Laminates, composite laminates, and packaging containing them

Abstract

The present invention provides a laminate with excellent gas barrier properties and flexibility, suitable for recycling, and packaging materials using the same. [Solution] A laminate in which an inorganic layer and a protective layer are laminated in this order on one side of a base film, wherein the protective layer contains a water-soluble resin, silicon alkoxide, and plate-shaped inorganic particles, and the average composition ratio of silicon (Si) to carbon (C) (Si / C) measured by X-ray photoelectron spectroscopy (XPS) in the thickness direction from the protective layer surface side opposite to the inorganic layer side up to 1 / 3 of the protective layer thickness is 1.30 to 3.00.

Description

[Technical Field] 【0001】 The present invention relates to laminates, composite laminates, and packaging materials using the same, which have excellent gas barrier properties and flexibility and are suitable for recycling. [Background technology] 【0002】 Various packaging materials have been used to package a wide range of items, including food and beverages, pharmaceuticals, and daily necessities. These packaging materials require oxygen barrier and water vapor barrier properties to prevent the deterioration of their contents. Aluminum foil, which has excellent gas barrier properties, is used as a packaging material for retort foods. However, packaging materials using aluminum foil are difficult to recycle, limiting their applications. 【0003】 Furthermore, packaging materials have been proposed that use films on which aluminum or aluminum oxide has been deposited as a gas barrier layer using physical vapor deposition methods such as vacuum deposition on thermoplastic films such as polyester films. For boiled and retort foods, which are used in harsh environments, a protective layer has been laminated on top of the gas barrier layer to prevent deterioration of the gas barrier performance, and a specific elemental composition has been applied to the protective layer (Patent Document 1). Alternatively, the protective layer has been proposed to improve gas barrier performance by including inorganic compounds such as layered shapes or nano-sized particles along with water-soluble polymers and metal alkoxides (Patent Documents 2-5). However, since these are used in combination with polyester films or other resin films, they are still considered disadvantageous from a recycling perspective. 【0004】 To improve recyclability, packaging materials using olefin-based films such as polyethylene and polypropylene have been proposed. For example, one proposed method involves providing a specific resin layer on an olefin-based film, then depositing a gas barrier layer such as a metal or inorganic compound, and further laminating a protective layer having a specific elemental composition including a metal alkoxide and not containing inorganic layered compounds (Patent Document 6). Another proposed method involves providing a base layer on a multi-layered olefin-based substrate, then depositing a gas barrier layer such as an inorganic compound, and further laminating a protective layer containing a metal alkoxide (Patent Document 7). 【0005】 Furthermore, packaging made of so-called single-material (monomaterial) components, which combine these recyclable components of the same type, has been proposed (Patent Document 6). In addition, packaging has been proposed that features optimized heat shrinkage rates of the components used in the monomaterial packaging and an optimized order in which the components are combined (Patent Documents 8 and 9). [Prior art documents] [Patent Documents] 【0006】 [Patent Document 1] Patent No. 7089709 [Patent Document 2] Patent No. 3780741 [Patent Document 3] Patent No. 3967734 [Patent Document 4] Patent No. 4739905 [Patent Document 5] Japanese Patent Publication No. 2018-126880 [Patent Document 6] Patent No. 7331537 [Patent Document 7] Patent No. 7377425 [Patent Document 8] Patent No. 7088138 [Patent Document 9] Patent No. 7231095 [Overview of the Initiative] 【Problems to be Solved by the Invention】 【0007】 All patent documents aim to improve gas barrier properties or apply olefin-based films / substrates to improve recyclability. However, among the substrate films, especially olefin-based materials have problems with heat resistance and mechanical properties. Therefore, with the combinations of the prior arts disclosed in the patent documents, it is difficult to apply them to the use environments where the heat is severe, such as the packaging materials for retort foods like retort pouches, for the use of boiled retort foods. There are problems that the gas barrier properties deteriorate due to heat deformation during the boil-in retort process or bending and deformation during the forming process of the package. 【0008】 In view of this problem, an object of the present invention is to stably provide a laminate excellent in gas barrier properties and flex resistance by clarifying a preferable state of the laminate, and a package using the same. 【Means for Solving the Problems】 【0009】 The laminate of the present invention is a laminate in which an inorganic layer and a protective layer are laminated in this order on one side of a base film, the protective layer contains a water-soluble resin, a silicon alkoxide, and plate-like inorganic particles, the inorganic layer does not correspond to the protective layer and contains at least one of an inorganic substance alone and an inorganic compound, and in the portion in the thickness direction from the surface side of the protective layer on the side opposite to the inorganic layer side to 1 / 3 of the protective layer thickness, the average composition ratio (Si / C) of silicon element (Si) and carbon element (C) measured by X-ray photoelectron spectroscopy (XPS) is 1.30 to 3.00. 【0010】 Moreover, it is the laminate as described above, in which the base film is an olefin-based base material. 【0011】 Moreover, it is the laminate as described above, in which the plate-like inorganic particles have a major axis of 0.1 to 2 μm and a minor axis of 10 to 500 nm. 【0012】 Furthermore, the plate-shaped inorganic particles are the laminate described above, having silanol groups. 【0013】 Furthermore, the laminate described above has a content of 0.03 to 20% by mass of the plate-shaped inorganic particles in 100% by mass of the protective layer. 【0014】 Furthermore, the protective layer is the laminate described above, further comprising a linear polysiloxane. 【0015】 Furthermore, the silicon alkoxide is the laminate described above, comprising a silicon alkoxide having a ureid group. 【0016】 Furthermore, the laminate described above has an anchor layer between the base film and the inorganic layer. 【0017】 Furthermore, the inorganic layer is the laminate described above, comprising aluminum (Al) and / or silicon (Si). 【0018】 Furthermore, the laminate described above has a solid content ratio of ureid group-containing silicon alkoxide to the solid content of the protective layer of 2.5% by mass or more. 【0019】 Furthermore, the laminate described above is characterized in that the mass ratio of the linear polysiloxane and silicon alkoxide contained in the protective layer, calculated on an SiO2 basis, is in the range of linear polysiloxane / silicon alkoxide = 15 / 85 to 90 / 10. 【0020】 Furthermore, the laminate described above has a protective layer thickness of 100 to 1000 nm. 【0021】 Furthermore, the laminate described above is wherein the inorganic layer contains aluminum oxide. 【0022】 Furthermore, the composite laminate is formed by laminating a second olefin layer containing an olefin-based resin on at least one side of the laminate described above, via a resin layer. 【0023】 Furthermore, the composite laminate described above is characterized in that the thermal shrinkage rate after heating at 120°C for 15 minutes is smaller for the second olefin layer than for the laminate. 【0024】 Furthermore, the composite laminate described above is further laminated on at least one side of the composite laminate, either the laminate side or the second olefin layer side, via a resin layer, with a third olefin layer containing an olefin resin. 【0025】 Furthermore, the composite laminate described above has a thermal shrinkage rate after heating at 120°C for 15 minutes that is smaller for at least one or both of the second olefin layer or the third olefin layer than for the laminate. 【0026】 Furthermore, the packaging includes the laminate described in any of the above and / or the composite laminate described in any of the above. [Effects of the Invention] 【0027】 According to the present invention, it is possible to provide a laminate that is excellent in gas barrier properties and flexibility, and is suitable for recycling, as well as a packaging material using the same. [Modes for carrying out the invention] 【0028】 The laminate of the present invention will be described in more detail below. 【0029】 The present invention provides a laminate in which an inorganic layer and a protective layer are laminated in that order on one side of a base film, wherein the protective layer contains a water-soluble resin, silicon alkoxide, and plate-shaped inorganic particles, and the average composition ratio of silicon (Si) to carbon (C) (Si / C), measured by X-ray photoelectron spectroscopy (XPS) in the thickness direction from the protective layer surface side opposite to the inorganic layer side up to 1 / 3 of the protective layer thickness, is 1.30 to 3.00. 【0030】 [Base film] The resin constituting the base film according to the present invention is not particularly limited and includes, for example, polyester resins such as polyethylene terephthalate, polyethylene-2,6-naphthalate, polypropylene terephthalate, and polybutylene terephthalate; polyolefin resins such as polyethylene, polystyrene, polypropylene, polyisobutylene, polybutene, and polymethylpentene; cyclic polyolefin resins; polyamide resins; polyimide resins; polyether resins; polyesteramide resins; polyether ester resins; acrylic resins; polyurethane resins; polycarbonate resins; or polyvinyl chloride resins; and even biodegradable resins such as polylactic acid, polycaprolactone, polyglycolic acid, and polyvinyl alcohol. Furthermore, polyester is preferred from the viewpoint of recyclability, adhesion to the inorganic layer, and handling, and it is preferable to include 3 to 55% by mass of recycled raw materials relative to the total amount of these resins. The recycled raw materials may be recycled by mechanical recycling or chemical recycling, and are not particularly limited. Furthermore, the resin constituting the base film may be a mixed resin containing biomass-derived (plant-derived) raw materials and chemical fuel-derived raw materials. For example, in the case of polyester, it is preferable that either or both of the diol or dicarboxylic acid raw materials contain biomass-derived (plant-derived) raw materials in an amount of 10 to 95% by mass relative to the entire resin composition. 【0031】 In particular, from the viewpoint of ease of recycling, the base film according to the present invention is preferably a base film containing an olefin-based resin. There are no particular limitations on the olefin-based resin, and examples include polyolefin resins such as polyethylene, polystyrene, polypropylene, polyisobutylene, polybutene, and polymethylpentene, cyclic polyolefin resins, and copolymerized or modified polyolefin resins such as ethylene-vinyl acetate copolymer resins and polyvinyl alcohol resins, as well as mixed resins thereof. Among these, polypropylene is preferred from the viewpoint of physical properties such as mechanical properties and heat resistance, and ease of recycling, and it is preferable to include 3 to 55% by mass of recycled raw materials relative to the total amount of these resins. The recycled raw materials may be recycled by mechanical recycling or by chemical recycling, and are not particularly limited. Furthermore, the resin constituting the base film may contain biomass-derived (plant-derived) raw materials and may be a mixed resin with chemical fuel-derived raw materials. 【0032】 The base film may be unstretched or stretched (uniaxially or biaxially), but from the viewpoint of thermal dimensional stability, it is preferably a biaxially oriented film, and particularly preferably a biaxially oriented polypropylene film. 【0033】 There are no particular restrictions on the thickness of the base film, but it is preferably 1 μm to 100 μm, more preferably 5 μm to 50 μm, and even more preferably 10 μm to 30 μm. 【0034】 The surface of the base film may be subjected to corona treatment, ozone treatment, plasma treatment, glow discharge treatment, etc., as needed, in order to improve adhesion with the inorganic layer. 【0035】 [Inorganic layer] The inorganic layer according to the present invention is a layer that does not fall under the protective layer described later and contains at least one of an inorganic substance and an inorganic compound, and may be a mixture of an inorganic substance and an inorganic compound. Examples of inorganic layers include aluminum, magnesium, titanium, tin, indium, silicon, zinc, and their oxides, and these may be used individually or as a mixture of two or more. Inorganic compounds containing metal oxides or metal nitrides are more preferable for the inorganic layer. When the inorganic layer contains metal oxides or metal nitrides, it is preferable because it improves durability against heat during boiling and retorting processes, and when the laminate of the present invention is used as a packaging body and its contents are acidic, it improves acid resistance to acidic contents. Examples of metal oxides include aluminum oxide, magnesium oxide, titanium oxide, tin oxide, indium oxide alloy, silicon oxide, and silicon oxide nitride, and examples of metal nitrides include aluminum nitride, titanium nitride, and silicon nitride, and these inorganic compounds may be used individually or as a mixture of two or more. Of these, it is more preferable that the inorganic layer in the present invention contains aluminum (Al) and / or silicon (Si) because this improves durability against the heat applied during the boiling and retorting process and acid resistance to acidic contents. Furthermore, the elemental composition within the inorganic layer may differ in the thickness direction. When the elemental composition of the inorganic layer differs in the thickness direction, the adhesion between the inorganic layer and the protective layer is improved, making it less likely for the inorganic layer and the protective layer to peel off when formed into a laminate. Among these, from the viewpoint of manufacturing cost, gas barrier properties, heat resistance against the heat applied during the boiling and retorting process and acid resistance to acidic contents, oxygen, aluminum, and silicon are preferred elements for the inorganic layer, and more preferably aluminum oxide consisting of oxygen and aluminum. It should be noted that the aluminum oxide in the inorganic layer of the present invention does not refer only to fully oxidized aluminum oxide (Al2O3), but as described above, it may also refer to sub-oxidized aluminum oxide or a mixture of aluminum oxide containing sub-oxidized aluminum oxide, where the elemental composition of the inorganic layer differs in the thickness direction. 【0036】 There are no particular restrictions on the method of forming the inorganic layer; it can be formed by known methods such as vapor deposition, sputtering, ion plating, and plasma vapor deposition. However, from the viewpoint of productivity, vacuum deposition is preferred. 【0037】 Furthermore, as an example of a method for forming an inorganic layer with different elemental compositions in the thickness direction, a method for forming an inorganic layer in which the composition continuously changes from an aluminum metal layer to an aluminum oxide layer will be described. In this case, a method of continuously changing the composition from an aluminum metal layer to an aluminum oxide layer in a vacuum chamber is preferred as the method for forming the inorganic layer. The inorganic layer can be formed by known methods such as vapor deposition, sputtering, ion plating, and plasma vapor deposition, but vapor deposition is preferred from the viewpoint of productivity. 