Manufacturing method of adhesive body

Abstract

To provide a manufacturing method of an adhesion body capable of forming a packaging container excellent in adhesive strength and anti-blocking property.SOLUTION: In a manufacturing method of an adhesion body (Z) formed by bonding a laminate (X) containing an adhesive layer (A) to a structure (Y), a water content in the adhesive layer (A) is 3-20 mass%. The method includes a step (I) for applying liquid (W) to an application area of 1-50 area% in the whole area of the adhesive layer (A); a step (II) for piling the adhesive layer (A) of the laminate (X) on the structure (Y); and a step (III) for compressing the piled laminate (X) and the structure (Y) on a pressure region.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for producing an adhesive article used for packaging food and the like, and a method for producing a packaging container using the adhesive article. [Background technology]

[0002] In food packaging, methods for sealing the contents include methods of melting and adhering sealant layers together, such as heat sealing and ultrasonic sealing, and methods of joining using adhesive materials such as hot melt adhesives. One such method is a sealing method using a rewettable adhesive layer, as typified by postage stamps (for example, Patent Documents 1 and 2), and packaging containers manufactured by subjecting the bonded body, which is bonded via a rewettable adhesive layer, to molding or the like, are being considered. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Patent No. 6423473 [Patent Document 2] International Publication No. 2015-015605 Summary of the Invention [Problem to be solved by the invention]

[0004] However, according to the inventors' investigations, it was found that with conventional methods, the adhesive strength of the adhesive joint of a packaging container using an adhesive may not be sufficient, and that when a load is applied to the packaging container, blocking may occur due to the adhesive material protruding into the opening, making it difficult to open the packaging container.

[0005] Therefore, an object of the present invention is to provide a method for producing an adhesive bonded body capable of forming a packaging container having excellent adhesive strength and blocking resistance, and a method for producing the packaging container. [Means for solving the problem]

[0006] As a result of extensive research to solve the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by a method for producing a bonded body (Z) comprising the steps of: adjusting the water content of the adhesive layer (A) contained in a laminate (X) to 3 to 20 mass % and applying a liquid (W) to 1 to 50 area % of the adhesive layer (A) in a coating area; and stacking the adhesive layer (A) of the laminate (X) on a structure (Y) in a step (II) and applying pressure to the stacked laminate (X) and structure (Y) in a pressure region; or folding the laminate (X) in a way that the adhesive layers (A) face each other or that the adhesive layer (A) faces a layer other than the adhesive layer (A) in a step (II') and applying pressure to the folded laminate (X) in a pressure region, thereby completing the present invention. That is, the present invention includes the following aspects.

[0007] [1] A method for producing an adhesive body (Z) obtained by bonding a laminate (X) including an adhesive layer (A) to a structure (Y), wherein the moisture content of the adhesive layer (A) is 3 to 20% by mass, a step (I) of applying a liquid (W) to a coating area of ​​1 to 50% by area of ​​the total area of ​​the adhesive layer (A); A step (II) of superposing the adhesive layer (A) of the laminate (X) on the structure (Y); and Step (III) of pressing the stacked laminate (X) and structure (Y) in a pressure region. A method comprising: [2] A method for producing an adhesive body (Z) comprising a laminate (X) containing an adhesive layer (A), wherein the moisture content of the adhesive layer (A) is 3 to 20% by mass, a step (I) of applying a liquid (W) to a coating area of ​​1 to 50% by area of ​​the total area of ​​the adhesive layer (A); A step (II') of folding the laminate (X) so that the adhesive layers (A) face each other or the adhesive layer (A) faces a layer other than the adhesive layer (A); and Step (III') of pressing the folded laminate (X) in a pressing area A method comprising: [3] The oxygen permeability of the adhesive layer (A) is 0.01 to 10 mL / 20 μm / (m 2 The method according to [1] or [2], wherein the temperature is 0.5°C / 100°F (.day.atm). [4] The method according to any one of [1] to [3], wherein the laminate (X) further contains paper (C). [5] The method according to any one of [1] to [4], wherein the pressurized region is heated in steps (III) and (III'). [6] In step (I), the amount of the liquid (W) applied to the application area is 10 to 30 g / m 2 The method according to any one of [1] to [5], wherein [7] The method according to any one of [1] to [6], wherein in step (I), the liquid (W) contains water in an amount of 50 mass % or more, and the viscosity of the liquid (W) is 0.3 to 100 cP. [8] The method according to any one of [1] to [7], wherein in step (I), a water supply roll (R) is brought into contact with the coating area of ​​the adhesive layer (A) to coat the liquid (W). [9] The method according to any one of [1] to [8], wherein in the step (I), the liquid (W) is applied to the application area of ​​the adhesive layer (A) using a slit coater.

[10] The method according to any one of [1] to [9], wherein in step (I), the liquid (W) is sprayed onto the application area of ​​the adhesive layer (A).

[11] The method according to any one of [1] to [7], which combines two or more methods selected from the group consisting of a method in which in step (I) a water supply roll (R) is brought into contact with the coating area of ​​the adhesive layer (A) to apply the liquid (W); a method in which the liquid (W) is applied to the coating area of ​​the adhesive layer (A) using a slit coater; and a method in which the liquid (W) is sprayed onto the coating area of ​​the adhesive layer (A).

[12] The method according to any one of [1] to

[11] , wherein in steps (III) and (III'), the pressure region is heated to 80 to 200°C.

[13] The method according to any one of [1] to

[12] , wherein in step (I), the liquid (W) contains at least one selected from the group consisting of an alcohol-based solvent, a polyvinyl alcohol-based resin, gelatin, xanthan gum, carrageenan, guar gum, carrageenan, sodium carboxymethylcellulose, and pectin.

[14] The method according to any one of [1] and [3] to

[13] , wherein the structure (Y) is a laminate (X') including an adhesive layer (A) or a laminate (Q) not including an adhesive layer (A).

[15] The method according to

[14] , wherein in step (II), the adhesive layer (A) of the laminate (X) and the adhesive layer (A) of the laminate (X') are superposed so as to be in contact with each other.

[16] The method according to any one of [1] to

[15] , wherein in steps (III) and (III'), the area of ​​the pressurized region is 1 to 50 area % of the total area of ​​the adhesive layer (A).

[17] The method according to any one of [1] to

[16] , wherein in steps (III) and (III'), the width of the pressurized region in the short-side direction is 5 to 30 mm.

[18] The method according to any one of [1] to

[17] , wherein in steps (III) and (III'), the area of ​​the pressurized region is 0.5 to 1.5 times the area of ​​the applied region, and includes an overlapping portion between the pressurized region and the applied region.

[19] The method according to any one of [1] to

[18] , wherein the area of ​​the overlapping portion between the pressurized region and the applied region is 0.5 to 1.5 times the area of ​​the pressurized region.

[20] A method for producing a packaging container using an adhesive (X) obtained by the method according to any one of [1] to

[19] .

[21] The method according to

[20] , wherein the packaging container is a flat pouch, a standing pouch, a gusset pouch, a twin pouch, or a spout pouch, a thermoformed container, or an injection-molded container. [Effects of the Invention]

[0008] According to the manufacturing method of the present invention, it is possible to form an adhesive body capable of forming a packaging container having excellent adhesive strength and blocking resistance, and to form the packaging container. [Brief explanation of the drawings]

[0009] [Figure 1] 1 is a schematic cross-sectional view showing the layer structure of a laminate according to one embodiment of the present invention. [Figure 2]FIG. 2 is a schematic view showing an example of a method for applying a liquid using a water supply roll in step (I) according to an embodiment of the present invention. [Figure 3] FIG. 2 is a schematic view showing an example of the process of laminating adhesive layer (A) of laminate (X) and structure (Y) in step (II) in one embodiment of the present invention. [Figure 4] FIG. 2 is a schematic view showing an example of a process in which the stacked laminate (X) and structure (Y) are pressed in a pressurizing region in step (III) in one embodiment of the present invention. [Figure 5] FIG. 2 is a schematic view showing an example of a process in which the stacked laminate (X) and structure (Y) are pressed in a pressurizing region in step (III) in one embodiment of the present invention. [Figure 6] FIG. 2 is a schematic view showing an example of a process in which the stacked laminate (X) and structure (Y) are pressed in a pressurizing region in step (III) in one embodiment of the present invention. [Figure 7] FIG. 2 is a schematic view showing an example of a process in which the stacked laminate (X) and structure (Y) are pressed in a pressurizing region in step (III) in one embodiment of the present invention. [Figure 8] 1 is a schematic diagram showing an adhesive body according to one embodiment of the present invention and a cutting line of the adhesive body. [Figure 9] 1 is a schematic diagram showing a three-sided pouch in one embodiment of the present invention. [Figure 10] 1 is a schematic diagram showing a water supply roll and a receiving tray according to an embodiment of the present invention. [Figure 11] FIG. 10 is a schematic view showing a water supply roll and a receiving tray of Comparative Example 5. [Figure 12] 1 is a schematic diagram showing a water supply roll according to one embodiment of the present invention. [Figure 13] 1 is a schematic diagram showing a gusset pouch in one embodiment of the present invention. [Figure 14] 1 is a schematic diagram showing a standing pouch in one embodiment of the present invention. [Figure 15] 1 is a schematic diagram showing a twin pouch in one embodiment of the present invention. [Figure 16] 1 is a schematic diagram showing a spout pouch in one embodiment of the present invention. [Figure 17] 1 is a schematic cross-sectional view showing an adhesive body (packaging container) according to one embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0010] The present invention relates to a method for producing an adhesive body (Z) obtained by bonding a laminate (X) including an adhesive layer (A) to a structure (Y). The method is characterized by comprising the steps of: (I) applying a liquid (W) to a coating area of ​​1 to 50 area % of the total area of ​​the adhesive layer (A); (II) overlapping the adhesive layer (A) of the laminate (X) with the structure (Y) and (III) pressing the overlapped laminate (X) and structure (Y) in a pressurized region; or (II') folding the laminate (X) so that the adhesive layers (A) face each other or so that the adhesive layer (A) faces a layer other than the adhesive layer (A) and (III') pressing the folded laminate (X) in a pressurized region.

[0011] [Laminate] The laminate (X) in the present invention includes an adhesive layer (A). <Adhesive layer (A)> The adhesive layer (A) is a layer that can be bonded by applying the liquid (W) and applying pressure. The adhesive layer (A) can be at least partially bonded to the laminate (X) of the present invention by applying the liquid (W) and applying pressure.

[0012] The moisture content of the adhesive layer (A) in the laminate (X) is 3 to 20% by mass. If the moisture content is less than 3% by mass, the adhesive strength of the resulting bonded body (Z) tends to be low, while if the moisture content exceeds 20% by mass, the blocking resistance tends to be low. In the present invention, the moisture content is adjusted to 3 to 20% by mass, so that the resulting bonded body (Z) can achieve both excellent adhesive strength (seal strength) and blocking resistance. In this specification, blocking resistance refers to the ease of opening the resulting bonded body or packaging container (pouch), and the higher the blocking resistance, the easier it is to open. Note that blocking refers to adhesion that exceeds the pressure range, preventing intended opening. Furthermore, appearance characteristics refer to the degree of wrinkles and unevenness in the bonded body (particularly in the bonded area), and improved appearance characteristics refer to the greater suppression of wrinkles and unevenness in the bonded body (particularly in the bonded area).

