Laminates, packaging materials, and anchor coating agents

Abstract

The present invention provides a laminate that exhibits blocking resistance, good adhesion and lamination strength between the anchor coat layer and the vapor-deposited layer, retort resistance, and gas barrier properties, particularly good gas barrier properties even after retort processing. [Solution] A laminate comprising, at least in this order, an anchor coat layer with a thickness of 0.05 to 1.5 μm, a vapor deposition layer, and a barrier coat layer on a polyolefin substrate, wherein the anchor coat layer is a layer comprising a resin material containing methyl (meth)acrylate and a polar group-containing (meth)acrylic acid ester or (meth)acrylic acid, a curing agent, and an anchor coat agent containing a silane coupling agent, and the polar group in the resin material is at least one polar group selected from hydroxyl groups, amide groups, amino groups, phosphoric acid groups, and epoxy groups. The silane coupling agent is a silane coupling agent containing at least one group selected from a nitrogen atom-containing group, a sulfur atom-containing group, and a vinyl group, and the mixing ratio of the (meth)acrylate and the polar group-containing (meth)acrylate ester or (meth)acrylic acid is 5 or more and less than 900 parts polar group-containing (meth)acrylate ester or (meth)acrylic acid per 100 parts methyl (meth)acrylate, and the contact angle of the anchor coat layer surface is 20 degrees or more and 75 degrees or less.

Description

[Technical Field]

[0001] This invention relates to laminates, packaging materials, and anchor coating agents. [Background technology]

[0002] In recent years, with the aim of improving the recyclability of packaging containers, polypropylene film has been applied as a base material, and packaging materials using laminates composed of the same material (monomaterialization) have been investigated. However, concerns have been raised about a decrease in gas barrier properties, so studies have been conducted to compensate for this by forming a vapor-deposited film on the surface of the polypropylene film. However, the adhesion between the polypropylene film and the vapor-deposited film has not been sufficient, and the desired gas barrier properties have not been met.

[0003] Patent Document 1 describes a laminate comprising at least a first substrate, a vapor-deposited film, a barrier coat layer, and a sealant layer, wherein the first substrate is a biaxially oriented resin film comprising a polypropylene resin layer, a surface resin layer provided on one side of the polypropylene resin layer, and an adhesive resin layer between the polypropylene resin layer and the surface resin layer, the adhesive resin layer is provided on the polypropylene resin layer, the surface resin layer is provided on the adhesive resin layer, the vapor-deposited film is provided on the surface resin layer of the first substrate, the surface resin layer contains a resin material having a melting point of 180°C or higher, the resin material is vinyl resin, nylon 6, nylon 6,6, MXD nylon, or polyester, the vapor-deposited film is composed of an inorganic oxide, and the sealant layer contains a polyolefin having a melting point of 110°C or higher, and this laminate can be suitably used for monomaterial packaging containers, significantly improves the adhesion between the substrate and the vapor-deposited film layers, achieves desirable gas barrier properties, and forms a heat-resistant laminate.

[0004] Patent Document 2 describes a packaging bag comprising a barrier laminate having a first substrate, a first adhesive layer, a second substrate, a second adhesive layer, and a sealant layer in this order in the thickness direction, wherein the first substrate is a stretched polypropylene resin substrate, the second substrate is a barrier substrate comprising a stretched polypropylene resin layer and a vapor-deposited film composed of an inorganic oxide, the second substrate is arranged such that the vapor-deposited film faces the first substrate side and the polypropylene resin layer faces the sealant layer side, the sealant layer is a polypropylene resin layer, the thickness of the first adhesive layer is 2 μm or less, and the thickness of the second adhesive layer is 2 μm or less, and this packaging bag can improve gas barrier properties and, in particular, can form a packaging bag that has excellent gas barrier properties even after retort processing.

[0005] Furthermore, Patent Document 3 describes a packaging bag comprising a barrier laminate having a first substrate, a first adhesive layer, a second substrate, a second adhesive layer, and a sealant layer in this order in the thickness direction, wherein the first substrate is a stretched polypropylene resin substrate, and the second substrate is a barrier substrate comprising a stretched polypropylene resin layer and a vapor-deposited film composed of an inorganic oxide, wherein the vapor-deposited film faces the first substrate side and the polypropylene resin layer faces the sealant layer side, the sealant layer is a polypropylene resin layer, the thickness of the first adhesive layer is 10 μm or less, and the thickness of the second adhesive layer is 10 μm or less, and this packaging bag can improve gas barrier properties and, in particular, can form a packaging bag that has excellent gas barrier properties even after retort processing.

[0006] However, in all of the patent documents 1 to 3, the first and second adhesive layers are composed of solvent-type adhesives, which may degrade the vapor-deposited film and destabilize the barrier laminate. Furthermore, while including a resin material with polar groups in the coating layer between the polypropylene resin layer and the vapor-deposited film (described as a surface resin layer in patent document 1, and a surface coating layer or surface resin layer in patent documents 2 and 3) is thought to contribute to improving gas barrier properties, especially after retort processing, this alone may be insufficient.

[0007] Patent Document 4 describes a liquid pouch packaging body comprising at least one transparent gas barrier film having a surface layer comprising a base film made of polyamide resin, an easy-adhesion layer formed on one side of the base film containing nitrogen atoms, adipic acid, and bisphenol glycidyl ether, a vapor-deposited anchor coat layer formed on the easy-adhesion layer with a thickness of 0.08 μm to 0.3 μm containing a polyol, an isocyanate compound, and its reaction product, and an inorganic oxide layer formed on the anchor coat layer by vapor deposition, with heat-adhesion resin layers sequentially laminated, and further comprising a packaging bag made by using this laminate, overlapping the heat-adhesion resin layers with their surfaces facing each other, and fusing the edges around the outer periphery, and a liquid pouch packaging body in which the contents are filled and packaged in the packaging bag through its opening, which has high barrier properties and excellent laminate strength even in wet conditions, is resistant to tearing, and is environmentally friendly. However, while the inclusion of two layers—an easy-adhesion layer containing a water-dispersible polyurethane resin to provide water resistance, heat resistance, adhesion, and film cohesiveness, and a vapor-deposited anchor coat layer containing a (urethane-bonded) reaction product of a polyol, isocyanate compound, and silane coupling agent to strengthen adhesion with the inorganic oxide layer—seems effective for adhesion to a polyamide resin substrate film, adhesion may be inferior with a polyolefin substrate. Furthermore, although it is stated that an intermediate film is preferable for boiling and retort sterilization, this is to increase the bag-breaking strength, and increasing the layer structure increases the environmental burden and may destabilize the laminate.

[0008] Patent Document 5 describes a laminate in which at least a base film, a gas barrier precursor laminate, an adhesive layer, and a thermoplastic resin layer are laminated in this order, wherein the gas barrier precursor laminate is a laminate containing a layer (A) containing a polycarboxylic acid polymer (A1) and at least one silicon-containing compound (A2) selected from the group consisting of a specific silane coupling agent, its hydrolysates, and condensates thereof, in a specific mass ratio, and a layer (B) containing a polyvalent metal compound, and further an anchor coat layer is formed on the base film, and the laminate is hot water treatable and has excellent gas barrier properties. However, a gas barrier precursor laminate is laminated on the anchor coat layer, and this gas barrier precursor laminate contains a polycarboxylic acid polymer and is not a vapor-deposited film. Comparative Examples 1 and 2 of Patent Document 5 show examples in which an alumina vapor-deposited film and a silica vapor-deposited film were formed, and it is clear that the oxygen barrier effect after retorting is not exhibited, and it is clear that the problem cannot be solved even if a vapor-deposited film is formed on the anchor coat layer formed using the anchor coat liquid of Patent Document 5. Furthermore, regarding the anchor coat layer, the claims and specification suggest that the anchor coat solution used is a composite of at least one metal compound (P) selected from the group consisting of trifunctional organosilanes (p1), metal alkoxides (p2), and their hydrolysates, a polyol compound (Q), and an isocyanate compound (R). However, since there is no specific disclosure, excessive trial and error occurs in selecting the anchor coat solution in an attempt to solve the problem described in Patent Document 5.

[0009] Patent Document 6 describes a metal vapor-deposited film in which at least an anchor coat layer and a metal thin film layer are sequentially formed on one side of a polypropylene film, wherein the anchor coat layer is a layer containing at least a urethane-based resin and a cellulose-based resin, and at least a curing agent, and the film can maintain excellent adhesion between the polypropylene film and the metal thin film layer, and excellent adhesion of the heat-sealed portion even after heat sealing. However, retort processing is not considered at all, and there is no description or indication of gas barrier properties after retort processing, which may result in inferior performance.

[0010] Patent Document 7 describes a gas barrier laminate in which an inorganic oxide vapor deposition layer and a barrier coat layer are laminated in this order on one surface of a base film made of a plastic material, wherein an anchor coat layer is provided between the vapor deposition surface of the base film and the inorganic oxide vapor deposition layer, and the anchor coat layer is a layer formed by the reaction curing of an anchor coat agent containing a hydroxyl group-containing acrylic resin, an isocyanate compound and a silane coupling agent, and the barrier coat layer is of general formula R 1 n M(OR 2 ) m (In the formula, R 1 , R 2is an organic group having 1 to 8 carbon atoms, M is a metal atom, n is an integer of 0 or more, m is an integer of 1 or more, and n + m is the valence of M), and one or more alkoxides represented by the formula are polycondensed with a water-soluble polymer by a sol-gel method to obtain a gas barrier composition, and the layer is formed by applying the gas barrier composition. The gas barrier laminate is described, has good gas barrier properties, and is less likely to cause delamination between layers against any stress. However, even the above anchor coat layer may have poor adhesion to the vapor deposition layer, and particularly there is a possibility that high gas barrier properties after retort treatment cannot be maintained.

Prior Art Documents

Patent Documents

[0011]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Patent Document 6

Patent Document 7

Summary of the Invention

[0013] The inventors of the present invention have found that a laminate having at least an anchor coat layer with a thickness of 0.05 to 1.5 μm, a vapor deposition layer, and a barrier coat layer in this order on a polyolefin substrate can achieve the above object, and thus completed the present invention. The anchor coat layer is a layer composed of an anchor coating agent containing methyl (meth)acrylate and a resin material containing a polar group-containing (meth)acrylate or (meth)acrylic acid, a curing agent, and a silane coupling agent. The polar group in the resin material is at least one polar group selected from a hydroxyl group, an amide group, an amino group, a phosphate group, and an epoxy group. The silane coupling agent is a silane coupling agent containing at least one group selected from a group containing a nitrogen atom, a group containing a sulfur atom, and a vinyl group. The mixing ratio of the methyl (meth)acrylate and the polar group-containing (meth)acrylate or (meth)acrylic acid is such that the polar group-containing (meth)acrylate or (meth)acrylic acid is 5 or more and less than 900 with respect to 100 of the methyl (meth)acrylate, and the contact angle of the surface of the anchor coat layer is 20 degrees or more and 75 degrees or less.

