag as a heat treatment was not acceptable.
< test for boiling with gas >
For each of examples II-1 to II-3 and comparative examples II-1 to II-3, two rectangular laminates of 150 mm. Times.200 mm were prepared, and packages for the gas-containing boiling test were produced in the same manner as in the production of the above-mentioned packages.
It should be noted that the package is different from the package for the lamination strength and the seal strength in that 300ml of water is introduced as the content in the package bag and 100ml of air is refilled after the seal portion 114 is completely sealed to seal the inside. Thus, packages for the gas-containing boiling test of examples II-1 to II-3 and comparative examples II-1 to II-3 were produced. As described above, the inside of the package is filled with 300ml of water and 100ml of air.
The packages of examples II-1 to II-3 and comparative examples II-1 to II-3 were each prepared in 3 pieces, and each was heated in water at 100℃for 60 minutes. The surface of the heated package was visually observed, and the surface of the laminate was observed for the presence or absence of swelling of the printed surface formed by the electrostatic ink composition. The measurement results are shown in Table 10.
TABLE 10
From the results of the above examples and comparative examples, it was confirmed that the adhesive composition containing a polyol, a polyisocyanate and an epoxy compound was resistant to heat treatment. As a factor of improving the resistance to such heat treatment, it is considered that the improvement in strength of the electrostatic ink composition and the improvement in adhesion strength between the layers are contributing. To verify these enhancement effects, the following experiments were performed.
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. The same aqueous primer resin as in example II-1 was coated on one side of the PET film, thereby forming a primer layer. The coating amount of the aqueous polyethyleneimine was the same as that of example II-1.
A predetermined printing was performed on the surface of the primer layer using the digital printer used in example II-1. As the electrostatic ink composition, an electrostatic 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 ink compositions, as shown in table 11, white (W), yellow (Y), magenta (M), and cyan (C) were used. A plurality of samples having different colors and ink coverage rates of the electrostatic ink composition were prepared. The ink coverage ratios of the respective colors and the total thereof are shown in table 11. As shown in table 11, the total ink coverage was 200 to 500%.
The same adhesive composition as in example II-1 was prepared, and the adhesive composition was coated on the printing surface by the same procedure as in example II-1, thereby forming an adhesive layer. The coating amount of the adhesive composition was set to 4.0g/m 2 。
A laminate film comprising an aluminum foil (manufactured by Toyo aluminum Co., ltd., thickness: 7 μm), a nylon film, and an unstretched polypropylene film in this order was prepared. The same dry lamination apparatus as in example II-1 was used to attach the aluminum foil and the adhesive layer together so that the adhesive layer on the substrate faced the aluminum foil of the laminated film, thereby obtaining a laminate. The curing time (aging) was set at 40℃for 2 days.
[ measurement of adhesive Strength (Normal temperature) ]
The adhesive strength of the laminate thus produced was measured in accordance with JIS K6854-1:1999. Specifically, the produced laminate was cut into 15mm wide pieces to be used as a measurement sample. After the interlayer of the end of the measurement sample was peeled off, the sample was subjected to a tensile tester at an angle: 90 °, stretching speed: the peel strength between layers of the laminate was measured at room temperature at 300 mm/min. The peel strength was set to be the adhesive strength at room temperature (20 ℃). The measurement results are shown in Table 11.
Reference examples II-2 to II-6
A laminate was produced in the same manner as in reference example II-1 except that the adhesive composition was blended as shown in tables 11 and 12, and the adhesive strength was measured. The measurement results are shown in tables 11 and 12.
Reference example II-7
A2-liquid adhesive was prepared in which a 1 st liquid composed of an aliphatic polyester polyol (A) (trade name: TALELACA626, manufactured by Mitsui chemical Co., ltd.) and a 2 nd liquid composed of a polyisocyanate (B) (trade name: TAKENATEA50, manufactured by Mitsui chemical Co., ltd.) and an epoxy compound (C) were respectively contained in a container. The 1 st liquid and the 2 nd liquid were mixed to prepare the adhesive compositions shown in table 12. A laminate was produced in the same manner as in reference example II-1 except that the adhesive composition was used, and the adhesive strength was measured. The measurement results are shown in Table 12.
Comparative example II-4
A laminate was produced in the same manner as in reference example II-1 except that the epoxy compound (C) was not blended in the preparation of the adhesive composition, and the adhesive strength was measured. The measurement results are shown in Table 12.
(comparative II-5)
A laminate was produced in the same manner as in reference example II-1 except that the epoxy compound of formula (1) was applied to the printed surface on which the electrostatic ink composition was printed to provide an epoxy coating layer, and the adhesive composition of comparative example II-4 was applied to the epoxy coating layer. The coating amount of the epoxy coating was 0.53 parts by mass in the formulation shown in table 11. The measurement results are shown in FIG. 12.