[0013] The moisture content of the adhesive layer (A) in the laminate (X) is preferably 4% by mass or more, more preferably 5% by mass or more, even more preferably 6% by mass or more, and preferably 18% by mass or less, more preferably 15% by mass or less, and even more preferably 13% by mass or less. When the moisture content of the adhesive layer (A) is at or above the lower limit, the adhesive strength and appearance characteristics are likely to be improved. When the moisture content is at or below the upper limit, the blocking resistance is likely to be improved. The moisture content of the adhesive layer (A) in the laminate (X) can be measured using a moisture meter, for example, by the method described in the Examples. The moisture content can be adjusted to within the above range by appropriately adjusting the storage temperature and humidity of the laminate (X). For example, increasing the storage humidity tends to increase the moisture content, while decreasing the humidity tends to decrease the moisture content. Furthermore, increasing the storage temperature or drying at high temperatures tends to decrease the moisture content.

[0014] From the viewpoint of easily improving biodegradability, gas barrier properties, and adhesive strength, the adhesive layer (A) preferably contains at least one selected from modified starch (a), water-soluble polymer (b), and ethylene-vinyl alcohol copolymer (c). In a preferred embodiment of the present invention, the adhesive layer (A) contains modified starch (a). In another preferred embodiment of the present invention, the adhesive layer (A) contains ethylene-vinyl alcohol copolymer (c). In such an embodiment, it is easier to further improve biodegradability, gas barrier properties, and adhesive strength. Adhesive strength refers to the strength of adhesion at the adhesive joint in the resulting adhesive body or packaging container.

[0015] (Modified starch (a)) As the modified starch (a), for example, at least one selected from the group consisting of etherified starch, esterified starch, cationized starch, and crosslinked starch can be used.

[0016] Examples of starches include starches derived from cassava, corn, potato, sweet potato, sago, tapioca, sorghum, beans, bracken, lotus, water chestnut, wheat, rice, oats, arrowroot, and peas. Among these, starches derived from corn and cassava are preferred, and starches derived from high-amylose corn are more preferred. Starches can be used alone or in combination of two or more types.

[0017] Examples of etherified starches include alkyl-etherified starches such as methyl-etherified starch, carboxyalkyl-etherified starches such as carboxymethyl-etherified starch, and hydroxyalkyl-etherified starches such as etherified starches having a hydroxyalkyl group having 2 to 6 carbon atoms. Allyl-etherified starches can also be used.

[0018] Examples of esterified starches include esterified starches having structural units derived from carboxylic acids, such as esterified starches having structural units derived from acetic acid; esterified starches having structural units derived from dicarboxylic acid anhydrides, such as esterified starches having structural units derived from maleic anhydride, phthalic anhydride, and octenylsuccinic anhydride; and esterified starches having structural units derived from oxoacids, such as nitrate-esterified starch, phosphate-esterified starch, and urea-phosphate-esterified starch. Other examples include xanthate-esterified starch, acetoacetate-esterified starch, and the like.

[0019] Examples of the cationized starch include a reaction product of starch with 2-diethylaminoethyl chloride, and a reaction product of starch with 2,3-epoxypropyltrimethylammonium chloride.

[0020] Examples of crosslinked starches include formaldehyde crosslinked starch, epichlorohydrin crosslinked starch, phosphate crosslinked starch, and acrolein crosslinked starch.

[0021] The modified starch (a) is preferably an etherified starch having a hydroxyalkyl group having 2 to 6 carbon atoms, an esterified starch having a structural unit derived from a dicarboxylic acid anhydride, or a combination thereof, and more preferably hydroxyethyl-etherified starch, hydroxypropyl-etherified starch, hydroxybutyl-etherified starch, an esterified starch having a structural unit derived from maleic anhydride, an esterified starch having a structural unit derived from phthalic anhydride, an esterified starch having a structural unit derived from octenylsuccinic anhydride, or a combination thereof. The modified starch (a) can be used alone or in combination of two or more kinds.

[0022] The amylose content in the modified starch (a) is preferably 45% by mass or more, more preferably 50% by mass or more, even more preferably 55% by mass or more, and particularly preferably 60% by mass or more. When the amylose content is above the lower limit, biodegradability, gas barrier properties, and adhesive strength are likely to be improved. The amylose content in the modified starch (a) is usually 90% by mass or less. The amylose content can be measured, for example, by the iodine coloration method described in "Starch 50 No. 4 158-163 (1998)." When two or more types of modified starch are used, the amylose content of the modified starch (a) refers to the average amylose content calculated by weighting the amylose contents of the two or more types of modified starches.

[0023] The modified starch (a) preferably has a water content of 10 to 15% by mass.

[0024] The etherified starch having a hydroxyalkyl group having 2 to 6 carbon atoms may be obtained by reacting starch with an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide, etc. The average number of hydroxy groups used for modification is preferably 0.05 to 2 per glucose unit in the starch.

[0025] The modified starch (a) may be commercially available. A typical example of a commercially available modified starch (a) is ECOFILM (registered trademark), a hydroxypropyl etherified starch available from Ingredión.

[0026] (Water-soluble polymer (b)) The water-soluble polymer (b) is preferably polyvinyl alcohol, from the viewpoint of easily increasing adhesive strength and gas barrier properties. The water-soluble polymer (b) may be used alone or in combination of two or more kinds.

[0027] The polyvinyl alcohol preferably has a saponification degree of 80 to 99.8 mol%. When the saponification degree of polyvinyl alcohol is within the above range, adhesive strength and gas barrier properties tend to be easily improved. The saponification degree is more preferably 85 mol% or more, even more preferably 88 mol% or more, and particularly preferably 90 mol% or more. The saponification degree indicates the molar fraction of hydroxyl groups relative to the total of hydroxyl groups and ester groups in polyvinyl alcohol. Polyvinyl alcohol is produced, for example, by hydrolysis of polyvinyl acetate obtained by polymerization of vinyl acetate monomer.

[0028] The viscosity of a 4% aqueous solution of polyvinyl alcohol at 20°C, measured in accordance with JIS Z 8803, is preferably 1 to 50 mPa·s. When the viscosity of polyvinyl alcohol is within the above range, adhesive strength and gas barrier properties tend to be easily improved. The viscosity is preferably 3 mPa·s or more, more preferably 5 mPa·s or more, and preferably 45 mPa·s or less, more preferably 35 mPa·s or less.

[0029] The polyvinyl alcohol may further contain other monomer units in addition to vinyl alcohol units, such as monomer units derived from ethylenically unsaturated monomers. Examples of ethylenically unsaturated monomers include α-olefins such as ethylene, propylene, n-butene, isobutylene, and 1-hexene; acrylic acid and its salts; unsaturated monomers having an acrylic ester group; methacrylic acid and its salts; unsaturated monomers having a methacrylic ester group; acrylamide, N-methylacrylamide, N-ethylacrylamide, N,N-dimethylacrylamide, diacetoneacrylamide, acrylamidopropanesulfonic acid and its salts, acrylamidopropyldimethylamine and its salts (e.g., quaternary salts); methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, methacrylamidopropanesulfonic acid and its salts, methacrylamidopropyldimethylamine and its salts (e.g., quaternary salts); methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, i-propyl vinyl ether, n-butyl vinyl ether, i-butyl vinyl ether, t-butyl vinyl ether, vinyl halides such as vinyl chloride and vinyl fluoride; vinylidene halides such as vinylidene chloride and vinylidene fluoride; allyl compounds such as allyl acetate, 2,3-diacetoxy-1-allyloxypropane and allyl chloride; unsaturated dicarboxylic acids such as maleic acid, itaconic acid and fumaric acid, and salts or esters thereof; vinyl silyl compounds such as vinyltrimethoxysilane; isopropenyl acetate; and vinyl ester monomers such as vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl versatate, vinyl caproate, vinyl carboxylate, vinyl laurate, vinyl palmitate, vinyl stearate, vinyl oleate and vinyl benzoate. The content of other monomer units is preferably 10 mol % or less, and more preferably 5 mol % or less.

[0030] The method for producing polyvinyl alcohol is not particularly limited. For example, a method can be used in which a vinyl alcohol monomer and optionally other monomers are polymerized, and the resulting polymer is saponified to convert it into vinyl alcohol units. Polymerization methods include batch polymerization, semi-batch polymerization, continuous polymerization, and semi-continuous polymerization. Polymerization methods include known methods such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. Known methods can be used for saponification of the polymer. For example, saponification can be performed in a state in which the polymer is dissolved in alcohol or aqueous alcohol. Examples of alcohols that can be used in this case include lower alcohols such as methanol and ethanol.

[0031] (Ethylene-vinyl alcohol copolymer (c)) Ethylene-vinyl alcohol copolymer (c) (hereinafter also referred to as EVOH (c)) is a polymer having ethylene units and vinyl alcohol units as main structural units. EVOH (c) may contain one or more types of other structural units in addition to the ethylene units and vinyl alcohol units. EVOH (c) is usually obtained by polymerizing ethylene and a vinyl ester and saponifying the resulting ethylene-vinyl ester copolymer.

[0032] In EVOH (c), the ethylene unit content (i.e., the ratio of ethylene units to the total molar amount of monomer units in EVOH (c)) is preferably 2 mol% or more, more preferably 10 mol% or more, even more preferably 20 mol% or more, and preferably 60 mol% or less, more preferably 50 mol% or less, even more preferably 40 mol% or less. An ethylene unit content within the above range is advantageous from the viewpoint of gas barrier properties and mechanical properties. As the ethylene unit content decreases, the oxygen transmission rate (OTR) tends to decrease.

[0033] In EVOH (c), the saponification degree of the vinyl alcohol unit is preferably 90 mol% or more, more preferably 95 mol% or more, even more preferably 99 mol% or more, and particularly preferably 99.5 mol% or more. When the saponification degree is within the above range, excellent gas barrier properties can be obtained. The saponification degree refers to the molar fraction of hydroxyl groups relative to the total of hydroxyl groups and ester groups in the vinyl alcohol unit. The EVOH (c) may be used together with the modified starch (a) and the water-soluble polymer (b).

[0034] EVOH (c) preferably has at least one of a structural unit (I) represented by the following formula (I), a structural unit (II) represented by the following formula (II), and a structural unit (III) represented by the following formula (III). When EVOH (c) has such a structural unit, the adhesive strength, appearance characteristics, gas barrier properties, flex resistance, etc. of the resulting bonded body or packaging container are likely to be improved.

[0035] [ka]

[0036] In the above formula (I), R 1 , R 2 and R 3 each independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, or a hydroxyl group. 1 , R 2 and R 3 One pair of these may be bonded to one another. In addition, some or all of the hydrogen atoms in the aliphatic hydrocarbon group having 1 to 10 carbon atoms, the alicyclic hydrocarbon group having 3 to 10 carbon atoms, and the aromatic hydrocarbon group having 6 to 10 carbon atoms may be substituted with hydroxyl groups, carboxyl groups, or halogen atoms.

[0037] In formula (II), R 4 , R 5 , R 6 and R 7each independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, or a hydroxyl group. 4 and R 5 , or R 6 and R 7 may be bonded to the aliphatic hydrocarbon group having 1 to 10 carbon atoms, the alicyclic hydrocarbon group having 3 to 10 carbon atoms, and the aromatic hydrocarbon group having 6 to 10 carbon atoms. Some or all of the hydrogen atoms in the aliphatic hydrocarbon group having 1 to 10 carbon atoms may be substituted with a hydroxyl group, an alkoxy group, a carboxyl group, or a halogen atom.

[0038] In formula (III), R 8 , R 9 , R 10 and R 11 R each independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, or a hydroxyl group. Some or all of the hydrogen atoms in the aliphatic hydrocarbon group having 1 to 10 carbon atoms, the alicyclic hydrocarbon group having 3 to 10 carbon atoms, and the aromatic hydrocarbon group having 6 to 10 carbon atoms may be substituted with a hydroxyl group, an alkoxy group, a carboxyl group, or a halogen atom. 12 and R 13 each independently represents a hydrogen atom, a formyl group, or an alkanoyl group having 2 to 10 carbon atoms.