[0014] That is, the present invention relates to (1) A laminate comprising at least an anchor coat layer with a thickness of 0.05 to 1.5 μm, a vapor deposition layer, and a barrier coat layer in this order on a polyolefin substrate, where the anchor coat layer is a layer composed of an anchor coating agent containing methyl (meth)acrylate and a resin material containing a polar group-containing (meth)acrylate or (meth)acrylic acid, a curing agent, and a silane coupling agent; the polar group in the resin material is at least one polar group selected from a hydroxyl group, an amide group, an amino group, a phosphate group, and an epoxy group; the silane coupling agent is a silane coupling agent containing at least one group selected from a group containing a nitrogen atom, a group containing a sulfur atom, and a vinyl group; The mixing ratio of the methyl (meth)acrylate and the polar group-containing (meth)acrylate ester or (meth)acrylic acid is such that the polar group-containing (meth)acrylate ester or (meth)acrylic acid is 5 or more and less than 900 parts per 100 parts methyl (meth)acrylate. Furthermore, the laminate is characterized in that the contact angle of the surface of the anchor coat layer is 20 degrees or more and 75 degrees or less. (2) Packaging material characterized by using the laminate described in (1), (3) An anchor coating agent used in the laminate described in (1), The anchor coating agent comprises a resin material containing methyl (meth)acrylate and a polar group-containing (meth)acrylic acid ester or (meth)acrylic acid, a curing agent, and a silane coupling agent. The polar group in the resin material is at least one polar group selected from hydroxyl groups, amide groups, amino groups, phosphate groups, and epoxy groups. The silane coupling agent is a silane coupling agent containing at least one group selected from a group containing a nitrogen atom, a group containing a sulfur atom, and a vinyl group. The mixing ratio of the methyl (meth)acrylate and the polar group-containing (meth)acrylic acid or (meth)acrylic acid is such that the polar group-containing (meth)acrylic acid ester or (meth)acrylic acid is 5 or more and less than 900 parts per 100 parts methyl (meth)acrylate. An anchor coating agent characterized in that the contact angle of the surface of the anchor coating layer formed by printing the anchor coating agent is 20 degrees or more and 75 degrees or less. (4) A step of preparing a polyolefin substrate, A step of forming an anchor coat layer with a thickness of 0.05 to 1.5 μm on at least one of the polyolefin substrates, The process of forming a vapor-deposited layer on the anchor coat layer, A method for manufacturing a laminate, comprising at least the step of forming a barrier coat layer on the vapor-deposited layer, The step of forming the anchor coat layer is a step of printing an anchor coat agent comprising a resin material containing methyl (meth)acrylate and a polar group-containing (meth)acrylic acid ester or (meth)acrylic acid, a curing agent, and a silane coupling agent. The polar group in the resin material is at least one group selected from hydroxyl groups, amide groups, amino groups, and phosphate groups. The silane coupling agent is a silane coupling agent containing at least one group selected from a group containing a nitrogen atom, a group containing a sulfur atom, and a vinyl group. The mixing ratio of the methyl (meth)acrylate and the polar group-containing (meth)acrylate ester or (meth)acrylic acid is such that the polar group-containing (meth)acrylate ester or (meth)acrylic acid is 5 or more and less than 900 parts per 100 parts methyl (meth)acrylate. A method for manufacturing a laminate, characterized in that the contact angle of the surface of the anchor coat layer formed by the anchor coat layer formation step is 20 degrees or more and 75 degrees or less. (5) The method for manufacturing a laminate according to (4), characterized in that the step of forming the anchor coat layer is a gravure printing step, (6) A method for manufacturing a laminate according to (4) or (5), characterized in that it includes a winding step after the anchor coat layer formation step, (7) A method for manufacturing a laminate according to (6), characterized in that, after the winding step, the method further includes a step of forming a vapor-deposited layer and a step of forming a barrier coat layer while unwinding, This concerns... [Effects of the Invention]

[0015] According to the present invention, it is possible to provide a laminate that has blocking resistance, good adhesion and lamination strength between the anchor coat layer and the vapor-deposited layer, retort resistance, gas barrier properties, and in particular good gas barrier properties even after retort treatment.

[0016] The embodiments for carrying out the present invention will be described in detail below. It should be noted that this embodiment is merely one embodiment for carrying out the present invention, and the present invention is not limited to this embodiment. Various modifications and embodiments are possible without departing from the spirit of the present invention.

[0017] In the following explanation, (meth)acrylic and (meth)acrylate refer to acrylic and methacrylic, and acrylate and methacrylate, respectively.

[0018] The laminate of the present invention is a laminate comprising, at least in this order, an anchor coat layer having a thickness of 0.05 to 1.5 μm, a vapor deposition layer, and a barrier coat layer on a polyolefin substrate, wherein the anchor coat layer is a layer comprising a resin material containing methyl (meth)acrylate and a polar group-containing (meth)acrylic acid ester or (meth)acrylic acid, a curing agent, and a silane coupling agent, and the polar group in the resin material is at least one polar group selected from hydroxyl groups, amide groups, amino groups, phosphoric acid groups, and epoxy groups, and The silane coupling agent is a silane coupling agent containing at least one group selected from a nitrogen atom-containing group, a sulfur atom-containing group, and a vinyl group, wherein the mixing ratio of the (meth)acrylate and the polar group-containing (meth)acrylate ester or (meth)acrylic acid is 5 or more and less than 900 parts of the polar group-containing (meth)acrylate ester or (meth)acrylic acid per 100 parts of the (meth)acrylate, and the contact angle of the anchor coat layer surface is preferably 20 degrees or more and 75 degrees or less.

[0019] In the present invention, the anchor coat layer is preferably a layer comprising a resin material containing methyl (meth)acrylate and a polar group-containing (meth)acrylic acid ester or (meth)acrylic acid, a curing agent, and an anchor coat agent containing a silane coupling agent.

[0020] The polar group-containing (meth)acrylic acid ester is preferably such that the polar group is at least one group selected from a hydroxyl group, an amide group, an amino group, a phosphate group, and an epoxy group. Having the polar group improves the wettability with the vapor-deposited layer and contributes to adhesion.

[0021] Examples of hydroxyl group-containing (meth)acrylic acid esters in which the polar group is a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and glycerol mono(meth)acrylate, with 2-hydroxyethyl methacrylate being more preferred.

[0022] Examples of amide-containing (meth)acrylic acid esters in which the polar group is an amide group include N-(1,1-dimethyl-3-oxybutyl)(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-dimethylaminopropyl(meth)acrylamide, N-isopropyl(meth)acrylamide, Nt-butyl(meth)acrylamide, N-(hydroxymethyl)acrylamide, and (2)-hydroxypropyl(meth)acrylamide, among which N-(1,1-dimethyl-3-oxybutyl)acrylamide is more preferred.

[0023] Examples of amino group-containing (meth)acrylic acid esters in which the polar group is an amino group include N,N-dimethylaminoethyl (meth)acrylate and N,N-diethylaminoethyl (meth)acrylate, with N,N-dimethylaminoethyl methacrylate being more preferred.

[0024] Examples of phosphate-containing (meth)acrylic acid esters in which the polar group is a phosphate group include phosphate (meth)acrylate, 2-(meth)acryloyloxyethyl acid phosphate, di-(2-methacryloyloxyethyl)-phosphate, 2-(meth)acryloyloxypropyl acid phosphate, 2-(meth)acryloyloxybutyl acid phosphate, acid phosphooxypolyoxypropylene glycol monomethacrylate, and acid phosphooxypolyoxyethylene glycol monomethacrylate, among which 2-methacryloyloxyethyl acid phosphate is more preferred.

[0025] Examples of epoxy group-containing (meth)acrylic acid esters in which the polar group is an epoxy group include glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, 3,4-epoxycyclohexylmethyl (meth)acrylate, 3-epoxycyclo-2-hydroxypropyl (meth)acrylate, 6-methyl-3,4-epoxycyclohexylmethyl (meth)acrylate, (meth)acrylate-3,4-epoxybutyl, (meth)acrylate-6,7-epoxyheptyl, α-ethyl (meth)acrylate-6,7-epoxyheptyl, α-ethyl acrylate glycidyl, α-n-propyl acrylate glycidyl, and α-n-butyl acrylate glycidyl, among which glycidyl methacrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, and 3,4-epoxycyclohexylmethyl (meth)acrylate are more preferred.

[0026] The mixture of methyl (meth)acrylate and polar group-containing (meth)acrylic acid ester or (meth)acrylic acid is preferably in a ratio of 5 to less than 900 units of polar group-containing (meth)acrylic acid ester or (meth)acrylic acid per 100 units of methyl (meth)acrylate, more preferably 10 to less than 500 units, and even more preferably 20 to less than 300 units. If the mixing ratio is less than 5, the contact angle will be large, and the adhesion between the anchor coat layer and the vapor-deposited layer may be poor. If the mixing ratio is 900 or more, the film will harden, and the adhesion between the polyolefin substrate and the anchor coat layer may be poor. By using a mixture of the aforementioned methyl (meth)acrylate and the aforementioned polar group-containing (meth)acrylic acid ester or the aforementioned (meth)acrylic acid, it is possible to improve heat resistance and adhesion to polyolefin substrates or vapor-deposited layers.

[0027] The amount of the resin material containing methyl (meth)acrylate and polar group-containing (meth)acrylic acid ester or (meth)acrylic acid added is preferably 3 to 90% by mass, more preferably 5 to 80% by mass, and even more preferably 10 to 70% by mass, based on 100% of the total amount of the anchor coating agent. These may be used individually or in combination of two or more types.

[0028] The curing agent is preferably a polyisocyanate compound, and is not particularly limited. It is selected from conventionally known polyisocyanates, and includes aliphatic polyisocyanates or aromatic aliphatic polyisocyanates. For example, aromatic diisocyanates such as tolylene diisocyanate and 4,4'-diphenylmethane diisocyanate, aliphatic diisocyanates such as hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, 4,4'-dicyclohexyl diisocyanate, and pentane-1,5-diisocyanate (Stavio PDI), as well as modified forms thereof such as trimethylolpropane trimers, isocyanurates, burettes, and allophanates. Commercially available products include LG curing agent C and LG curing agent D (both manufactured by Tokyo Ink Co., Ltd.). These may be used individually or in combination of two or more types.

[0029] The amount of the curing agent added is preferably 1 to 20% by mass, more preferably 2 to 18% by mass, and even more preferably 4 to 15% by mass, based on 100% of the total amount of the anchor coating agent. These may be used individually or in combination of two or more types.

[0030] Preferably, the silane coupling agent contains at least one group selected from a nitrogen atom-containing group, a sulfur atom-containing group, and a vinyl group. Including a silane coupling agent having the specific group contributes to improving the adhesion between the anchor coat layer and the vapor-deposited layer.

[0031] Groups containing a nitrogen atom include amino groups, imino groups, isocyanate groups (-N=C=O), ureido groups (-NH-CO-NH2), nitro groups (=NO), carbamate groups (-O-CO-N<), and quaternary ammonium salts.

[0032] Examples of silane coupling agents containing an amino group include 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltripropoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, bis(3-triethoxysilylpropyl)amine, bis(3-trimethoxysilylpropyl)amine, bis(3-methyldimethoxysilylpropyl)amine, bis(triethoxysilylmethyl)amine, and N-(2-aminoethyl)-3 Examples of trialkoxysilanes include aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldiethoxysilane, N-(n-butyl)-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N,N'-bis[3-(trimethoxysilyl)propyl]ethylenediamine, and hydrochloride salts of N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane. Among these, 3-aminopropyltrimethoxysilane and N-(2-aminoethyl)-3-aminopropyltrimethoxysilane are more preferred.

[0033] Examples of commercially available products include KBP-64, KBP-90, KBE-9103P, KBE-903, KBM-6803, KBM-573, KBM-575, KBM-602, KBM-603, KBM-903, KBM-6103, X-12-1172ES, X-12-972F, X-12-5263HP, and X-88-475 (all manufactured by Shin-Etsu Chemical Co., Ltd.).

[0034] Examples of silane coupling agents having an isocyanate group include trialkoxysilanes such as 3-isocyanatetopropyltrimethoxysilane, 3-isocyanatetopropyltriethoxysilane, 3-isocyanatetopropylmethyldimethoxysilane, and 3-isocyanatetopropylmethyldiethoxysilane, as well as trimers (isocyanurates) of these compounds, with 3-isocyanatetopropyltrimethoxysilane being more preferred.

[0035] Commercially available products include KBE-9007N, X-12-1159, X-12-1159L, KBM-9659 (all manufactured by Shin-Etsu Chemical Co., Ltd.), SILQUEST Silane A-1310, and SILQUEST Silane Y-5187 (both manufactured by MOMENTIVE).

[0036] Examples of silane coupling agents having a ureido group include trialkoxysilanes such as 3-ureidopropyltrialkoxysilane.

[0037] Examples of commercially available products include KBE-585A and KBM-585 (both manufactured by Shin-Etsu Chemical Co., Ltd.).

[0038] Examples of silane coupling agents having a nitro group include trialksylanes such as 3-nitropropyltrimethoxysilane and 3-nitropropyltriethoxysilane.

[0039] Examples of silane coupling agents having a carbamate group include (3-carbamate ethyl)propyltrimethoxysilane, (3-carbamate ethyl)propyltripropaxysilane, (3-carbamate propyl)propyltriethoxysilane, (3-carbamate propyl)propyltrimethoxysilane, (3-carbamate propyl)propyltripropaxysilane, (3-carbamate butyl)propyltriethoxysilane, (3-carbamate butyl)propyltrimethoxysilane, (3-carbamate butyl)propyltripropaxysilane, (3-carbamate butyl)butyltripropaxysilane, (3-carbamate butyl Examples of trialksylanes include (3-carbamate pentyl)propyltriethoxysilane, (3-carbamate hexyl)propyltriethoxysilane, (3-carbamate octyl)pentyltributoxysilane, (3-carbamate ethyl)propylsilyl trichloride, (3-carbamate ethyl)propyltrimethylsilane, (3-carbamate ethyl)propyldimethylsilane, (3-carbamate ethyl)propyltributylsilane, (3-carbamate ethyl)ethyl-p-xylentriethoxysilane, and (3-carbamate ethyl)-p-phenylentriethoxysilane.

