Structure

Abstract

The present invention pertains to: a structure including a multilayer part (I) which includes a glass layer (B) and a resin layer (A) containing a specific ethylene-vinyl alcohol copolymer (a), and in which a portion or all of at least one surface of the resin layer (A) and a portion or all of at least one surface of the glass layer (B) are layered without having an adhesive agent layer interposed therebetween; an automotive component including said structure; and a method for manufacturing a structure (Z) that includes a multilayer part (Iz) in which a portion or all of at least one surface of a resin layer (X) containing an ethylene-vinyl alcohol copolymer and a portion or all of at least one surface of a glass layer (Y) are layered without having an adhesive agent layer interposed therebetween, the method comprising a step for performing specific laser welding.

Description

structure

[0001] The present invention relates to a structure including a resin layer and a glass layer, and a method for manufacturing the same.

[0002] Composite materials consisting of glass and resin components are widely used in applications such as automobiles, electronic devices, and buildings. For example, Patent Document 1 discloses a glass-resin laminate having a laminated structure of at least three layers, comprising a layer made of a glass sheet, a layer made of a resin layer, and an adhesive layer that bonds the glass sheet and the resin layer, wherein the adhesive layer has a spectral transmittance of 90% or more in the wavelength range of at least 430 nm to 680 nm. Patent Document 2 discloses a molded product formed by laser welding a transparent resin component and an absorbing resin component, comprising a joint portion where the transparent resin component and the absorbing resin component are joined by laser welding, wherein a molten pool is observed in the joint portion in a cross-section that includes the normal to the transparent resin component or the absorbing resin component and is perpendicular to the scanning direction of the laser beam, and the area of ​​the molten pool is 0.210 mm². ２ Above 1.00 mm ２ The following is disclosed: the permeable resin member and the absorbent resin member are each molded from a resin composition, the resin composition contains a thermoplastic resin, the thermoplastic resin contains at least a polyamide resin (A1), and the resin composition has a glass transition temperature of 85°C or higher.

[0003] Japanese Patent Publication No. 2014-12373 Japanese Patent Publication No. 2024-63097

[0004] Conventionally, an adhesive layer has been required to join resin members and glass members, as seen in the glass-resin laminate described in Patent Document 1. However, in recent years, there has been a demand for structures that join resin members and glass members without using an adhesive layer. If the adhesive layer can be omitted when joining resin members and glass members, it is expected that this will lead to improvements such as thinner and lighter composite members, solvent-free manufacturing, and reduced waste. For example, laser welding is known as a method for joining two members without using adhesive. Patent Document 2 describes joining resin members together by laser welding, but it is not used to join resin members and glass members. Therefore, there is a need to investigate structures that join resin members and glass members without using adhesive, and methods for manufacturing them.

[0005] Therefore, the present invention aims to provide a structure that enables good bonding between a resin member and a glass member without the use of adhesives.

[0006] As a result of diligent research, the inventors have found that the above problems can be solved by providing a structure that satisfies specific requirements. That is, the present invention encompasses the following inventions: [1] A structure comprising a resin layer (A) and a glass layer (B) containing an ethylene-vinyl alcohol copolymer (a) in which the vinyl alcohol unit content is 50 mol% or more of the total amount of structural units constituting the ethylene-vinyl alcohol copolymer (a), wherein a laminated portion (I) is formed in which at least one surface of the resin layer (A) and at least one surface of the glass layer (B) are laminated without an adhesive layer. [2] The structure according to [1], wherein the resin layer (A) contains alkali metal ions at a concentration of 50 ppm or more in the resin layer (A). [3] The structure according to [1] or [2], wherein the vinyl alcohol unit content is 65 mol% or more of the total amount of structural units constituting the ethylene-vinyl alcohol copolymer (a). [4] The structure according to any one of [1] to [3], wherein the resin layer (A) contains an infrared absorbing material. [5] The structure according to [4], wherein the infrared absorbing material is carbon black. [6] The structure according to any one of [1] to [5], wherein the resin layer (A) contains a reinforcing material. [7] The structure according to [6], wherein the reinforcing material is glass fiber. [8] The structure according to any one of [1] to [7], wherein the content of the ethylene-vinyl alcohol copolymer (a) in the resin layer (A) is 50% by mass or more of the total amount of the resin layer (A) by 100% by mass. [9] The structure according to any one of [1] to [8], wherein the resin layer (A) is an injection molded body.