[0039] The content of the structural units (I), (II), or (III) relative to the total structural units is preferably 0.5 mol% or more, more preferably 1 mol% or more, and even more preferably 1.5 mol% or more. On the other hand, the content of the structural units (I), (II), or (III) is preferably 30 mol% or less, more preferably 15 mol% or less, and even more preferably 10 mol% or less. When EVOH (c) contains the structural units shown in (I), (II), or (III) in the above-mentioned ranges, the adhesive strength, appearance characteristics, gas barrier properties, flexibility, processability, thermoformability, etc. of the resulting bonded article or packaging container are likely to be improved.

[0040] In the structural unit (I), (II), or (III), examples of the aliphatic hydrocarbon group having 1 to 10 carbon atoms include an alkyl group, an alkenyl group, etc., examples of the alicyclic hydrocarbon group having 3 to 10 carbon atoms include a cycloalkyl group, a cycloalkenyl group, etc., and examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms include a phenyl group, etc.

[0041] In the structural unit (I), R 1 , R 2 and R 3 are preferably each independently a hydrogen atom, a methyl group, an ethyl group, a hydroxyl group, a hydroxymethyl group, or a hydroxyethyl group, and among these, are more preferably each independently a hydrogen atom, a methyl group, a hydroxyl group, or a hydroxymethyl group. 1 , R 2 and R 3 This makes it easy to improve the adhesive strength, appearance characteristics, gas barrier properties, flexibility, processability, thermoformability, etc. of the resulting adhesive body or packaging container.

[0042] The method for incorporating the structural unit (I) into the EVOH (c) is not particularly limited, and examples thereof include a method in which a monomer derived from the structural unit (I) is copolymerized in the polymerization of ethylene and a vinyl ester. Monomers derived from this structural unit (I) include alkenes such as propylene, butylene, pentene, and hexene; 3-hydroxy-1-propene, 3-acyloxy-1-propene, 3-acyloxy-1-butene, 4-acyloxy-1-butene, 3,4-diacyloxy-1-butene, 3-acyloxy-4-hydroxy-1-butene, 4-acyloxy-3-hydroxy-1-butene, 3-acyloxy-4-methyl-1-butene, 4-acyloxy-2-methyl-1-butene, 4-acyloxy-3-methyl-1-butene, 3,4-diacyloxy-2-methyl-1-butene, 4-hydroxy-1-pentene, 5-hydroxy-1-pentene, Examples of alkenes having a hydroxyl group or an ester group include 4,5-dihydroxy-1-pentene, 4-acyloxy-1-pentene, 5-acyloxy-1-pentene, 4,5-diacyloxy-1-pentene, 4-hydroxy-3-methyl-1-pentene, 5-hydroxy-3-methyl-1-pentene, 4,5-dihydroxy-3-methyl-1-pentene, 5,6-dihydroxy-1-hexene, 4-hydroxy-1-hexene, 5-hydroxy-1-hexene, 6-hydroxy-1-hexene, 4-acyloxy-1-hexene, 5-acyloxy-1-hexene, 6-acyloxy-1-hexene, and 5,6-diacyloxy-1-hexene. Among these, propylene, 3-acetoxy-1-propene, 3-acetoxy-1-butene, 4-acetoxy-1-butene, and 3,4-diacetoxy-1-butene are preferred from the viewpoint of copolymerization reactivity and the gas barrier properties of the resulting adhesive or packaging container. In the case of an alkene having an ester, it is derived into the above structural unit (I) during the saponification reaction.

[0043] In the structural unit (II), R 4 and R 5 Preferably, both R are hydrogen atoms. 4 and R 5 are both hydrogen atoms, and R 6 and R 7It is more preferable that one of R is an aliphatic hydrocarbon group having 1 to 10 carbon atoms, and the other is a hydrogen atom. The aliphatic hydrocarbon group is preferably an alkyl group or an alkenyl group. From the viewpoint of easily improving the gas barrier properties of the resulting adhesive body or packaging container, 6 and R 7 It is particularly preferred that one of the R 6 and R 7 One of them is (CH2) h It is particularly preferred that the other of the substituents represented by OH (wherein h is an integer of 1 to 8) is a hydrogen atom. h In the substituent represented by OH, h is preferably an integer of 1 to 4, more preferably 1 or 2, and particularly preferably 1.

[0044] The method for incorporating the structural unit (II) into EVOH (c) is not particularly limited, but may include a method in which the structural unit (II) is incorporated by reacting a monofunctional epoxy compound with EVOH obtained by a saponification reaction. As the monofunctional epoxy compound, compounds represented by the following formulas (IV) to (X) are preferably used.

[0045] [ka]

[0046] In formulas (IV) to (X), R 14 , R 15 , R 16 , R 17 and R 18 each independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms (such as an alkyl group or an alkenyl group), an alicyclic hydrocarbon group having 3 to 10 carbon atoms (such as a cycloalkyl group or a cycloalkenyl group), or an aliphatic hydrocarbon group having 6 to 10 carbon atoms (such as a phenyl group). Also, i, j, k, p, and q each independently represent an integer of 1 to 8.

[0047] Examples of the monofunctional epoxy compound represented by formula (IV) include epoxyethane (ethylene oxide), epoxypropane, 1,2-epoxybutane, 2,3-epoxybutane, 3-methyl-1,2-epoxybutane, 1,2-epoxypentane, 3-methyl-1,2-epoxypentane, 1,2-epoxyhexane, 2,3-epoxyhexane, 3,4-epoxyhexane, 3-methyl-1,2-epoxyhexane, 3-methyl-1,2-epoxyheptane, 4-methyl-1,2-epoxyheptane, 1,2-epoxyoctane, 2,3-epoxyoctane, 1,2-epoxynonane, 2,3-epoxynonane, 1,2-epoxydecane, 1,2-epoxydodecane, epoxyethylbenzene, 1-phenyl-1,2-epoxypropane, and 3-phenyl-1,2-epoxypropane. Examples of the monofunctional epoxy compound represented by formula (V) include various alkyl glycidyl ethers. Examples of the monofunctional epoxy compound represented by formula (VI) include various alkylene glycol monoglycidyl ethers. Examples of the monofunctional epoxy compound represented by formula (VII) include various alkenyl glycidyl ethers. Examples of the monofunctional epoxy compound represented by formula (VIII) include various epoxy alkanols such as glycidol. Examples of the monofunctional epoxy compound represented by formula (IX) include various epoxy cycloalkanes. Examples of the monofunctional epoxy compound represented by formula (X) include various epoxy cycloalkenes.

[0048] Among monofunctional epoxy compounds, epoxy compounds having 2 to 8 carbon atoms are preferred. In particular, from the viewpoints of ease of handling the compound and reactivity, the number of carbon atoms in the monofunctional epoxy compound is more preferably 2 to 6, and even more preferably 2 to 4. Furthermore, among the above formulas, the monofunctional epoxy compound is particularly preferably a compound represented by formula (IV) or (V). Specifically, from the viewpoints of reactivity with EVOH (c) and ease of improving the gas barrier properties of the resulting adhesive or packaging container, 1,2-epoxybutane, 2,3-epoxybutane, epoxypropane, epoxyethane, and glycidol are preferred, and among these, epoxypropane and glycidol are particularly preferred.

[0049] In the structural unit (III), R 8 , R 9 , R 10 and R 11 is preferably a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms. Particularly preferred aliphatic hydrocarbon groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, and pentyl.

[0050] The method for incorporating the structural unit (III) into the EVOH (c) is not particularly limited, and the EVOH (c) can be produced, for example, by the method described in JP-A-2014-034647.

[0051] The adhesive layer (A) of the laminate (X) of the present invention may further contain a fatty acid having 12 to 22 carbon atoms and / or a fatty acid salt thereof. Examples of fatty acids having 12 to 22 carbon atoms and fatty acid salts thereof include stearic acid, calcium stearate, sodium stearate, palmitic acid, lauric acid, myristic acid, linoleic acid, and behenic acid. Among these, stearic acid, calcium stearate, and sodium stearate are preferred from the viewpoint of processability. The fatty acids having 12 to 22 carbon atoms and fatty acid salts thereof can be used alone or in combination of two or more.

[0052] When the adhesive layer (A) contains a fatty acid having 12 to 22 carbon atoms and / or a fatty acid salt thereof, the content in the adhesive layer is preferably 0.01 to 3 mass%, more preferably 0.03 to 2 mass%, and even more preferably 0.1 to 1 mass%, relative to the mass of the adhesive layer (A). A content of the fatty acid having 12 to 22 carbon atoms and / or a fatty acid salt thereof within the above range tends to be advantageous in terms of processability.

[0053] The adhesive layer (A) may further contain clay. Examples of clay include synthetic or natural layered silicate clays such as montmorillonite, bentonite, beidellite, mica, hectorite, saponite, nontronite, sauconite, vermiculite, ledikite, magadite, kenyaite, stevensite, and vulkonskoite. The clays can be used alone or in combination.

[0054] When the adhesive layer (A) contains clay, the content in the adhesive layer (A) is preferably 0.1 to 5 mass %, more preferably 0.1 to 3 mass %, and even more preferably 0.5 to 2 mass %, based on the mass of the adhesive layer (A). A clay content within the above range tends to be advantageous in terms of transparency and strength.

[0055] The adhesive layer (A) in the laminate (X) of the present invention contains water, and as described above, its water content is 3 to 20% by mass. The adhesive layer (A) may contain plasticizers other than water. Examples of plasticizers include sorbitol, glycerol, maltitol, xylitol, mannitol, glycerol trioleate, epoxidized linseed oil, epoxidized soybean oil, tributyl citrate, acetyltriethyl citrate, glyceryl triacetate, 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, polyethylene oxide, and polyethylene glycol. Plasticizers can be used alone or in combination.

[0056] The adhesive layer (A) may further contain additives such as fillers, processing stabilizers, weather resistance stabilizers, colorants, ultraviolet absorbers, light stabilizers, antioxidants, antistatic agents, flame retardants, other thermoplastic resins, lubricants, fragrances, antifoaming agents, deodorizers, extenders, release agents, mold release agents, reinforcing agents, crosslinking agents, mildew inhibitors, preservatives, and crystallization rate retarders, as required.

[0057] The adhesive layer (A) is preferably in the form of a film or sheet. From the viewpoint of easily improving adhesive strength, biodegradability, gas barrier properties, and appearance characteristics, the thickness of the adhesive layer (A) is preferably 0.1 μm or more, more preferably 1 μm or more, particularly preferably 10 μm or more, and is preferably 1000 μm or less, more preferably 500 μm or less, and even more preferably 100 μm or less. The thickness of the adhesive layer (A) can be measured using an optical microscope, a film thickness meter, or the like, for example, by the method described in the Examples. One or more adhesive layers (A) may be provided, and may be a single layer or multiple layers. When the adhesive layer (A) is two or more layers, the thickness and composition of each layer may be different or the same.

[0058] The adhesive layer (A) has excellent gas barrier properties, especially oxygen barrier properties. The oxygen permeability (mL / 20μm / (m)) of the adhesive layer (A) at 23°C and 50% RH is 2 .day.atm)) is preferably 10.0 or less, more preferably 8.0 or less, even more preferably 6.0 or less, even more preferably 4.0 or less, particularly preferably 2.0 or less, and most preferably 1.0 or less. When the oxygen permeability is equal to or less than the above upper limit, the resulting adhesive body (Z) can exhibit excellent oxygen barrier properties. The oxygen permeability can be measured by an oxygen permeability measuring device after storing the adhesive layer (A) at 23°C and 50% RH for two weeks to condition the humidity, and can be measured, for example, by the method described in the Examples. Here, for example, "10 mL 20 μm / (m 2 The oxygen permeability of "·day·atm" is the rate at which oxygen gas passes through 1m of a 20μm thick film in one day at 1 atmosphere. 2 This indicates that 10 mL of oxygen permeates.