【0038】 Let me explain in more detail. A roll-shaped base film is set in a vacuum chamber, the base film is unwound, and the aluminum is heated and evaporated. Methods such as resistance heating, high-frequency heating, and electron beam heating can be applied to heat and evaporate the aluminum. The heated and evaporated aluminum adheres to the base film, forming an aluminum metal layer. After the formation of the aluminum metal layer, oxygen gas is introduced into the latter half of the deposition process. As the introduced oxygen gas diffuses from the winding side to the unwinding side of the base film, the oxygen reaction proceeds continuously from the aluminum metal layer to the aluminum oxide layer, forming an inorganic layer with a gradient structure in which the composition continuously changes in the direction of film thickness. 【0039】 Furthermore, the gradient structure of the inorganic layer can be controlled by adjusting and changing the amount and speed of oxygen introduced when introducing the oxygen gas, the position, shape, and number of inlet ports such as oxygen nozzles, and the transport speed of the base film, but is not limited to these. 【0040】 To measure the film thickness in a gradient structure, X-ray photoelectron spectroscopy (XPS) is used to perform compositional analysis in the depth direction, and the film composition of inorganic compounds is confirmed by the depth profile. For metal elements, the oxide and metal components are separated and profiled. Data is collected from the surface layer of the protective layer until it reaches the substrate while performing ion etching, and the presence or absence of a continuous increase or decrease in composition is confirmed from the depth profile of each element obtained. A continuous increase or decrease is determined if the length of the increase or decrease is 2 nm or more. 【0041】 Next, the total thickness of the inorganic layer is determined using the method described later. The film thickness in the gradient structure is calculated from the total thickness of the inorganic layer and the region of the depth profile corresponding to the inorganic layer. 【0042】 In the present invention, the thickness of the inorganic layer is preferably 5 nm to 150 nm, and more preferably 7 nm to 100 nm, as this makes it easier to avoid gas barrier properties and cohesive failure within the inorganic layer, as described later, and to obtain good adhesion. If the thickness is 5 nm or less, the gas barrier properties may be insufficient, while if it is 150 nm or more, the cohesive force of the inorganic layer decreases, which can lead to cohesive failure within the inorganic layer, causing it to crack or peel off. 【0043】 [Protective layer] The protective layer according to the present invention contains a water-soluble resin, silicon alkoxide, and plate-shaped inorganic particles. The average composition ratio of silicon (Si) to carbon (C) (Si / C), measured by X-ray photoelectron spectroscopy (XPS) from the protective layer surface side opposite the inorganic layer side up to 1 / 3 of the protective layer thickness, is 1.30 to 3.00. With the protective layer constructed as described above, it is estimated that the protective layer will become dense even when laminated on an olefin-based substrate film, which has particular issues with heat resistance and mechanical properties. This allows for excellent gas barrier properties and flexibility even after boiling and retorting in harsh operating environments. 【0044】 In the present invention, the protective layer has an average composition ratio (Si / C) of silicon (Si) and carbon (C) of 1.30 to 3.00, measured by X-ray photoelectron spectroscopy (XPS) in the thickness direction from the protective layer surface side opposite to the inorganic layer side up to 1 / 3 of the protective layer thickness. The statement that the protective layer contains silicon (Si) and carbon (C) means that, when evaluated by XPS (X-ray Photoelectron Spectroscopy; sometimes also known as ESCA (Electron Spectroscopy for Chemical Analysis)) under the conditions described in the examples, the content ratio of each element is 5.0 atm% or more in the total 100.0 atm% of atoms constituting the protective layer. Therefore, if the content ratio of either silicon (Si) or carbon (C) in the total 100.0 atm% of atoms constituting the protective layer is less than 5.0 atm%, it is considered different from the protective layer in the present invention. Furthermore, the detailed evaluation conditions for the XPS method in this invention are as described in the examples. 【0045】 This method allows obtaining the composition ratio in the depth direction from the protective layer surface side opposite to the inorganic layer side. However, since the region up to 0.4 nm from the surface of the protective layer contains information on surface contamination, the composition of the protective layer is calculated from a position deeper than 0.4 nm from the surface, and the average composition ratio (Si / C) in the depth direction up to the inorganic layer is determined. At this time, the thickness of the protective layer is first determined by the method described later, and the depth from the surface of the protective layer to the interface with the inorganic layer, as measured by X-ray photoelectron spectroscopy (XPS), is taken as the thickness of the protective layer. The average composition ratio measurements at each measurement point in the thickness direction up to 1 / 3 of that thickness are then averaged to obtain the average composition ratio (Si / C) in this invention. In the present invention, the average composition ratio (Si / C) of the protective layer is 1.30 to 3.00, but preferably 1.50 to 2.00, and more preferably 1.70 to 1.90. It is estimated that when laminated on an olefin-based substrate film, which has particular issues with heat resistance and mechanical properties, the protective layer tends to become a denser film. Therefore, by blocking gas permeation paths such as water vapor and oxygen, it is easier to exhibit gas barrier properties and adhesion after boiling and retorting, which are harsh operating environments. If the average composition ratio (Si / C) is less than 1.30, it is estimated that the density of the protective layer will be insufficient. As a result, the gas barrier properties will be poor, and when used in composite laminates or packaging described later, the gas barrier properties will be insufficient after boiling and retorting, which are harsh operating environments. Furthermore, it is estimated that if the average composition ratio (Si / C) is greater than 3.00, the protective layer becomes excessively dense and hard, increasing the risk of cracks and fractures occurring in the protective layer and inorganic layer. As a result, the gas barrier properties are insufficient, similar to the case where the average composition ratio (Si / C) is less than 1.30. 【0046】 The protective layer in the present invention contains a water-soluble resin. Examples of water-soluble resins include polyvinyl alcohol, ethylene-vinyl alcohol copolymer, and modified polyvinyl alcohol. These polymers may be used individually or as a mixture of two or more, but vinyl alcohol-based polymers (including modified polyvinyl alcohol) are preferred. Vinyl alcohol-based polymers (including modified polyvinyl alcohol) are generally obtained by saponifying polyvinyl acetate. This may be partial saponification, where only a portion of the acetate groups are saponified, or complete saponification, but a higher degree of saponification is preferred. The degree of saponification is preferably 90% or higher, and more preferably 95% or higher. If the degree of saponification is low and the polymer contains many acetate groups with high steric hindrance, the free volume of the protective layer may increase. The degree of polymerization of the vinyl alcohol-based resin is preferably 1,000 to 3,000, and more preferably 1,000 to 2,000. If the degree of polymerization is low, the polymer may not be easily fixed, and adhesion and gas barrier properties may not be easily achieved. 【0047】 Furthermore, a particularly preferred water-soluble resin is a vinyl polymer having carbonyl groups in its cyclic structure. By including a vinyl polymer having carbonyl groups in its cyclic structure as the water-soluble resin in the protective layer, the hydrophobicity due to the cyclic structure and the interaction around the polymer due to the carbonyl groups result in a dense film structure, improving water resistance and creating a dense protective layer with low hydrophilicity. This reduces interaction with gas molecules such as oxygen and water vapor, blocking the permeation pathways of gas molecules, thereby exhibiting excellent gas barrier properties along with adhesion. In this invention, the vinyl polymer having carbonyl groups in its cyclic structure is preferably present in an amount of 20 to 100% by mass of 100% by mass of the water-soluble resin in the protective layer. If it is less than 20% by mass, the effect of improving gas barrier properties may be poor, and 100% by mass, where all water-soluble resins are vinyl polymers having carbonyl groups in their cyclic structure, is most preferable. 【0048】 The cyclic structure is not particularly limited as long as it is a ring with three or more members (for example, a ring with three to six members). Furthermore, it may be a heterocyclic structure containing heteroatoms other than carbon, such as nitrogen, oxygen, sulfur, or phosphorus. The carbonyl group portion within this cyclic structure may be located in the main chain, side chain, or crosslinking chain of the vinyl polymer. Specific examples of vinyl polymers having carbonyl groups in these cyclic structures include lactone structures (cyclic esters) and lactam structures (cyclic amides). These may be used individually or in combination of two or more, and are not particularly limited, but lactone structures are preferred. Using a vinyl polymer with a lactone structure as a water-soluble polymer makes it stable against the acid catalyst used for hydrolysis of silicon alkoxides (described later) and helps maintain gas barrier properties. Examples of vinyl polymers with a lactone structure include α-acetolactone, β-propiolactone, γ-butyrolactone, and δ-valerolactone. 【0049】 The protective layer in the present invention contains a silicon alkoxide. Examples of silicon alkoxides include those represented as Si(OR)4. In the silicon alkoxide, R is preferably a lower alkyl group, such as a methyl group, ethyl group, n-propyl group, or n-butyl group. Specifically, examples of silicon alkoxides include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane, which may be used individually or as a mixture of two or more. In particular, in the present invention, it is more preferable to further include a linear polysiloxane in the protective layer. It is presumed that by including a linear polysiloxane in the protective layer, the molecular chains become tightly intertwined, forming and fixing a molecular chain network within the protective layer, thereby suppressing the movement of molecular chains of the components constituting the protective layer and limiting the pathways through which gas molecules such as oxygen and water vapor permeate. In particular, linear polysiloxanes have few pores in their molecular chains, and the molecular chains can exist at a high density. Therefore, especially when further containing plate-like inorganic particles as described later, the linear polysiloxanes strongly interact with the surface of the plate-like inorganic particles, which have a large surface area, and form and fix a network of molecular chains in the protective layer. This suppresses the movement of molecular chains of the components constituting the protective layer, thus resulting in a more densely structured protective layer. As a result, the gas barrier properties are improved, and a densely structured protective layer is formed that can suppress the expansion of gas permeation pathways of oxygen and water vapor gas molecules due to environmental changes such as temperature. It is predicted that even when laminated on olefin-based substrate films, which have particular issues with heat resistance and mechanical properties, excellent gas barrier properties will be exhibited even after high-temperature hot water treatment such as boiling and retorting. Linear polysiloxanes are represented by the following chemical formula (1), where n is an integer of 2 or more. In chemical formula (1), R can be a lower alkyl group such as a methyl group, ethyl group, n-propyl group, or n-butyl group, or a branched alkyl group such as an iso-propyl group or t-butyl group. In the present invention, the longer the linear structure of the linear polysiloxane, the easier it is to form a network and fix it in the protective layer, so n is preferably 5 or more, and more preferably 10 or more.There is no particular upper limit to n, but if it exceeds 30, some components may take on a ring-shaped network structure, and conversely, the protective layer may become sparse, so it is preferable to adjust it as appropriate. 【0050】 [ka] 【0051】 Linear polysiloxanes can be obtained from silicon alkoxides, which can be hydrolyzed, for example, to obtain linear polysiloxanes. Silicon alkoxides are hydrolyzed in the presence of Si(OR)4, water, a catalyst, and an organic solvent. The amount of water used for hydrolysis is preferably 0.8 equivalents to 5 equivalents, and more preferably 1.0 equivalent to 4 equivalents, relative to the alkoxy groups of Si(OR)4. If the amount of water is less than 0.8 equivalents, hydrolysis may not proceed sufficiently, and linear polysiloxanes may not be obtained. If the amount of water is more than 5 equivalents, the reaction of the silicon alkoxide, described later, may proceed randomly, forming a large amount of non-linear polysiloxanes, and linear polysiloxanes may not be obtained. 【0052】 The catalyst used for hydrolysis is preferably an acid catalyst. Examples of acid catalysts include, but are not limited to, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, and tartaric acid. Normally, the hydrolysis and polycondensation reactions of silicon alkoxides can proceed with either an acid catalyst or a base catalyst. However, when an acid catalyst is used, the monomers in the system are more easily hydrolyzed on average and tend to become linear. On the other hand, when a base catalyst is used, the reaction mechanism is such that the hydrolysis and polycondensation reactions of alkoxides bonded to the same molecule tend to proceed more easily, so the reaction proceeds randomly and the reaction product tends to have many voids. The amount of catalyst used is preferably 0.1 mol% to 0.5 mol% relative to the total molar amount of silicon alkoxide. 【0053】 The organic solvent used for hydrolysis can be alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, or n-butyl alcohol, which are miscible with water and silicon alkoxide. 【0054】 The hydrolysis temperature is preferably between 20°C and 45°C. If the reaction is carried out at a temperature below 20°C, the reactivity may be low, and the hydrolysis of Si(OR)4 may not proceed smoothly. On the other hand, if the reaction is carried out at a temperature above 45°C, the hydrolysis and polycondensation reactions proceed rapidly, which may result in gelation or the formation of a random, sparse polysiloxane that is not linear. 【0055】 In the present invention, the protective layer preferably further contains a silicon alkoxide having a ureid group. By including a silicon alkoxide having a ureid group, when a composite laminate is formed as described later, the protective layer interacts with the functional groups contained in other adjacent layers (printing ink layer, adhesive layer, resin layer, etc.), and is also bonded and incorporated into the molecular chain network of the aforementioned water-soluble resin and linear polysiloxane. As a result, when peeling force is applied, the component remains without detaching, thus improving adhesion. Consequently, even when laminated on an olefin-based substrate film, which has particular issues with heat resistance and mechanical properties, even after high-temperature hot water treatment such as boiling and retorting, even better gas barrier properties are more likely to be exhibited. The silicon alkoxide having a ureid group in the present invention only needs to have a ureid group in its structure, and the ureid group may be a 1- to 3-functional silicon alkoxide, or the ureid group may be bonded to a silicon atom in the silicon alkoxide via a linear or branched alkyl chain such as methyl, ethyl, or propyl, or one or more types may be mixed depending on the required properties and productivity. Examples of such silicon alkoxides having a ureid group include KBM-585 and KBM-585A from Shin-Etsu Chemical Co., Ltd., A-1160 from Momentive Performance Materials Japan LLC, and "DOWSIL" (registered trademark) Z-6119 Silan, "DOWSIL" Z-6120 Silan, and "DOWSIL" Z-6675 Silan from Dow Toray Industries, Inc., and commercially available products from various manufacturers can be used. 