[0040] Examples of silane coupling agents containing quaternary ammonium salts include commercially available products such as X-12-1126, KBM-9418-40, POLON-V8, X-12-1139, and X-12-1354-1 (all manufactured by Shin-Etsu Chemical Co., Ltd.).

[0041] Examples of functional groups containing sulfur atoms include mercapto groups and sulfide groups.

[0042] Examples of silane coupling agents having a mercapto group include trialksylanes such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltripropoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, 2-mercaptoethyltrimethoxysilane, and 2-mercaptoethyltriethoxysilane.

[0043] Examples of commercially available products include KBM-802, KBM-803, X-12-1307, X-12-1056ES, and X-12-1154 (all manufactured by Shin-Etsu Chemical Co., Ltd.).

[0044] Examples of silane coupling agents having a sulfide group include bis(3-triethoxysilylpropyl)tetrasulfide, bis(2-triethoxysilylethyl)tetrasulfide, bis(4-triethoxysilylbutyl)tetrasulfide, bis(3-trimethoxysilylpropyl)tetrasulfide, Bis(2-trimethoxysilylethyl)tetrasulfide, Bis(4-trimethoxysilylbutyl)tetrasulfide, Bis(3-triethoxysilylpropyl) trisulfide, Bis(2-triethoxysilylethyl) trisulfide, Bis(4-triethoxysilylbutyl) trisulfide, Bis(3-trimethoxysilylpropyl) trisulfide, Bis(2-trimethoxysilylethyl) trisulfide, Bis(4-trimethoxysilylbutyl) trisulfide, Bis(3-triethoxysilylpropyl) disulfide, Bis(2-triethoxysilylethyl) disulfide, Bis(4-triethoxysilylbutyl) disulfide, Bis(3-trimethoxysilylpropyl) disulfide, Bis(2-trimethoxysilylethyl) dis Examples of trialksylanes include rufid, bis(4-trimethoxysilylbutyl) disulfide, 3-trimethoxysilylpropyl-N,N-dimethylthiocarbamoyl tetrasulfide, 3-triethoxysilylpropyl-N,N-dimethylthiocarbamoyl tetrasulfide, 2-triethoxysilylethyl-N,N-dimethylthiocarbamoyl tetrasulfide, 2-trimethoxysilylethyl-N,N-dimethylthiocarbamoyl tetrasulfide, 3-trimethoxysilylpropylbenzothiazolyl tetrasulfide, 3-triethoxysilylpropylbenzothiazole tetrasulfide, 3-triethoxysilylpropyl methacrylate monosulfide, and 3-trimethoxysilylpropyl methacrylate monosulfide.

[0045] Examples of silane coupling agents having a vinyl group include trialkoxysilanes such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, vinyltributoxysilane, vinylmethyldimethoxysilane, and vinylmethyldiethoxysilane.

[0046] Examples of commercially available products include KBE-1003, KBM-1003, KBM-1083, and X-12-1290 (all manufactured by Shin-Etsu Chemical Co., Ltd.).

[0047] The amount of silane coupling agent added is preferably 0.1 to 10% by mass, more preferably 0.5 to 7% by mass, and even more preferably 1 to 5% by mass, based on 100% of the total amount of anchor coating agent. These may be used individually or in combination of two or more types.

[0048] In addition to the resin material containing methyl (meth)acrylate and polar group-containing (meth)acrylic acid ester or (meth)acrylic acid, a curing agent, and a silane coupling agent, the anchor coating agent may also contain, as needed, organic solvents, colorants, inorganic fillers, organic fillers, defoamers, leveling agents, pigment dispersants, antistatic agents, slip agents, plasticizers, tackifiers, etc. One or more of these may be added.

[0049] The anchor coating agent of the present invention is preferably used in gravure printing and can be applied as is. However, depending on the coating conditions and coating effect, it can be diluted with a diluent solvent using Zahn Cup #3 (manufactured by Rigosha Co., Ltd.) to adjust the viscosity to the desired level. In this case, the viscosity is preferably 10 to 40 seconds at 25°C. If it is less than 10 seconds, it will be too fluid, and if it is greater than 40 seconds, the transferability during printing will be poor.

[0050] The anchor coat layer in the present invention is a layer made of the anchor coat agent, and is preferably formed by gravure printing on a polyolefin substrate to a thickness of 0.05 to 1.5 μm, more preferably to a thickness of 0.08 to 1.2 μm, and even more preferably to a thickness of 0.1 to 1.0 μm. If the thickness is less than 0.05 μm, the vapor deposition layer on the anchor coat layer is susceptible to cracking due to substrate shrinkage caused by heat treatment such as retort processing, which may result in poor gas barrier properties. If the thickness exceeds 1.5 μm, adhesion to the polyolefin substrate and blocking resistance may be poor. In particular, it is more preferable to form the layer by gravure printing using a multi-color gravure printing machine. This allows the anchor coat layer to be printed and wound up by gravure printing. The anchor coat layer formed by the anchor coat agent of the present invention is stable after printing, allowing it to be stored in a rolled state. Furthermore, a vapor deposition layer and a barrier coat layer can be formed on the anchor coat layer.

[0051] In the present invention, the contact angle of the anchor coat layer surface is preferably 20 degrees or more and 75 degrees or less, more preferably 30 degrees or more and 65 degrees or less, and even more preferably 40 degrees or more and 55 degrees or less. When the contact angle is within the above range, the adhesion between the polyolefin substrate and the vapor-deposited layer is dramatically improved, and cracks are less likely to occur in the vapor-deposited layer, thereby obtaining good gas barrier properties, especially good gas barrier properties even after retort treatment. If the contact angle is less than 20 degrees, the adhesion with the vapor-deposited layer may be poor, and if the contact angle exceeds 75 degrees, the polarity of the anchor coat layer itself becomes high, which may result in poor adhesion with the polyolefin substrate.

[0052] The aforementioned contact angle was measured 1 second after dropping distilled water at a rate of 2 μm onto the surface of the anchor coat layer under the conditions of a measurement temperature of 5°C and a relative humidity of 50% (50% RH). The aforementioned contact angle can be measured using a contact angle meter (portable contact angle meter PCA-1, manufactured by Kyowa Interface Science Co., Ltd.).

[0053] The laminate of the present invention preferably comprises a vapor-deposited layer on the anchor coat layer, wherein the vapor-deposited layer is a vapor-deposited film made of an inorganic oxide or a metal thin film.

[0054] Examples of the inorganic oxides include aluminum oxide (alumina), silicon oxide (silica), magnesium oxide, calcium oxide, zirconium oxide, titanium oxide, boron oxide, hafnium oxide, barium oxide, silicon carbide oxide (carbon-containing silicon oxide), or mixtures thereof. Among these, silica, silicon carbide oxide, and alumina are preferred, and silica is even more preferred because it does not require aging treatment after the deposition film is formed. The metal used in the deposited film consisting of the aforementioned thin metal film can be any of the conventionally known metals such as aluminum, chromium, tin, gold, silver, copper, zinc, and nickel, and can be appropriately selected depending on the desired purpose. Furthermore, the metal deposited film may be a thin film of an oxide, sulfide, or nitride of the conventionally known metal. The metal deposited film may also consist of a single layer, or multiple layers of different or identical metals. Among these, aluminum is more preferred.

[0055] For forming the aforementioned vapor-deposited layer, for example, physical vapor deposition (PVD) methods such as vacuum deposition, sputtering, ion plating, and ion cluster beam deposition, or chemical vapor deposition (CVD) methods such as plasma CVD, thermal CVD, photoCVD, and MOCVD can be used. When using vacuum deposition, for example, electron beam heating, resistance heating, or induction heating can be used as the heating method for the vaporized material. When using electron beam heating, there is a greater degree of freedom in selecting the vaporized material. By using plasma-assisted or ion beam-assisted deposition during deposition, a denser vapor-deposited layer can be formed. Furthermore, by using reactive deposition, which involves blowing in gases such as oxygen during chemical deposition, a vapor-deposited layer with excellent transparency can be formed.

[0056] The thickness of the vapor-deposited layer is preferably in the range of 1 to 150 nm, more preferably in the range of 5 to 60 nm, and even more preferably in the range of 10 to 40 nm. If the thickness is less than 1 nm, the desired gas barrier properties may not be achieved, and if the thickness exceeds 150 nm, the polyolefin substrate may deform or deteriorate due to the heat generated when forming the vapor-deposited layer, and cracks may easily occur in the vapor-deposited layer, impairing the gas barrier properties.

[0057] The laminate of the present invention preferably includes a barrier coat layer on the vapor deposition layer, and the barrier coat layer is a coating film of a gas barrier coating agent obtained by polycondensing an alkoxide and a water-soluble polymer by a sol-gel method. As a coating method for forming the barrier coat layer, known coating methods can be used. For example, printing methods such as gravure printing and flexographic printing, wet coating methods using roll coaters, reverse roll coaters, gravure offset coaters, gravure coaters, microgravure coaters, knife coaters, bar coaters, wire bar coaters, die coaters, dip coaters, spin coaters, spray coaters, etc. can be used. Among them, gravure printing, roll coaters, etc. are more preferable.

[0058] As the alkoxide that can be used in the gas barrier coating agent, one or more alkoxides selected from alkoxides represented by the general formula R 1 n M(OR 2 ) m and their hydrolyzates are preferable. In the formula, R 1 , R 2 are organic groups having 1 to 8 carbon atoms, M is a metal atom, n is an integer of 0 or more, m is an integer of 1 or more, and n + m is the valence of M.

[0059] As the metal atom M, for example, silicon, zirconium, titanium, aluminum, etc. are preferable. Also, alkoxides of one or two or more different metal atoms may be mixed in the same solution.

[0060] Further, in the alkoxide, the organic group represented by R 1 is an alkyl group, cycloalkyl group, aryl group or aralkyl group, and may have a substituent. For example, alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-hexyl group, n-octyl group, etc. can be mentioned.

[0061] Also, R 2 The organic group represented by is an alkyl group having 1 to 4 carbon atoms. Examples include the methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, and sec-butyl group.

[0062] Note, R 1 , R 2 In this case, these alkyl groups may be the same or different.

[0063] The general formula R 1 n M(OR 2 ) m Alkoxides represented by and their hydrolysates include those in which the metal atom M is Si (in the case of Si, also called silane coupling agents), such as tetraethoxysilane (TEOS), tetramethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, butyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, propyltriethoxysilane, butyltriethoxysilane, methyltripropoxysilane, ethyltripropoxysilane, dimethyldimethoxysilane, diethyldimethoxysilane, dipropyldimethyl Examples of alkoxysilanes include xysilane, dimethyldiethoxysilane, diethyldiethoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, diphenyldimethoxysilane, and diphenyldiethoxysilane. Tetraethoxysilane and tetramethoxysilane are more preferred because they provide good gas barrier properties.

[0064] The water-soluble polymer can be one or more water-soluble polymers selected from vinyl alcohol polymers such as polyvinyl alcohol, ethylene vinyl alcohol polymers, vinylpyrrolidone polymers, acrylic acid polymers, starch, methylcellulose, carboxymethylcellulose, sodium alginate, etc., and it is preferable that one or more polymers selected from vinyl alcohol polymers, ethylene vinyl alcohol polymers, vinylpyrrolidone polymers, and acrylic acid polymers are used because suitable gas barrier properties can be obtained.

[0065] The vinyl alcohol polymer can generally be one obtained by saponifying polyvinyl acetate. A degree of saponification of 95% or higher is preferable. Furthermore, a degree of polymerization of 300 or higher is preferable, more preferably 300 to 2400, and even more preferably 450 to 2000. A degree of saponification of 95% or higher easily provides sufficient gas barrier properties, and a degree of polymerization of 300 or higher provides excellent gas barrier properties and film cohesive strength. Examples of commercially available polyvinyl alcohols include POVAL (manufactured by Kuraray Co., Ltd.) and GoseNol (manufactured by Mitsubishi Chemical Corporation).

[0066] Furthermore, as the ethylene vinyl alcohol copolymer, a saponified product of a copolymer of ethylene and vinyl acetate, i.e., one obtained by saponifying an ethylene-vinyl acetate random copolymer, can be used. For example, commercially available polyethylene vinyl alcohol products include EVAL (manufactured by Kuraray Co., Ltd.) and Soanol (manufactured by Mitsubishi Chemical Corporation).