[0059] The adhesive layer (A) may be a commercially available product, such as "Plantic (registered trademark) HP 50" or "Eval (registered trademark) F101B" available from Kuraray Co., Ltd.

[0060] The laminate (X) of the present invention may further comprise a substrate layer (B).

[0061] <Base material layer (B)> The substrate layer (B) is not particularly limited, and examples thereof include paper or a resin film. Examples of paper include, but are not limited to, kraft paper, fine paper, construction paper, glassine paper, parchment paper, synthetic paper, white cardboard, Manila cardboard, milk carton base paper, cup base paper, ivory paper, and silver paper. Among these, kraft paper and glassine paper are preferred because they easily improve adhesion to the adhesive layer (A). The resin film is also not particularly limited, and examples thereof include polyethylene terephthalate (PET) film, polypropylene (PP) film, polyethylene (PE) film (preferably low-density polyethylene (LDPE) film), and polylactic acid film. Among these, PET film and PP film are preferred because they easily improve adhesion to the adhesive layer (A). The substrate layer is preferably paper because it easily improves adhesion to the adhesive layer (A) and biodegradability. That is, the laminate (X) preferably includes paper as the substrate layer (B).

[0062] The thickness of the substrate layer (B) is not particularly limited, and is preferably 1 to 1000 μm, more preferably 1 to 500 μm, even more preferably 5 to 300 μm, and particularly preferably 10 to 200 μm. The thickness of the substrate layer (B) can be measured using an optical microscope, a film thickness meter, or the like, for example, by the method described in the Examples. One or more substrate layers (B) may be provided, and may be a single layer or multiple layers. When the substrate layer (B) is two or more layers, the thicknesses and materials of the layers may be different or the same.

[0063] The laminate (X) of the present invention may include one or more adhesive layers (C) other than the adhesive layer (A) and the base layer (B). Examples of adhesives constituting the adhesive layer (C) include acrylic adhesives, urethane adhesives, epoxy adhesives, vinyl acetate adhesives, ethylene-vinyl acetate adhesives, vinyl chloride adhesives, silicone adhesives, nitrile cellulose adhesives, phenolic adhesives, polyvinyl alcohol adhesives, melamine adhesives, and styrene adhesives. Urethane adhesives are preferred from the viewpoint of adhesiveness. The thickness of the adhesive layer (C) is preferably 0.1 to 30 μm, more preferably 1 to 20 μm. The thickness of the adhesive layer (C) can be measured using an optical microscope, a film thickness meter, or the like, for example, by the method described in the Examples.

[0064] In one embodiment of the present invention, when the laminate (X) of the present invention has an adhesive layer (C), the adhesive layer (C) is preferably disposed between the adhesive layer (A) and the substrate layer (B). In a preferred embodiment of the present invention, the laminate (X) has the adhesive layer (A), adhesive layer (C) and substrate layer (B) in this order, or has the adhesive layer (A) and substrate layer (B) adjacent to each other.

[0065] The laminate (X) may include an adhesive layer (A), a substrate layer (B), an adhesive layer (C), and other layers. The other layers are not particularly limited and may include, for example, a protective layer, a gas barrier layer different from the adhesive layer (A), a moisture-proof layer, a light-shielding layer, a printed layer, a reinforcing layer, and a recovery layer (e.g., a layer formed by melt-kneading and remolding a laminate consisting of a substrate layer / adhesive layer / adhesive layer / substrate layer). Examples of materials for forming the other layers include polyethylene, polypropylene, ethylene-vinyl acetate copolymer, EVOH, polyvinyl chloride, polyurethane, polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, polyamides such as nylon, polyacrylonitrile, cellulose or its derivatives, glass, and wood. One or more other layers may be provided, and they may be single-layered or multi-layered. When there are two or more other layers, the thicknesses and materials of the layers may be the same or different. The other layers may be laminated to the adhesive layer (A) or the substrate layer (B) via an adhesive layer (C). The thickness of the other layers is not particularly limited, but is preferably 1 to 1000 μm, more preferably 5 to 500 μm.

[0066] The shape of the laminate (X) is not limited to a sheet or film, and can be appropriately selected depending on the shape of the target bonded body (Z). For example, when forming the bonded body (container) shown in Figure 17, the laminate (X) can be molded into the shape of the container (tray) body before step (I). The molding method is not particularly limited, and conventional methods such as thermoforming and injection molding can be used.

[0067] <Method for producing laminate (X)> The method for producing the laminate (X) is not particularly limited, but examples include a method in which an adhesive layer (A) is produced, an adhesive layer (C) is formed on the obtained adhesive layer (A), and a base layer (B) is formed on the adhesive layer (C).

[0068] The adhesive layer (A) can be produced, for example, by a method including the steps of: (1) mixing at least one selected from modified starch (a), water-soluble polymer (b), and ethylene-vinyl alcohol copolymer (c), and optionally other components, such as the fatty acid having 12 to 22 carbon atoms and / or its fatty acid salt, the clay, the plasticizer, and the additives, to obtain a mixture; (2) extruding the mixture; and (3) cooling and drying the extruded mixture.

[0069] Step (1) is usually carried out using an extruder in which the components are mixed homogeneously while being subjected to shear stress by the screw and heated by applying external heat to the barrel.

[0070] The extruder may be, for example, a twin-screw extruder. The twin-screw extruder may be either co-rotating or counter-rotating. The screw diameter may be, for example, 20 to 150 mm, and the L / D ratio, which is the ratio of the extruder length (L) to the screw diameter (D), may be, for example, 20 to 50. The screw rotation speed is preferably 80 rpm or higher, more preferably 100 rpm or higher. The extrusion molding pressure is preferably 5 bar (0.5 MPa) or higher, more preferably 10 bar (1.0 MPa) or higher. Each component may be directly introduced into the extruder. Alternatively, the components may be premixed using a mixer and then introduced into the extruder.

[0071] In step (1), from the viewpoints of easily adjusting the water content of the adhesive layer (A) to 3 to 20% by mass and easily improving film-forming properties, it is preferable to mix water in an amount of preferably 3% by mass or more, more preferably 5% by mass or more, even more preferably 10% by mass or more, particularly preferably 15% by mass or more, and most preferably 20% by mass or more, and preferably 50% by mass or less, more preferably 45% by mass or less, and even more preferably 40% by mass or less, based on the mass of the mixture. Here, the mass of the mixture refers to the total mass of the mixture including water. In step (1), water may be added at the initial stage of extrusion or before the temperature reaches the temperature for the cooking treatment described below, for example, when the temperature is below 100°C. The modified starch (a) is subjected to a cooking treatment by a combination of moisture, heat, and shear stress, and can be gelatinized (gelated). Separately adding water can dissolve the water-soluble polymer (b), soften the mixture, and reduce its modulus and brittleness.

[0072] In step (1), the cooking treatment is preferably carried out by heating to a temperature of more than 100°C and not more than 150°C, more preferably from 115°C to 140°C. Here, the cooking treatment is a treatment for crushing and gelling starch granules. Heating can be carried out by applying heat externally to the barrels of the extruder. By applying a temperature that changes stepwise to each barrel, heating to the desired temperature is possible. Cooking at a temperature above 120°C is advantageous in terms of processability.

[0073] To prevent foaming, the cooked mixture is preferably forced toward the die while the temperature is reduced to preferably 85 to 120°C, more preferably 90 to 110°C. In addition, foaming can be prevented and moisture can be removed by venting the barrel.

[0074] The residence time in the extruder can be set depending on the temperature profile and the screw speed, and is preferably 1 to 2.5 minutes.

[0075] In the step (2) of extruding the mixture, the molten mixture that has been forced through the extruder while being melt-kneaded is extruded through a die at a temperature of preferably 85 to 120°C, more preferably 90 to 110°C.

[0076] In step (3) of cooling and drying the extruded mixture, the mixture is extruded into a film or sheet to form the adhesive layer (A). The extruded mixture is usually in the form of a melt.

[0077] When the mixture is extruded into a film, it can be cooled and dried while being extruded through a film-forming die and then wound up on a take-up roller. Cooling between the die and the roller is preferred to prevent the mixture from sticking to the roller. For drying, the roll may be heated, and dehumidified air may be supplied during winding. In the case of the blown tube method, dehumidified air can be used to expand the film as it exits the die. Talc can also be entrained in the air stream to prevent film blocking.

[0078] The method for forming the adhesive layer (C) on the adhesive layer (A) is not particularly limited, but examples thereof include a method in which the adhesive constituting the adhesive layer (C) is applied to the adhesive layer (A) and then dried.

[0079] The method for forming the substrate layer (B) on the adhesive layer (C) is not particularly limited, but examples thereof include a method in which the substrate layer (B) is laminated on the adhesive layer (C) and then laminated. The laminate (X) of the present invention may be produced by extruding the mixture onto the substrate layer (B) using the above-mentioned extruder. Alternatively, the laminate may be produced by a sand lamination method in which the adhesive layer (C) is extruded between the adhesive layer (A) and the substrate layer (B).

[0080] Structure The structure (Y) in the present invention is not particularly limited, and may include, for example, at least one selected from the adhesive layer (A), the base layer (B), the adhesive layer (C), and the other layers. The structure (Y) may be a single layer or a laminate. When the structure (Y) includes one or more of the adhesive layer (A), the base layer (B), and the adhesive layer (C), the structure (Y) may have the same composition and film thickness as or different from the adhesive layer (A), the base layer (B), and the adhesive layer (C) that constitute the laminate (X).

[0081] In one embodiment of the present invention, the structure (Y) is a laminate (X') containing an adhesive layer (A) or a laminate (Q) not containing an adhesive layer (A), and is preferably a laminate (X') containing an adhesive layer (A) from the viewpoint of easily increasing adhesive strength. In particular, when the structure (Y) is a laminate (X') and an adhesive structure formed by bonding (sealing) the adhesive layer (A) of the laminate (X) with the adhesive layer (A) of the laminate (X') is easily able to exhibit superior adhesive strength. The laminate (X') is a laminate including the adhesive layer (A) and may include, in addition to the adhesive layer (A), at least one layer selected from the base layer (B), the adhesive layer (C), and the other layers. The laminate (X') may be the same as or different from the laminate (X), but is preferably the same as the laminate (X) from the viewpoint of easily improving gas barrier properties, biodegradability, appearance characteristics, and adhesive strength. The laminate (Q) is a laminate that does not include the adhesive layer (A), and can include, for example, at least one layer selected from the base material layer (B), the adhesive layer (C), and the other layers.

[0082] The layer structure of the structure (Y) is not particularly limited, and examples thereof include a layer structure having a substrate layer (B) / adhesive layer (C) / adhesive layer (A) in this order; a layer structure having another layer / adhesive layer (C) / substrate layer (B) / adhesive layer (A) in this order; a layer structure having another layer / substrate layer (B) / adhesive layer (A) in this order; a layer structure having a substrate layer (B) / adhesive layer (C) / adhesive layer (A) / adhesive layer (C) / substrate layer (B) in this order; a substrate Examples of the layer structure include a layer structure having the following in this order: layer (B) / other layer / adhesive layer (C) / adhesive layer (A) / adhesive layer (C) / substrate layer (B); a layer structure having the following in this order: substrate layer (B) / other layer / adhesive layer (C) / adhesive layer (A) / adhesive layer (C) / other layer / substrate layer (B); a layer structure having the following in this order: substrate layer (B) / adhesive layer (C) / adhesive layer (A) / adhesive layer (C) / other layer / substrate layer (B); a layer structure consisting of substrate layer (B), etc. The structure (Y) can be produced, for example, by the method described in the section <Production method of laminate>.