[10] The structure according to any one of [1] to [9], wherein the glass layer (B) is infrared absorbing glass.

[11] The structure according to any one of [1] to

[10] , further comprising a thermoplastic resin layer (C).

[12] The structure according to

[11] , having a laminated portion (II) in which part or all of the thermoplastic resin layer (C) and part or all of the resin layer (A) are directly laminated, or part or all of the thermoplastic resin layer (C) and part or all of the resin layer (A) are laminated via an adhesive layer (D).

[13] The structure according to

[12] , wherein the laminated portion (II) is an in-mold molded body in which a thermoplastic resin layer (C) is laminated by injection molding on one surface of the resin layer (A) or on the surface of the adhesive layer (D) opposite to the resin layer (A).

[14] The structure according to any one of [1] to

[13] , wherein the laminated portion (I) includes a portion in which at least a part or all of the interface between the resin layer (A) and the glass layer (B) is joined by laser welding.

[15] The structure according to any one of [1] to

[14] , wherein both sides of the resin layer (A) in the laminated portion (I) are not directly sandwiched between the glass layer (B).

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

[15] , wherein the resin layer (A) is laminated on both sides of the glass layer (B) in the laminated portion (I) without an adhesive layer in between.

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

[16] , wherein the resin layer (A) is laminated on a part of the surface of the glass layer (B) on which the resin layer (A) is laminated without an adhesive layer in between, and the resin layer (A) is not laminated on the remaining part of the surface of the glass layer (B) on which the resin layer (A) is laminated.

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

[17] , wherein the glass layer (B) is laminated on a part of the surface of the resin layer (A) on which the glass layer (B) is laminated without an adhesive layer in between, and the glass layer (B) is not laminated on the remaining part of the surface of the resin layer (A) on which the glass layer (B) is laminated.

[19] An automobile part having the structure according to any one of [1] to

[18] .

[20] A method for manufacturing a structure (Z) including a laminated portion (Iz) in which at least one surface of a resin layer (X) containing an ethylene-vinyl alcohol copolymer and at least one surface of a glass layer (Y) are laminated without an adhesive layer, comprising the step of laminating a part or all of the surface of at least one surface of a glass layer (Y) without an adhesive layer in between, and laser welding at least a part or all of the interface of the laminated portion (Iz) of the layer (X) and the layer (Y).

[0007] According to the present invention, it is possible to provide a structure that enables good bonding between a resin member and a glass member without using an adhesive.

[0008] This is a schematic plan view of a structure, showing an example of the structure's configuration. This is a schematic cross-sectional view of the structure shown in Figure 1, taken along line A-A. This is a schematic cross-sectional view of the structure shown along line B-B. This is a schematic cross-sectional view of a structure, showing an example of the structure's configuration. This is a schematic plan view of the structure shown in Figure 1, where only the resin layer (A) is viewed through, and the laser-welded portion on the interface between the resin layer (A) and the glass layer (B) is shown.