【0056】 In addition to water-soluble resins, linear polysiloxanes, and silicon alkoxides having ureid groups, the protective layer in the present invention may also contain other silicon alkoxides having functional groups such as silane coupling agents, and is not particularly limited as long as it does not hinder the effects of the present invention. 【0057】 The protective layer of the present invention contains plate-shaped inorganic particles (hereinafter, plate-shaped inorganic particles may also be simply referred to as inorganic particles). By including plate-shaped inorganic particles, silicon alkoxides (and their hydrolysates), water-soluble resins and mixtures / cured products thereof, and especially the aforementioned linear polysiloxanes, strongly interact with the surface of the plate-shaped inorganic particles, which have a large surface area, resulting in a protective layer with a dense structure. As a result, the protective layer is reinforced by the strongly interacting plate-shaped inorganic particles, and it is presumed that even when laminated on olefin-based substrate films, which have particular issues with heat resistance and mechanical properties, the resistance to thermal deformation during boiling and retorting, and to bending and deformation during the molding process of the packaging body will be improved. 【0058】 In this invention, the plate-like shape includes flaky, flattened, leaf-like, and disc-like shapes, and unlike a perfect sphere, the inorganic particles have a major axis and a minor axis at some point within the particle. By using such plate-like inorganic particles, several layers of inorganic particles can be included in the thickness direction of the protective layer, and consequently, the inorganic particles are stacked in layers perpendicular to the surface of the laminate, with silicon alkoxide (and its hydrolysates), water-soluble resins and mixtures / cured products thereof, and especially the aforementioned linear polysiloxane, embedded between the plate-like inorganic particles. As a result, a protective layer with a dense structure is formed by strong interaction on the surface of the plate-like inorganic particles, which have a large surface area. This is expected to improve the resistance to thermal deformation during boiling and retorting, and to bending and deformation during the molding process of the packaging, even when laminated on olefin-based substrate films, which have particular issues with heat resistance and mechanical properties. 【0059】 The plate-shaped inorganic particles of the present invention are preferably such that the major axis is 0.1 to 2 μm and the minor axis is 10 to 500 nm, as this allows them to interact more strongly with silicon alkoxides (and their hydrolysates), water-soluble resins and mixtures / cured products thereof, and especially with the aforementioned linear polysiloxanes, thus exhibiting excellent boil-retort properties and flexibility. More preferably, the major axis is 0.1 to 1 μm and the minor axis is 10 to 100 nm. 【0060】 Here, the major and minor axes of the inorganic particles are determined as follows. First, the laminate of the present invention is prepared by cutting a sample for cross-sectional observation of the protective layer of the laminate in a direction perpendicular to the laminate surface using the FIB method with a microsampling system (FB-2000A, Hitachi, Ltd.) (specifically, based on the method described in "Polymer Surface Processing" (by Akira Iwamori), pp. 118-119). Next, the cross-section of the protective layer of the obtained laminate is observed using a transmission electron microscope (H-9000UHRII, Hitachi, Ltd.) at an accelerating voltage of 300kV. The observation magnification is set so that at least two inorganic particles contained in the protective layer are visible in one field of view. The length of the shortest inorganic particle portion present in this one field of view is measured, and the average value is calculated. In the same manner, any total of five fields of view are observed, and the average value of these five fields of view is taken as the minor axis. Next, the protective layer surface is observed in the same manner from a direction perpendicular to the laminate surface, the length of the longest part of the inorganic particle portion is measured, and the average value is calculated. In the same way, any five fields of view are observed, and the average value of these five fields of view is taken as the major axis. 【0061】 The inorganic particles of the present invention contain inorganic substances. The inorganic substances may be individual inorganic substances or inorganic compounds, and examples include aluminum, magnesium, titanium, tin, indium, silicon, zinc, and their oxides, which may be used individually or as a mixture of two or more. Examples of inorganic substances include inorganic oxides such as aluminum oxide, magnesium oxide, anatase-type titanium oxide, rutile-type titanium oxide, tin oxide, indium oxide alloy, silicon oxide, silicon oxide nitride, calcium carbonate, zinc oxide, and mineral-derived compounds such as kaolin. Other examples include metal nitrides such as aluminum nitride, titanium nitride, and silicon nitride. 【0062】 Of these, it is preferable that the inorganic particles have silanol groups in order to facilitate interaction with silicon alkoxides (and their hydrolysates), water-soluble resins and mixtures / cured products thereof, and especially with the linear polysiloxanes mentioned above. Among the inorganic materials, silicon oxide is an example of a material having silanol groups, but other inorganic particles can also exhibit similar effects by surface treatment to make them have silanol groups. The presence or absence of silanol groups can be determined by separating and extracting the inorganic particles from the protective layer, then measuring them by FT-IR using the method described later, and observing the presence or absence of a peak (950~970 cm-1) representing the Si-OH bond, which is the silanol group. 【0063】 In the present invention, the content of plate-like inorganic particles in the protective layer can be determined by the method described later and is not particularly limited, but in order to improve boil-retort properties and flexural resistance, the content in 100% by mass of the protective layer is preferably 0.03 to 20% by mass, and more preferably 0.5 to 10% by mass. If the content is less than 0.03% by mass, there may be insufficient inorganic particles, resulting in poor improvement of boil-retort properties and flexural resistance. If the content is higher than 20% by mass, the overlapping of particles only within the protective layer increases, reducing interaction with silicon alkoxide (its hydrolysates), water-soluble resins and their mixtures / cured products, and linear polysiloxanes, resulting in poor improvement of boil-retort properties and flexural resistance, or a protective layer that is brittle and easily cracked, similar to the case of less than 0.03% by mass. 【0064】 [Composition of the protective layer] In the present invention, it is preferable that the solid content ratio of silicon alkoxide having ureid groups to the total solid content in the protective layer is 2.5% by mass or more. When the solid content ratio of silicon alkoxide having ureid groups is 2.5% by mass or more, binding and entanglement are more likely to occur within the molecular chain network of the water-soluble resin and linear polysiloxane, and the components are more likely to remain without being removed during peeling, resulting in better adhesion. The solid content ratio of silicon alkoxide having ureid groups is preferably 5.0% by mass or more, more preferably 8.0% by mass or more. Furthermore, there is no particular upper limit to the solid content ratio of silicon alkoxide having ureid groups, but if it is higher than 50% by mass, the amount of water-soluble resin and linear polysiloxane in the protective layer will decrease, the molecular chain network will become sparser, and the gas barrier properties may decrease, so it is preferable that it be 50% by mass or less. The solid content ratio of silicon alkoxide having ureid groups can be measured by the method described later. 【0065】 In the present invention, it is preferable that the total content of all water-soluble resins in the protective layer is 20 to 80% by mass of 100% by mass of the protective layer. When the water-soluble resin content is 20 to 80% by mass, the protective layer tends to have a dense structure, and it is easier to achieve good adhesion and excellent gas barrier properties. If the water-soluble resin content is less than 20% by mass, the protective layer tends to harden, and cracks may occur, which may reduce the gas barrier properties. If the water-soluble resin content is more than 80% by mass, it may not be possible to immobilize the water-soluble resin, which may reduce the gas barrier properties. The water-soluble resin content is more preferably 25 to 60% by mass, and even more preferably 30 to 50% by mass. 【0066】 In the present invention, the total content of all linear polysiloxanes in the protective layer may be 20 to 80% by mass of 100% by mass of the protective layer. However, as mentioned above, silicon alkoxides having / not having ureid groups (including hydrolysates of silicon alkoxides) may also be included separately. Therefore, the content of linear polysiloxanes and silicon alkoxides is calculated on an SiO2 basis, and the total content of inorganic components in the protective layer (hereinafter, inorganic components in the protective layer may be referred to as protective layer inorganic components) is preferably 20 to 80% by mass of 100% by mass of the protective layer, and more preferably 30 to 65% by mass. The content of water-soluble resin and protective layer inorganic components in the protective layer can be measured by the method described later. 【0067】 In the present invention, the mixing ratio of linear polysiloxane and silicon alkoxide in the protective layer can be adjusted. The mixing ratio is the mass ratio of linear polysiloxane and silicon alkoxide on an SiO2 basis, preferably in the range of linear polysiloxane / silicon alkoxide = 15 / 85 to 90 / 10, more preferably in the range of 40 / 60 to 85 / 15, and even more preferably in the range of 40 / 60 to 65 / 35. If this value exceeds 90 / 10, the interaction between the linear polysiloxanes becomes stronger, which may prevent the immobilization of the water-soluble resin and the silicon alkoxide having ureid groups, and the adhesion and gas barrier properties may decrease. On the other hand, if it is less than 15 / 85, the amount of Si-OH bonds derived from the silicon alkoxide increases, which may increase hydrophilicity and decrease the gas barrier properties. The mixing ratio of linear polysiloxane and silicon alkoxide in the protective layer can be measured by the method described later. 【0068】 Furthermore, by using an oligomer raw material with multiple Si(OR)4 groups already bonded as the linear polysiloxane, the mixing ratio of the linear polysiloxane and silicon alkoxide can be easily adjusted. Examples of oligomer raw materials with multiple Si(OR)4 groups already bonded include linear oligomers in which alkyl silicates such as methyl silicate (where R in chemical formula (1) is a methyl group) and ethyl silicate (where R is an ethyl group) are formed. 【0069】 In this invention, a protective layer can be formed by causing a polycondensation reaction between the linear polysiloxane and silicon alkoxide contained in the protective layer using heat. When the polycondensation reaction proceeds, the silanol groups contained in the inorganic particles and the alkoxy and / or hydroxyl groups contained in the linear polysiloxane and silicon alkoxide decrease, resulting in a protective layer with a dense and tough structure. Furthermore, the polycondensation reaction increases the molecular weight of the linear polysiloxane and silicon alkoxide, thereby increasing their ability to fix water-soluble resins and silicon alkoxides having ureid groups. Therefore, since the gas barrier properties, flexibility, and adhesion of the protective layer can be improved by causing the reaction to proceed with heat, a higher temperature is preferable when forming the protective layer by causing a polycondensation reaction with heat. However, if the temperature exceeds 180°C, the olefin-based substrate film, which has particular issues with heat resistance and mechanical properties among the substrate films, may shrink due to the heat, or strain and cracks may occur in the inorganic layer, reducing the gas barrier properties. 【0070】 The protective layer can be obtained by coating an inorganic layer with a coating liquid containing the components of the protective layer (hereinafter sometimes abbreviated as "protective layer coating liquid") and drying it. Therefore, the drying temperature of the coating film, which is the temperature required to carry out the polycondensation reaction, is preferably 100°C to 200°C, more preferably 120°C to 180°C, and even more preferably 150°C to 180°C. If the temperature is below 100°C, the water contained as a solvent, as described later, may not evaporate sufficiently, and the layer may not harden. 【0071】 The protective layer coating solution can be obtained by mixing a solution of a water-soluble resin dissolved in water or a water / alcohol mixed solvent with a solution containing linear polysiloxane or silicon alkoxide having / not having a ureid group, and dispersing plate-shaped inorganic particles. Examples of alcohols used as solvents include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, and n-butyl alcohol. 【0072】 The method for applying the protective coating liquid onto the inorganic layer is not particularly limited and any known method can be used, such as direct gravure, reverse gravure, microgravure, rod coat, bar coat, die coat, or spray coat. 【0073】 The protective layer according to the present invention may contain leveling agents, crosslinking agents, curing agents, adhesion promoters, stabilizers, ultraviolet absorbers, antistatic agents, etc., as long as they do not impair gas barrier properties and adhesion. Examples of crosslinking agents include metal alkoxides and complexes of aluminum, titanium, zirconium, etc. 【0074】 In this invention, the thickness of the protective layer is preferably 10 nm to 1,000 nm, more preferably 100 nm to 600 nm, and even more preferably 250 nm to 500 nm. If the thickness is less than 10 nm, it may not be possible to sufficiently fill pinholes and cracks in the inorganic layer, and sufficient gas barrier properties may not be achieved. On the other hand, if the thickness exceeds 1,000 nm, cracks may occur due to the thickness. 【0075】 As mentioned above, the protective layer undergoes a condensation reaction due to heat, improving its gas barrier properties, flexibility, and adhesion. Therefore, it is preferable to further heat-treat the laminate after forming the protective layer to improve gas barrier properties, flexibility, and adhesion. The heat treatment temperature is preferably 30°C to 100°C, and more preferably 40°C to 80°C. The heat treatment time is preferably 1 day to 14 days, and more preferably 3 days to 7 days. If the heat treatment temperature is below 30°C, the thermal energy required to promote the reaction may be insufficient, resulting in a small effect. If it exceeds 100°C, curling of the olefin-based substrate film may occur, oligomers and additives may bleed out, and the costs for equipment and manufacturing may increase. 【0076】 [Analysis of the laminate. This will be explained later, but also here.] The presence of linear polysiloxane in the protective layer according to the present invention can be confirmed by laser Raman spectroscopy. In laser Raman spectroscopy, the Raman bands of linear polysiloxane and metal alkoxide (including hydrolysates of metal alkoxides) are 400-500 cm⁻¹, and the Raman bands of the 4-membered ring structure are 400-500 cm⁻¹. -1 These are observed at 495 cm². Because these Raman bands are superimposed, the four-membered ring structure is 495 cm². -1 Linear polysiloxanes are 488 cm³. -1 Because the random network structure is not a single regular structure, 450cm -1 These are observed as bands with a certain extent, and the peaks can be separated by fitting them with a Gaussian function approximation. 