[0067] The content of the water-soluble polymer is preferably in the range of 5 to 500 parts by mass per 100 parts by mass of the total amount of the alkoxide. If the content of the water-soluble polymer is less than 5 parts by mass, the gas barrier properties will be poor. If it exceeds 500 parts by mass, the heat resistance and water resistance will be poor.

[0068] In polycondensation by the sol-gel method, it is preferable to include an acid or amine compound as the sol-gel catalyst. The amine compound is preferably a tertiary amine that is substantially insoluble in water and soluble in organic solvents, such as N,N-dimethylbenzylamine, tripropylamine, tributylamine, and tripentylamine. Among these, N,N-dimethylbenzylamine is more preferred.

[0069] The sol-gel catalyst is preferably in the range of 0.01 to 1.0 parts by mass, and more preferably in the range of 0.03 to 0.3 parts by mass, per 100 parts by mass of the alkoxide. The catalytic effect of the sol-gel catalyst can be improved by using 0.01 parts by mass or more per 100 parts by mass of alkoxide. Furthermore, by using 1.0 part by mass or less per 100 parts by mass of alkoxide, the thickness of the formed barrier coat layer can be made uniform.

[0070] The aforementioned gas barrier coating agent may further contain an acid. The acid is used as a sol-gel catalyst, mainly as a catalyst for hydrolysis of alkoxides and silane coupling agents. Examples of the acid include mineral acids such as sulfuric acid, hydrochloric acid, and nitric acid, as well as organic acids such as acetic acid and tartaric acid. The amount of acid used is preferably 0.001 to 0.05 moles relative to the total molar amount of the alkoxide portion (e.g., silicate portion) of the alkoxide (or silane coupling agent). The catalytic effect can be improved by using an amount of acid equal to 0.001 moles or more relative to the total molar amount of the alkoxide component (e.g., silicate portion) of the alkoxide (or silane coupling agent). Furthermore, by using an amount of acid equal to 0.05 moles or less relative to the total molar amount of the alkoxide component (e.g., silicate portion) of the alkoxide (or silane coupling agent), the thickness of the formed barrier coat layer can be made uniform.

[0071] The aforementioned gas barrier coating agent preferably contains 0.1 to 100 moles of water, and more preferably 0.8 to 2 moles of water, per mole of the total molar amount of alkoxide. By setting the water content to 0.1 moles or more per mole of total alkoxide, the gas barrier properties of the laminate can be improved. Furthermore, by setting the water content to 100 moles or less per mole of total alkoxide, the hydrolysis reaction can be carried out rapidly.

[0072] The aforementioned barrier coating agent having gas barrier properties may contain an organic solvent. Examples of organic solvents include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, and n-butanol.

[0073] The aforementioned gas barrier coating agent may optionally contain colorants, inorganic fillers, organic fillers, defoamers, leveling agents, pigment dispersants, antistatic agents, slip agents, plasticizers, tackifiers, and other additives. These may be added one or more times.

[0074] The aforementioned gas barrier coating agent is preferably used in gravure printing and can be applied as is. However, depending on the coating conditions and coating effect, it can be diluted with a diluent solvent using Zahn Cup #3 (manufactured by Rigosha Co., Ltd.) to adjust the viscosity to the desired level. In this case, the viscosity is preferably 12 to 15 seconds at 25°C. If it is less than 12 seconds, it will be too fluid, and if it is greater than 15 seconds, the transferability during printing will be poor.

[0075] The barrier coat layer preferably has a coating thickness of 0.01 to 10.0 μm, more preferably 1.0 to 5.0 μm, and even more preferably 2.0 to 5.0 μm. If the thickness is less than 0.01 μm, the gas barrier properties may be poor, and if the thickness exceeds 10.0 μm, the adhesion may be poor.

[0076] The polyolefin substrate may be polyethylene, polypropylene, ethylene-vinyl acetate, copolymers thereof, or co-extruded films thereof, and may be stretched. Alternatively, it may be a sealant substrate such as low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), high-density polyethylene (HDPE), acid-modified polyethylene, unstretched polypropylene (CPP), acid-modified polypropylene, or copolymerized polypropylene. The thickness of the polyolefin substrate is not particularly limited as long as it does not impair printability, winding suitability, etc., but is preferably 5 to 300 μm, and more preferably 6 to 250 μm.

[0077] In addition to the anchor coat layer, the vapor-deposited layer, and the barrier coat layer, the laminate of the present invention may also include an adhesive layer, a bonding layer, a printed layer, a heat-seal layer, and other substrates. The laminate may be composed of a polyolefin substrate / anchor coat layer / vapor deposition layer / barrier coat layer / adhesive layer / printed layer / other substrate, a polyolefin substrate / anchor coat layer / vapor deposition layer / barrier coat layer / printed layer / other substrate, a heat seal layer / adhesive layer / polyolefin substrate / anchor coat layer / vapor deposition layer / barrier coat layer / adhesive layer / printed layer / other substrate, an adhesive layer / polyolefin substrate / anchor coat layer / vapor deposition layer / barrier coat layer / adhesive layer / printed layer / other substrate, or a release layer / adhesive layer / polyolefin substrate / anchor coat layer / vapor deposition layer / barrier coat layer / adhesive layer / printed layer / other substrate, etc.

[0078] The aforementioned other base material is preferably a polyolefin base material equivalent to that of the present invention, but may also be a base material commonly used as a packaging material. In particular, it is more preferable that it is a base material used on the outermost surface as a packaging material.

[0079] The adhesive layer is formed by methods such as dry lamination, non-solvent lamination, wet lamination, extrusion lamination, heat lamination, or application of adhesives or adhesive inks.

[0080] When using an adhesive with the laminate, commercially available adhesives are acceptable, such as two-component or one-component urethane resin adhesives, acrylic, epoxy, polyester, polyethyleneimine, polybutadiene, water-based urethane, isocyanate, organotitanium, starch-based water-soluble adhesives, or water-based adhesives such as vinyl acetate emulsion.

[0081] The adhesive ink preferably contains a polyolefin resin, a chlorinated polyolefin resin, or a (meth)acrylic resin. The polyolefin resin and chlorinated polyolefin resin can be polyethylene, polypropylene, polybutene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, or blends thereof, chlorinated polyethylene, chlorinated polypropylene, chlorinated ethylene-propylene copolymer, or acid anhydride modified products thereof. Among these, chlorinated polypropylene, acid-modified polyolefin, acid-modified chlorinated polyolefin, and chlorinated ethylene-vinyl acetate copolymer (chlorinated EVA) are more preferred.

[0082] The adhesive or adhesive ink may also contain other different resins, solvents, inorganic fillers, organic fillers, defoamers, leveling agents, antiblocking agents, waxes, pigment dispersants, antistatic agents, slip agents, plasticizers, tackifiers, antioxidants, surfactants, UV absorbers, surface modifiers, pH adjusters, charge imparters, bactericides, deodorants, wetting agents, anti-skinning agents, metal chelating agents, and the like.

[0083] The aforementioned printed layer is a layer formed by applying a printing ink containing resins commonly used in gravure printing inks, such as polyurethane resins, polyolefin resins, shellacs, rosin-modified maleic acid resins, rosin-modified phenolic resins, cellulose acetate, cellulose acetyl propionate, cellulose acetyl butyrate, chlorinated rubber, cyclized rubber, halogenated vinyl resins (e.g., vinyl chloride resins, fluorine-containing vinyl resins, etc.), polyvinyl acetate, vinyl chloride-vinyl acetate copolymers, polystyrene resins, acrylic resins, acrylic styrene copolymers, polyacrylic acid esters, polyester resins, polyvinylidene chloride resins, ketone resins, polyamide resins, nitrocellulose resins, rosin resins, styrene maleic acid resins, alkyd resins, and ethylene-vinyl alcohol resins. In addition to the resin, the printing ink may also contain colorants, solvents, inorganic fillers, organic fillers, defoamers, leveling agents, antiblocking agents, waxes, pigment dispersants, antistatic agents, slip agents, plasticizers, tackifiers, antioxidants, surfactants, UV absorbers, surface modifiers, pH adjusters, charge imparters, bactericides, deodorants, wetting agents, anti-skinning agents, metal chelating agents, and the like.

[0084] The heat-seal layer is preferably a layer that is provided with heat-sealing properties, and may be the sealant substrate or a sealant film in general. Examples of sealant films include the polyolefin film, colored film, polystyrene film, polyacrylonitrile film, and ethylene-vinyl alcohol resin film, and may be stretched or unstretched, and may be laminated in the form of one or more types. Preferably, the heat seal layer is made of a sealant material having a melting point of 150°C or higher. This is because, when used as packaging material for retort or boil pouches, after the contents are filled and subjected to retort or boil treatment, the heat seal layer being made of a sealant material having a melting point of 150°C or higher allows the packaging material made using the laminate with the heat seal layer to suppress the deterioration of gas barrier properties and heat seal properties even during heat treatment such as retort or boil treatment. Here, retorting is a process in which the contents are filled into packaging materials such as retort pouches, sealed, and then the retort pouches are heated under pressure using steam or hot water. Retorting is performed, for example, at 121°C for 30 minutes. Boiling is performed, for example, at 90°C for 30 minutes.

[0085] The adhesive layer is a layer formed by applying an adhesive. Furthermore, a release layer may be formed.

[0086] The laminate of the present invention has gas barrier properties. Specifically, the oxygen permeability of the laminate in an atmosphere of 23°C and 50% RH is 1 cc / m³. 2 It is preferable that the humidity is 24h·atm or less. Also, the water vapor transmission rate of the laminate in an atmosphere of 40°C and 90% RH relative humidity should be 1 g / m³. 2 It is preferable that the time is 24 hours or less. Furthermore, it is preferable that there is no change in the oxygen permeability or water vapor permeability of the packaging material using the laminate before and after retort processing (for example, at a temperature of 121°C for 30 minutes) or boiling processing (for example, at a temperature of 90°C for 30 minutes).

[0087] The oxygen permeability of the laminate of the present invention can be measured using an oxygen gas permeability measuring device (OX-TRAN 2 / 22, manufactured by MOCON) under conditions of a measurement temperature of 23°C and a relative humidity of 50%RH, in accordance with JIS K 7126-2A:2006 (Plastics - Films and Sheets - Gas Permeability Test Methods - Part 2: Isobaric Method, Annex A: Test Method for Oxygen Gas Permeability by Electrolytic Sensor Method). For example, the measurement is performed by placing the laminate inside the measuring device so that the outermost surface side is in contact with oxygen gas, and the permeability area is 50 cm². 2 It will be carried out under these conditions.

[0088] The water vapor permeability of the laminate of the present invention can be measured using a water vapor permeability measuring device (PERMATRAN-W 3 / 34, manufactured by MOCON) under the conditions of a measurement temperature of 40°C and a relative humidity of 90%RH, in accordance with JIS K 7129-1:2019 (Plastics - Films and sheets - Method for determining water vapor permeability - Part 1: Humidity sensor method). For example, the measurement is performed by placing the laminate inside the measuring device so that the outermost surface side is in contact with water vapor, and the permeability area is 50 cm². 2 It will be carried out under these conditions.

[0089] The packaging material of the present invention is preferably made using the laminate described above, and may be a packaging bag, a label, and a lid material (collectively referred to as "packaging material").

[0090] The heat-sealed layers of the laminated material are joined together to form a packaging bag, which may be any of the well-known forms such as two-side seals, three-side seals, four-side seals, pillow seals, standing pouches, envelope seals, gussets, or heat-sealed seals.

[0091] The lid material may be any of the well-known forms, such as a cover, lid, or cap.

[0092] Furthermore, it is preferable that the container be sealed by making close contact with it. This sealing can be done manually, or by using machinery such as an automatic sealing device. The appropriate method can be selected depending on the type, form, size, and quantity of food, the container to be sealed, the equipment, and the environment. This can be done by heat sealing (heat pressure sealing), surface sealing, or by using adhesives or bonding agents. The container is more preferably a cylindrical container with a bottom. In this case, it is preferable that the lid material covers the opening of the cylindrical container with a bottom and seals it, and it is even more preferable that the seal is made by heat sealing. Examples of resins used in the aforementioned containers include thermoplastic resins such as polyethylene, polypropylene, polyethylene terephthalate, polyvinyl chloride, polystyrene, and polyacrylonitrile.

[0093] A label can be formed, for example, by forming an adhesive layer or bonding layer on a polyolefin substrate on the other side of which a barrier coat layer has been formed, and then forming a release layer. The adhesive layer or bonding layer can be any material that adheres closely to the substrate film and the release layer, and allows the release layer to be easily peeled off, such as a rubber-based adhesive material or an acrylic resin-based adhesive material. The release layer can be any material such as polyethylene film, polyester film, or paper (release paper).