TABLE 11
TABLE 12
The [ (B)/(a) ] x 100 column of tables 11 and 12 shows the blending amount (parts by mass) of the polyisocyanate with respect to 100 parts by mass of the aliphatic polyester polyol. The [ (C)/(A) ] x 100 column of tables 11 and 12 shows the blending amount (parts by mass) of the epoxy compound with respect to 100 parts by mass of the aliphatic polyester polyol. The column "epoxy group/isocyanate group" in tables 11 and 12 indicates the molar ratio of the epoxy group contained in the epoxy compound (C) to the isocyanate group contained in the polyisocyanate (B).
As shown in table 11 and table 12, it can be confirmed that: the adhesive strength of the laminates of reference examples II-1 to II-7, in which the adhesive layer containing an epoxy compound was bonded to the printed surface, was higher than that of the laminate of comparative example II-4, in which the adhesive layer containing no epoxy compound was bonded to the printed surface. In comparative example II-5, although a high adhesive strength was obtained, the number of steps was increased because an epoxy coating layer was formed in addition to the adhesive layer. Curing (aging) of the epoxy coating takes 2 days and productivity is lowered.
In the laminate of comparative example II-4, peeling occurred near the interface of the electrostatic ink layer and the primer layer. In the laminate of comparative example II-5, the electrostatic ink layer was broken by coagulation. On the other hand, in the laminates of reference examples II-1 to II-7, peeling at the interface between the electrostatic ink layer and the adhesive layer and coagulation failure of the electrostatic ink layer were not observed. This indicates that the cohesive force of the electrostatic ink layer is improved. In reference examples II-1 to II-7, the molar ratio of the isocyanate groups contained in the polyisocyanate (B) to the hydroxyl groups of the aliphatic polyester polyol (A) was in the range of 0.5 to 10.
Next, the adhesive strength, hot water adhesive strength and seal strength of the laminate of reference example II-5 and comparative example II-5 were measured. In the measurement, a sample having a total of 500% of ink coverage and a sample having a total of 200% of ink coverage were used. The details of the measurement procedure are as follows.
[ measurement of Hot Water adhesive Strength ]
The laminate of reference example II-5 and comparative example II-5 was cut into 15mm widths to obtain measurement samples. After the interlayer of the end portion of the measurement sample was peeled off, the peel strength was measured by using a tensile tester in a state immersed in hot water at 90 ℃. Namely, the peeling angle: free, stretching speed: 300 mm/min. The peel strength is shown in table 13 as hot water adhesion strength.
[ measurement of seal Strength (before Heat treatment) ]
A pair of laminates of reference example II-5 was used, and heat-sealing was performed in such a manner that the unstretched polypropylene films overlapped each other, thereby forming a sealed portion. Thus, the unstretched polypropylene films were heat-welded to each other to prepare a measurement sample having a width of 15 mm. The seal strength of the seal portion of the measurement sample thus prepared was measured in accordance with JIS K7127:1999. In this measurement, a tensile tester was used, and the tensile tester was used at a peeling angle: 90 °, stretching speed: the peel strength between heat seals was measured at room temperature (20 ℃ C.) at 300 mm/min. The peel strength was used as the seal strength before heat treatment. The measurement results are shown in Table 13. The same measurement samples were prepared using the laminate of comparative example II-5, and the same measurement was performed. The measurement results are shown in Table 13.
[ measurement of seal Strength (after boiling) ]
The measurement sample prepared in the above "measurement of seal strength (before heat treatment)" was heated in water at 100℃for 30 minutes. Then, the seal strength was measured by the same procedure as the above-mentioned "measurement of seal strength (before heat treatment)". The measurement results are shown in the column "after boiling" of Table 13.
[ measurement of seal Strength after steaming (120 ℃ C.) ]
The measurement sample prepared in the above "measurement of seal strength (before heat treatment)" was subjected to a retort heat treatment (120 ℃ C..times.30 minutes). The peel strength was measured by a tensile tester in the same manner as "measurement of seal strength (before heat treatment)". The measurement results are shown in column "120 ℃ C..times.30 minutes" of Table 13.
[ measurement of seal Strength after cooking (130 ℃ C.) ]
The measurement sample prepared in the above "measurement of seal strength (before heat treatment)" was subjected to a retort heat treatment (130 ℃ C..times.30 minutes). The peel strength was measured by a tensile tester in the same manner as "measurement of seal strength (no heat treatment)". The measurement results are shown in column "130 ℃ C..times.30 minutes" of Table 13.