【0077】 This document describes a method for determining the content of water-soluble resin and inorganic components (linear polysiloxane and silicon alkoxide (including hydrolysates of silicon alkoxide)) in the protective layer. As mentioned above, the amount of the inorganic components, linear polysiloxane and silicon alkoxide (including hydrolysates of silicon alkoxide), can be replaced by the amount of silicon, which can be obtained by X-ray fluorescence analysis. First, five standard samples with known silicon amounts and different silicon amounts are prepared, and X-ray fluorescence analysis is performed on each sample. X-ray fluorescence analysis generates element-specific fluorescent X-rays by X-ray irradiation and detects them. Since the amount of X-rays generated is proportional to the amount of the element contained in the sample being measured, the X-ray intensity S (unit: cps / μA) of silicon obtained by the measurement is proportional to the amount of silicon. Here, the thickness of the standard sample is calculated in the same way as the protective layer thickness described later, and the X-ray intensity S obtained by fluorescence X-ray analysis is divided by the thickness of the standard sample to calculate the X-ray intensity S per unit thickness. A calibration curve is then created by plotting the known silicon content against the X-ray intensity S per unit thickness. Subsequently, in the laminate of the present invention, the X-ray intensity S per unit thickness is similarly determined from fluorescence X-ray analysis and the protective layer thickness, and the silicon content is calculated from the calibration curve and its value. From this silicon content, the total number of moles of silicon atoms contained in the linear polysiloxane and silicon alkoxide is determined and converted to SiO2 mass, thereby determining the total mass ratio S of the inorganic components of the protective layer, and the content of the water-soluble resin and various inorganic components can be determined. 【0078】 The mixing ratio of linear polysiloxane to silicon alkoxide in the inorganic components of the protective layer is determined by the laser Raman spectroscopy method, and the ratio A2 / A1, which is the ratio of the area A1 of the Raman band showing a random network structure to the area A2 of the Raman band showing linear polysiloxane, represents the mixing ratio of linear polysiloxane to silicon alkoxide (mass ratio in terms of SiO2). 【0079】 Furthermore, after determining the mixing ratio (mass ratio in terms of SiO2) of the water-soluble resin and linear polysiloxane / silicon alkoxide using the method described above, five standard samples are prepared in which the solid content ratio of silicon alkoxide having ureid groups is known and different, and fluorescence X-ray analysis is performed on each sample as described above to detect the amount of X-rays generated. Here, the X-ray intensity S of silicon (unit: cps / μA) differs depending on the solid content ratio of silicon alkoxide having ureid groups. As described above, the thickness of the standard sample is calculated in the same way as the protective layer thickness described later, and a calibration curve is created by plotting the known solid content ratio of silicon alkoxide having ureid groups against the X-ray intensity S per unit thickness. Subsequently, in the laminate of the present invention, the X-ray intensity S per unit thickness is similarly determined from fluorescence X-ray analysis and the protective layer thickness, and the solid content ratio of silicon alkoxide having ureid groups is calculated by converting it to the solid content ratio of silicon alkoxide having ureid groups from the calibration curve and its value. 【0080】 [Anchor layer] The laminate of the present invention preferably has an anchor layer between the base film and the inorganic layer. By having an anchor layer as an underlayer on the base film, the adhesion between the base film and the inorganic layer can be improved, and adhesion can be more easily achieved when used as a composite laminate or packaging, even after boiling and retorting, which are harsh environments in which the product is used. 【0081】 The anchor layer is not particularly limited as long as it can improve the adhesion between the base film and the inorganic layer, but organic or inorganic polymers are preferred. 【0082】 Examples of inorganic polymers include inorganic oxides, such as silicon oxides, tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, and tetra-n-butoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, n- Butyltrimethoxysilane, n-butyltriethoxysilane, n-pentyltrimethoxysilane, n-pentyltriethoxysilane, n-hexyltrimethoxysilane, n-heptyltrimethoxysilane, n-octyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3,3 ,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 2-hydroxyethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane, 2-hydroxypropyltrimethoxysilane, 2-hydroxypropyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl Polymers obtained by hydrolysis and polymerization reactions from trialkoxysilanes such as trimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 3-(meth)acrylooxypropyltrimethoxysilane, 3-(meth)acrylooxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, vinyltriacetoxysilane, and other trialksoxysilanes, as well as organoalkosisilanes such as methyltriacetyloxysilane and methyltriphenoxysilane, can be used. 【0083】 Examples of organic polymers include thermoplastic resins, thermosetting resins, and photocurable resins. Examples include polyester resins, polycarbonate resins, (meth)acrylic resins, polyurethane resins, polyether resins, polyepoxy resins, polyamide resins, ABS resins, polyimide resins, olefin resins such as polyethylene and polypropylene, polystyrene resins, polyvinyl acetate resins, melamine resins, phenolic resins, resins containing chlorine (Cl) elements such as polyvinyl chloride and polyvinylidene chloride, and cellulose resins. At least one of these can be selected based on the required properties and productivity, and two or more can be mixed. Furthermore, a curing agent can be added to the organic polymer before use. Examples of curing agents include aliphatic, aromatic, and alicyclic isocyanate curing agents, and monomers such as aromatic tolylene diisocyanate (TDI) and diphenylmethane diisocyanate (MDI), and aliphatic xylene diisocyanate (XDI), hexalene diisocyanate (HMDI), and isophorone diisocyanate (IPDI), as well as polymers and derivatives thereof, are preferably used, and these may be used individually or in mixtures. 【0084】 [Composite Laminate] The composite laminate of the present invention is a composite laminate in which a second olefin layer containing an olefin resin is laminated on at least one side of the laminate via a resin layer, and further a third olefin layer containing an olefin resin is laminated on at least one side of either the laminate side or the second olefin layer side via a resin layer. Therefore, the side on which the second olefin layer is laminated may be the side of the laminate that is protected by the protective layer, or the side of the laminate that is opposite to the protective layer. 【0085】 Methods for laminating the resin layer when laminating the laminate of the present invention with the second olefin layer and the third olefin layer include, but are not limited to, a method in which molten resin is extruded onto either the laminate side or the second olefin layer or the third olefin layer side to form a resin layer, and then the laminate is laminated with the second olefin layer and the third olefin layer, or a method in which an adhesive is used as the resin layer and the laminate is laminated with the second olefin layer and the third olefin layer via the adhesive. 【0086】 When a resin layer is formed by extrusion as in the former method, the resin layer is preferably made of olefin-based resins such as polyethylene or polypropylene, or mixtures thereof, in order to reduce thermal damage from the extruded molten resin and to consider recyclability. 【0087】 Furthermore, when laminating using an adhesive as a resin layer, as in the latter case, preferred adhesives include, for example, one-component or two-component curing type vinyl, (meth)acrylic, polyamide polyester, polyether, polyurethane, epoxy, and rubber-based solvent-type, water-based, and emulsion-type adhesives. Commercially available examples include the two-component curing polyester adhesives TM-570 / CAT-RT37 from Toyo Ink Co., Ltd., LX500 / KO55 from DIC Corporation, RU-77T / H-7 from Rock Paint Co., Ltd., A-620 / A-6 from Mitsui Chemicals, Inc., A4210R / CA75 from Dainichi Seika Co., Ltd., and LA2760 / LA5891 from Henkel. Additionally, PASLIM VM001 / VM108CP from DIC Corporation can be applied to improve gas barrier properties. 【0088】 The above adhesive can be applied using methods such as direct gravure, reverse roll coating, kiss coating, or fountain coating, without any particular limitations. The amount applied after drying is 0.1 g / m². 2 More than 10g / m 2 The following is preferable, and more preferably, 1 g / m²2 More than 5g / m 2 The following applies: 【0089】 The second and third olefin layers contain olefin resins, and examples of olefin resins include copolymers or modified polyolefin resins such as polyethylene resin, polypropylene resin, polyisobutylene resin, polybutene resin, polymethylpentene resin, cyclic polypropylene resin, cyclic polyolefin resin, cyclic olefin copolymer resin, ethylene-vinyl acetate copolymer resin, and polyvinyl alcohol resin, or copolymer resins or mixed resins mainly composed of these resins. In particular, in the present invention, from the viewpoint of ease of forming the packaging described later, physical properties such as mechanical properties and heat resistance, and ease of recycling, a resin film containing polyethylene resin or polypropylene resin as a heat-sealable olefin resin is preferred. Examples include low-density polyethylene (LDPE), medium-density polyethylene (MDPE), high-density polyethylene (HDPE), linear low-density polyethylene (LLDPE), unstretched or stretched polypropylene (PP), ethylene-α-olefin copolymer polymerized using a metallocene catalyst, random or block copolymer of ethylene-polypropylene, ethylene-vinyl acetate copolymer (EVA), ethylene-acrylic acid copolymer (EAA), ethylene-ethyl acrylate copolymer (EEA), ethylene-methacrylic acid copolymer (EMAA), ethylene-methyl methacrylate copolymer (EMMA), and ethylene-maleic acid copolymer. 【0090】 In the composite laminate of the present invention, it is preferable that the thermal shrinkage rate of the second olefin layer and / or the third olefin layer after heating at 120°C for 15 minutes is smaller than that of the laminate. When the thermal shrinkage rate of the second olefin layer and / or the third olefin layer is smaller than that of the laminate, it is easier to form the packaging described later, and when used as packaging, it is easier to obtain physical properties such as gas barrier properties with less curling and wrinkling. The method for measuring the thermal shrinkage rate in the present invention is as described in the examples. 【0091】 Furthermore, a printing ink may be laminated as a printing ink layer in the composite laminate of the present invention. The printing ink layer may be laminated on either the protective layer side, the opposite side of the protective layer, or both sides of the laminate, and may also be laminated on either or both sides of the second and third olefin layers. Generally, the printing ink layer is laminated for purposes such as displaying content information, light shielding, decorative properties, and design, and therefore the printing ink layer consists of a colorant and a resin. Optional additives may be included as needed, such as curing agents, lubricants, anti-blocking agents, leveling agents, defoaming agents, pigment dispersants, silane coupling agents, ultraviolet absorbers, rust inhibitors, plasticizers, flame retardants, reinforcing agents, antistatic agents, and viscosity modifiers. The colorant is not particularly limited, and inorganic pigments, organic pigments, dyes, etc., can be appropriately selected and used. Furthermore, the resin used for the printing ink layer may include, but is not limited to, castor oil, polyester resin, polyurethane resin, epoxy resin, (meth)acrylic resin, melamine resin, polystyrene resin, phenolic resin, polyvinyl chloride resin, polyvinyl acetate resin, polyamide resin, nitrocellulose, acrylate compound polymer, or mixtures thereof. In addition, methods for forming the above-mentioned printing ink layer include letterpress printing, gravure printing, offset printing, flexographic printing, and screen printing, which can be arbitrarily selected. Commercially available printing inks can be used, including gravure inks for reverse printing such as the LP Bio series and Rio Alpha S series from Toyo Ink Co., Ltd., the Finato S series and Finato BM series from DIC Corporation, the Bellcolor series and Bellflora series from Sakata Inx Co., Ltd., the Lamic SR series, Lamic BP series and NB300BP series from Dainichi Seika Co., Ltd., and the LG-NT series from Tokyo Ink Co., Ltd. 【0092】 [Packaging] The package of the present invention is formed into a bag shape using either the laminate or the composite laminate of the present invention. By using the laminate or the composite laminate of the present invention, not only is it suitable for recycling, but it also has excellent gas barrier properties and bending resistance. When applied to packaging materials for retort foods such as retort pouches, it can maintain its gas barrier properties even due to thermal deformation during boil-in-bag retort processing or bending and deformation during the molding process of the package. Therefore, it is possible to provide a package that can safely store the contents without any defects such as deterioration of the gas barrier properties after filling the contents. 【0093】 The laminate of the present invention is a laminate with excellent gas barrier properties and suitable for recycling. The composite laminate and the package containing it are preferably used for applications where such properties are required. 【Examples】 【0094】 Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. 【0095】 (1) Component analysis and structure identification of the protective layer (water-soluble resin, linear polysiloxane, silicon alkoxide having a ureido group) The protective layer was peeled off from the sample and dissolved in a soluble solvent. Next, the solution was filtered to separate the particles and the filtrate. If necessary, general chromatography such as silica gel column chromatography, gel permeation chromatography, liquid high-speed chromatography, etc. was applied to separate and purify the components contained in the protective layer and the resin layer into single substances. Thereafter, DMSO-d6 was added to each single substance, heated to 60 °C and dissolved, and this solution was used as nuclear magnetic resonance spectroscopy, 1 1H-NMR, 1313C-NMR measurements were performed. Subsequently, qualitative analysis was conducted on each individual substance using a combination of IR (infrared spectroscopy), various mass spectrometry methods (gas chromatography-mass spectrometry (GC-MS), pyrolysis gas chromatography-mass spectrometry (pyrolysis GC-MS), matrix-assisted laser desorption / ionization mass spectrometry (MALDI-MS), time-of-flight mass spectrometry (TOF-MS), time-of-flight matrix-assisted laser desorption / ionization mass spectrometry (MALDI-TOF-MS), dynamic secondary ion mass spectrometry (Dynamic-SIMS), and time-of-flight secondary ion mass spectrometry (TOF-SIMS)) as appropriate to identify the components and structures contained in the sample. When combining these qualitative analyses, priority was given to those that could be measured with fewer combinations. 【0096】 (2) Thickness of protective layer, thickness of inorganic layer The thickness of the protective layer and the inorganic layer was determined by observing their cross-sections using a TEM. First, samples for cross-sectional observation were prepared using a microsampling system (Hitachi, Ltd. FB-2000A) by the FIB method (specifically, based on the method described in "Polymer Surface Processing" (by Akira Iwamori), pp. 118-119). Next, observations were performed using a transmission electron microscope (Hitachi, Ltd. H-9000UHRII) at an acceleration voltage of 300kV. The obtained cross-sections were observed by adjusting the observation magnification so that the layer thickness occupied 30-70% of the observed image. A total of 5 samples were measured in the same manner, the average value of the 5 points was calculated, and the value converted to nm was defined as the thickness of the protective layer and the thickness of the inorganic layer. 