[0094] The anchor coating agent of the present invention is used in a laminate and comprises a resin material containing methyl (meth)acrylate and a polar group-containing (meth)acrylic acid ester or (meth)acrylic acid, a curing agent and a silane coupling agent, wherein the polar group in the resin material is at least one polar group selected from hydroxyl groups, amide groups, amino groups, phosphoric acid groups and epoxy groups, the silane coupling agent is a silane coupling agent containing at least one group selected from a nitrogen atom-containing group, a sulfur atom-containing group and a vinyl group, the mixing ratio of methyl (meth)acrylate and the polar group-containing (meth)acrylic acid or (meth)acrylic acid is 10 or more and less than 900 parts polar group-containing (meth)acrylic acid ester or (meth)acrylic acid per 100 parts methyl (meth)acrylate, and the contact angle of the surface of the anchor coating layer formed by printing the anchor coating agent is preferably 20 degrees or more and 75 degrees or less.

[0095] The anchor coating agent of the present invention preferably comprises a resin material containing methyl (meth)acrylate and a polar group-containing (meth)acrylic acid ester or (meth)acrylic acid, a curing agent, and a silane coupling agent.

[0096] The polar group-containing (meth)acrylic acid ester is preferably such that the polar group is at least one group selected from a hydroxyl group, an amide group, an amino group, a phosphate group, and an epoxy group. Having the polar group improves the wettability with the vapor-deposited layer and contributes to adhesion.

[0097] Examples of hydroxyl group-containing (meth)acrylic acid esters in which the polar group is a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and glycerol mono(meth)acrylate, with 2-hydroxyethyl methacrylate being more preferred.

[0098] Examples of amide-containing (meth)acrylic acid esters in which the polar group is an amide group include N-(1,1-dimethyl-3-oxybutyl)(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-dimethylaminopropyl(meth)acrylamide, N-isopropyl(meth)acrylamide, Nt-butyl(meth)acrylamide, N-(hydroxymethyl)acrylamide, and (2)-hydroxypropyl(meth)acrylamide, among which N-(1,1-dimethyl-3-oxybutyl)acrylamide is more preferred.

[0099] Examples of amino group-containing (meth)acrylic acid esters in which the polar group is an amino group include N,N-dimethylaminoethyl (meth)acrylate and N,N-diethylaminoethyl (meth)acrylate, with N,N-dimethylaminoethyl methacrylate being more preferred.

[0100] Examples of the polar group being a phosphate group include phosphate group-containing (meth)acrylate polypropylene film phosphate, 2-(meth)acryloyloxyethyl acid phosphate, di-(2-methacryloyloxyethyl)-phosphate, 2-(meth)acryloyloxypropyl acid phosphate, 2-(meth)acryloyloxybutyl acid phosphate, acid phosphooxypolyoxypropylene glycol monomethacrylate, acid phosphooxypolyoxyethylene glycol monomethacrylate, and others, among which 2-methacryloyloxyethyl acid phosphate is more preferred.

[0101] Examples of epoxy group-containing (meth)acrylic acid esters in which the polar group is an epoxy group include glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, 3,4-epoxycyclohexylmethyl (meth)acrylate, 3-epoxycyclo-2-hydroxypropyl (meth)acrylate, 6-methyl-3,4-epoxycyclohexylmethyl (meth)acrylate, (meth)acrylate-3,4-epoxybutyl, (meth)acrylate-6,7-epoxyheptyl, α-ethyl (meth)acrylate-6,7-epoxyheptyl, α-ethyl acrylate glycidyl, α-n-propyl acrylate glycidyl, and α-n-butyl acrylate glycidyl, among which glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, and 3,4-epoxycyclohexylmethyl (meth)acrylate are more preferred.

[0102] The mixture of methyl (meth)acrylate and polar group-containing (meth)acrylic acid ester or (meth)acrylic acid is preferably in a ratio of 5 to less than 900 units of polar group-containing (meth)acrylic acid ester or (meth)acrylic acid per 100 units of methyl (meth)acrylate, more preferably 10 to less than 500 units, and even more preferably 20 to less than 300 units. If the mixing ratio is less than 5, the contact angle will be large, and the adhesion between the anchor coat layer and the vapor-deposited layer may be poor. If the mixing ratio is 900 or more, the film will harden, and the adhesion between the polyolefin substrate and the anchor coat layer may be poor.

[0103] The amount of the resin material containing methyl (meth)acrylate and polar group-containing (meth)acrylic acid ester or (meth)acrylic acid added is preferably 3 to 90% by mass, more preferably 5 to 80% by mass, and even more preferably 10 to 70% by mass, based on 100% of the total amount of the anchor coating agent. These may be used individually or in combination of two or more types.

[0104] The curing agent is preferably a polyisocyanate compound, and is not particularly limited. It is selected from conventionally known polyisocyanates, and includes aliphatic polyisocyanates or aromatic aliphatic polyisocyanates. For example, aromatic diisocyanates such as tolylene diisocyanate and 4,4'-diphenylmethane diisocyanate, aliphatic diisocyanates such as hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, 4,4'-dicyclohexyl diisocyanate, and pentane-1,5-diisocyanate (Stavio PDI), as well as modified forms thereof such as trimethylolpropane trimers, isocyanurates, burettes, and allophanates. Commercially available products include LG curing agent C and LG curing agent D (both manufactured by Tokyo Ink Co., Ltd.). These may be used individually or in combination of two or more types.

[0105] The amount of the curing agent added is preferably 1 to 20% by mass, more preferably 2 to 18% by mass, and even more preferably 4 to 15% by mass, based on 100% of the total amount of the anchor coating agent. These may be used individually or in combination of two or more types.

[0106] Preferably, the silane coupling agent contains at least one group selected from a nitrogen atom-containing group, a sulfur atom-containing group, and a vinyl group. Including a silane coupling agent having the specific group contributes to improving the adhesion between the anchor coat layer and the vapor-deposited layer.

[0107] Groups containing a nitrogen atom include amino groups, imino groups, isocyanate groups (-N=C=O), ureido groups (-NH-CO-NH2), nitro groups (=NO), carbamate groups (-O-CO-N<), and quaternary ammonium salts.

[0108] Examples of silane coupling agents containing an amino group include 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltripropoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, bis(3-triethoxysilylpropyl)amine, bis(3-trimethoxysilylpropyl)amine, bis(3-methyldimethoxysilylpropyl)amine, bis(triethoxysilylmethyl)amine, and N-(2-aminoethyl)-3 Examples of trialkoxysilanes include aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldiethoxysilane, N-(n-butyl)-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N,N'-bis[3-(trimethoxysilyl)propyl]ethylenediamine, and hydrochloride salts of N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane. Among these, 3-aminopropyltrimethoxysilane and N-(2-aminoethyl)-3-aminopropyltrimethoxysilane are more preferred.

[0109] Examples of commercially available products include KBP-64, KBP-90, KBE-9103P, KBE-903, KBM-6803, KBM-573, KBM-575, KBM-602, KBM-603, KBM-903, KBM-6103, X-12-1172ES, X-12-972F, X-12-5263HP, and X-88-475 (all manufactured by Shin-Etsu Chemical Co., Ltd.).

[0110] Examples of silane coupling agents having an isocyanate group include trialkoxysilanes such as 3-isocyanatetopropyltrimethoxysilane, 3-isocyanatetopropyltriethoxysilane, 3-isocyanatetopropylmethyldimethoxysilane, and 3-isocyanatetopropylmethyldiethoxysilane, as well as trimers (isocyanurates) of these compounds, with 3-isocyanatetopropyltrimethoxysilane being more preferred.

[0111] Commercially available products include KBE-9007N, X-12-1159, X-12-1159L, KBM-9659 (all manufactured by Shin-Etsu Chemical Co., Ltd.), SILQUEST Silane A-1310, and SILQUEST Silane Y-5187 (both manufactured by MOMENTIVE).

[0112] Examples of silane coupling agents having a ureido group include trialkoxysilanes such as 3-ureidopropyltrialkoxysilane.

[0113] Examples of commercially available products include KBE-585A and KBM-585 (both manufactured by Shin-Etsu Chemical Co., Ltd.).

[0114] Examples of silane coupling agents having a nitro group include trialksylanes such as 3-nitropropyltrimethoxysilane and 3-nitropropyltriethoxysilane.

[0115] Examples of silane coupling agents having a carbamate group include (3-carbamate ethyl)propyltrimethoxysilane, (3-carbamate ethyl)propyltripropaxysilane, (3-carbamate propyl)propyltriethoxysilane, (3-carbamate propyl)propyltrimethoxysilane, (3-carbamate propyl)propyltripropaxysilane, (3-carbamate butyl)propyltriethoxysilane, (3-carbamate butyl)propyltrimethoxysilane, (3-carbamate butyl)propyltripropaxysilane, (3-carbamate butyl)butyltripropaxysilane, (3-carbamate butyl Examples of trialksylanes include (3-carbamate pentyl)propyltriethoxysilane, (3-carbamate hexyl)propyltriethoxysilane, (3-carbamate octyl)pentyltributoxysilane, (3-carbamate ethyl)propylsilyl trichloride, (3-carbamate ethyl)propyltrimethylsilane, (3-carbamate ethyl)propyldimethylsilane, (3-carbamate ethyl)propyltributylsilane, (3-carbamate ethyl)ethyl-p-xylentriethoxysilane, and (3-carbamate ethyl)-p-phenylentriethoxysilane.

[0116] Examples of silane coupling agents containing quaternary ammonium salts include commercially available products such as X-12-1126, KBM-9418-40, POLON-V8, X-12-1139, and X-12-1354-1 (all manufactured by Shin-Etsu Chemical Co., Ltd.).

[0117] Examples of functional groups containing sulfur atoms include mercapto groups and sulfide groups.

[0118] Examples of silane coupling agents having a mercapto group include trialksylanes such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltripropoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, 2-mercaptoethyltrimethoxysilane, and 2-mercaptoethyltriethoxysilane.

[0119] Examples of commercially available products include KBM-802, KBM-803, X-12-1307, X-12-1056ES, and X-12-1154 (all manufactured by Shin-Etsu Chemical Co., Ltd.).

[0120] Examples of silane coupling agents having a sulfide group include bis(3-triethoxysilylpropyl)tetrasulfide, bis(2-triethoxysilylethyl)tetrasulfide, bis(4-triethoxysilylbutyl)tetrasulfide, bis(3-trimethoxysilylpropyl)tetrasulfide, bis(2-trimethoxysilylethyl)tetrasulfide, bis(4-trimethoxysilylbutyl)tetrasulfide, bis(3-triethoxysilylpropyl) trisulfide, bis(2-triethoxysilylethyl) trisulfide, bis(4-triethoxysilylbutyl) trisulfide, bis(3-trimethoxysilylpropyl) trisulfide, bis(2-trimethoxysilylethyl) trisulfide, bis(4-trimethoxysilylbutyl) trisulfide, bis(3-triethoxysilylpropyl) disulfide, bis(2-triethoxysilylethyl) disulfide, bis Examples of trialksylanes include (4-triethoxysilylbutyl) disulfide, bis(3-trimethoxysilylpropyl) disulfide, bis(2-trimethoxysilylethyl) disulfide, bis(4-trimethoxysilylbutyl) disulfide, 3-trimethoxysilylpropyl-N,N-dimethylthiocarbamoyl tetrasulfide, 3-triethoxysilylpropyl-N,N-dimethylthiocarbamoyl tetrasulfide, 2-triethoxysilylethyl-N,N-dimethylthiocarbamoyl tetrasulfide, 2-trimethoxysilylethyl-N,N-dimethylthiocarbamoyl tetrasulfide, 3-trimethoxysilylpropylbenzothiazolyl tetrasulfide, 3-triethoxysilylpropylbenzothiazole tetrasulfide, 3-triethoxysilylpropyl methacrylate monosulfide, and 3-trimethoxysilylpropyl methacrylate monosulfide.

[0121] Examples of silane coupling agents having a vinyl group include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, Examples of trialkoxysilanes include vinyltributoxysilane, vinylmethyldimethoxysilane, and vinylmethyldiethoxysilane.

[0122] Examples of commercially available products include KBE-1003, KBM-1003, KBM-1083, and X-12-1290 (all manufactured by Shin-Etsu Chemical Co., Ltd.).

[0123] The amount of silane coupling agent added is preferably 0.1 to 10% by mass, more preferably 0.5 to 7% by mass, and even more preferably 1 to 5% by mass, based on 100% of the total amount of anchor coating agent. These may be used individually or in combination of two or more types.