[0083] [Method of manufacturing the bonded body] Hereinafter, a method for producing a bonded structure according to one embodiment of the present invention will be described in detail with reference to the accompanying drawings, although the production method of the present invention is not limited to this embodiment.

[0084] Fig. 1 is a schematic diagram showing the layer structure of a laminate in one embodiment of the present invention, and Figs. 2 to 8 are schematic diagrams showing a method for producing an adhesive bonded body in one embodiment of the present invention. In this embodiment, a laminate 1a having a base layer 4a, an adhesive layer 3a, and an adhesive layer 2a in this order as shown in Fig. 1 is used as the laminate (X), and the same laminate 1a is also used as the structure (Y). In explaining the drawings, to ensure ease of viewing, (X), (Y), (A), and (W) in the laminate (X), structure (Y), adhesive layer (A), and liquid (W), etc., are omitted.

[0085] [Process (I)] Step (I) is a step of applying the liquid (W) to a coating area of ​​1 to 50% by area of ​​the total area of ​​the adhesive layer (A). The coating area is the area on the surface of the adhesive layer (A) to which the liquid (W) is applied.

[0086] FIG. 2 is a schematic diagram showing an example of the process of applying the liquid (W) to the application area in the step (I). As shown in FIG. 2, the water supply roll 7a has a sponge portion 6a attached to the outer periphery of the metal roll 5a, which can come into contact with the coating area while rotating. The sponge portion 6a contains liquid 8. As the laminate 1a is moved by the transport roll (not shown), the coating area on the adhesive layer 2a comes into contact with the sponge portion 6a of the rotatably fixed water supply roll 7a. As the water supply roll 7a rotates in the rotation direction 101, the liquid 8 is applied to the coating area. In this way, the liquid 8 can be efficiently and continuously applied to the coating area, which is formed by two rectangular frames arranged in the lateral direction of the laminate 1a. The coating area accounts for 20 to 50% of the total area of ​​the adhesive layer 2a. From the viewpoint of production efficiency, the laminate 1a is usually wound by the unwinding roll and then unwound from the unwinding roll and transported by the transport roll.

[0087] In the embodiment shown in Figure 2, the water supply roll 7a is fixed and the laminate 1a is moved by a transport roll, but it is also possible to fix the laminate 1a and apply the liquid 8 by rolling the water supply roll in the application area.

[0088] The adhesive layer (A) can exhibit sealing properties when it comes into contact with the liquid (W), and is then adhered to the structure (Y) by applying pressure in the step (III) described below. Therefore, in step (I), the position where the laminate (X) and the structure (Y) are adhered is determined as a coating area depending on the shape of the desired bonded body, and the liquid (W) is applied to the coating area. In the embodiment shown in Figures 2 to 8, a coating area in the form shown in Figure 2 is provided to finally produce the three-sided pouch (three-sided bag) shown in Figure 9.

[0089] In step (I), the coating area is 1 to 50 area % of the total area (100 mass %) of the adhesive layer (A). If the area of ​​the coating area is outside the above range, the shape of the resulting adhesive body will be limited. The coating area can be appropriately selected depending on the shape of the resulting adhesive body, for example, the shape of the packaging container when used as a packaging container, and is preferably 3 area % or more, more preferably 5 area % or more, even more preferably 10 area % or more, and preferably 45 area % or less, more preferably 40 area % or less.

[0090] The amount of liquid (W) applied to the application area is preferably 10 g / m 2 More preferably, 12 g / m 2 or more, and preferably 30 g / m 2 More preferably, 25 g / m 2 More preferably, 20 g / m or less 2 When the amount of liquid (W) applied in the application area is equal to or greater than the above lower limit, the adhesive strength is easily increased and the occurrence of unevenness in the adhesive joint is easily suppressed. When the amount of liquid (W) applied in the application area is equal to or less than the above upper limit, the blocking property is easily increased and the occurrence of wrinkles in the adhesive joint is easily suppressed. The adhesive joint refers to the part of the laminate where the adhesive layer (A) is bonded.

[0091] The liquid (W) is not particularly limited as long as it can adhere the adhesive layer (A) by application and pressure, and can be appropriately selected depending on the composition of the adhesive layer (A). Examples of components constituting the liquid (W) include water; alcohol-based solvents such as methanol, ethanol, propanol, and butanol; ester-based solvents such as methyl acetate and ethyl acetate; aromatic hydrocarbon-based solvents such as benzene, toluene, and xylene; nitrile-based solvents such as acetonitrile; ketone-based solvents such as acetone, methyl ethyl ketone, cyclopentanone, and cyclohexanone; ether-based solvents such as tetrahydrofuran and dimethoxyethane; amide-based solvents such as N,N-dimethylacetamide and N,N-dimethylformamide; chlorine-containing solvents such as chloroform and chlorobenzene; polyvinyl alcohol-based resins such as polyvinyl alcohol; gelatin, xanthan gum, carrageenan, and guar gum. ,mosquitoExamples of the components include sodium carboxymethylcellulose and pectin. These components can be used alone or in combination. Among these, from the viewpoint of easily increasing adhesive strength, the liquid (W) is preferably water, an alcohol-based solvent, a polyvinyl alcohol-based resin, gelatin, xanthan gum, carrageenan, guar gum, etc. ,mosquito It is preferable that the liquid (W) contains at least one selected from sodium carboxymethylcellulose and pectin, and more preferable that the liquid (W) contains at least one selected from water, an alcohol-based solvent, and a polyvinyl alcohol-based resin. In one embodiment of the present invention, the liquid (W) contains 50% by mass or more of water based on the mass of the liquid (W), and further contains at least one selected from an alcohol-based solvent, a polyvinyl alcohol-based resin, gelatin, xanthan gum, carrageenan, guar gum, and the like. M, Ka Preferably, the adhesive contains at least one selected from sodium carboxymethylcellulose and pectin, more preferably an alcohol-based solvent or a polyvinyl alcohol-based resin, and even more preferably a polyvinyl alcohol-based resin. In this embodiment, the adhesive strength is more likely to be increased. Note that, in this specification, the term "alcohol-based solvent" does not include polyvinyl alcohol-based resin.

[0092] When the liquid (W) contains water, the content of water in the liquid (W) is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, even more preferably 80% by mass or more, particularly preferably 90% by mass or more, and may be 100% by mass, based on the mass of the liquid (W). The content of water in the liquid (W) is preferably 99% by mass or less, more preferably 98% by mass or less, even more preferably 97% by mass or less, and particularly preferably 96% by mass or less. When the water content of the liquid (W) is within the above range, it is easy to increase the adhesive strength with the structure (Y) and the like, and it is easy to form an adhesive body (Z) having excellent adhesive strength.

[0093] The viscosity of liquid (W) is preferably 0.3 cP or more, more preferably 1.0 cP or more, even more preferably 1.5 cP or more, even more preferably 5 cP or more, particularly preferably 10 cP or more, especially preferably 20 cP or more, and preferably 100 cP or less, more preferably 80 cP or less, and even more preferably 60 cP or less. When the viscosity of liquid (W) is at least the above lower limit, it is easy to increase the adhesive strength and to suppress the occurrence of unevenness in the adhesive joint. On the other hand, when the viscosity of liquid (W) is at most the above upper limit, it is easy to increase the blocking resistance.

[0094] Methods for applying the liquid (W) to the coating area of ​​the adhesive layer (A) include, for example, a method in which the liquid (W) is applied by contacting a water supply roll (R) with the coating area of ​​the adhesive layer (A) (see Figure 2); a method in which the liquid (W) is applied to the coating area of ​​the adhesive layer (A) using a slit coater; and a method in which the liquid (W) is sprayed onto the coating area of ​​the adhesive layer (A).

[0095] By using a method of applying the liquid (W) by bringing a water supply roll (R) into contact with the application area of ​​the adhesive layer (A), the liquid (W) can be applied uniformly to the application area. In this method, it is preferable to apply the liquid (W) while replenishing the water supply roll (R). As a method of replenishing the liquid (W), from the viewpoint of easily improving production efficiency, a method of replenishing the liquid (W) by immersing the water supply roll (R) in the liquid (W) or a method of reinforcing the liquid (W) from the inside of the water supply roll (R) is preferred.

[0096] The method of dipping the water supply roll (R) in the liquid (W) to replenish it may be a method using a water supply roll 7a and a tray 15 as shown in Fig. 10, in which the tray 15 is filled with liquid 8 in advance, and the water supply roll 7a is immersed in the liquid 8 and rotated to replenish the liquid 8 to the sponge portion 6a. In the embodiment shown in Fig. 2, the liquid 8 may be applied to the application area while being replenished from the tray 15 while the water supply roll 7a is rotated. In this case, the laminate 1a moves while contacting the upper part of the water supply roll 7a.

[0097] A method for reinforcing the liquid (W) from inside the water supply roll (R) may be a method of supplying the liquid (W) into the inside of the water supply roll 7b shown in FIG. 12 and replenishing the liquid 8 to the sponge portion 6a. More specifically, the water supply roll 7b is a metal roll 5b with a sponge portion 6a attached to the outer periphery thereof. The metal roll 5b is a hollow roll closed on one side, and has a plurality of holes 16 formed so as to contact the inside of the sponge portion 6a. Alternatively, the liquid (W) may be introduced into the water supply roll 7b and replenished while permeating the sponge portion 6a through the holes 16. In the embodiment shown in FIG. 2, when the water supply roll 7b is used instead of the water supply roll 7a, the liquid 8 may be applied to the application area while the water supply roll 7b is rotating and replenishing the liquid 8 inside the water supply roll 7b. In this case, the laminate 1a moves while being in contact with the upper or lower part of the water supply roll 7b.

[0098] In the method of applying the liquid (W) to the coating area of ​​the adhesive layer (A) using a slit coater, the slit coater is not particularly limited as long as it is capable of applying the liquid (W) to the coating area, and a conventional slit coater can be used.

[0099] In the method of spraying the liquid (W) onto the coating area of ​​the adhesive layer (A), for example, a sprayer may be used to spray the liquid (W) onto the coating area. In this method, the position of the spray coating can be easily changed. In this specification, the term "coating" includes spraying.

[0100] In step (I), two or more methods selected from the group consisting of a method of applying the liquid (W) by contacting a water supply roll (R) with the coating area of ​​the adhesive layer (A); a method of applying the liquid (W) to the coating area of ​​the adhesive layer (A) using a slit coater; and a method of spraying the liquid (W) onto the coating area of ​​the adhesive layer (A) can be combined.

[0101] [Process (II)] Step (II) is a step of overlaying the adhesive layer (A) of the laminate (X) and the structure (Y).

[0102] FIG. 3 is a schematic diagram showing an example of the process of overlapping the adhesive layer (A) of the laminate (X) and the structure (Y) in step (II). As shown in FIG. 3, the adhesive layer 2a of the laminate 1a coated with the liquid 8 and the adhesive layer 2a of the structure 9a are overlapped so that they come into contact. In FIG. 3, the structure (Y) is a laminate (X') including the adhesive layer (A). By overlapping so that the adhesive layers 2a come into contact with each other, it is easy to improve adhesive strength, blocking resistance, and appearance characteristics. In the embodiment shown in FIG. 3, the laminate 1a and the structure 9a identical to the laminate 1a are overlapped with their edges aligned, but the method of overlapping the laminate (X) and the structure (Y) can be selected appropriately depending on the shape of the resulting adhesive body or container. In step (II), it is sufficient that at least the adhesive layer (A) coated with the liquid (W) and the structure (Y) overlap entirely or partially, and for example, a layer other than the adhesive layer of the structure (Y) may be overlapped with the adhesive layer (A).