【0097】 (3) Measurement of the content ratio of water-soluble resin and inorganic components (linear polysiloxane, silicon alkoxide) in the protective layer The mixture consisted of polyvinyl alcohol (hereinafter sometimes abbreviated as PVA; degree of polymerization 1,700, degree of saponification 98.5%) as a water-soluble resin and a hydrolyzed tetraalkoxysilane (hereinafter sometimes abbreviated as TEOS) as an inorganic component. Films obtained by mixing these materials in ratios of water-soluble resin to inorganic component (inorganic component calculated on a SiO2 mass basis) of 80 / 20, 65 / 35, 50 / 50, 35 / 65, and 20 / 80 were prepared as standard samples with different content ratios. 【0098】 Next, the intensity of the specific silicon X-ray Kα was measured for each standard sample using a Shimadzu EDX-700 X-ray fluorescence analyzer, and the resulting X-ray intensity S (unit: cps / μA) was determined. The thickness of each standard sample was measured using the method described in (2) above, and the X-ray intensity S per unit thickness was calculated to create a calibration curve between the water-soluble resin and the inorganic component content (inorganic component is calculated on a SiO2 mass basis). 【0099】 Next, for the laminate of the present invention, the X-ray intensity S per unit thickness was determined from fluorescent X-ray analysis and protective thickness, and the content of water-soluble resin and inorganic components was determined from the calibration curve. 【0100】 (4) Analysis of the silicon bonding state (presence or absence of linear polysiloxane), (mixing ratio of linear polysiloxane / silicon alkoxide (mass ratio in terms of SiO2)) The protective layer of the laminate was separated by cutting and analyzed by Raman spectroscopy under the following conditions. Measuring device: Jobin Yvon / Atago Bussan T-6400 Measurement mode: Micro-Raman Objective lens: 100x Beam diameter: 1 μm Light source:Ar + Laser / 514.5nm Laser power: 200mW Diffraction grating: Single 600gr / mm Slit: 100 μm Detector: CCD / Jobin Yvon, 1,024 x 256. 【0101】 The following conditions were used to analyze the Raman spectra to calculate area A1 representing the random network structure of silicon alkoxides and area A2 representing the linear polysiloxane. The obtained Raman spectra were analyzed using the spectral analysis software GRAMS / Thermo Scientific. After baseline correction of the Raman spectra using linear approximation, the range was 600-250 cm⁻¹. -1 The fitting was performed within the specified range. The fitting was a 4-membered ring structure (peak wavenumber 495 cm²). -1 , half-width 35cm -1 ), linear polysiloxane (peak wavenumber 488 cm⁻¹) -1 , half-width 35cm -1 The random network structure, composed of silicon alkoxides, was separated into three components. Since the random network structure of silicon alkoxides exhibits a broad peak reflecting the continuous structure, it was automatically fitted by assuming separation into three components—the four-membered ring structure and the linear polysiloxane—using a Gaussian function approximation. 【0102】 By calculating the area of ​​the region enclosed by the obtained bands and the baseline, the presence or absence of linear polysiloxane was determined. Additionally, the area representing the random network structure consisting of silicon alkoxides was designated as A1, and the area representing the linear polysiloxane as A2, and the mixing ratio of linear polysiloxane to silicon alkoxide (mass ratio in terms of SiO2) was calculated as A2 / A1. 【0103】 (5) Solid content ratio of silicon alkoxide having a ureid group relative to the solid content in the protective layer The mixing ratio (mass ratio in terms of SiO2) of the water-soluble resin and linear polysiloxane / silicon alkoxide was determined using the methods described in (3) and (4) above. Subsequently, five standard samples were prepared in which the solid content ratio of silicon alkoxide having ureid groups was known and different, and fluorescence X-ray analysis was performed on each sample in the same manner as in (3) above to detect the amount of X-rays generated. Then, in the same manner as in (2) and (3) above, a calibration curve was created by plotting the solid content ratio of silicon alkoxide having ureid groups against the X-ray intensity S per unit thickness. 【0104】 Next, in the laminate of the present invention, the X-ray intensity S per unit thickness was similarly determined from fluorescent X-ray analysis and protective thickness, and the solid content ratio of silicon alkoxide having a ureid group was calculated from the calibration curve and its value, thereby determining the solid content ratio of silicon alkoxide having a ureid group. 【0105】 (6) Gas barrier properties (oxygen barrier properties: oxygen permeability, water vapor barrier properties: water vapor permeability) Samples to be evaluated were prepared. Next, oxygen permeability (hereinafter sometimes abbreviated as OTR) was measured in accordance with JIS K7126-2 (2006) using a MOCON oxygen permeability measuring device ("OX-TRAN" (registered trademark) 2 / 21) under conditions of a temperature of 23°C and a humidity of 90% RH. Measurements were performed twice on each of two test specimens, and the average of the four measured values ​​was taken as the oxygen permeability value. In addition, water vapor permeability (hereinafter sometimes abbreviated as WVTR) was measured in accordance with JIS K7129-2 (2019) using a MOCON water vapor permeability measuring device ("PERMATRAN" (registered trademark)-W 3 / 31) under conditions of a temperature of 40°C and a humidity of 90% RH. Measurements were performed twice on each of two test specimens, and the average of the four measured values ​​was taken as the water vapor permeability value. 【0106】 Next, a 60 μm thick unoriented polypropylene film (Toray Film Processing Co., Ltd., ZK100) was laminated as a second olefin layer on the protective layer side of the laminate of the present invention via an adhesive consisting of a polyester urethane main component (DIC Corporation, LX500) and an aromatic isocyanate curing agent (DIC Corporation, KW75). The adhesive was then cured by aging in an oven heated to 40°C for 3 days to obtain composite laminate A. 【0107】 Next, a 60 μm thick unoriented polypropylene film (ZK100, manufactured by Toray Film Processing Co., Ltd.) was prepared as the second olefin layer, and a 20 μm thick biaxially oriented polypropylene film (FOR, manufactured by Futamura Chemical Co., Ltd.) was prepared as the third olefin layer. The third olefin layer, the biaxially oriented polypropylene film, was laminated to the protective layer side of the laminate of the present invention via an adhesive consisting of a polyester urethane main component (LX500, manufactured by DIC Corporation) and an aromatic isocyanate curing agent (KW75, manufactured by DIC Corporation) on the corona-treated side. Then, the 60 μm thick unoriented polypropylene film (ZK100, manufactured by Toray Film Processing Co., Ltd.) was laminated to the substrate side of the laminate opposite the protective layer via an adhesive consisting of a polyester urethane main component (LX500, manufactured by DIC Corporation) and an aromatic isocyanate curing agent (KW75, manufactured by DIC Corporation) as the second olefin layer. Finally, the adhesive was cured by aging in an oven heated to 40°C for 3 days to obtain composite laminate B. 【0108】 Next, composite laminates A and B were subjected to retort sterilization (high-temperature hot water treatment) at 130°C for 30 minutes to prepare composite laminates A and B for barrier evaluation after retort treatment. Using the same method as described above, measurements were taken twice for each of the two test pieces, and the average of the four measured values ​​was taken as the oxygen permeability and water vapor permeability values ​​after retort treatment. 【0109】 (7) Adhesion evaluation (laminate strength) Adhesion was evaluated using the following method. 【0110】 First, composite laminates A and B obtained in (6) were cut to a width of 15 mm and a length of 150 mm to prepare composite laminates A and B for adhesion evaluation. Then, for composite laminate A for adhesion evaluation, the peel strength was measured using a tensile testing machine (Tensilon) at a peeling speed of 50 mm / min so that the peel angle between the laminate of the present invention and the second olefin layer, which is an unoriented polypropylene film, was 180°. Similarly, for composite laminate B for adhesion evaluation, the peel strength was measured so that the peel angle between the laminate of the present invention and the third olefin layer, which is a biaxially oriented polypropylene film, was 180°. A total of three samples were measured using the above measurement method, and the average of the measured values ​​for composite laminates A and B was taken as the initial laminate strength. Furthermore, composite laminates A and B were retort sterilized at 130°C for 30 minutes, cut to a width of 15 mm and a length of 150 mm in the same manner, and the peel strength of a total of three samples was measured using the same method, and the average of the measured values ​​for composite laminates A and B was taken as the laminate strength after retort treatment. 【0111】 (8) Thermal shrinkage Each of the laminated body and the second and third olefin layers of the present invention was cut into 200 mm squares, and 100 mm long lines were drawn in the MD direction (traveling direction) and the TD direction (direction at a 90-degree angle to the MD direction). The lengths of the lines in the MD and TD directions were measured using a projector (Mitutoyo PJ-H3000) and recorded as the lengths before heating. Furthermore, each of the laminated body and the second and third olefin layers was heated at 120°C for 15 minutes, and similarly, the lengths of the lines in the MD and TD directions were measured using a projector (Mitutoyo PJ-H3000) and recorded as the lengths after heating. The heat shrinkage rates in the MD and TD directions were calculated using (Equation 1). 【0112】 Heat shrinkage rate (%) = 100 × (length before heating - length after heating) / length before heating (Equation 1) Next, the thermal shrinkage rates of the laminate, the second and third olefin layers were compared, both in terms of smaller values ​​and larger values. If the thermal shrinkage rate of either the second or third olefin layer, or both, was smaller than that of the laminate, it was deemed acceptable. If any of the thermal shrinkage rates of the laminate were larger than that of either the second or third olefin layer, it was deemed unacceptable. 【0113】 (9) Silicon (Si) and carbon (C) elements and average composition ratio (Si / C) of the protective layer Compositional analysis and evaluation were performed using X-ray photoelectron spectroscopy (XPS) under the following conditions, starting from the surface of the protective layer of the laminate and moving in the depth direction. The film structure was confirmed by the depth profile. Data was collected while performing ion etching from the protective layer until the inorganic layer was reached, and the presence or absence of a continuous increase or decrease in composition was confirmed from the depth profiles of each element obtained. A continuous increase or decrease was determined to exist if the length of the increase or decrease was 2 nm or longer. 【0114】 First, the thickness of the protective layer was determined using the method described in (2) above. The depth from the surface of the protective layer to the interface of the inorganic layer in the depth profile of the composition ratio in the depth direction measured by X-ray photoelectron spectroscopy (XPS) was defined as the thickness of the protective layer. The average composition ratio (Si / C) was calculated by averaging the composition ratio measurements at each measurement point in the thickness direction up to 1 / 3 of the protective layer thickness. 【0115】 The measurement conditions were as follows: • Equipment: X-ray photoelectron spectrometer (Quantera SXM, manufactured by PHI Corporation) • Excitation X-ray: monochromatic AlKα 1,2 Line (1486.6eV) • X-ray diameter: 100 μm • Photoelectron escape angle: 45° (detector tilt relative to the sample surface) Ion etching conditions: Ar + Ion 3kV Raster size: 2 x 2 mm (etching area) Etching rate: 12.0 nm / min. 【0116】 (10) Major and minor diameters of inorganic particles The laminate was prepared by cutting a sample for cross-sectional observation of the protective layer in a direction perpendicular to the laminate surface using the FIB method with a microsampling system (FB-2000A, Hitachi, Ltd.) (specifically, based on the method described in "Polymer Surface Processing" (by Akira Iwamori), pp. 118-119). 【0117】 Next, the cross-section of the protective layer of the obtained laminate was observed using a transmission electron microscope (Hitachi, Ltd. H-9000UHRII) at an acceleration voltage of 300kV. The observation magnification was set so that at least two inorganic particles contained in the protective layer were visible within one field of view. The length of the shortest inorganic particle portion within this field of view was measured, and its average value was calculated. In the same manner, a total of five arbitrary fields of view were observed, and the average value of these five fields of view was taken as the minor axis. Next, the protective layer surface was observed in the same manner from a direction perpendicular to the laminate surface, the length of the longest inorganic particle portion was measured, and its average value was calculated. In the same manner, a total of five arbitrary fields of view were observed, and the average value of these five fields of view was taken as the major axis. 【0118】 (11) Presence or absence of silanol groups in inorganic particles The presence or absence of silanol groups in inorganic particles was measured by FT-IR (Fourier Transform Infrared Spectroscopy). First, as described in (1) above, "Component Analysis and Structural Identification of the Protective Layer," particles were separated and extracted from the protective layer and then deposited onto a silicon wafer. Subsequently, the surface was pressed onto an ATR crystal and measured under reduced pressure under the following measurement conditions. The peak representing the Si-OH bond, which is a silanol group, was measured at 950-970 cm⁻¹. -1 The determination was made based on the presence or absence of ). The measurement conditions were as follows: • Equipment: Fourier transform infrared spectrophotometer FT / IR-6100 (manufactured by JASCO Corporation) ·Light source: Standard light source • Detector: GTS ·Resolution: 4cm -1 • Total number of times: 256 • Measurement method: Attenuated Total Reflectance (ATR) method • Measurement wavefrequency range: 4,000~600cm⁻¹ • ATR crystal: Ge prism ·Incidence angle: 45°. 【0119】 (12) Content of plate-like inorganic particles in the protective layer The mass of a sample of any size is measured. Then, in the "Component Analysis and Structural Identification of the Protective Layer" section (2) above, the protective layer is dissolved in a solvent capable of dissolving it, and the mass of the sample after peeling off the protective layer is measured to calculate the total mass of the protective layer. Next, the solution in which the protective layer is dissolved is filtered to separate and collect the particles, and the collected particles are classified into plate-shaped inorganic particles using an ultrafine particle precision classifier KFSH-150 (manufactured by Aisin Nanotechnologies Corporation), and their mass is measured. The value obtained by dividing the mass of the plate-shaped inorganic particles by the total mass of the protective layer was defined as the "inorganic particle content". 【0120】 (13) Flexural resistance (gas barrier properties after flexural fatigue test) The test was conducted using a Gelboflex tester (manufactured by Tester Industries) under conditions compliant with ASTM F392. Specifically, the composite laminates A and B obtained in (6) were first cut to a size of 200 mm x 300 mm to create composite laminates A and B for bending evaluation. Next, the ends of the 300 mm side of each test piece of the bending evaluation composite laminate were bonded together and rolled into a cylinder. The ends of the cylindrical test piece were fixed to a fixed head and a drive head, and while applying a 440-degree twist, the distance between the fixed head and the drive head was narrowed from 7 inches to 3.5 inches, then the distance between the heads was narrowed further to 1 inch while maintaining the twist, then the distance between the heads was widened to 3.5 inches, and then the distance between the heads was widened to 7 inches while untwisting. This reciprocating motion was performed 10 times at a speed of 40 times / minute, and the gas barrier properties were measured using each test piece before and after the bending fatigue test in the same manner as in (6). 