[0124] In addition to the resin material containing methyl (meth)acrylate and polar group-containing (meth)acrylic acid ester or (meth)acrylic acid, a curing agent, and a silane coupling agent, the anchor coating agent of the present invention may also optionally contain organic solvents, colorants, inorganic fillers, organic fillers, defoamers, leveling agents, pigment dispersants, antistatic agents, slip agents, plasticizers, tackifiers, etc. One or more of these may be added.

[0125] The anchor coating agent of the present invention may be an anchor coating set comprising: a resin solution A containing methyl (meth)acrylate and a polar group-containing (meth)acrylic acid ester or (meth)acrylic acid, and an organic solvent; a curing solution B containing a curing agent and an organic solvent; and a silane coupling solution C containing a silane coupling agent and an organic solvent. Alternatively, the components contained in the silane coupling solution C may be mixed with the resin solution A and combined with the curing solution B to form a two-component anchor coating set.

[0126] The resin solution A, curing solution B, and silane coupling solution C in the anchor coat set may optionally contain organic solvents, colorants, inorganic fillers, organic fillers, defoamers, leveling agents, pigment dispersants, antistatic agents, slip agents, plasticizers, tackifiers, etc. Any known and commonly used substances can be appropriately selected as long as they do not impair the properties of the curing agent.

[0127] The methyl (meth)acrylate and polar group-containing (meth)acrylic acid ester or (meth)acrylic acid used in the resin solution A are preferably mixed in a ratio of 5 to less than 900 parts polar group-containing (meth)acrylic acid ester or (meth)acrylic acid per 100 parts methyl (meth)acrylate, more preferably 10 to less than 500 parts, and even more preferably 20 to less than 300 parts. If the mixing ratio is less than 5, the contact angle will be large, and the adhesion between the anchor coat layer and the vapor-deposited layer may be poor. If the mixing ratio is 900 or more, the film will harden, and the adhesion between the polyolefin substrate and the anchor coat layer may be poor.

[0128] The aforementioned anchor coat set uses the resin solution A, curing solution B, and silane coupling solution C together. In other words, it is used as a three-component mixture. The preferred ratio of resin solution A, curing liquid B, and silane coupling liquid C is resin solution A / curing liquid B / silane coupling liquid C = 91 / 3 / 6 to 40 / 25 / 35, more preferably 85 / 5 / 10 to 45 / 23 / 32, and even more preferably 80 / 6 / 14 to 50 / 20 / 30. Using the resin solution A, curing liquid B, and silane coupling liquid C as a three-component mixture within the above range provides excellent adhesion. Alternatively, the components contained in silane coupling liquid C may be mixed with resin solution A and used as a two-component mixture with curing liquid B.

[0129] The three-component mixture can be produced by mixing or dispersing the resin solution A, the curing liquid B, and the silane coupling liquid C by known methods. Mixing or dispersing in a printing factory or similar facility is particularly preferable. Mixing or dispersion can be easily achieved by manual stirring, but various stirrers or dispersers such as dissolvers, paint shakers, and homomixers can be used. These devices may be used individually or in combination of two or more types. A two-component mixture can be produced in the same manner.

[0130] The aforementioned three-component mixture is preferably used in gravure printing and can be applied as is. However, depending on the coating conditions and coating effect, it can be diluted with a diluent solvent using a Zahn Cup #3 (manufactured by Rigosha Co., Ltd.) to adjust the viscosity to the desired level. In this case, the viscosity is preferably 10 to 40 seconds at 25°C. If it is less than 10 seconds, it will be too fluid, and if it is greater than 40 seconds, the transferability during printing will be poor.

[0131] The aforementioned diluent can be any solvent that can be used to adjust the viscosity of the three-liquid mixture, and examples include organic solvents. Commercially available solvents can also be used, and there are no particular restrictions. Examples of commercially available solvents include TS32 solvent (ester-based solvent), PU533 solvent (toluene-containing solvent), PU515 solvent (toluene-free solvent), SL9155 solvent (toluene-free solvent), CN104 solvent (toluene-free solvent), AC372 solvent (toluene-free solvent), PP575 solvent (toluene-containing solvent), SL9164 solvent (non-ketone solvent), and SL9170 solvent (non-ketone solvent) (all manufactured by Tokyo Ink Co., Ltd.).

[0132] The resin solution A can be produced by known methods by uniformly dissolving or dispersing methyl (meth)acrylate, a polar group-containing (meth)acrylic acid ester or (meth)acrylic acid, and various additives in the aforementioned organic solvent. Dissolution or dispersion can be carried out using various stirrers or dispersers such as dissolvers, roll mills, ball mills, bead mills, sand mills, attritors, paint shakers, agitators, Henschel mixers, colloid mills, pearl mills, ultrasonic homogenizers, wet jet mills, kneaders, and homomixers. These devices may be used individually or in combination of two or more types. If the resin solution contains air bubbles or coarse particles, it is preferable to remove them using known filters or centrifuges, as these can reduce printability and print quality.

[0133] The curing solution B can be manufactured by known methods by uniformly dissolving or dispersing a polyisocyanate compound and various additives in the aforementioned organic solvent. Dissolution or dispersion can be carried out using various stirrers or dispersers such as dissolvers, roll mills, ball mills, bead mills, sand mills, attritors, paint shakers, agitators, Henschel mixers, colloid mills, pearl mills, ultrasonic homogenizers, wet jet mills, kneaders, and homomixers. These devices may be used individually or in combination of two or more types. If the curing solution contains air bubbles or coarse particles, it is preferable to remove them using known filters or centrifuges, as these can reduce printability and print quality.

[0134] The silane coupling solution C can be manufactured by known methods by uniformly dissolving or dispersing a silane coupling agent and various additives in the aforementioned organic solvent. Dissolution or dispersion can be carried out using various agitators or dispersers such as dissolvers, roll mills, ball mills, bead mills, sand mills, attritors, paint shakers, agitators, Henschel mixers, colloid mills, pearl mills, ultrasonic homogenizers, wet jet mills, kneaders, and homomixers. These devices may be used individually or in combination of two or more types. If the silane coupling solution contains air bubbles or coarse particles, it is preferable to remove them using known filters or centrifuges, as these can reduce printability and print quality.

[0135] Using the aforementioned anchor coat set, it is preferable to form an anchor coat layer with a thickness of 0.05 to 1.5 μm on a polyolefin substrate by gravure printing, more preferably with a thickness of 0.08 to 1.2 μm, and even more preferably with a thickness of 0.1 to 1.0 μm. If the thickness is less than 0.05 μm, the vapor-deposited layer on the anchor coat layer is susceptible to cracking due to substrate shrinkage caused by heat treatment such as retort processing, which may result in poor gas barrier properties. If the thickness exceeds 1.5 μm, adhesion to the polyolefin substrate and blocking resistance may be poor. In particular, it is more preferable to form the anchor coat by gravure printing using a multi-color gravure printing machine. This allows the anchor coat layer to be formed by gravure printing and then wound up. The anchor coat layer formed using the aforementioned anchor coat set is stable after printing, allowing it to be stored in a rolled state. Furthermore, a vapor deposition layer and a barrier coat layer can be formed on the anchor coat layer.

[0136] In the present invention, the contact angle of the anchor coat layer surface is preferably 20 degrees or more and 75 degrees or less, more preferably 30 degrees or more and 65 degrees or less, and even more preferably 40 degrees or more and 55 degrees or less. When the contact angle is within the above range, the adhesion between the polyolefin substrate and the vapor-deposited layer is dramatically improved, and cracks are less likely to occur in the vapor-deposited layer, thereby obtaining good gas barrier properties, especially good gas barrier properties even after retort treatment. If the contact angle is less than 20 degrees, the adhesion with the vapor-deposited layer may be poor, and if the contact angle exceeds 75 degrees, the polarity of the anchor coat layer itself becomes high, which may result in poor adhesion with the polyolefin substrate.

[0137] The aforementioned contact angle was measured 1 second after dropping distilled water at a rate of 2 μm onto the surface of the anchor coat layer under the conditions of a measurement temperature of 5°C and a relative humidity of 50% (50% RH). The aforementioned contact angle can be measured using a contact angle meter (portable contact angle meter PCA-1, manufactured by Kyowa Interface Science Co., Ltd.).

[0138] The present invention provides a method for manufacturing a laminate, comprising at least the steps of: preparing a polyolefin substrate; forming an anchor coat layer having a thickness of 0.05 to 1.5 μm on at least one side of the polyolefin substrate; forming a vapor-deposited layer on the anchor coat layer; and forming a barrier coat layer on the vapor-deposited layer, wherein the step of forming the anchor coat layer is a step of printing an anchor coat agent comprising a resin material containing methyl (meth)acrylate and a polar group-containing (meth)acrylic acid ester or (meth)acrylic acid, a curing agent, and a silane coupling agent, and the polar group in the resin material is a hydroxyl group, an amide group, Preferably, the silane coupling agent contains at least one group selected from an amino group and a phosphate group, and the silane coupling agent contains at least one group selected from a group containing a nitrogen atom, a group containing a sulfur atom, and a vinyl group, and the mixing ratio of the methyl (meth)acrylate and the polar group-containing (meth)acrylate ester or (meth)acrylic acid is 5 or more and less than 900 parts methyl (meth)acrylate to polar group-containing (meth)acrylate ester or (meth)acrylic acid, and the contact angle of the surface of the anchor coat layer formed by the anchor coat layer forming step is 20 degrees or more and 75 degrees or less.

[0139] The step of forming the anchor coat layer is preferably a step of gravure printing the anchor coat agent onto a polyolefin substrate to a thickness of 0.05 to 1.5 μm, more preferably a step of gravure printing to a thickness of 0.08 to 1.2 μm, and even more preferably a step of gravure printing to a thickness of 0.1 to 1.0 μm. If the thickness is less than 0.05 μm, the vapor deposition layer on the anchor coat layer is susceptible to cracking due to substrate shrinkage caused by heat treatment such as retort processing, which may result in poor gas barrier properties. If the thickness exceeds 1.5 μm, adhesion to the polyolefin substrate and blocking resistance may be poor. In particular, it is more preferable to use a multi-color gravure printing machine for the gravure printing step. This allows for the inclusion of a winding step after the step of forming the anchor coat layer by gravure printing.

[0140] Since the anchor coat layer formed by the anchor coat layer formation process in the present invention is stable, a winding step may be included after the anchor coat layer formation process, thereby allowing storage in a wound state.

[0141] After the winding process, the system can be further modified to include a step of forming a vapor-deposited layer and a barrier coat layer while unwinding the wire.

[0142] The contact angle of the anchor coat layer surface formed by the gravure printing process is preferably 20 degrees or more and 75 degrees or less, more preferably 30 degrees or more and 65 degrees or less, and even more preferably 40 degrees or more and 55 degrees or less. When the contact angle is within the above range, the adhesion between the polyolefin substrate and the vapor-deposited layer is dramatically improved, and cracks are less likely to occur in the vapor-deposited layer, thereby obtaining good gas barrier properties, especially good gas barrier properties even after retort processing. If the contact angle is less than 20 degrees, the adhesion with the vapor-deposited layer may be poor, and if the contact angle exceeds 75 degrees, the polarity of the anchor coat layer itself becomes high, which may result in poor adhesion with the polyolefin substrate.

[0143] The aforementioned contact angle was measured 1 second after dropping distilled water at a rate of 2 μm onto the surface of the anchor coat layer under the conditions of a measurement temperature of 5°C and a relative humidity of 50% (50% RH). The aforementioned contact angle can be measured using a contact angle meter (portable contact angle meter PCA-1, manufactured by Kyowa Interface Science Co., Ltd.).

[0144] The method for manufacturing the laminate of the present invention preferably includes a step of forming a vapor-deposited layer on the anchor coat layer, and the step of forming the vapor-deposited layer is a step of forming a vapor-deposited film made of an inorganic oxide or a metal thin film.

[0145] The process for forming the aforementioned vapor-deposited layer can utilize, for example, a vacuum deposition process, sputtering process, ion plating process, or ion cluster beam process using the Physical Vapor Deposition (PVD) method, or a plasma CVD process, thermal CVD process, photoCVD process, or MOCVD process using the Chemical Vapor Deposition (CVD) method. When using a vacuum deposition process, the heating method for the vaporized material can be, for example, electron beam heating, resistance heating, or induction heating. When using electron beam heating, there is a greater degree of freedom in selecting the vaporized material. By using a plasma-assisted process or an ion beam-assisted process during deposition, a denser vapor-deposited layer can be formed. Furthermore, by using reactive deposition, which involves blowing in a gas such as oxygen during chemical deposition, a vapor-deposited layer with excellent transparency can be formed.