[0103] In step (II), the adhesive layer (A) of the laminate (X) may be laminated so as to be in contact with any layer contained in the laminate (X') (for example, the base layer (B), another layer, or the adhesive layer (A)). From the viewpoint of easily improving adhesive strength, blocking resistance, and appearance characteristics, it is preferable to laminate the laminate (X) and the adhesive layer (A) of the laminate (X') so as to be in contact with each other, as described above.

[0104] [Process (III)] Step (III) is a step of pressurizing the stacked laminate (X) and structure (Y) in a pressurized region. In the production method of the present invention, the application of liquid (W) in step (I) and the application of pressure in step (III) are performed in combination, so that an adhesive bond having excellent adhesive strength can be formed. The pressurized region is a region on the surface of the laminate (X) or structure (Y) where pressure is applied.

[0105] 4 to 7 are schematic diagrams showing an example of the process of pressing the stacked laminate (X) and structure (Y) in the pressurizing region in step (III).

[0106] As shown in Figures 4 and 5, the stacked laminate 1a and structure 9a are pressed by a long hot plate 10 from the base layer 4a side of the structure 9a along the MD of the coating region. Next, the long hot plate 10 is removed, and as shown in Figures 6 and 7, pressure is applied by a long hot plate 11 from the base layer 4a side of the structure 9a along the TD of the coating region. In this embodiment, pressure is applied so that the area ratio of the pressurized region is 0.8 to 1.2 times the area of ​​the coating region and the area ratio of the overlapping area between the pressurized region and the coating region is 0.8 to 1.2 times the area of ​​the pressurized region. This results in a bonded body 12a in which the laminate 1a and structure 9a are bonded at the overlapping portion between the pressurized region and the coating region, i.e., the adhesive joint 13a, as shown in Figure 13. The adhesive bonded structure 12a has a moisture content of 3 to 20% by mass in the adhesive layer of the laminate 1a, and is produced by combining coating in the coating region and pressurization in the pressurization region, thereby achieving both excellent adhesive strength and excellent blocking resistance. The pressurization region occupies 10 to 40% by area of ​​the total area (100% by mass) of the adhesive layer 2a. The MD direction refers to the machine flow direction during production of the adhesive bonded structure 12a, and the TD direction refers to the direction perpendicular to the machine flow direction during production of the adhesive bonded structure 12a. The resulting adhesive bonded structure 12a can be wound up on a take-up roll. When continuously produced using an unwinding roll, a transport roll, and a take-up roll, transport may be stopped between steps (II) and (III).

[0107] The long hot plate 10 and the long hot plate 11 can be pressed once or more, preferably twice or more, more preferably three times or more. Pressurizing twice or more can increase the adhesive strength. In the embodiment shown in Fig. 4 to Fig. 7, the long hot plate 10 presses the sheet along the MD direction, and then the long hot plate 11 presses the sheet along the TD direction. However, the long hot plate 10 may be used to press the sheet along the MD direction and the TD direction at the same time, for example, by using a grid-shaped hot plate. In the embodiment shown in Figures 4 to 7, pressure is applied from the base layer 4a side of the structure 9a, but the side (or surface) to which pressure is applied is not particularly limited, and pressure may be applied, for example, from the surface of the laminate 1a, i.e., the base layer 4a side of the laminate 1a.

[0108] In step (III), it is preferable to heat the pressure application area. By heating the pressure application area, the adhesive strength can be further improved. The temperature of the pressure application area is preferably 80°C or higher, more preferably 90°C or higher, even more preferably 120°C or higher, particularly preferably 150°C or higher, and preferably 200°C or lower. When the temperature of the pressure application area is above the lower limit, adhesive strength is easily improved, and when the temperature of the pressure application area is below the upper limit, the occurrence of wrinkles in the adhesive joints is easily suppressed. The pressure of application is preferably 0.1 kgf / cm 2 More than 0.5kgf / cm 2 More preferably, 1.0 kgf / cm 2 or more, preferably 10 kgf / cm 2 Less than 5kgf / cm, preferably 5kgf / cm 2 When the pressure of the pressurization is equal to or greater than the above lower limit, the adhesive strength is easily improved, and when the pressure of the pressurization is equal to or less than the above upper limit, the occurrence of wrinkles in the adhesive joint is easily suppressed. The pressurization time is not particularly limited, and is preferably 0.05 seconds or more, more preferably 0.1 seconds or more, and preferably 60 seconds or less, more preferably 10 seconds or less, and even more preferably 5 seconds or less. When the pressurization time is equal to or greater than the above lower limit, the adhesive strength is easily improved, and when the pressurization time is equal to or less than the above upper limit, the occurrence of wrinkles in the adhesive joint is easily suppressed. When pressurization is performed multiple times, the pressurization pressure refers to the pressure for one pressurization, and the pressurization time refers to the total time for multiple pressurizations.

[0109] In step (III), the width (or length) of the pressure region in the lateral direction is preferably 5 to 30 mm, more preferably 8 to 20 mm. When the width of the pressure region in the lateral direction is within this range, pressure can be easily applied, which may be advantageous from the viewpoint of adhesive strength and suppression of wrinkles. Furthermore, many commercially available hot plates are within the above range, for example, 10 mm or 15 mm. Note that, for example, when a hot plate is used for pressure application, the width (or length) of the pressure region in the lateral direction can be adjusted by adjusting the width (or length) of the hot plate in the lateral direction to the above range.

[0110] In step (III), the area of ​​the pressurized region can be appropriately selected depending on the area of ​​the coating region, etc., and is preferably 1 area% or more, more preferably 3 area% or more, even more preferably 5 area% or more, particularly preferably 10 area% or more, and preferably 45 area% or less, more preferably 40 area% or less, relative to the total area (100% by mass) of the adhesive layer (A). When the area of ​​the pressurized region relative to the total area of ​​the adhesive layer (A) is within the above range, adhesive strength and blocking resistance are likely to be improved.

[0111] The area of ​​the pressurized region is preferably 0.5 to 1.5 times the area of ​​the coated region and includes the overlapping portion of the pressurized region and the coated region. The area of ​​the pressurized region is preferably 0.7 to 1.3 times, more preferably 0.8 to 1.2 times, the area of ​​the coated region. When the area of ​​the pressurized region relative to the coated region is within the above range, adhesive strength, blocking resistance, and appearance properties are likely to be improved.

[0112] The area of ​​the overlapping portion between the pressurized region and the coated region is preferably 0.5 to 1.5 times, more preferably 0.7 to 1.3 times, and even more preferably 0.8 to 1.2 times the area of ​​the pressurized region. When the area of ​​the overlapping portion between the pressurized region and the coated region is within the above range, adhesive strength and blocking resistance are likely to be improved.

[0113] The pressure application in step (III) is preferably carried out for 1 to 20 seconds, more preferably 2 to 15 seconds, and even more preferably 3 to 10 seconds from the time when the liquid (W) is applied to the application area, which makes it easier to improve adhesive strength, blocking resistance, and appearance properties.

[0114] The method of pressurization is not particularly limited, and examples include a method of applying pressure using a hot plate as shown in Figures 4 to 7; a method of using ultrasound in combination with applying pressure using a hot plate or the like; and in the case of an adhesive body consisting of a main body (laminate) and a lid (structure), a method of applying pressure by replacing the atmosphere inside the container with a mixed gas containing nitrogen, carbon dioxide, and oxygen.

[0115] In the above embodiment, adhesive portion 13a is formed by arranging two rectangular frames in the short direction of adhesive body 12a, but adhesive portions of various shapes can be formed by appropriately changing the shapes of the application area and pressure application area.

[0116] As described above, the manufacturing method of the present invention includes a method including steps (I) to (III) and a method including steps (II') and (III') instead of steps (II) and (III). The former method is a method of bonding a laminate (X) and a structure (Y), while the latter method is a method of folding and bonding the laminate (X) itself. For example, in the embodiment shown in FIGS. 2 to 8, the laminate 1a and structure 9a (the same as the laminate 1a) were used by the former method, i.e., the bonded body 12a was formed using two laminates, whereas the latter method can form the bonded body 12a' using a single laminate. The bonded body 12a' is the same as the bonded body 12a except that one end is connected.

[0117] [Process (II')] Step (II') is a step of folding the laminate (X) so that the adhesive layers (A) face each other or so that the adhesive layer (A) faces a layer other than the adhesive layer (A). The layer other than the adhesive layer (A) is not particularly limited as long as it is a layer other than the adhesive layer (A) contained in the laminate (X), and examples thereof include the base layer (B), the adhesive layer (C), and the other layers.

[0118] For example, the laminate 1a (FIG. 3) coated with the liquid 8 in step (I) can be folded so that the adhesive layers 2a are on the inside, allowing the adhesive layers 2a to be stacked so that they face each other.

[0119] [Process (III')] Step (III') is a step of pressing the folded laminate (X) in the pressurizing region. For example, as described above, by pressing the laminate obtained by folding the laminate 1a in the pressurizing region, an adhered body 12a' can be formed in which the adhesive layers 2a of the laminate 1a are adhered to each other. The same pressurizing conditions as those in step (III) can be adopted for the pressurizing. The adhered body 12a' has a moisture content of 3 to 20 mass % in the adhesive layers 2a of the laminate 1a and is produced by a method that combines coating in the coating region and pressurizing in the pressurizing region, so that it can achieve both excellent adhesive strength and excellent blocking resistance.

[0120] Even in an embodiment including steps (I), (II'), and (III') [sometimes referred to as steps (I) to (III')], adhesive joints of various shapes can be formed by appropriately changing the shapes of the application area and the pressure application area.

[0121] [Adhesive and packaging container] The adhesive bonded article (Z) obtained by the production method of the present invention is formed by bonding the laminate (X) or the laminate (X) to the structure (Y). Since the production method of the present invention includes steps (I) to (III) or steps (I) to (III'), the adhesive bonded article (Z) obtained has excellent adhesive strength and blocking resistance. Furthermore, in a preferred embodiment of the present invention, the adhesive bonded article (Z) also has excellent appearance characteristics and gas barrier properties. Therefore, the adhesive bonded article (Z) of the present invention can be suitably used as a material for packaging containers for foods and the like.

[0122] The bonded article of the present invention has excellent adhesive strength. The adhesive strength of the bonded portion of the bonded article is preferably 100 g / 15 mm or more, more preferably 150 g / 15 mm or more, even more preferably 200 g / 15 mm or more, even more preferably 250 g / 15 mm or more, and particularly preferably 300 g / 15 mm or more. The upper limit of the adhesive strength is not particularly limited, but is usually 1000 g / 15 mm or less. The adhesive strength can be measured using a tensile tester at a tensile speed of 50 mm / min, an initial chuck distance of 50 mm, and a T-peel mode after storing and regulating the humidity at 23°C and 50% RH for 7 days, and is the average value of five measurements. For example, it can be measured by the method described in the Examples.

[0123] The use of the adhesive body is not particularly limited, and the adhesive body may be cut into pieces for use, or may be used as is.

[0124] The present invention includes a method for producing a packaging container using the adhesive body (Z).

[0125] First, an example of producing a packaging container by cutting an adhesive bonded body is shown. Fig. 8 is a schematic diagram showing an adhesive bonded body in one embodiment of the present invention and the cutting lines of the adhesive bonded body. More specifically, Fig. 8 shows an adhesive bonded body 12a produced by the method shown in Figs. 2 to 7. The adhesive bonded body 12a has adhesive sections in which two rectangular frames are arranged in the lateral direction of the adhesive bonded body 12a. Therefore, by cutting the adhesive bonded body 12a along cutting planes obtained by moving cutting lines 102 along the longitudinal and lateral directions of the adhesive sections perpendicular to the thickness direction, the three-sided pouch 14 shown in Fig. 9 can be produced.