TABLE 13
As shown in Table 13, the hot water bond strength of reference example II-5 was significantly higher than that of comparative example II-5. In addition, it was confirmed that the seal strength of reference example II-5 was also superior to that of comparative example II-5. In particular, the seal strength of reference example II-5 was sufficiently high even after boiling, whereas the seal strength of comparative example II-5 was greatly lowered after boiling. It can be confirmed that: the laminate of comparative examples II-5 was significantly reduced in both adhesive strength and seal strength when heated in the presence of moisture.
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. The same aqueous primer resin as in example II-1 was coated on one side of the PET film, thereby forming a primer layer. The coating amount of the aqueous polyethyleneimine was the same as that of example II-1.
A predetermined printing was performed on the surface of the primer layer using the digital printer used in example II-1. As the color of the electrostatic ink composition, white (W), yellow (Y), magenta (M), and cyan (C) are used. Samples were prepared having an ink coating ratio of W200% and samples having an ink coating ratio of C100% + M100% + Y100% + W200%. In table 14, the former is "ink coating ratio (1)", and the latter is "ink coating ratio (2)". Thus, 2 samples having different ink coverage rates of the electrostatic ink composition were prepared.
The same adhesive composition as in example II-1 was prepared, and the adhesive composition was coated on the printing surface by the same procedure as in example II-1, thereby forming an adhesive layer. The coating amount of the adhesive composition was set to 4.0g/m 2 。
In the same manner as in example II-1, the laminate film used in example II-1 (laminate film obtained by adhering a nylon film to an unstretched polypropylene film using a commercially available adhesive) was adhered to an adhesive layer of a base material, thereby obtaining a laminate. The curing time (aging) was set at 40℃for 2 days.
The seal strength (before heat treatment) and seal strength (after boiling) of the laminate thus obtained were measured. The measurement results are shown in Table 14. The adhesive strength (before heat treatment) and the heat adhesive strength (120 ℃ C.) were measured by the following procedures.
Using the pair of laminates of reference examples II-8, heat sealing was performed in such a manner that the unstretched polypropylene films overlapped each other, thereby producing a three-sided pouch having a sealed portion. The three-sided bag is filled with water. Then, a retort heat treatment (120 ℃ C...times.30 minutes) was performed using a retort treatment apparatus (manufactured by Osaka). After the retort heat treatment, a sample was cut into a width of 15mm, and the seal was sampled to measure the interlayer strength between the electrostatic ink layer and the layer in contact with the electrostatic ink layer. The peel strength measured is shown in the column "hot bond strength (120 ℃ C.)" of Table 14. Table 14 also shows the bonding strength before the steaming heat treatment.
Reference examples II-9 to II-12
A laminate was produced in the same manner as in reference example II-8, except that the blending amount of the polyisocyanate (B) was changed as shown in Table 14 at the time of producing the adhesive composition. The laminate thus produced was evaluated in the same manner as in reference examples II to 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 the printed surface on which the electrostatic ink composition was printed was laminated using a manual laminator without using a dry lamination apparatus. The color and ink coverage of the electrostatic ink composition are shown in table 14. The laminate thus produced was evaluated in the same manner as in reference examples II to 8. The evaluation results are shown in Table 14.
TABLE 14
As shown in table 14, it was confirmed that high adhesive strength and sealing strength were obtained even under heating in each reference example. In addition, it was confirmed that the heat bonding strength (120 ℃) and the seal strength (before heat treatment and after boiling) can be sufficiently improved by adjusting the blending ratio of the polyisocyanate (B) to the aliphatic polyester polyol (a). 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 seal strength were significantly lowered when exposed to the high-temperature hot water treatment conditions. In reference examples II-8 to II-12, the molar ratio of the isocyanate groups contained in the polyisocyanate (B) to the hydroxyl groups contained in the aliphatic polyester polyol (A) was in the range of 0.5 to 10.
Reference examples II-13 to II-17
An adhesive composition was prepared by compounding an aliphatic polyester polyol (A1) (talacla 525, manufactured by samini chemical corporation), a polyisocyanate (B1) (TAKENATE A, manufactured by samini chemical corporation), and 3',4' -epoxycyclohexylmethyl-3, 4 epoxycyclohexane carboxylate as the epoxy compound (C). The blending ratios are shown in Table 15. Laminates were produced and evaluated in the same manner as in reference examples II-8 to II-12, except that the adhesive composition was used. The evaluation results are shown in Table 15.
Comparative examples II-7
An aliphatic polyester polyol (A1) (talac a525, manufactured by tikoku corporation) and a polyisocyanate (B1) (TAKENATE A, manufactured by tikoku corporation) were blended as polyols to prepare an adhesive composition. The blending ratios are shown in Table 15. A laminate was produced and evaluated in the same manner as in comparative example II-4, except that the adhesive composition was used. The evaluation results are shown in Table 15.