[0146] The thickness of the vapor-deposited layer formed by the vapor deposition layer formation process is preferably in the range of 1 to 150 nm, more preferably in the range of 5 to 60 nm, and even more preferably in the range of 10 to 40 nm. If the thickness is less than 1 nm, the desired gas barrier properties may not be achieved, and if the thickness exceeds 150 nm, the polyolefin substrate may deform or deteriorate due to the heat generated during the vapor deposition layer formation process, and cracks may easily occur in the vapor-deposited layer, impairing the gas barrier properties.

[0147] The present invention provides a method for manufacturing a laminate, which preferably includes a step of forming a barrier coat layer on the vapor-deposited layer. The step of forming the barrier coat layer is a step of forming a coating film of a gas barrier composition obtained by polycondensation of an alkoxide and a water-soluble polymer by a sol-gel method. Known steps can be used for the step of forming the barrier coat layer, such as printing steps like gravure printing and flexographic printing, or wet coating steps using a roll coater, reverse roll coater, gravure offset coater, gravure coater, microgravure coater, knife coater, bar coater, wire bar coater, die coater, or dip coater. Among these, the printing step by gravure printing and the wet coating step by roll coater are more preferred.

[0148] The step of preparing the polyolefin substrate may be any step of preparing polyethylene, polypropylene, ethylene-vinyl acetate, copolymers thereof, or co-extruded films thereof, or it may be a step of preparing stretched material. Alternatively, it may be a step of preparing a sealant substrate such as low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), high-density polyethylene (HDPE), acid-modified polyethylene, unstretched polypropylene (CPP), acid-modified polypropylene, or copolymerized polypropylene. The thickness of the polyolefin substrate is not particularly limited as long as it does not impede printability, winding suitability, etc., but 5 to 300 μm is preferred, and 6 to 250 μm is more preferred.

[0149] In addition to the steps of forming the anchor coat layer, forming the vapor-deposited layer, and forming the barrier coat layer, the method for manufacturing the laminate of the present invention may also include steps of forming an adhesive layer, forming a tacky layer, forming a printed layer, forming a heat seal layer, and preparing other substrates.

[0150] The step of preparing the other substrate is preferably a step of preparing a polyolefin substrate equivalent to that of the present invention, but it may also be a step of preparing a substrate commonly used as a packaging material. In particular, it is more preferable that it is a step of preparing a substrate used for the outermost surface as a packaging material.

[0151] The step of forming the adhesive layer may be a dry lamination step, a non-solvent lamination step, a wet lamination step, an extrusion lamination step, a heat lamination step, or a coating step such as applying an adhesive or adhesive ink.

[0152] If an adhesive is used in the lamination process, a commercially available adhesive may be used. Examples include two-component or one-component urethane resin adhesives, acrylic, epoxy, polyester, polyethyleneimine, polybutadiene, water-based urethane, isocyanate, organotitanium, starch-based water-soluble adhesives, and water-based adhesives such as vinyl acetate emulsion.

[0153] The adhesive ink preferably contains a polyolefin resin, a chlorinated polyolefin resin, or a (meth)acrylic resin. The polyolefin resin and chlorinated polyolefin resin can be polyethylene, polypropylene, polybutene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, or blends thereof, chlorinated polyethylene, chlorinated polypropylene, chlorinated ethylene-propylene copolymer, or acid anhydride modified products thereof. Among these, chlorinated polypropylene, acid-modified polyolefin, acid-modified chlorinated polyolefin, and chlorinated ethylene-vinyl acetate copolymer (chlorinated EVA) are more preferred.

[0154] The adhesive or adhesive ink may also contain other different resins, solvents, inorganic fillers, organic fillers, defoamers, leveling agents, antiblocking agents, waxes, pigment dispersants, antistatic agents, slip agents, plasticizers, tackifiers, antioxidants, surfactants, UV absorbers, surface modifiers, pH adjusters, charge imparters, bactericides, deodorants, wetting agents, anti-skinning agents, metal chelating agents, and the like.

[0155] The process of forming the aforementioned printed layer involves applying a printing ink containing resins commonly used in gravure printing inks, such as polyurethane resins, polyolefin resins, shellacs, rosin-modified maleic acid resins, rosin-modified phenolic resins, cellulose acetate, cellulose acetyl propionate, cellulose acetyl butyrate, chlorinated rubber, cyclized rubber, halogenated vinyl resins (e.g., vinyl chloride resins, fluorine-containing vinyl resins, etc.), polyvinyl acetate, vinyl chloride-vinyl acetate copolymers, polystyrene resins, acrylic resins, acrylic styrene copolymers, polyacrylic acid esters, polyester resins, polyvinylidene chloride resins, ketone resins, polyamide resins, nitrocellulose resins, rosin resins, styrene maleic acid resins, alkyd resins, and ethylene-vinyl alcohol resins. In addition to the resin, the printing ink may also contain colorants, solvents, inorganic fillers, organic fillers, defoamers, leveling agents, antiblocking agents, waxes, pigment dispersants, antistatic agents, slip agents, plasticizers, tackifiers, antioxidants, surfactants, UV absorbers, surface modifiers, pH adjusters, charge imparters, bactericides, deodorants, wetting agents, anti-skinning agents, metal chelating agents, and the like.

[0156] The step of forming the heat seal layer is preferably a step of imparting heat sealability, and may be a step of preparing the sealant substrate or a sealant film in general. Examples of the step of preparing the sealant film include preparing the polyolefin film, colored film, polystyrene film, polyacrylonitrile film, ethylene-vinyl alcohol resin film, etc., and the film may be stretched or unstretched, and may be a step of preparing a film in which one or more types are laminated.

[0157] The step of forming the adhesive layer is preferably a step of applying an adhesive. Furthermore, it may include a step of forming a release layer. [Examples]

[0158] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these. In the examples and comparative examples, "parts" refers to parts by mass, and "%" refers to mass percent.

[0159] [Preparation of resin solution A] (Manufacturing example 1) 100 parts methyl methacrylate (MMA), 200 parts 2-hydroxyethyl methacrylate (HEMA), and 1200 parts of a mixed solvent of n-propyl acetate / isopropyl alcohol (6 / 4) were placed in a beaker and stirred at 600 rpm for 30 minutes to prepare Solution A1. Similarly, resin solutions for Production Examples 2 to 12 were prepared according to the formulations shown in Tables 1 and 2. Production Example 12 is similar to Example 2 of Patent Document 1.

[0160] [Preparation of hardening solution B] (Manufacturing example 21) To prepare Solution B1, 50 parts of tolylene diisocyanate TMP (trimethylolpropane) trimer (TDI3TMP) and 50 parts of ethyl acetate were placed in a beaker and stirred at 600 rpm for 30 minutes. Similarly, cured solutions for each of the production examples 22-25 were prepared according to the formulations in Table 3. Production example 25 is similar to Example 2 of Patent Document 1.

[0161] [Preparation of Silane Coupling Solution C] (Production Example 31) 10 parts of KBM-903 (3-aminopropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) and 90 parts of a mixed solvent of n-propyl acetate / isopropyl alcohol = 7 / 3 were placed in a beaker and stirred at 600 rpm for 30 minutes to prepare Solution C1. Similarly, silane coupling solutions for Production Examples 32 to 35 were prepared according to the formulations in Table 4. Production Example 35 uses a silane coupling agent that does not contain at least one of the following groups: a nitrogen atom-containing group, a sulfur atom-containing group, or a vinyl group.

[0162] The materials used were as follows: MA: Methyl acrylate DAAM: Diacetone acrylamide (N-(1,1-dimethyl-3-oxybutyl)acrylamide) DAM:N,N-dimethylaminoethyl methacrylate Kayamer PM-1:2-methacryloyloxyethyl acid phosphate, manufactured by Nippon Kayaku Co., Ltd. GMA: Glycidyl methacrylate MAA: Methacrylic acid HDI3TMP: Hexamethylene diisocyanate trimethylolpropane trimer HDI Nurate: Isocyanurate of hexamethylene diisocyanate XDI3TMP: Xylylene diisocyanate trimethylolpropane trimer TDI: Tolylene diisocyanate KBE-9007N: 3-Isocyanate-propyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) KBM-803:3-mercaptopropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd. KBE-1003: Vinyltriethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd. KBE-403:3-Glycidoxypropyltriethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.

[0163] [Table 1]

[0164] [Table 2]

[0165] [Table 3]

[0166] [Table 4]

[0167] [Preparation of anchor coating agent] Anchor coating agent 1 (Example 1) 100 parts of Solution A1, 15 parts of Solution B1, and 30 parts of Solution C1 were placed in separate beakers and stirred at 600 rpm for 30 minutes to prepare 145 parts of Anchor Coating Agent 1 of Example 1.

[0168] Similarly, anchor coating agents for Examples 2-20 and Comparative Examples 1-7 were prepared according to the formulations shown in Tables 5-7. Comparative Example 7 is similar to Example 2 of Patent Document 1.

[0169] [Table 5]

[0170] [Table 6]

[0171] [Table 7]

[0172] [Preparation of barrier coating agent] 385 g of water, 67 g of isopropyl alcohol, and 9.1 g of 0.5 N hydrochloric acid were mixed to prepare a pH 2.2 solution. To this solution, 175 g of tetraethoxysilane as a metal alkoxide and 9.2 g of glycidoxypropyltrimethoxysilane as a silane coupling agent were mixed while cooling to 10°C to obtain solution A. Solution B was obtained by mixing 14.7 g of polyvinyl alcohol with a saponification value of 99% or higher and a degree of polymerization of 2400 as a water-soluble polymer, 324 g of water, and 17 g of isopropyl alcohol. Solution A and solution B were mixed in a ratio of 6.5:3.5 by mass to obtain barrier coating agent 1.

[0173] [Fabrication of laminates] (Example 30) Using a two-head coater, an anchor coat layer coating film was formed by printing anchor coat agent 1 to a thickness of 1.0 μm on one side of a 20 μm thick OPP film (P2171, abbreviated as OPP, manufactured by Toyobo Co., Ltd.) as a polyolefin substrate using the first unit, thereby creating AC laminate 1. At this time, anchor coat agent 1 was diluted with WA734 (a non-toluene solvent, manufactured by Tokyo Ink Co., Ltd.) and adjusted to a viscosity of 17 seconds using a Zahn cup No. 3. Similarly, by changing the anchor coat agent and film thickness according to Tables 8 to 10, AC laminates 2 to 24 and AC laminates 31 to 40 were obtained.

[0174] Furthermore, a silicon oxide film (evaporated layer film) with a thickness of 12 nm was deposited on the anchor coat layer of the AC laminate 1 by PVD, and an evaporated laminate 1 was fabricated. Similarly, evaporated laminates 2 to 24 and evaporated laminates 31 to 41 were obtained according to Tables 8 to 10.

[0175] Furthermore, the barrier coating agent 1 was coated onto the vapor-deposited layer of the vapor-deposited laminate 1 using a roll coater, and the laminate was heated in an oven at 80°C for 60 seconds to form a barrier coating film with a thickness of 300 nm, thereby producing the barrier laminate 1. Similarly, barrier laminates 2 to 24 and barrier laminates 31 to 40 were obtained according to Tables 8 to 10.

[0176] Furthermore, Takelac A-525 / Takenate A-52 (abbreviated as DL, manufactured by Mitsui Chemicals, Inc.) was coated onto the barrier coat layer of barrier laminate 1 using A-Bar OSP-10 (manufactured by OSG System Products Co., Ltd.), and a 60 μm thick unoriented polypropylene film for retort processing, ZK207 (abbreviated as RetoCP, manufactured by Toray Film Processing Co., Ltd.), was laminated onto it. After aging at 40°C for 72 hours, laminate 1 consisting of OPP / anchor coat layer / deposition layer / barrier coat layer / DL / RetoCP was obtained. Laminates 2 to 24 and laminates 31 to 41 were obtained in the same manner as in Example 30, according to Tables 8 to 10. Laminate 38 did not have an anchor coat layer (a vapor-deposited layer was formed on the polyolefin substrate). Laminate 41 did not have a barrier coat layer (a heat seal layer was fabricated on the vapor-deposited layer).