[0009] The following description is based on examples of embodiments of the present invention (hereinafter also referred to as "one aspect of the present invention"). However, the embodiments shown below are illustrative examples for realizing the technical concept of the present invention, and the present invention is not limited to the following description. Embodiments in which any part of the description in this specification is arbitrarily selected or arbitrarily combined are also included in the present invention. In this specification, preferred forms of embodiments are shown, but combinations of two or more individual preferred forms are also preferred forms. Preferred provisions can be arbitrarily selected, and for example, a combination of preferred provisions can be said to be more preferred. In this specification, unless otherwise specified, the description of a numerical range as "XX to YY" means "XX or more and YY or less" (XX represents the lower limit and YY represents the upper limit). For example, when the numerical range is simply described as "10 to 90", it represents a range of 10 or more and 90 or less. In this specification, the lower and upper limits described in stages for numerical ranges (each characteristic value, each component content, each structural unit content, each manufacturing condition, and the values ​​calculated from them, each characteristic, and each condition, etc.) can be combined independently. For example, based on the description "preferably 10 to 90, more preferably 30 to 60" for the same item, it is possible to combine the "preferred lower limit (10)" and the "more preferred upper limit (60)" to arrive at "10 to 60". Regarding the numerical range, for example, based on the description "preferably 10 to 90, more preferably 30 to 60", it is possible to specify only the lower limit as "10 or more" or "30 or more" without specifically specifying the upper limit, and similarly, it is possible to specify only the upper limit as "90 or less" or "60 or less" without specifically specifying the lower limit. The same applies when the upper limit of the numerical range is "less than" and when the lower limit is "greater than". Similarly, for example, based on the descriptions "preferably 10 or more, more preferably 30 or more" and "preferably 90 or less, more preferably 60 or less" for the same item, it is possible to combine the "preferred lower limit (10)" and the "more preferred upper limit (60)" to arrive at "10 or more and 60 or less". Furthermore, as described above, the lower limit can be specified as "10 or more" or "30 or more," and similarly, the upper limit can be specified as "90 or less" or "60 or less."The same applies when the terms "greater than or equal to" and "less than or equal to" in the above explanation are replaced with "greater than" and "less than," respectively. That is, for example, based on the statement "preferably more than 10 and less than 90, more preferably 30 or more and 60 or less," the upper and lower limits can be combined to become "more than 10 and 60 or less" and "30 or more and less than 90."

[0010] In this specification, unless otherwise specified, the following terms have the meanings described below: “Main component” means the component that is present in the largest quantity by mass. “ppm” means the mass content (mass ppm). “Polyolefin resin” means polyolefin resin and modified polyolefin resin. Modified polyolefin resin means a polymer obtained by modifying polyolefin resin (acid-modified polyolefin resin, polyolefin resin ionomer, etc.). Also, “polyolefin resin” refers to a polymer having structural units derived from olefin monomers (excluding ethylene vinyl alcohol copolymers), such as polyethylene resin and polypropylene resin. “Acid-modified polyolefin resin” means a polymer obtained by modifying polyolefin resin with acid. Acid-modified polyolefin resin may be a polymer in which at least one of an acidic group and an acid anhydride group is introduced to the polyolefin resin. “Polyethylene resin” means polyethylene resin and modified polyethylene resin. Modified polyethylene resin means a polymer obtained by modifying polyethylene resin (acid-modified polyethylene resin, polyethylene resin ionomer, etc.). "Polyethylene resin" refers to a homopolymer of ethylene; a copolymer of ethylene and 80 mol% or more of ethylene and 20 mol% or less of α-olefin monomer in a total monomer amount of 100 mol%; and a copolymer obtained by copolymerizing 80 mol% or more of ethylene and 20 mol% or less of a non-olefin monomer whose functional groups do not contain atoms other than carbon, oxygen, and hydrogen atoms in a total monomer amount of 100 mol% (excluding ethylene vinyl alcohol copolymer). "Acid-modified polyethylene resin" refers to a polymer obtained by modifying polyethylene resin with acid. Acid-modified polyethylene resin may be a polymer in which at least one of an acidic group and an acid anhydride group is introduced to polyethylene resin. "Polypropylene resin" refers to polypropylene resin and modified polypropylene resin. Modified polypropylene resin refers to a polymer obtained by modifying polypropylene resin (acid-modified polypropylene resin, polypropylene resin ionomer, etc.)."Polypropylene resin" refers to a homopolymer of propylene; a copolymer of propylene and at least one selected from the group consisting of ethylene and α-olefin monomers having 4 or more carbon atoms (excluding the polyethylene resin mentioned above); and a copolymer of propylene and a non-olefin monomer whose functional groups do not contain atoms other than carbon atoms, oxygen atoms, and hydrogen atoms. "Acid-modified polypropylene resin" refers to a polymer obtained by modifying polypropylene resin with an acid. Acid-modified polypropylene resin may be a polymer in which at least one of an acidic group and an acid anhydride group is introduced to polypropylene.