TABLE 15
As shown in table 15, it was confirmed that high adhesive strength and sealing strength were obtained in each reference example even when the combination of the aliphatic polyester polyol and the polyisocyanate was changed. In addition, it was confirmed that the heat bonding strength (120 ℃) and the seal strength (after no heat treatment and boiling) can be sufficiently improved by adjusting the blending ratio of the polyisocyanate (B1) to the aliphatic polyester polyol (A1). 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 seal strength were significantly lowered when exposed to the high-temperature hot water treatment conditions. In reference examples II-13 to II-17, the molar ratio of the isocyanate groups contained in the polyisocyanate (B1) to the hydroxyl groups contained in the aliphatic polyester polyol (A1) was in the range of 0.5 to 10.
Industrial applicability
According to the present disclosure, it is possible to provide a container having a printing surface on which printing is performed by a digital printer, and capable of suppressing peeling at the interface between the electrostatic ink layer and the primer layer and at the interface between the electrostatic ink layer and the adhesive layer even in a curved portion generated during the manufacturing process.
According to the present disclosure, a package having an electrostatic ink layer using a digital printer and having sufficient resistance to heat treatment can be provided.
Description of symbols
10 … substrate, 20 … seal layer, 30 … adhesive layer, 40 … primer layer, 50, 51 … electrostatic ink layer, 52 … print, 60 … bend, 70 … plug, 72 … injection port, 74 … flange, 100, 110 … container, 101, 103, 111, 114, 121, 122 … seal portion, 102, 112, 124, 132 … container portion, 120, 130 … package bag, 140 … opening mechanism, 141 … half cut line, 144 … easy open processing portion, 200 … body portion, 300, 302, 304, 306, 310 … laminate, 400 … package.
Claims (15)
1. A container comprising a main body having a curved portion,
the body portion is formed of at least one laminate,
the laminate comprises a substrate, a primer layer, an adhesive layer, and a sealing layer in this order, and has a printed portion made of an electrostatic ink composition on at least a part of the main surface of the primer layer on the sealing layer side,
The adhesive layer includes at least one of an adhesive composition containing an epoxy compound and a cured product thereof.
2. The container of claim 1, wherein,
the curved portion has the printing portion.
3. The container according to claim 1 or 2, wherein,
the epoxy compound comprises a 2-functional alicyclic epoxy compound.
4. A container according to any one of claim 1 to 3, wherein,
the adhesive composition further comprises a polyol,
the polyol includes an aliphatic polyester polyol, and the epoxy compound includes a compound having epoxy groups at both ends.
5. The container of claim 4, wherein,
the adhesive composition further comprises a polyisocyanate,
the polyisocyanate comprises a xylene diisocyanate derivative.
6. The container according to any one of claims 1 to 5, further comprising a plug connected to the main body.
7. The container of claim 6, wherein,
the plug has a cylindrical injection port and a flange extending outward from a peripheral edge of a lower end of the injection port.
8. The container according to any one of claims 1 to 7, wherein,
The main body portion is formed of one sheet of the laminate.
9. The container according to any one of claims 1 to 8, wherein,
the main body portion is composed of two laminated bodies serving as side sheets and one laminated body serving as a bottom sheet.
10. A heat-treating packaging bag comprising a laminate having a base material, a primer layer, an electrostatic ink layer, an adhesive layer and a sealing layer in this order,
the adhesive layer includes at least one of an adhesive composition containing an epoxy compound and a cured product thereof.
11. The heating packaging bag according to claim 10, wherein,
the primer layer includes a polyethyleneimine resin.
12. The heating bag according to claim 10 or 11, wherein,
the outer peripheral portion includes a sealing portion for adhering the sealing layers of the two laminated bodies to each other,
the ink coating rate of the electrostatic ink layer in the sealing portion is 300% or less.
13. The heating bag according to any one of claim 10 to 12, wherein,
the epoxy compound comprises a 2-functional alicyclic epoxy compound.
14. The heating bag according to any one of claim 10 to 13, wherein,
The adhesive composition further comprises a polyol,
the polyol includes an aliphatic polyester polyol, and the epoxy compound includes a compound having epoxy groups at both ends.
15. The heating packaging bag according to claim 14, wherein,
the adhesive composition further comprises a polyisocyanate,
the polyisocyanate comprises a xylene diisocyanate derivative.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2021-003413 | 2021-01-13 | ||
| JP2021-004251 | 2021-01-14 | ||
| JP2021004251 | 2021-01-14 | ||
| PCT/JP2021/044265 WO2022153705A1 (en) | 2021-01-13 | 2021-12-02 | Container and heating packaging bag |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116710277A true CN116710277A (en) | 2023-09-05 |
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ID=87831657
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202180090138.3A Pending CN116710277A (en) | 2021-01-13 | 2021-12-02 | Container and heating packaging bag |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116710277A (en) |
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2021
- 2021-12-02 CN CN202180090138.3A patent/CN116710277A/en active Pending
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