[0177] <Contact angle of the anchor coat layer surface> Distilled water was dropped onto the anchor coat layer surface of the AC laminate 1 at a rate of 2 μm. One second after application, the contact angle was measured using a contact angle meter (portable contact angle meter PCA-1, manufactured by Kyowa Interface Science Co., Ltd.) under conditions of a measurement temperature of 25°C and a relative humidity of 50% (50% RH). A contact angle between 20 and 75 degrees ensures good adhesion between the polyolefin substrate and the vapor-deposited layer. The contact angle was evaluated on the following five-point scale. Similarly, the contact angles were measured for AC laminates 2 to 24 and AC laminates 31 to 40. The results are shown in Tables 8 to 10. Laminate 38, which did not have an anchor coat layer coating, was not measured, and its contact angle is listed as "-". ◎: Contact angle is between 40 degrees and 55 degrees ○: Contact angle is 30 degrees or more but less than 40 degrees, or greater than 55 degrees but 65 degrees or less. △: Contact angle is 20 degrees or more but less than 30 degrees, or greater than 65 degrees but less than or equal to 75 degrees (no practical problem) ×: Contact angle is 10 degrees or more but less than 20 degrees, or greater than 75 degrees and greater than 85 degrees. ××: Contact angle is less than 10 degrees or greater than 85 degrees.

[0178] For laminates 1 to 24 and laminates 31 to 41, the adhesion, blocking resistance, laminate strength, gas barrier properties, and retort resistance were evaluated and are shown in Tables 8 to 10.

[0179] <Adhesion> Adhesive tape (cellophane tape, 28 mm, manufactured by Nichiban Co., Ltd.) was applied to the barrier coat layer surface of barrier laminate 1, rubbed firmly five times with a thumb, and then the adhesive tape was slowly peeled off, and then rapidly peeled off from the middle. The degree to which the barrier coat layer surface or anchor coat layer surface adhered to the adhesive tape was visually observed and evaluated. Those with less adhesion to the adhesive tape were judged to have good adhesion. The degree to which the adhesive tape was removed was evaluated on a four-point scale: ◎: none at all, ○: slightly removed (less than 10% of the area as peeled area), △: a little removed (10% to less than 20% of the area as peeled area, no practical problem), and ×: almost all removed (more than 20% of the area as peeled area). Similarly, the adhesion of barrier laminates 2 to 24 and barrier laminates 31 to 40 was also evaluated. The results are shown in Tables 8 to 10. Laminate 41, which did not have a barrier coat layer film formed on it, was not measured, and its adhesion was recorded as "-".

[0180] <Blocking resistance> Two barrier laminates 1, each measuring 3cm x 3cm, are placed with the barrier coat layer coated side facing the polyolefin substrate side opposite the barrier coat layer coated side, and then subjected to a 20 N / cm² load at 50°C for 24 hours. 2After applying the load, the peeling state between the polyolefin substrate and the anchor coat layer, or between the anchor coat layer and the barrier coat layer, was checked when the overlapping portion of the barrier coat layer surface and the opposite polyolefin substrate surface was peeled off, and the ink peeling and peeling resistance at that time were evaluated. Ink peeling and peeling resistance were evaluated in two stages: ○: Peeled off without resistance, and no peeling of the coating surface; ×: High resistance during peeling, and peeling of the coating surface was observed. Similarly, the blocking resistance was evaluated for barrier laminates 2 to 24 and barrier laminates 31 to 40. The results are shown in Tables 8 to 10. Laminate 41, which did not have a barrier coat layer film formed on it, was not measured, and its blocking resistance was recorded as "-".

[0181] <Lamination Strength> Laminate 1 was cut into 15mm wide strips to form test specimens. Five of these specimens were prepared, and each specimen was subjected to a T-type peel test using a universal tensile testing machine (RTE-1210, manufactured by Orientec Co., Ltd.) at a tensile speed of 300mm / min. The laminate strength of each specimen was measured five times, and the average value was calculated. The same test was performed on laminate 38 (a polyolefin substrate with a vapor-deposited layer and a barrier coat layer applied, a blank specimen) without an anchor coat agent, and the average value was calculated. Laminate strength was evaluated in two stages: ○: Laminate strength is 50% or more of the average value of the blank test specimen, and ×: Laminate strength is less than 50% of the average value of the blank test specimen. Similarly, the lamination strength was evaluated for laminates 2 to 24 and laminates 31 to 41. The results are shown in Tables 8 to 10. The lamination strength of laminate 38 was recorded as "-".

[0182] <Oxygen barrier properties> For laminate 1, the oxygen permeability was measured using an oxygen gas permeability measuring device (OX-TRAN 2 / 22, MOCON Corporation) under conditions of a measurement temperature of 23°C and a humidity of 50% RH. Each laminate was measured three times under the same conditions, and the average was taken as the oxygen permeability of the laminate before retorting. Furthermore, the same type of packaging as that used in the <Retort Resistance> section below was used, and after undergoing the same retort treatment, the laminate was opened, and the oxygen permeability of the retort-treated laminate was measured under the same conditions as described above. Each laminate was measured three times under the same conditions, and the average was taken as the oxygen permeability of the retort-treated laminate. The change in oxygen permeability of the laminate before and after retorting was evaluated. A smaller change in oxygen permeability indicates better oxygen barrier properties. Oxygen permeability was evaluated on a three-point scale: ○: no change at all, △: change rate between 0.1% and less than 10% (no practical problem), and ×: change rate of 10% or more. Similarly, the oxygen barrier properties of laminates 2 to 24 and laminates 31 to 41 were also evaluated. The results are shown in Tables 8 to 10.

[0183] <Water vapor barrier properties> For laminate 1, the water vapor transmission rate was measured using a water vapor transmission rate measuring device (PERMATRAN-W 3 / 34, MOCON) under conditions of a measurement temperature of 40°C and a relative humidity of 90%RH. Each laminate was measured three times under the same conditions, and the average was taken as the water vapor transmission rate of the laminate before retorting. Furthermore, the same type of packaging as that used in the <Retort Resistance> section below was used, and after undergoing the same retort treatment, the laminate was opened, and the water vapor permeability of the retorted laminate was measured under the same conditions as described above. Each laminate was measured three times under the same conditions, and the average was taken as the water vapor permeability of the retorted laminate. The change in water vapor permeability of the laminate before and after retorting was evaluated. A smaller change in water vapor permeability indicates better water vapor barrier properties. Water vapor transmission was evaluated on a three-point scale: ○: no change at all, △: change rate between 0.1% and less than 10% (no practical problem), and ×: change rate of 10% or more. Similarly, the water vapor barrier properties of laminates 2 to 24 and laminates 31 to 41 were also evaluated. The results are shown in Tables 8 to 10.

[0184] <Retort resistance> Two layers of laminate 1 are subjected to 3 kgf / cm² 2 The two halves were then heat-sealed at 180°C for 1 second to obtain a 15cm x 10cm packaging bag 1 with an opening. A mixture of salad oil, ketchup, and vinegar (1 / 1 / 1) was filled into packaging bag 1 as the contents, and the opening was sealed by heat sealing under the same conditions as described above to create a package. This packaging bag was retorted at 120°C for 40 minutes using a hot water shower method, and the appearance of the package was visually observed and evaluated. The appearance of the package was evaluated to see if any bulging due to the peeling of the anchor coat layer and the vapor-deposited layer could be observed. Packages in which no bulging was observed were judged to have good retort resistance. The appearance of the package was evaluated on a three-point scale: ○: no change observed, △: slight bulging observed (no practical problem), ×: bulging observed. Similarly, the retort resistance of packaging bags 2 to 24 and packaging bags 31 to 41 was also evaluated. The results are shown in Tables 8 to 10.

[0185] [Table 8]

[0186] [Table 9]

[0187] [Table 10]

[0188] According to Tables 8 to 10, in laminates 1 to 24 of Examples 30 to 53, which used the anchor coating agents of Examples 1 to 20, it is clear that the adhesion between the polyolefin substrate and the anchor coating layer, or between the anchor coating layer and the vapor-deposited layer, is excellent because the contact angle of the anchor coating layer is within a specific range. It is also clear that the blocking resistance is excellent. Furthermore, it is clear that the laminate strength, gas barrier properties, and retort resistance are also excellent. In Comparative Example 10, the laminate 31 using anchor coating agent 21 (Comparative Example 1), which contains a resin material that does not contain at least one polar group among hydroxyl groups, amide groups, amino groups, phosphate groups, and epoxy groups, clearly exhibits inferior adhesion, blocking resistance, laminate strength, gas barrier properties, and retort resistance due to the contact angle of the anchor coating layer being outside a specific range. In Comparative Example 11, the laminate 32 using anchor coating agent 22 (Comparative Example 2) that does not contain a silane coupling agent clearly exhibits inferior adhesion, blocking resistance, laminate strength, gas barrier properties, and retort resistance, as the contact angle of the anchor coating layer falls outside a specific range. Laminates 33 to 35 of Comparative Examples 12 to 14, which used anchor coating agents 23 to 25 (Comparative Examples 3 to 5) containing a silane coupling agent that does not contain at least one of the groups that contain a nitrogen atom, a sulfur atom, or a vinyl group, clearly have inferior adhesion, blocking resistance, laminate strength, gas barrier properties, and retort resistance, as the contact angle of the anchor coating layer falls outside a specific range. In Comparative Example 15, the laminate 36, which uses anchor coating agent 26 (Comparative Example 6) containing a resin material with a mixing ratio of methyl methacrylate (MMA) and the polar group-containing methacrylate ester (HEMA) outside the specified range, clearly exhibits inferior adhesion, blocking resistance, laminate strength, gas barrier properties, and retort resistance due to the anchor coating layer's contact angle being outside a specific range. In Comparative Example 16, the laminate 37 using an anchor coating agent 27 (Comparative Example 7) similar to Patent Document 1 that does not contain a silane coupling agent clearly exhibits inferior adhesion, blocking resistance, laminate strength, gas barrier properties, and retort resistance, as the contact angle of the anchor coating layer falls outside a specific range. The laminate 38 of Comparative Example 17, which lacks an anchor coat layer, clearly exhibits inferior adhesion, blocking resistance, gas barrier properties, and retort resistance. However, the laminate 38 possesses a certain degree of lamination strength. In Comparative Example 18, the laminate 39, whose anchor coat layer thickness is outside the specified range, clearly exhibits inferior adhesion, blocking resistance, laminate strength, gas barrier properties, and retort resistance, although the contact angle of the anchor coat layer is within a specific range. In Comparative Example 19, the laminate 40, whose anchor coat layer thickness is outside the specified range, clearly exhibits inferior adhesion, blocking resistance, laminate strength, gas barrier properties, and retort resistance due to the anchor coat layer contact angle being outside the specified range. It is clear that the laminate 41 of Comparative Example 20, which lacks a barrier coat layer, has inferior lamination strength, gas barrier properties, and retort resistance.

Claims

1. A laminate comprising, on a polyolefin substrate, an anchor coat layer having a thickness of 0.05 to 1.5 μm, a vapor-deposited layer, and a barrier coat layer, in at least this order, The anchor coat layer is a layer comprising a resin material containing methyl (meth)acrylate and a polar group-containing (meth)acrylic acid ester or (meth)acrylic acid, a curing agent, and an anchor coat agent containing a silane coupling agent. The polar group in the resin material is at least one polar group selected from hydroxyl groups, amide groups, amino groups, phosphate groups, and epoxy groups. The silane coupling agent is a silane coupling agent containing at least one group selected from a group containing a nitrogen atom, a group containing a sulfur atom, and a vinyl group. The mixing ratio of the methyl (meth)acrylate and the polar group-containing (meth)acrylate ester or (meth)acrylic acid is such that the polar group-containing (meth)acrylate ester or (meth)acrylic acid is 5 or more and less than 900 parts per 100 parts methyl (meth)acrylate. A laminate characterized in that the contact angle of the surface of the anchor coat layer is 20 degrees or more and 75 degrees or less.

2. A packaging material characterized by being made using the laminate described in claim 1.

3. An anchor coating agent used in the laminate described in claim 1, The anchor coating agent comprises a resin material containing methyl (meth)acrylate and a polar group-containing (meth)acrylic acid ester or (meth)acrylic acid, a curing agent, and a silane coupling agent. The polar group in the resin material is at least one polar group selected from hydroxyl groups, amide groups, amino groups, phosphate groups, and epoxy groups. The silane coupling agent is a silane coupling agent containing at least one group selected from a group containing a nitrogen atom, a group containing a sulfur atom, and a vinyl group. The mixing ratio of the methyl (meth)acrylate and the polar group-containing (meth)acrylic acid or (meth)acrylic acid is such that the polar group-containing (meth)acrylic acid ester or (meth)acrylic acid is 5 or more and less than 900 parts per 100 parts methyl (meth)acrylate. An anchor coating agent characterized in that the contact angle of the surface of the anchor coating layer formed by printing the anchor coating agent is 20 degrees or more and 75 degrees or less.

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