[0011] In this specification, unless otherwise specified, with respect to units other than vinyl alcohol units, "ZZ unit" (where ZZ is the monomer name) refers to a structural unit derived from the monomer ZZ that constitutes the polymer. For example, "ethylene unit" refers to a structural unit derived from ethylene that constitutes the polymer.

[0012] [Structure] A structure according to one aspect of the present invention (hereinafter also referred to as "the structure") comprises a resin layer (A) and a glass layer (B) containing an ethylene-vinyl alcohol copolymer (a) in which the vinyl alcohol unit content is 50 mol% or more of the total amount of structural units constituting the ethylene-vinyl alcohol copolymer (a) of 100 mol%, and includes a laminated portion (I) in which at least one surface of the resin layer (A) and at least one surface of the glass layer (B) are laminated without an adhesive layer. The structure, in this aspect, can achieve the excellent effects of the present invention. In this specification, the term "adhesive layer" in the phrase "laminated without an adhesive layer" refers to a layer provided primarily for the purpose of bonding the resin layer (A) and the glass layer (B), and the structure does not have such an adhesive layer between the resin layer (A) and the glass layer (B). Here, as will be described later, when infrared absorbing glass is used as the glass layer (B), the glass member may have an infrared absorbing coating on its surface. The infrared absorbing coating is a layer that is provided in advance as part of the glass layer (B) so that the infrared absorbing glass can perform its original function of absorbing infrared rays. Therefore, it is clear that the infrared absorbing coating is not a layer provided when laminating the resin layer (A) and the glass layer (B) for the purpose of bonding them together, and therefore does not fall under the category of adhesive layer. In this specification, "surface" of each layer refers to the surface that forms the boundary between the inside and outside of the layer, and the "outside" of the layer may be a solid, liquid, gas, or vacuum, such as another layer in contact with the layer, and therefore, the "surface" does not refer only to a surface that can be confirmed by the naked eye. The same applies when it is simply referred to as "surface".

[0013] In one embodiment of the present invention, it is preferable that the glass surface of the glass layer (B) and the resin layer (A) are directly laminated in the laminated portion (I). In this specification, "direct lamination" means that the layers or components to be laminated are laminated to each other without any other layers or components in between. Therefore, "the glass surface of the glass layer (B) and the resin layer (A) are directly laminated" means that the glass surface of the glass layer (B) and the resin layer (A) are laminated in this order without any other layers in between. The structure, by including the laminated portion (I), is composed of at least two types of components: a resin which is an organic material and glass which is an inorganic material. Therefore, in one embodiment of the present invention, the structure can also be said to be a composite component including a resin component and a glass component.

[0014] In this specification, the term "layer" in expressions such as "resin layer (A)" and "glass layer (B)" is not limited to sheet-like or film-like forms, such as the individual layers of a multilayer film. For example, when observing a cross-section taken perpendicular to the interface at any one point in the interface where the component corresponding to resin layer (A) and the component corresponding to glass layer (B) are in contact within the laminated portion (I), it is sufficient that the components overlap in a layered manner at the cross-section. That is, "resin layer (A)" is a concept that includes a resin component composed of the components contained in the resin layer (A) described later, and similarly, "glass layer (B)" is a concept that includes a glass component composed of the materials contained in the glass layer (B) described later. For example, an example of the structure will be explained using Figures 1 to 3, which are schematic diagrams showing an example of the structure. Figure 1 is a schematic plan view of a structure 10 that includes a laminated portion (I) 3 in which a part of resin layer (A) 1 and a part of glass layer (B) 2 are laminated without an adhesive layer in between. Figure 2 is a schematic cross-sectional view of the cross-section observed when the structure is cut perpendicular to the interface where the resin layer (A) 1 and the glass layer (B) 2 in the laminated portion (I) 3 are in contact, along line A-A in Figure 1. Figure 3 is a schematic cross-sectional view of the cross-section observed when the structure is cut perpendicular to the interface where the resin layer (A) 1 and the glass layer (B) 2 in the laminated portion (I) 3 are in contact, along line B-B in Figure 1. Here, the structure 10 shown in Figures 1 to 3, which is one embodiment of the present invention, has a layer structure of resin layer (A) 1 / glass layer (B) 2 / resin layer (A) 1 in the laminated portion (I) 3, as can be understood from Figures 2 and 3. However, as can be understood from Figure 2, the resin layer (A) 1 present on both sides of the glass layer (B) 2 in the laminated portion (I) 3 is a continuous single member, and a part of its cross-section has a U-shape or a U-shape. Furthermore, the end of the glass layer (B) 2 is sandwiched between the portion of the member corresponding to the resin layer (A) 1 that has a U-shaped or U-shaped cross-section. Thus, the members constituting each of the resin layers (A) 1 may be composed of a single continuous member, as can be seen from the cross-section in Figure 2. The same applies to the glass layer (B). This is because the structure 10 is a structure that includes a laminated portion (I) 3 in which a part of the resin layer (A) 1 and a part of the glass layer (B) 2 are laminated without an adhesive layer in between.