【0121】 The pass / fail judgment for flexural resistance is made based on the change in gas barrier properties (oxygen permeability and water vapor permeability) after the flexural fatigue test, according to the following criteria. Pass 1 indicates the highest level of flexural resistance, followed by Pass 2 and then Pass 3. (Passed 1) • Change in oxygen permeability value is 0.5 cc / m³ 2• Below 24hr·atm and with a change in water vapor transmission rate of 0.5 g / m³ 2 • 24-hour ATM operation is available. (Passed 2) • Change in oxygen permeability value is 0.5 cc / m³ 2 • Larger than 24hr·atm, 1.0cc / m³ 2 • Below 24hr·atm, and with a change in water vapor transmission rate of 0.5g / m³. 2 • Larger than 24hr·atm, 1.0g / m³ 2 • 24-hour ATM operation; one of the following conditions must be met. (Passed 3) • Change in oxygen permeability value is 1.0 cc / m³ 2 • Larger than 24hr·atm, at 2.0cc / m³ 2 • Below 24hr·atm, and with a change in water vapor transmission rate of 1.0 g / m³. 2 • Larger than 24hr·atm, 2.0g / m³ 2 • 24-hour ATM operation; one of the following conditions must be met. (Fail) If none of the conditions 1-3 for passing are met. 【0122】 [Example 1] <Inorganic layer> As a base film, a 15 nm thick aluminum oxide layer was formed by vacuum deposition on the corona-treated surface of a 25 μm thick uniaxially oriented polyethylene film (PE3K-BT, manufactured by Futamura Chemical Co., Ltd.) to create an inorganic layer. 【0123】 <Protective layer> (Organic component solution) As a water-soluble resin, polyvinyl alcohol (degree of polymerization 1,700, degree of saponification 98.5%) was added to a solvent of water / isopropyl alcohol in a mass ratio of 97 / 3, and heated and stirred at 90°C to obtain an organic component solution with a solid content of 12% by mass. 【0124】 (Inorganic component solution) A ureid group-containing silicon alkoxide hydrolysate (hydrolysate A) was obtained by mixing 11.7 g of KBM-585A, manufactured by Shin-Etsu Chemical Co., Ltd., with 4.7 g of methanol, and then adding 18.6 g of a 0.02 N hydrochloric acid aqueous solution dropwise while stirring. 【0125】 Next, 11.2 g of ethyl silicate 40 (a linear oligomer with an average of five molars) manufactured by Colcoat Co., Ltd. was mixed with 16.9 g of methanol as a linear polysiloxane. To this solution, 7.0 g of 0.06 N hydrochloric acid aqueous solution was added dropwise to obtain a hydrolysis solution of the five molar silicate (hydrolysis solution B). 【0126】 (Protective layer formation) A dispersion containing flake-like silica as plate-shaped inorganic particles (Sun Lovely LFS, Type Name: HN-50, manufactured by AGC SI-TEC Co., Ltd.; Material: Silica, with silanol groups; Major axis = 1.9 μm, Minor axis = 120 nm) was prepared, and coarse particles were classified and removed from this dispersion using an ultrafine particle precision classifier KFSH-150 (manufactured by Aisin Nanotechnologies Corporation) to obtain minute particles (Major axis = 0.8 μm, Minor axis = 75 nm). 【0127】 Next, the organic component solution, hydrolysis solution A, and hydrolysis solution B were mixed and stirred so that the PVA content was 20% by mass, the solid content ratio of silicon alkoxide having a ureid group was 2.0% by mass, and the mass ratio of linear polysiloxane to silicon alkoxide, each calculated on an SiO2 basis, was 97 / 3. Then, the aforementioned micronized particles of flake silica (major axis = 0.8 μm, minor axis = 75 nm) were mixed and stirred as plate-shaped inorganic particles so that the particle content was 0.48% by mass, and the mixture was diluted with water to obtain a coating solution with a solid content of 12% by mass. This coating solution was applied to the inorganic layer and dried at 80°C to form a protective layer with a thickness of 100 nm after drying, forming a laminate. [Example 2] <Inorganic layer> As a base film, a 20 μm thick biaxially oriented polypropylene film (OP ME-1, manufactured by Mitsui Chemicals Tohcello Co., Ltd.) was used, and a 15 nm thick aluminum oxide layer was deposited on the corona-treated surface by vacuum deposition to create an inorganic layer. 【0128】 <Protective layer> (Organic component solution) A solution of the organic components of PVA was obtained in the same manner as in Example 1. 【0129】 (Inorganic component solution) Similar to Example 1, a hydrolyzed silicon alkoxide solution containing a ureid group (hydrolyzed solution A) and a hydrolyzed pentamer silicate solution (hydrolyzed solution B) were obtained. 【0130】 (Protective layer formation) A dispersion containing flake-shaped silica (Sun Lovely LFS, Type Name: PN-020, manufactured by AGC SI-TEC Co., Ltd.; Material: Silica, with silanol groups; Major axis = 1.2 μm, Minor axis = 11 nm) was used as the plate-shaped inorganic particles to be mixed. Except for adjusting the particle content to 0.53% by mass, a protective layer with a thickness of 100 nm after drying was formed and a laminate was constructed in the same manner as in Example 1. 【0131】 [Example 3] <Inorganic layer> As a base film, a 20 μm thick biaxially oriented polypropylene film (OP ME-1, manufactured by Mitsui Chemicals Tohcello Co., Ltd.) was used, and a 15 nm thick silicon oxide layer was deposited on the corona-treated surface using vacuum deposition to create an inorganic layer. 【0132】 <Protective layer> (Organic component solution) A solution of the organic components of PVA was obtained in the same manner as in Example 1. 【0133】 (Inorganic component solution) Similar to Example 1, a hydrolyzed silicon alkoxide solution containing a ureid group (hydrolyzed solution A) and a hydrolyzed pentamer silicate solution (hydrolyzed solution B) were obtained. 【0134】 (Protective layer formation) Except for ensuring that the particle content of the plate-shaped inorganic particles to be mixed was 0.68% by mass, the same procedure as in Example 2 was followed to form a laminate with a protective layer 100 nm thick after drying. 【0135】 [Example 4] <Inorganic layer> A 20 μm thick biaxially oriented polypropylene film (OP ME-1, manufactured by Mitsui Chemicals Tohcello Co., Ltd.) was prepared as the base film. Next, a resin composition prepared by mixing a polyester resin (Takelac A-3210, manufactured by Mitsui Chemicals, Inc.) and an aliphatic isocyanate curing agent (Takelac A-3070, manufactured by Mitsui Chemicals, Inc.) in a weight ratio of 3:1 was applied to the base film as an anchor layer. After drying at 80°C, it was aged at 40°C for 72 hours to form a 400 nm thick anchor layer. Next, a 15 nm thick aluminum oxide layer was formed on the anchor layer by vacuum deposition to create an inorganic layer. 【0136】 <Protective layer> (Organic component solution) A solution of the organic components of PVA was obtained in the same manner as in Example 1. 【0137】 (Inorganic component solution) Similar to Example 1, a hydrolyzed silicon alkoxide solution containing a ureid group (hydrolyzed solution A) and a hydrolyzed pentamer silicate solution (hydrolyzed solution B) were obtained. 【0138】 (Protective layer formation) Except for ensuring that the particle content of the plate-shaped inorganic particles to be mixed was 8.70% by mass, the laminate was formed by creating a protective layer with a thickness of 100 nm after drying, similar to Example 2. 【0139】 [Example 5] <Inorganic layer> An inorganic layer was formed in the same manner as in Example 4. 【0140】 <Protective layer> (Organic component solution) Modified polyvinyl alcohol (hereinafter sometimes abbreviated as modified PVA; degree of polymerization 1,700, degree of saponification 93.0%), which has a cyclic structure with a carbonyl group and a lactone structure called γ-butyrolactone, as a water-soluble resin, was added to a solvent of water / isopropyl alcohol = 97 / 3 by mass ratio, and heated and stirred at 90°C to obtain an organic component solution with a solid content of 12% by mass. 【0141】 (Inorganic component solution) Similar to Example 1, a hydrolyzed silicon alkoxide solution containing a ureid group (hydrolyzed solution A) and a hydrolyzed pentamer silicate solution (hydrolyzed solution B) were obtained. 【0142】 (Protective layer formation) The organic component solution, hydrolysis solution A, and hydrolysis solution B were mixed and stirred so that the modified PVA content was 20% by mass, the solid content ratio of silicon alkoxide having ureido groups was 2.0% by mass, and the mass ratio of linear polysiloxane to silicon alkoxide on an SiO2 basis was 97 / 3. Then, a dispersion containing flake silica as plate-shaped inorganic particles (Sun Lovely LFS, type name: PN-020, manufactured by AGC SI-TEC Co., Ltd.; material: silica, with silanol groups; major axis = 1.2 μm, minor axis = 11 nm) was mixed and stirred while stirring until the particle content was 13.00% by mass, and then diluted with water to obtain a protective layer coating solution with a solid content of 12% by mass. This coating solution was applied to the inorganic layer and dried at 80°C to form a protective layer with a thickness of 100 nm after drying, forming a laminate. 【0143】 [Example 6] <Inorganic layer> An inorganic layer was formed in the same manner as in Example 4. 【0144】 <Protective layer> (Organic component solution) Similar to Example 5, an organic component solution of modified PVA was obtained. 【0145】 (Inorganic component solution) Similar to Example 1, a silicon alkoxide hydrolysate (hydrolysate A) having a ureid group was obtained. 【0146】 Next, 11.2 g of ethyl silicate 48 (a linear oligomer with an average of 10 decamers) manufactured by Colcoat Co., Ltd. was mixed with 16.9 g of methanol as a linear polysiloxane. To this solution, 7.0 g of 0.06 N hydrochloric acid aqueous solution was added dropwise to obtain a hydrolysis solution of the decamer silicate (hydrolysis solution B). 【0147】 (Protective layer formation) The organic component solution, hydrolysate A, and hydrolysate B were mixed and stirred so that the modified PVA content was 30% by mass, the solid content ratio of silicon alkoxide having ureido groups was 3.2% by mass, and the mass ratio of linear polysiloxane to silicon alkoxide on an SiO2 basis was 95 / 5. Then, a dispersion containing flake silica as plate-shaped inorganic particles (Sun Lovely LFS, Type Name: HN-50, manufactured by AGC SI-TEC Co., Ltd.; Material: Silica, with silanol groups; Major axis = 1.9 μm, Minor axis = 120 nm) was mixed and stirred while stirring until the particle content was 0.04% by mass, and then diluted with water to obtain a protective layer coating solution with a solid content of 12% by mass. This coating solution was applied to the inorganic layer and dried at 80°C to form a protective layer with a thickness of 350 nm after drying, forming a laminate. 【0148】 [Example 7] <Inorganic layer> An inorganic layer was formed in the same manner as in Example 4. 【0149】 <Protective layer> (Organic component solution) Similar to Example 5, an organic component solution of modified PVA was obtained. 【0150】 (Inorganic component solution) Similar to Example 1, a silicon alkoxide hydrolysate (hydrolysate A) having a ureid group was obtained. 【0151】 Next, 11.2 g of methyl silicate 51 (a linear oligomer with an average of tetramers) manufactured by Colcoat Co., Ltd. was mixed with 16.9 g of methanol as a linear polysiloxane. To this solution, 7.0 g of 0.06 N hydrochloric acid aqueous solution was added dropwise to obtain a hydrolysis solution of the tetramer silicate (hydrolysis solution B). 【0152】 Next, as a silicon alkoxide without a ureido group, 11.7 g of KBE-04 (tetraethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. was mixed with 4.7 g of methanol to obtain a silicon alkoxide hydrolysate without a ureido group (hydrolysate C) by adding 18.6 g of 0.02 N hydrochloric acid aqueous solution dropwise while stirring. 【0153】 (Protective layer formation) The organic component solution, hydrolysate A, hydrolysate B, and hydrolysate C were mixed and stirred so that the modified PVA content was 30% by mass, the solid content ratio of silicon alkoxide having ureido groups was 3.2% by mass, and the mass ratio of linear polysiloxane to silicon alkoxide on an SiO2 basis was 15 / 85. Then, a dispersion containing plate-shaped inorganic particles of flake-like silica (Sun Lovely LFS, Type Name: HN-150, manufactured by AGC SI-TEC Co., Ltd.; Material: Silica, with silanol groups; Major axis = 3.1 μm, Minor axis = 500 nm) was mixed and stirred while stirring until the particle content was 0.03% by mass, and then diluted with water to obtain a protective layer coating solution with a solid content of 12% by mass. This coating solution was applied to the inorganic layer and dried at 80°C to form a protective layer with a thickness of 500 nm after drying, forming a laminate. 【0154】 [Example 8] <Inorganic layer> An inorganic layer was formed in the same manner as in Example 4. 【0155】 <Protective layer> (Organic component solution) Similar to Example 5, an organic component solution of modified PVA was obtained. 【0156】 (Inorganic component solution) Similar to Example 1, a silicon alkoxide hydrolysate (hydrolysate A) having a ureid group was obtained. 【0157】 Next, 11.2 g of methyl silicate 53A (a linear oligomer with an average of 7 heptomers) manufactured by Colcoat Co., Ltd. was mixed with 16.9 g of methanol as a linear polysiloxane. To this solution, 7.0 g of 0.06 N hydrochloric acid aqueous solution was added dropwise to obtain a hydrolyzed heptomer silicate solution (hydrolyzed solution B). 【0158】 Next, a silicon alkoxide hydrolysate (hydrolysate C) without a ureid group was obtained, similar to Example 7. 【0159】 (Protective layer formation) The organic component solution, hydrolysate A, hydrolysate B, and hydrolysate C were mixed and stirred so that the modified PVA content was 30% by mass, the solid content ratio of silicon alkoxide having ureido groups was 3.2% by mass, and the mass ratio of linear polysiloxane to silicon alkoxide on an SiO2 basis was 15 / 85. Then, a dispersion containing flake silica as plate-shaped inorganic particles (Sun Lovely LFS, type name: PN-020, manufactured by AGC SI-TEC Co., Ltd.; material: silica, with silanol groups; major axis = 1.2 μm, minor axis = 11 nm) was mixed and stirred while stirring until the particle content was 21.00% by mass, and then diluted with water to obtain a protective layer coating solution with a solid content of 12% by mass. This coating solution was applied to the inorganic layer and dried at 80°C to form a protective layer with a thickness of 500 nm after drying, forming a laminate. 【0160】 [Example 9] <Inorganic layer> An inorganic layer was formed in the same manner as in Example 4. 【0161】 <Protective layer> (Organic component solution) Similar to Example 5, an organic component solution of modified PVA was obtained. 【0162】 (Inorganic component solution) Similar to Example 1, a silicon alkoxide hydrolysate (hydrolysate A) having a ureid group was obtained. 【0163】 Next, a decamer silicate hydrolysis solution (hydrolysis solution B) was obtained in the same manner as in Example 6. 【0164】 Next, a silicon alkoxide hydrolysate (hydrolysate C) without a ureid group was obtained, similar to Example 7. 【0165】 (Protective layer formation) The organic component solution, hydrolysate A, hydrolysate B, and hydrolysate C were mixed and stirred so that the modified PVA content was 50% by mass, the solid content ratio of silicon alkoxide having ureido groups was 5.5% by mass, and the mass ratio of linear polysiloxane and silicon alkoxide on an SiO2 basis was 50 / 50. Then, a dispersion containing flake-like silica as plate-shaped inorganic particles, similar to that in Example 8, was mixed and stirred to this mixture until the particle content was 0.53% by mass, and the mixture was diluted with water to obtain a protective layer coating solution with a solid content of 12% by mass. This coating solution was applied to the inorganic layer and dried at 80°C to form a protective layer with a thickness of 250 nm after drying, forming a laminate. 【0166】 [Example 10] <Inorganic layer> An inorganic layer was formed in the same manner as in Example 4. 【0167】 <Protective layer> (Organic component solution) Similar to Example 5, an organic component solution of modified PVA was obtained. 【0168】 (Inorganic component solution) Similar to Example 1, a silicon alkoxide hydrolysate (hydrolysate A) having a ureid group was obtained. 【0169】 Next, a decamer silicate hydrolysis solution (hydrolysis solution B) was obtained in the same manner as in Example 6. 【0170】 Next, a silicon alkoxide hydrolysate (hydrolysate C) without a ureid group was obtained, similar to Example 7. 