[0126] Next, we will show a case where the adhesive bonded body (Z) is used as a packaging container as is. Figure 17 is a schematic cross-sectional view of an adhesive bonded body 12b in one embodiment of the present invention. The adhesive bonded body 12b is obtained by applying the liquid (W) to the flange portion (coating area) of a container-shaped laminate 1b having a base layer 4b, an adhesive layer 3b, and an adhesive layer 2b in this order, overlapping the container-shaped laminate 1b and a structure 9b (same as the laminate 1a) so that the adhesive layer 2b of the laminate 1b contacts the adhesive layer 2a of the structure 9b, and then pressing the overlapped container-shaped laminate 1b and structure 9b from the base layer 4a side of the structure 9b in a pressure region corresponding to the flange portion. In this embodiment, the adhesive bonded body 12b can be used as a packaging container as is.

[0127] The shape of the packaging container is not particularly limited, but the packaging container is preferably a flat pouch, a standing pouch, a gusset pouch, a twin pouch, a spout pouch, a thermoformed container, or an injection-molded container. [Example]

[0128] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these embodiments.

[0129] <Test Method> (1) Moisture content of adhesive layer After storing the laminate under the conditions described in the Examples and Comparative Examples, the moisture content of the adhesive layer contained in the laminate obtained in the Examples and Comparative Examples was measured using an "UMAREX Moisture Finder Compact" manufactured by UMAREX GmbH & Co.

[0130] (2) Oxygen transmission rate (OTR) The adhesive layers used in the examples and comparative examples were stored at 23°C and 50% RH for two weeks to condition the humidity, and then attached to an oxygen transmission rate measuring device and measured for oxygen transmission rate (mL / 20μm / (m)) in accordance with the method described in JIS K7126 (constant pressure method). 2 The measurement conditions were as follows: Equipment: Modern Controls "MOCON OX-TRAN2 / 20" Temperature: 23℃ Humidity on the oxygen supply side and carrier gas side: 50% RH Oxygen pressure: 1.0 atm Carrier gas pressure: 1.0 atm

[0131] (3) Appearance characteristics (wrinkles at adhesive joints) The adhesive bonded structures obtained in the Examples and Comparative Examples were visually inspected for appearance after storage at 23°C and 50% RH for 7 days, and the occurrence of wrinkles was evaluated according to the following criteria. If it was rated as A or B, the appearance characteristics were evaluated as good. A: No wrinkles and no abnormalities were observed in appearance. B: Some wrinkles occurred, but not to the extent that they would cause problems for the product. C: Wrinkles were observed and the appearance was judged to be abnormal.

[0132] (4) Appearance characteristics (deadsmosomes) The adhesive structures obtained in the examples and comparative examples were visually inspected for appearance after storage at 23°C and 50% RH for 7 days, and the occurrence of adhesive spots (seal spots) was evaluated according to the following criteria. If it was rated as A or B, the appearance characteristics could be evaluated as good. A: No adhesion spots and no abnormalities were observed in appearance B: There was some adhesion, but it was still adhered and was not a problem for the product. C: There was adhesion, but it was not at a level that would cause problems for the product. D: Adhesive patches were observed and the appearance was judged to be abnormal.

[0133] (5) Adhesive strength The adhesive portions of the packaging containers obtained in the Examples and Comparative Examples were cut into 15mm x 150mm strips and stored at 23°C and 50% RH for 7 days to condition the humidity. The adhesive strength of the adhesive portions was then measured using a tensile tester (Instron Corporation, Instron 3367) at a speed of 50mm / min, an initial chuck distance of 50mm, and a T-peel mode. The same test was performed five times, and the average value was used as the adhesive strength value. Evaluation was based on the following criteria: <Adhesive strength judgment criteria> Judgment criteria A :300g / 15mm or more B: 200g / 15mm or more, less than 300g / 15mm C: 100g / 15mm or more, less than 200g / 15mm D: Less than 100g / 15mm

[0134] (6) Blocking resistance A 1 kg weight was placed on the entire packaging container obtained in the Examples and Comparative Examples, and after storing at 23°C and 50% RH for 7 days, the ease of opening the opening was evaluated according to the following criteria. If it was rated as A or B, it could be evaluated as having good blocking resistance. A: It was easy to open. B: There was some adhesion between the laminate and the structure outside the pressurized area, but it was possible to open it. C: The laminate and the structure were stuck together in areas other than the pressurized area, and opening was not possible.

[0135] (7) Thickness measurement The bonded structures obtained in the Examples and Comparative Examples were cut in the TD (width direction) using a microtome to prepare cross sections in the thickness direction. Subsequently, using an optical microscope, the average thickness of the adhesive layer, base layer, and adhesive layer at five arbitrarily selected points was determined as the average thickness of each layer.

[0136] [Example 1] <Preparation of laminates and structures> A laminate 1a having the layer structure shown in FIG. 1 was obtained as follows. Gas barrier film (manufactured by Kuraray Co., Ltd., product name "Plantic (registered trademark) HP 50 μm", thickness: 50 μm, oxygen permeability: 5.2 cc / 20 μm / (m 2 .day.atm)) was used as the adhesive layer 2a, and kraft paper (basis weight 100 g / m 2 A two-component urethane adhesive (Takelac™ A-385 / Takenate™ A-50, manufactured by Mitsui Chemicals, Inc.) was applied to one side of the adhesive layer 2a at a solid content of 2.5 g / m 2After coating with a basis weight of 1000 ppm, a base layer 4a was laminated by dry lamination to obtain a laminate 1a. The obtained laminate 1a was stored at 20°C and 65% RH for 1 week, and the moisture content of the adhesive layer 2a in the laminate 1a was measured by the above method and was found to be 12.4% by mass.

[0137] <Production of adhesive body> The obtained laminate 1a was wound around a winding roll. Next, the laminate 1a was unwound from the winding roll, and an adhesive bonded body 12a was produced according to the following steps, and then wound around a winding roll. Specifically, first, the adhesive layer 2 A water supply roll 7a was prepared by attaching a sponge portion 6a cut out from a "PVA sponge roller" manufactured by AION Co., Ltd. to a metal roll 5a so as to fit the application area on the surface a. Next, a liquid 8 was prepared by dissolving polyvinyl alcohol ("POVAL 22-88" manufactured by Kuraray Co., Ltd.) in ion-exchanged water at a concentration of 5% by mass, and this was placed in a tray 15 (see Figure 10). Next, while the sponge portion 6a of the metal roll 5a was soaked in the liquid 8, the water supply roll 7a and the adhesive layer were attached. 2 a) and the coating amount was adjusted to 12 g / m 2 (See FIG. 2.) The coated area was 37% by area of ​​the total area of ​​the adhesive layer 2a. The laminate 1a and the structure 9a were overlapped (see FIG. 3) so that the adhesive layer 2a of the laminate 1a coated with the liquid 8 came into contact with the adhesive layer 2a of the structure 9a, and the overlapped laminate 1a and structure 9a were pressed in the pressurized region (see FIGS. 4 to 7). In this pressurizing step, long hot plates 10 and 11 with a width of 15 mm in the short direction were used. Pressurization was performed so that the area ratio of the pressurized region to the area of ​​the coated region was 1.0, and the area ratio of the coated region and the pressurized region overlapping each other was 1.0 to the area of ​​the pressurized region. More specifically, first, the long hot plate 10 was placed along the MD direction of the coated region, and the pressurized region was pressed at a pressurized region temperature of 170°C and a pressurized pressure of 2 kgf / cm. 2Pressure was applied for 0.5 seconds under the above conditions (see Figures 4 and 5). This was repeated three times. Next, a long hot plate 11 was placed along the TD direction of the coating area, and pressure was applied for 0.5 seconds under the same conditions (see Figures 6 and 7). This was repeated three times. The first pressure application was performed 5 seconds after the liquid 8 was applied to the coating area. In this way, an adhered body 12a was obtained. In the adhered body 12a, the laminate 1a and the structure 9a were adhered to each other at an adhesive portion 13a corresponding to the overlapping portion of the applied region and the pressurized region.

[0138] <Manufacturing of packaging containers (pouches)> The adhesive portion 13a of the obtained adhesive body 12a was cut along cutting lines 102 extending in the longitudinal and lateral directions, which were moved perpendicular to the thickness direction (see FIG. 8). In this way, a three-sided pouch 14, which was an adhesive body having both ends and the bottom sealed and measuring 15 cm in length and 10 cm in width, was obtained (see FIG. 9).

[0139] [Examples 2 to 18 and Comparative Examples 1 to 3] A laminate 1a, an adhesive body 12a, and a three-sided pouch 14 were obtained in the same manner as in Example 1, except that the conditions were changed as shown in Table 1. In Examples 15, 16, and Comparative Example 3, an ethylene-vinyl alcohol copolymer sheet (manufactured by Kuraray Co., Ltd., trade name "EVAL F101B", ethylene unit content 32 mol%) was used as the material for forming the adhesive layer.

[0140] Comparative Example 4 11 was used instead of the water supply roll 7a in the coating step, and the entire surface of the adhesive layer 2a of the laminate 1a was used as the coating area, and liquid 8 was applied to the coating area. Except for this, the laminate 1a, adhesive body, and three-sided pouch were obtained in the same manner as in Example 1. The water supply roll 7c was prepared by attaching a sponge portion 6b cut out from a "PVA sponge roller" manufactured by AION Co., Ltd. to a metal roll 5a so as to fit the coating area.

[0141] Comparative Example 5 A laminate 1a, an adhesive body 12a and a three-sided pouch 14 were obtained in the same manner as in Example 1, except that the liquid (W) was not applied.

[0142] [Example 19] A laminate 1a, an adhesive body 12a, and a three-sided pouch 14 were obtained in the same manner as in Example 1, except that a water supply roll 7b shown in FIG. 12 was used in place of the water supply roll 7a and the tray 15 in the coating step. The water supply roll 7b was a metal roll 5b to which a sponge portion 6a was attached. The metal roll 5b was a hollow roll with one side closed, and had multiple holes 16 formed so as to contact the inside of the sponge portion 6a. In the coating step, the liquid 8 was introduced into the water supply roll 7b and applied to the coating area on the surface of the adhesive layer 2a of the laminate 1a while being allowed to penetrate into the sponge portion 6a through the holes 16.

[0143] [Example 20] A laminate 1a, an adhesive body 12a and a three-sided pouch 14 were obtained in the same manner as in Example 1, except that in the coating process, a slot coater was used to apply the liquid 8 to the coating area instead of the water supply roll 7a.

[0144] [Example 21] A laminate 1a, an adhesive body 12a and a three-sided pouch 14 were obtained in the same manner as in Example 1, except that in the coating step, the liquid 8 was sprayed onto the coating area using a dispenser device.

[0145] [Example 22] In the coating process, the liquid 8 was applied to the coating area using a slot coater in the MD direction and a water supply roll 7a in the TD direction, but the same method as in Example 1 was used to obtain the laminate 1a, adhesive body 12a, and three-sided pouch 14.

[0146] [Example 23] A laminate, an adhesive body, and a gusset pouch were obtained in the same manner as in Example 1, except that the coating area in step (I) (coating step), the pressurizing area in step (III) (pressurizing step), and the overlapping method and cutting locations in step (III) (overlapping step) were adjusted so as to obtain the shape of the gusset pouch shown in Figure 13.

[0147] [Example 24] A laminate, an adhesive body, and a standing pouch were obtained in the same manner as in Example 1, except that the coating area in step (I) (coating step), the pressurizing area in step (III) (pressurizing step), and the overlapping method and cutting locations in step (III) (overlapping step) were adjusted to obtain the shape of the standing pouch shown in FIG. 14 .