[0015] In this specification, the same applies to "thermoplastic resin layer (C)", "adhesive layer (D)", and "other layers" other than "resin layer (A)" and "glass layer (B)". For example, in one embodiment of the structure, as shown in Figure 4, there is a structure 20 having a laminated portion (II) 6 in which a thermoplastic resin layer (C) 4 is laminated via an adhesive layer (D) 5 to the surface of the resin layer (A) 1 opposite to the glass layer (B) 2 of the structure 10 shown in Figures 1 to 3 (a schematic plan view of the structure 20 corresponding to Figure 1 and a schematic cross-sectional view along line A-A corresponding to Figure 2 are omitted. Note that, as shown in Figure 4, the structure 20 also includes a laminated portion (I) 3 in which the glass layer (B) 2 and the resin layer (A) 1 are laminated). In Figure 4, the resin layer (A) 1, adhesive layer (D) 5, and thermoplastic resin layer (C) 4 are laminated in this order on both sides of the glass layer (B) 2, but each of these layers may be a continuous single member, similar to the resin layer (A) 1 shown in Figure 2. The following describes in more detail each layer, layer configuration, etc., of the structure according to one aspect of the present invention.

[0016] <Resin Layer (A)> The resin layer (A) (hereinafter also referred to as "Layer (A)") contains an ethylene-vinyl alcohol copolymer (a) (hereinafter also abbreviated as "EVOH(a)") in which the vinyl alcohol unit content is 50 mol% or more of the total amount of structural units constituting the ethylene-vinyl alcohol copolymer (100 mol%). From the viewpoint of making the effects of the present invention easier to achieve, it is preferable that the resin layer (A) contains EVOH(a) as the main component, and the content of EVOH(a) in the resin layer (A) is more preferably 50% by mass or more, even more preferably 70% by mass or more, even more preferably 90% by mass or more, and even more preferably 95% by mass or more, of the total amount of the resin layer (A) (100% by mass). There is no particular upper limit to the EVOH(a) content in the resin layer (A). The EVOH(a) content may be, for example, 100% by mass or less, 99.99% by mass or less, 99.9% by mass or less, 99.8% by mass or less, or 99.5% by mass or less, based on 100% by mass of the total amount of the resin layer (A). As mentioned above, these stepped lower and upper limits can be combined independently. For example, in one embodiment of the structure, the content of EVOH(a) in the resin layer (A) is more preferably 50 to 100% by mass, even more preferably 70 to 100% by mass, even more preferably 90 to 100% by mass, and even more preferably 95 to 100% by mass, of 100% by mass of the total amount of the resin layer (A). Alternatively, it may be, for example, 50 to 99.99% by mass, 70 to 99.9% by mass, 90 to 99.8% by mass, or 95 to 99.5% by mass. In the resin layer (A), one type of EVOH(a) may be used alone, or two or more types may be used in combination. When two or more types of EVOH(a) are contained in the resin layer (A), the content of EVOH(a) is the total content of the two or more types of EVOH(a) contained.