【0171】 (Protective layer formation) The organic component solution, hydrolysate A, hydrolysate B, and hydrolysate C were mixed and stirred so that the modified PVA content was 30% by mass, the solid content ratio of silicon alkoxide having ureido groups was 8.4% by mass, and the mass ratio of linear polysiloxane to silicon alkoxide on an SiO2 basis was 60 / 40. Then, a dispersion containing flake-like silica as plate-like inorganic particles, similar to that in Example 8, was mixed and stirred to this mixture until the particle content was 0.53% by mass, and the mixture was diluted with water to obtain a protective layer coating solution with a solid content of 12% by mass. This coating solution was applied to the inorganic layer and dried at 80°C to form a protective layer with a thickness of 250 nm after drying, forming a laminate. 【0172】 [Example 11] <Inorganic layer> An inorganic layer was formed in the same manner as in Example 4. 【0173】 <Protective layer> (Organic component solution) Similar to Example 5, an organic component solution of modified PVA was obtained. 【0174】 (Inorganic component solution) Similar to Example 1, a silicon alkoxide hydrolysate (hydrolysate A) having a ureid group was obtained. 【0175】 Next, a decamer silicate hydrolysis solution (hydrolysis solution B) was obtained in the same manner as in Example 6. 【0176】 Next, a silicon alkoxide hydrolysate (hydrolysate C) without a ureid group was obtained, similar to Example 7. 【0177】 (Protective layer formation) The organic component solution, hydrolysate A, hydrolysate B, and hydrolysate C were mixed and stirred so that the modified PVA content was 30% by mass, the solid content ratio of silicon alkoxide having ureido groups was 8.4% by mass, and the mass ratio of linear polysiloxane to silicon alkoxide on an SiO2 basis was 40 / 60. Then, a dispersion containing flake-like silica as plate-like inorganic particles, similar to that in Example 8, was mixed and stirred to this mixture until the particle content was 0.53% by mass, and the mixture was diluted with water to obtain a protective layer coating solution with a solid content of 12% by mass. This coating solution was applied to the inorganic layer and dried at 80°C to form a protective layer with a thickness of 250 nm after drying, forming a laminate. 【0178】 [Example 12] <Inorganic layer> An inorganic layer was formed in the same manner as in Example 4. 【0179】 <Protective layer> (Organic component solution) Similar to Example 5, an organic component solution of modified PVA was obtained. 【0180】 (Inorganic component solution) Similar to Example 1, a silicon alkoxide hydrolysate (hydrolysate A) having a ureid group was obtained. 【0181】 Next, a decamer silicate hydrolysis solution (hydrolysis solution B) was obtained in the same manner as in Example 6. 【0182】 Next, a silicon alkoxide hydrolysate (hydrolysate C) without a ureid group was obtained, similar to Example 7. 【0183】 (Protective layer formation) The organic component solution, hydrolysate A, hydrolysate B, and hydrolysate C were mixed and stirred so that the modified PVA content was 30% by mass, the solid content ratio of silicon alkoxide having ureido groups was 7.8% by mass, and the mass ratio of linear polysiloxane to silicon alkoxide on an SiO2 basis was 40 / 60. Then, a dispersion containing flake-like silica as plate-like inorganic particles, similar to that in Example 8, was mixed and stirred to this mixture until the particle content was 0.53% by mass, and the mixture was diluted with water to obtain a protective layer coating solution with a solid content of 12% by mass. This coating solution was applied to the inorganic layer and dried at 80°C to form a protective layer with a thickness of 250 nm after drying, forming a laminate. 【0184】 [Example 13] <Inorganic layer> An inorganic layer was formed in the same manner as in Example 4. 【0185】 <Protective layer> (Organic component solution) Similar to Example 5, an organic component solution of modified PVA was obtained. 【0186】 (Inorganic component solution) Similar to Example 1, a silicon alkoxide hydrolysate (hydrolysate A) having a ureid group was obtained. 【0187】 Next, a decamer silicate hydrolysis solution (hydrolysis solution B) was obtained in the same manner as in Example 6. 【0188】 Next, a silicon alkoxide hydrolysate (hydrolysate C) without a ureid group was obtained, similar to Example 7. 【0189】 (Protective layer formation) The organic component solution, hydrolysate A, hydrolysate B, and hydrolysate C were mixed and stirred so that the modified PVA content was 30% by mass, the solid content ratio of silicon alkoxide having ureido groups was 3.2% by mass, and the mass ratio of linear polysiloxane to silicon alkoxide on an SiO2 basis was 40 / 60. Then, a dispersion containing flake-like silica as plate-shaped inorganic particles, similar to that in Example 8, was mixed and stirred to this mixture until the particle content was 0.53% by mass, and the mixture was diluted with water to obtain a protective layer coating solution with a solid content of 12% by mass. This coating solution was applied to the inorganic layer and dried at 80°C to form a protective layer with a thickness of 250 nm after drying, forming a laminate. 【0190】 [Example 14] <Inorganic layer> An anchor layer was formed on the substrate film in the same manner as in Example 4. Next, in a roll-to-roll vacuum deposition machine, aluminum was evaporated from the unwound substrate film using a crucible-type aluminum evaporation source with high-frequency induction heating, and the aluminum was deposited onto the anchor layer of the substrate film. By supplying oxygen gas to the position closest to the winding end where the evaporated aluminum adheres to the anchor layer of the substrate film, inorganic layers were continuously formed such that the aluminum metal layer thickness was 40 nm and the aluminum oxide layer thickness was 4 nm. The thickness of the aluminum metal layer and the aluminum oxide layer thickness were measured by the following method. 【0191】 First, compositional analysis was performed in the depth direction using X-ray photoelectron spectroscopy (XPS), and the inorganic film composition was confirmed by depth profiling. For metallic elements, the oxide and metallic components were separated and profiled. Data was collected from the surface layer of the resin layer and protective layer while performing ion etching until it reached the substrate, and the presence or absence of a continuous increase or decrease in composition was confirmed from the depth profiles of each element obtained. A continuous increase or decrease was determined if the length of the increase or decrease was 2 nm or more. 【0192】 The measurement conditions were as follows: • Equipment: X-ray photoelectron spectrometer (Quantera SXM, manufactured by PHI Corporation) • Excitation X-ray: monochromatic AlKα 1,2 Line (1486.6eV) • X-ray diameter: 100 μm • Photoelectron escape angle: 45° (detector tilt relative to the sample surface) Ion etching conditions: Ar + Ion 3kV Raster size: 2 x 2 mm (etching area) Etching rate: 12.0 nm / min Next, the total thickness of the inorganic layer was determined using the method described above. From the total thickness of the inorganic layer and the region of the depth profile corresponding to the inorganic layer, the thickness of the aluminum metal layer and the thickness of the aluminum oxide layer were calculated. 【0193】 <Protective layer> (Organic component solution) Similar to Example 5, an organic component solution of modified PVA was obtained. 【0194】 (Inorganic component solution) Similar to Example 1, a silicon alkoxide hydrolysate (hydrolysate A) having a ureid group was obtained. 【0195】 Next, a decamer silicate hydrolysis solution (hydrolysis solution B) was obtained in the same manner as in Example 6. 【0196】 Next, a silicon alkoxide hydrolysate (hydrolysate C) without a ureid group was obtained, similar to Example 7. 【0197】 (Protective layer formation) The organic component solution, hydrolysate A, hydrolysate B, and hydrolysate C were mixed and stirred so that the modified PVA content was 30% by mass, the solid content ratio of silicon alkoxide having ureido groups was 3.2% by mass, and the mass ratio of linear polysiloxane to silicon alkoxide on an SiO2 basis was 40 / 60. Then, a dispersion containing flake-like silica as plate-shaped inorganic particles, similar to that in Example 8, was mixed and stirred to this mixture until the particle content was 0.53% by mass, and the mixture was diluted with water to obtain a protective layer coating solution with a solid content of 12% by mass. This coating solution was applied to the inorganic layer and dried at 80°C to form a protective layer with a thickness of 250 nm after drying, forming a laminate. 【0198】 [Example 15] <Inorganic layer> An inorganic layer was formed in the same manner as in Example 4. 【0199】 <Protective layer> (Organic component solution) Similar to Example 5, an organic component solution of modified PVA was obtained. 【0200】 (Inorganic component solution) Similar to Example 1, a silicon alkoxide hydrolysate (hydrolysate A) having a ureid group was obtained. 【0201】 Next, a silicon alkoxide hydrolysate (hydrolysate C) without a ureid group was obtained, similar to Example 7. 【0202】 (Protective layer formation) The modified PVA content was 30% by mass, the solid content ratio of silicon alkoxide having ureido groups was 3.2% by mass, and without using linear polysiloxane, the organic component solution, hydrolysis solution A, and hydrolysis solution C were mixed and stirred. Then, a dispersion containing flake-shaped silica surface-treated with aluminic acid as plate-shaped inorganic particles (Sun Lovely LFS, type name: DPAA-020, manufactured by AGC SI-TEC Co., Ltd.; material: silica, no silanol groups (surface functional group: Al-OH group), major axis = 1.2 μm, minor axis = 11 nm) was mixed and stirred while stirring until the particle content was 18.00% by mass, and diluted with water to obtain a protective layer coating solution with a solid content of 12% by mass. This coating solution was applied to the inorganic layer and dried at 80°C to form a protective layer with a thickness of 350 nm after drying, forming a laminate. This protective layer contains plate-like inorganic particles that do not have silanol groups and does not contain linear polysiloxane (the mass ratio of linear polysiloxane and silicon alkoxide, calculated on an SiO2 basis, is 0 / 100). As a result, the laminate of the present invention exhibits inferior gas barrier properties, adhesion, and flexural resistance after retort treatment. 【0203】 [Example 16] <Inorganic layer> An inorganic layer was formed in the same manner as in Example 4. 【0204】 <Protective layer> (Organic component solution) Similar to Example 5, an organic component solution of modified PVA was obtained. 【0205】 (Inorganic component solution) A decamer silicate hydrolysis solution (hydrolysis solution B) was obtained in the same manner as in Example 6. 【0206】 Next, a silicon alkoxide hydrolysate (hydrolysate C) without a ureid group was obtained, similar to Example 7. 【0207】 (Protective layer formation) Hydrolyzed solutions B and C were mixed and stirred so that the modified PVA content was 30% by mass, and the mass ratio of linear polysiloxane and silicon alkoxide (tetraethoxysilane only), calculated on an SiO2 basis, was 40 / 60, without using silicon alkoxides containing ureid groups. Then, a dispersion containing flake silica as plate-shaped inorganic particles (Sun Lovely LFS, type name: PN-010, manufactured by AGC SI-TEC Co., Ltd.; material: silica, with silanol groups; major axis = 0.4 μm, minor axis = 9 nm) was mixed and stirred while stirring until the particle content reached 30.00% by mass, and then diluted with water to obtain a coating solution with a solid content of 12% by mass. This coating solution was applied to an inorganic layer and dried at 80°C to form a protective layer with a thickness of 350 nm after drying, forming a laminate. Although this protective layer contains many plate-like inorganic particles, it does not contain silicon alkoxides having ureid groups. Therefore, the laminate of the present invention has poor adhesion and flexibility. 【0208】 [Example 17] A 60 μm thick unoriented polypropylene film (ZK100, manufactured by Toray Film Processing Co., Ltd.) was annealed at 100°C for 1 minute. Next, a laminate of Example 14 was prepared, and the annealed unoriented polypropylene film was laminated as the second olefin layer via an adhesive consisting of a polyester urethane main agent (LX500, manufactured by DIC Corporation) and an aromatic isocyanate curing agent (KW75, manufactured by DIC Corporation) on the protective layer side. The adhesive was then cured by aging in an oven heated to 40°C for 3 days to obtain composite laminate A'. Composite laminate A' failed the heat shrinkage test and passed the bending resistance test (rated 2), indicating it was inferior to composite laminate A. 【0209】 [Example 18] A 20 μm thick biaxially oriented polypropylene film (FOR, manufactured by Futamura Chemical Co., Ltd.) was annealed at 100°C for 1 minute. Next, the laminate of Example 14 was prepared, along with a 60 μm thick unoriented polypropylene film (ZK100 manufactured by Toray Film Processing Co., Ltd.) as the second olefin layer, and the annealed biaxially oriented polypropylene film as the third olefin layer. The third olefin layer, the annealed biaxially oriented polypropylene film, was laminated to the protective layer side of the laminate of the present invention via an adhesive consisting of a polyester urethane main component (LX500 manufactured by DIC Corporation) and an aromatic isocyanate curing agent (KW75 manufactured by DIC Corporation) on the corona-treated side. Then, the 60 μm thick unoriented polypropylene film (ZK100 manufactured by Toray Film Processing Co., Ltd.) was laminated to the substrate side of the laminate opposite to the protective layer via an adhesive consisting of a polyester urethane main component (LX500 manufactured by DIC Corporation) and an aromatic isocyanate curing agent (KW75 manufactured by DIC Corporation) as the second olefin layer. Finally, the adhesive was cured by aging in an oven heated to 40°C for 3 days to obtain composite laminate B'. Composite laminate B' failed the thermal shrinkage test and was inferior to composite laminate A. 【0210】 [Comparative Example 1] Evaluation was performed using only laminates with an inorganic layer similar to that in Example 1, without a protective layer. However, the gas barrier properties of the laminate, the gas barrier properties after retort treatment, adhesion, and flexibility were all inferior. 【0211】 [Comparative Example 2] <Inorganic layer> An inorganic layer was formed in the same manner as in Example 4. 【0212】 <Protective layer> (Organic component solution) none. 【0213】 (Inorganic component solution) Similar to Example 1, a silicon alkoxide hydrolysate (hydrolysate A) having a ureid group was obtained. 【0214】 Next, in the same manner as in Example 6, a decamer silicate hydrolysis solution (hydrolysis solution B) was obtained. 【0215】 (Formation of protective layer) Without using a water-soluble resin, only hydrolysis solution A and hydrolysis solution B were mixed and stirred such that the solid content ratio of the silicon alkoxide having an ureido group was 2.0% by mass, and further the mass ratio in terms of SiO2 of the linear polysiloxane and the silicon alkoxide was 98 / 2. Next, while stirring, a dispersion containing plate-like inorganic particles, flaky silica (manufactured by AGC Inc., trade name: Sun Lovely LFS type: PN-020, material: silica, with silanol groups, major diameter = 1.2 μm, minor diameter = 11 nm) was mixed and stirred so that the particle content rate became 0.53% by mass, and then diluted with water to obtain a protective layer coating liquid having a solid content of 12% by mass. This coating liquid was coated on the inorganic layer, dried at 80°C, and a protective layer without a water-soluble resin having a thickness of 350 nm after drying was formed to obtain a laminate. However, cracks occurred in the protective layer and thus it could not be evaluated. 【0216】 [Comparative Example 3] <Inorganic layer> An inorganic layer was formed in the same manner as in Example 4. 【0217】 <Protective layer> (Organic component solution) In the same manner as in Example 1, an organic component solution of PVA was obtained. 【0218】 (Inorganic component solution) None. 