[0148] [Example 25] A laminate, an adhesive body, and a twin pouch were obtained in the same manner as in Example 1, except that the coating area in step (I) (coating step), the pressurizing area in step (III) (pressurizing step), the overlapping method and cutting locations in step (III) (overlapping step) were adjusted to obtain the twin pouch shape shown in Figure 15.

[0149] [Example 26] A laminate, an adhesive body, and a spout pouch were obtained in the same manner as in Example 1, except that the coating area in step (I) (coating step), the pressurizing area in step (III) (pressurizing step), and the overlapping method and cutting locations in step (III) (overlapping step) were adjusted so as to obtain the shape of the spout pouch shown in FIG. 16 .

[0150] [Example 27] <Preparation of laminates and structures> A single-layer polypropylene sheet (600 μm thick) was obtained as a substrate layer using polypropylene (PP, product name "Novatec (trademark) PP EA7AD") by the following method / conditions. The film-forming equipment had a temperature-controllable take-up roll after an extruder with a film-forming die, and the obtained polypropylene sheet was wound up by a winder. PP extruder: 40mmφ extruder PP extrusion temperature feeding section / compression section / metering section / die =150℃ / 200℃ / 210℃ / 220℃ Die: 300mm wide coat hanger die Take-up roll temperature: 80℃ A two-component urethane adhesive (Takelac™ A-385 / Takenate™ A-50, manufactured by Mitsui Chemicals, Inc.) was applied to one side of the polypropylene sheet at a solid content of 2.5 g / m. 2 After coating with a basis weight of 1000 ppm, an ethylene-vinyl alcohol copolymer sheet (manufactured by Kuraray Co., Ltd., product name "EF-F 15 μm") was laminated as an adhesive layer by dry lamination to obtain a laminate having a polypropylene sheet (substrate layer), an adhesive layer, and an ethylene-vinyl alcohol copolymer sheet (adhesive layer) in this order. Furthermore, the laminate 1a obtained in Example 1 was used as a structure (referred to as structure 9b).

[0151] <Manufacturing of adhesive bodies and packaging containers> A packaging container, which is an adhesive body shown in FIG. 17 (schematic cross-sectional view), was produced as follows. The laminate obtained above was thermoformed (compressed air: 5 kg / cm) into a container shape (12 cm length x 9 cm width x 3 cm height) at a sheet temperature of 150°C using a thermoforming machine (manufactured by Asano Seisakusho). 2 A container-shaped laminate 1b (a laminate having a base layer 4b, an adhesive layer 3b, and an adhesive layer 2b in this order) with a flange width of 15 mm was obtained. The obtained container-shaped laminate 1b was stored at 20°C and 65% RH for one week, and the moisture content of the adhesive layer 2b in the container-shaped laminate 1b was measured by the above method and found to be 12.4%. Next, the flange surface of the container-shaped laminate 1b was used as a coating area, and a solution of water / methanol = 60 / 40 (mass %) was applied to the coating area in an amount of 12 g / m 2The liquid was applied using the water supply roll 7c used in Comparative Example 4 so that the adhesive layer 2b of the container-shaped laminate 1b covered 30.7% of the total area of ​​the adhesive layer 2b. Next, using a "Tray sealer T200" manufactured by MULTIVAC, the laminate 1b and the structure 9b were overlapped so that the adhesive layer 2b of the laminate 1b to which the liquid had been applied came into contact with the adhesive layer 2a of the structure 9b. After evacuating the container, the container was filled with nitrogen, and the overlapped laminate 1b and the structure 9b were pressed in the pressurization area (flange portion) using a hot plate at a pressure of 2 kgf / cm. 2 Pressurization was performed at a temperature of 170° C. Pressurization was performed so that the area ratio of the pressurized region to the area of ​​the coated region was 1.0, and the area ratio of the coated region and the pressurized region overlapping each other was 1.0 to the area of ​​the pressurized region. In this way, a packaging container was obtained which was an adhesive body 12b in which the container-shaped laminate (tray main body) 1b and the structure (lid) 9b were adhered together at the adhesive portion 13b.

[0152] The moisture content (mass%) of the adhesive layer in the laminates obtained in Examples 1 to 27 and Comparative Examples 1 to 5 and the oxygen permeability (OTR, mL / 20 μm / (m 2 The results of measuring the temperature (°C / day) and the appearance characteristics of the adhesive joint of the adhesive body (wrinkles and spots in the adhesive joint), and the adhesive strength and blocking resistance of the packaging container (pouch) are shown in Table 1. Table 1 also shows the material and thickness (μm) of the adhesive layer, the type and viscosity (cp) of the liquid used, the material and thickness (μm) of the structure, the application method in the application process, the amount applied and the area ratio of the applied region (area%), the pressing temperature (°C) in the pressing process, and the shape of the container.

[0153] [Table 1]

[0154] As shown in Table 1, the packaging containers obtained in Comparative Examples 1 and 4 had adhesion at unintended locations, making it impossible to open the openings, and were confirmed to have poor blocking resistance. Furthermore, the packaging containers obtained in Comparative Examples 2, 3, and 5 had adhesive strengths of less than 100 g / 15 mm, confirming poor adhesive strength. In contrast, the packaging containers obtained in Examples 1 to 27 were confirmed to have superior blocking resistance compared to Comparative Examples 1 and 4, and superior adhesive strength compared to Comparative Examples 2, 3, and 5. Therefore, it was found that the adhesive body of the present invention can form a packaging container having excellent adhesive strength and blocking resistance. [Explanation of symbols]

[0155] 1a... Laminate, 1b... Container-shaped laminate, 2a, 2b... Adhesive layer, 3a, 3b... Adhesive layer, 4a, 4b... Base material layer, 5a, 5b... Metal roll, 6a, 6b... Sponge part, 7a, 7b, 7c... Water supply roller 8...Liquid, 9a,9b...Structure, 10,11...Long hot plate, 12a,12b...Adhesive, 13a,13b...Adhesive part, 14...Three-sided bag, 15...Saucer, 16...Hole, 101...Rotation direction, 102...Cutting line

Claims

1. A method for producing a bonded body (Z) obtained by bonding a laminate (X) including an adhesive layer (A) and a structure (Y), comprising: A step (I) of applying the liquid (W) to a coating area of ​​1 to 45 area % of the total area of ​​the adhesive layer (A); A step (II) of superposing the adhesive layer (A) of the laminate (X) on the structure (Y); and A step (III) of pressing the stacked laminate (X) and the structure (Y) in a pressure region. Including, In the step (I), the water content of the adhesive layer (A) before the application of the liquid (W) is 3 to 20% by mass, the adhesive layer (A) is a film or sheet containing modified starch (a) as a main component or a film or sheet containing ethylene-vinyl alcohol copolymer (c) as a main component; The adhesive strength of the adhesive joint of the adhesive body (Z) is 100 g / 15 mm or more, The amount of the liquid (W) applied to the application area is 5 to 35 g / m 2 , When the adhesive layer (A) is a film or sheet containing modified starch (a) as a main component, the water content of the adhesive layer (A) before applying the liquid (W) in the step (I) is 6 to 19% by mass, When the adhesive layer (A) is a film or sheet containing the ethylene-vinyl alcohol copolymer (c) as a main component, the water content of the adhesive layer (A) before applying the liquid (W) in the step (I) is 3.5 to 12.4 mass%. method.

2. A method for producing a bonded body (Z) obtained by bonding a laminate (X) including an adhesive layer (A), comprising: A step (I) of applying the liquid (W) to a coating area of ​​1 to 45 area % of the total area of ​​the adhesive layer (A); A step (II') of folding the laminate (X) so that the adhesive layers (A) face each other or the adhesive layer (A) faces a layer other than the adhesive layer (A); and Step (III') of pressing the folded laminate (X) in a pressing region Including, In the step (I), the water content of the adhesive layer (A) before the application of the liquid (W) is 3 to 20% by mass, the adhesive layer (A) is a film or sheet containing modified starch (a) as a main component or a film or sheet containing ethylene-vinyl alcohol copolymer (c) as a main component; The adhesive strength of the adhesive joint of the adhesive body (Z) is 100 g / 15 mm or more, The amount of the liquid (W) applied to the application area is 5 to 35 g / m 2 , When the adhesive layer (A) is a film or sheet containing modified starch (a) as a main component, the water content of the adhesive layer (A) before applying the liquid (W) in the step (I) is 6 to 19% by mass, When the adhesive layer (A) is a film or sheet containing the ethylene-vinyl alcohol copolymer (c) as a main component, the water content of the adhesive layer (A) before applying the liquid (W) in the step (I) is 3.5 to 12.4 mass%. method.

3. The oxygen permeability of the adhesive layer (A) is 0.01 to 10 mL / min. ２ 3. The method according to claim 1 or 2, wherein the temperature is 100°C / day, 100°F / day, ...

4. The method according to any one of claims 1 to 3, wherein the laminate (X) further comprises paper (C).

5. The method according to any one of claims 1 to 4, wherein the pressure application region is heated in steps (III) and (III').

6. In step (I), the amount of liquid (W) applied to the application area is 10 to 30 g / m ２ The method according to any one of claims 1 to 5, wherein

7. 7. The method according to claim 1, wherein in step (I), the liquid (W) contains 50% by mass or more of water and has a viscosity of 0.3 to 100 cP.

8. 8. The method according to claim 1, wherein in step (I), the liquid (W) is applied by bringing a water supply roll (R) into contact with the application area of ​​the adhesive layer (A).

9. 9. The method according to claim 1, wherein in step (I), the liquid (W) is applied to the application area of ​​the adhesive layer (A) using a slit coater.

10. The method according to any one of claims 1 to 9, wherein in step (I), the liquid (W) is sprayed onto the application area of ​​the adhesive layer (A).

11. The method according to any one of claims 1 to 7, wherein in step (I), two or more methods selected from the group consisting of a method of bringing a water supply roll (R) into contact with the coating area of ​​the adhesive layer (A) to coat the liquid (W); a method of coating the coating area of ​​the adhesive layer (A) with the liquid (W) using a slit coater; and a method of spraying the liquid (W) onto the coating area of ​​the adhesive layer (A) are combined.

12. The method according to any one of claims 1 to 11, wherein the pressure zone is heated to 80 to 200°C in steps (III) and (III').

13. 13. The method according to any one of claims 1 to 12, wherein in step (I), the liquid (W) contains at least one selected from the group consisting of an alcohol-based solvent, a polyvinyl alcohol-based resin, gelatin, xanthan gum, carrageenan, guar gum, sodium carboxymethylcellulose, and pectin.

14. The method according to any one of claims 1 and 3 to 13, wherein the structure (Y) is a laminate (X') including an adhesive layer (A) or a laminate (Q) not including an adhesive layer (A).

15. The method according to claim 14, wherein in step (II), the adhesive layer (A) of the laminate (X) and the adhesive layer (A) of the laminate (X') are superposed so as to be in contact with each other.

16. The method according to any one of claims 1 to 15, wherein in steps (III) and (III'), the width of the pressurized region in the lateral direction is 5 to 30 mm.

17. 17. The method according to claim 1, wherein in steps (III) and (III'), the area of ​​the pressurized region is 0.5 to 1.5 times the area of ​​the coated region, and includes an overlapping portion between the pressurized region and the coated region.

18. The method according to any one of claims 1 to 17, wherein the area of ​​the overlapping portion between the pressurized region and the applied region is 0.5 to 2.0 times the area of ​​the pressurized region.

19. A method for producing a packaging container using an adhesive (Z) obtained by the method according to any one of claims 1 to 18.

20. 20. The method of claim 19, wherein the packaging container is a flat pouch, a stand-up pouch, a gusset pouch, a twin pouch, a spout pouch, a thermoformed container, or an injection molded container.

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