【0219】 (Formation of protective layer) Without using silicon components from silicon alkoxide, linear polysiloxane, or silicon alkoxide with ureid groups, a dispersion containing flake-shaped silica as plate-shaped inorganic particles (Sun Lovely LFS, type name: PN-020, manufactured by AGC SI-TEC Co., Ltd.; material: silica, with silanol groups, major axis = 1.2 μm, minor axis = 11 nm) was mixed and stirred while stirring until the particle content was 0.53 mass%, to obtain a protective layer coating solution with a solid content of 12 mass%. This coating solution was applied to an inorganic layer and dried at 80°C to form a laminate with a thickness of 350 nm, consisting only of water-soluble resin and plate-shaped inorganic particles. However, the gas barrier properties of the laminate, gas barrier properties after retort treatment, adhesion, and flexural resistance were all inferior. 【0220】 [Comparative Example 4] <Inorganic layer> An inorganic layer was formed in the same manner as in Example 4. 【0221】 <Protective layer> (Organic component solution) A solution of the organic components of PVA was obtained in the same manner as in Example 1. 【0222】 (Inorganic component solution) Similar to Example 1, a hydrolyzed silicon alkoxide solution containing a ureid group (hydrolyzed solution A) and a hydrolyzed pentamer silicate solution (hydrolyzed solution B) were obtained. 【0223】 (Protective layer formation) The organic component solution, hydrolysis solution A, and hydrolysis solution B were mixed and stirred so that the PVA content was 15% by mass, the solid content ratio of silicon alkoxide having ureido groups was 2.0% by mass, and the mass ratio of linear polysiloxane to silicon alkoxide on an SiO2 basis was 97 / 3. Then, a dispersion containing flake silica as plate-shaped inorganic particles (Sun Lovely LFS, type name: PN-020, manufactured by AGC SI-TEC Co., Ltd.; material: silica, with silanol groups; major axis = 1.2 μm, minor axis = 11 nm) was mixed and stirred until the particle content was 30.00% by mass to obtain a protective layer coating solution with a solid content of 12% by mass. This coating solution was applied to the inorganic layer and dried at 80°C to form a protective layer with a thickness of 100 nm after drying, forming a laminate. The average composition ratio (Si / C) in the protective layer of this laminate was high at 3.14, resulting in poor performance in terms of gas barrier properties, gas barrier properties after retort treatment, adhesion, and flexural resistance of the laminate. 【0224】 [Comparative Example 5] <Inorganic layer> An inorganic layer was formed in the same manner as in Example 4. 【0225】 <Protective layer> (Organic component solution) A solution of the organic components of PVA was obtained in the same manner as in Example 1. 【0226】 (Inorganic component solution) Similar to Example 1, a hydrolyzed silicon alkoxide solution containing a ureid group (hydrolyzed solution A) and a hydrolyzed pentamer silicate solution (hydrolyzed solution B) were obtained. 【0227】 (Protective layer formation) The organic component solution, hydrolysate A, and hydrolysate B were mixed and stirred so that the PVA content was 82% by mass, the solid content ratio of silicon alkoxide having ureido groups was 2.0% by mass, and the mass ratio of linear polysiloxane to silicon alkoxide on an SiO2 basis was 97 / 3. Then, a dispersion containing flake silica as plate-shaped inorganic particles (Sun Lovely LFS, type name: PN-020, manufactured by AGC SI-TEC Co., Ltd.; material: silica, with silanol groups; major axis = 1.2 μm, minor axis = 11 nm) was mixed and stirred until the particle content was 0.53% by mass to obtain a protective layer coating solution with a solid content of 12% by mass. This coating solution was applied to the inorganic layer and dried at 80°C to form a protective layer with a thickness of 100 nm after drying, forming a laminate. The average composition ratio (Si / C) in the protective layer of this laminate was low at 1.22, resulting in inferior performance in terms of gas barrier properties, gas barrier properties after retort treatment, adhesion, and flexural resistance of the laminate. 【0228】 [Comparative Example 6] <Inorganic layer> An inorganic layer was formed in the same manner as in Example 2. 【0229】 <Protective layer> (Organic component solution) A solution of the organic components of PVA was obtained in the same manner as in Example 2. 【0230】 (Inorganic component solution) Similar to Example 2, a hydrolyzed silicon alkoxide solution containing a ureid group (hydrolyzed solution A) and a hydrolyzed pentamer silicate solution (hydrolyzed solution B) were obtained. 【0231】 (Protective layer formation) The organic component solution, hydrolysis solution A, and hydrolysis solution B were mixed and stirred so that the PVA content was 20% by mass, the solid content ratio of the silicon alkoxide having a ureido group was 2.0% by mass, and the mass ratio of linear polysiloxane to silicon alkoxide in terms of SiO2 was 97 / 3, and then diluted with water to obtain a coating solution with a solid content of 12% by mass. This coating solution was applied onto the inorganic layer, dried at 80°C, and a protective layer with a thickness of 100 nm after drying and containing no plate-like inorganic particles was formed to obtain a laminate. Since the protective layer of this laminate contains no plate-like inorganic particles, its flexural resistance is inferior compared to Example 2 containing plate-like inorganic particles. 【0232】 [Comparative Example 7] <Inorganic layer> An inorganic layer was formed in the same manner as in Example 2. 【0233】 <Protective layer> (Organic component solution) An organic component solution of PVA was obtained in the same manner as in Example 2. 【0234】 (Inorganic component solution) A hydrolysis solution of silicon alkoxide having a ureido group (hydrolysis solution A) and a hydrolysis solution of pentamer silicate (hydrolysis solution B) were obtained in the same manner as in Example 2. 【0235】 (Formation of protective layer) The organic component solution, hydrolysis solution A, and hydrolysis solution B were mixed and stirred so that the PVA content was 20% by mass, the solid content ratio of silicon alkoxide having ureido groups was 2.0% by mass, and the mass ratio of linear polysiloxane to silicon alkoxide on an SiO2 basis was 97 / 3. Then, flattened polystyrene resin particles made of organic resin (TECHPOLYMER (trademark registered) LMX series L-XX-883Z, manufactured by Sekisui Chemical Co., Ltd.; material: polystyrene, no silanol groups, major axis = 3 μm, minor axis = 1,600 nm) were mixed and stirred so that the particle content was 0.027% by mass to obtain a protective layer coating solution with a solid content of 12% by mass. This coating solution was applied to the inorganic layer and dried at 80°C to form a protective layer with a thickness of 100 nm after drying, forming a laminate. The particles in this protective layer are flattened, a type of plate-like shape, but their material is organic, resulting in poor performance in terms of gas barrier properties of the laminate, gas barrier properties after retort treatment, adhesion, and flexibility. Furthermore, because the particle material is organic, it has poor compatibility with water-soluble resins (PVA), inorganic component solutions (including silicon alkoxide components and linear polysiloxane components), and aqueous solvents, leading to poor mixing. 【0236】 [Comparative Example 8] <Inorganic layer> An inorganic layer was formed in the same manner as in Example 2. 【0237】 <Protective layer> (Organic component solution) A solution of the organic components of PVA was obtained in the same manner as in Example 2. 【0238】 (Inorganic component solution) Similar to Example 2, a hydrolyzed silicon alkoxide solution containing a ureid group (hydrolyzed solution A) and a hydrolyzed pentamer silicate solution (hydrolyzed solution B) were obtained. 【0239】 (Protective layer formation) The organic component solution, hydrolysate A, and hydrolysate B were mixed and stirred so that the PVA content was 20% by mass, the solid content ratio of silicon alkoxide having ureido groups was 2.0% by mass, and the mass ratio of linear polysiloxane to silicon alkoxide on an SiO2 basis was 97 / 3. Then, a dispersion containing spherical silica particles (Nissan Chemical Corporation's "Snowtex" (registered trademark), type name: ST-O; material: silica, with silanol groups, major axis = 0.012 μm, minor axis = 12 nm) was mixed and stirred so that the particle content was 0.53% by mass to obtain a protective layer coating solution with a solid content of 12% by mass. This coating solution was applied to an inorganic layer and dried at 80°C to form a protective layer with a thickness of 100 nm after drying, forming a laminate. Because the particles in this protective layer are spherical rather than plate-shaped, the flexibility is inferior compared to Example 2, which contains plate-shaped inorganic particles. 【0240】 For each of the above examples and comparative examples, Table 1 shows the composition of the laminate, Table 2 shows the properties of the laminate, and Tables 3 and 4 show the properties of the composite laminate. 【0241】 [Table 1-1] 【0242】 [Table 1-2] 【0243】 [Table 2] 【0244】 [Table 3] 【0245】 [Table 4] 【0246】 As is clear from the results of each of the above embodiments, the laminate of the present invention exhibits excellent gas barrier properties, and the composite laminate using this laminate exhibits excellent gas barrier properties, adhesion, and flexibility after retort treatment. 【0247】 In Example 1, an inorganic layer and a protective layer were laminated onto a polyethylene film, which is an olefin-based base film. The protective layer contained a water-soluble resin, silicon alkoxide, and plate-shaped inorganic particles, with an average composition ratio (Si / C) in the range of 1.30 to 3.00. Compared to cases where no protective layer was provided (Comparative Example 1), cases where a protective layer was provided but did not contain any of the components (Comparative Examples 2 and 3), cases where the average composition ratio (Si / C) of the protective layer was not met (Comparative Examples 4 and 5), cases where plate-shaped inorganic particles were not included (Comparative Example 6), and cases where particles were included but the material (organic component) or shape (perfectly spherical) differed (Comparative Examples 7 and 8), the gas barrier properties of the laminate, gas barrier properties after retort treatment, adhesion, and flexural resistance were improved. Furthermore, when the type of olefin-based base film was changed (Example 3) or the type of inorganic layer was changed (Examples 4 and 14), similar improvements in the gas barrier properties of the laminate, gas barrier properties after retort treatment, and flexural resistance were observed. In particular, when an anchor layer was provided (Example 4), adhesion was further improved. 【0248】 Furthermore, compared to Example 1, the gas barrier properties were improved by using a vinyl polymer having a carbonyl group in its cyclic structure as the water-soluble resin in the protective layer (Example 5). Moreover, by having a solid content ratio of silicon alkoxide having a ureid group to the solid content of the protective layer of 2.5% or more, not only the gas barrier properties but also the adhesion was further improved (Example 6). 【0249】 By including silicon alkoxide without ureid groups in the protective layer, and by changing the type of linear polysiloxane used (tetramer or heptamer) and the thickness of the protective layer, adhesion and gas barrier properties after retort treatment were improved (Examples 7 and 8). Furthermore, by changing the solid content ratio of silicon alkoxide with ureid groups in the protective layer and the SiO2-calculated mass ratio of linear polysiloxane and silicon alkoxide (Examples 9-13), various physical properties could be adjusted while improving adhesion, gas barrier properties, and resistance after retort treatment (adhesion, gas barrier properties). 【0250】 Furthermore, by adjusting the size (major and minor diameters), type (presence or absence of silanol groups), and content of the inorganic particles included in the protective layer, it was possible to adjust not only the flexibility but also the adhesion and gas barrier properties (Examples 1-9, 15, 16). 【0251】 On the other hand, when no protective layer was provided (Comparative Example 1), adhesion, gas barrier properties, and flexural resistance were inferior. Even when a protective layer was provided, if it did not contain a water-soluble resin and did not meet the average composition ratio (Si / C) (Comparative Example 2), cracks appeared on the side where each layer was laminated, making evaluation impossible. Furthermore, when the protective layer did not contain silicon alkoxide and did not meet the average composition ratio (Si / C) (Comparative Example 3), various gas barrier properties, adhesion after retort treatment, and flexural resistance were inferior. Moreover, even when water-soluble resin and silicon alkoxide were included, if the average composition ratio (Si / C) was not met (Comparative Examples 4 and 5), one or more of the gas barrier properties, adhesion, or flexural resistance were insufficient, making it difficult to achieve a combination of physical properties as a composite. 【0252】 Furthermore, in the composite laminate, when the thermal shrinkage rate of either or both of the second olefin layer or the third olefin layer was smaller than that of the laminate (Example 14), the results were superior in various gas barrier properties, adhesion, and bending resistance compared to when the thermal shrinkage rate was larger (Examples 17 and 18).

Claims

[Claim 1] A laminate comprising an inorganic layer and a protective layer laminated in this order on one side of a base film, wherein the protective layer contains a water-soluble resin, silicon alkoxide, and plate-shaped inorganic particles, the inorganic layer does not correspond to the protective layer and contains at least one of an inorganic substance and an inorganic compound, and the average composition ratio of silicon (Si) to carbon (C) (Si / C) measured by X-ray photoelectron spectroscopy (XPS) in the thickness direction from the protective layer surface side opposite to the inorganic layer side up to 1 / 3 of the protective layer thickness is 1.30 to 3.

00. [Claim 2] The laminate according to claim 1, wherein the base film is an olefin-based base material. [Claim 3] The laminate according to claim 1, wherein the plate-shaped inorganic particles have a major axis of 0.1 to 2.0 μm and a minor axis of 10 to 500 nm. [Claim 4] The laminate according to claim 1, wherein the plate-shaped inorganic particles have silanol groups. [Claim 5] The laminate according to claim 1, wherein the content of the plate-shaped inorganic particles in 100% by mass of the protective layer is 0.03 to 20% by mass. [Claim 6] The laminate according to claim 1, wherein the protective layer further comprises a linear polysiloxane. [Claim 7] The laminate according to claim 1, wherein the silicon alkoxide comprises a silicon alkoxide having a ureid group. [Claim 8] The laminate according to claim 1, further comprising an anchor layer between the base film and the inorganic layer. [Claim 9] The laminate according to claim 1, wherein the inorganic layer comprises aluminum (Al) and / or silicon (Si). [Claim 10] The laminate according to claim 7, wherein the solid content ratio of the silicon alkoxide having a ureid group to the solid content of the protective layer is 2.5% by mass or more. [Claim 11] The SiO2 of the linear polysiloxane and silicon alkoxide contained in the protective layer ２ The laminate according to claim 6, wherein the converted mass ratio is in the range of linear polysiloxane / silicon alkoxide = 15 / 85 to 90 / 10. [Claim 12] The laminate according to claim 1, wherein the thickness of the protective layer is 100 to 1000 nm. [Claim 13] The laminate according to claim 1, wherein the inorganic layer contains aluminum oxide. [Claim 14] A composite laminate comprising a second olefin layer containing an olefin resin laminated on at least one side of the laminate according to claim 1, via a resin layer. [Claim 15] The composite laminate according to claim 14, wherein the thermal shrinkage rate after heating at 120°C for 15 minutes is smaller for the second olefin layer than for the laminate. [Claim 16] The composite laminate according to claim 14, wherein a third olefin layer containing an olefin resin is further laminated on at least one side of the composite laminate, either on the laminate side and / or the second olefin layer side, via a resin layer. [Claim 17] The composite laminate according to claim 16, wherein the thermal shrinkage rate after heating at 120°C for 15 minutes is smaller for at least one or both of the second olefin layer or the third olefin layer than for the laminate. [Claim 18] A packaging comprising the laminate according to any one of claims 1 to 13 and / or the composite laminate according to any one of claims 14 to 17.

Images