[0017] (Ethylene vinyl alcohol copolymer (a)) The ethylene-vinyl alcohol copolymer (a) has a vinyl alcohol unit content of 50 mol% or more of the total amount of structural units constituting the ethylene-vinyl alcohol copolymer (a) in 100 mol%, and from the viewpoint of easily improving the elastic modulus of the resulting layer (A), it is preferably 65 mol% or more, more preferably 70 mol% or more, even more preferably 72 mol% or more, and even more preferably 75 mol% or more. There is no particular upper limit to the vinyl alcohol unit content of EVOH(a) as long as the effects of the present invention are achieved, but from the viewpoint of thermal stability, the vinyl alcohol unit content of EVOH(a) is preferably 90 mol% or less, more preferably 85 mol% or less, and even more preferably 80 mol% or less of the total amount of structural units constituting the ethylene-vinyl alcohol copolymer (a) in 100 mol%. As described above, these lower and upper limits described in steps can be combined independently. For example, in one embodiment of the structure, the vinyl alcohol unit content of EVOH(a) is preferably 50 to 90 mol%, more preferably 65 to 90 mol%, even more preferably 70 to 90 mol%, even more preferably 72 to 85 mol%, and even more preferably 75 to 80 mol%, out of 100 mol% of the total amount of structural units constituting the ethylene-vinyl alcohol copolymer (a).

[0018] EVOH(a) is a copolymer having at least ethylene units and vinyl alcohol units. EVOH(a) is usually obtained by saponification of an ethylene-vinyl ester copolymer. Therefore, the vinyl alcohol units are usually structural units obtained by saponifying vinyl ester units derived from vinyl ester monomers in the ethylene-vinyl ester copolymer, and the "vinyl alcohol unit content" in EVOH(a) refers to the content (mol%) of such structural units. The vinyl alcohol unit content of EVOH(a) is, １ It can be determined by 1H-NMR measurement. Specifically, it can be measured by the method described in the examples below.

[0019] The ethylene-vinyl alcohol copolymer (a) has an ethylene unit content of 50 mol% or less, preferably 35 mol% or less, more preferably 30 mol% or less, even more preferably 28 mol% or less, and even more preferably 25 mol% or less, out of 100 mol% of the total amount of structural units constituting the ethylene-vinyl alcohol copolymer (a). The lower limit of the ethylene unit content of EVOH(a) is not particularly limited as long as the effects of the present invention are achieved, but from the viewpoint of thermal stability, the ethylene unit content of EVOH(a) is preferably 10 mol% or more, more preferably 15 mol% or more, and even more preferably 20 mol% or more, out of 100 mol% of the total amount of structural units constituting the ethylene-vinyl alcohol copolymer (a). As described above, these lower and upper limits described in stages can be combined independently. For example, in one embodiment of the structure, the ethylene unit content of EVOH(a) is preferably 10 to 50 mol%, more preferably 15 to 35 mol%, even more preferably 20 to 30 mol%, even more preferably 20 to 28 mol%, and even more preferably 20 to 25 mol% of the total amount of structural units constituting the ethylene-vinyl alcohol copolymer (a).

[0020] EVOH(a) may have residual vinyl ester units. The ethylene-vinyl ester copolymer can be produced and saponified by known methods. Examples of vinyl esters include vinyl acetate, vinyl formate, vinyl propionate, vinyl valerate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl pivalate, vinyl versaticate, and other aliphatic carboxylic acid vinyl esters. Among these vinyl esters, vinyl acetate is preferred.

[0021] In EVOH(a), the total content of vinyl alcohol units, ethylene units, and vinyl ester units is preferably 90 to 100 mol%, more preferably 95 to 100 mol%, even more preferably 97 to 100 mol%, and even more preferably 99 to 100 mol%, and may also be 100 mol%, out of 100 mol% of the total amount of structural units constituting EVOH(a). The content of vinyl alcohol units, ethylene units, and vinyl ester units in EVOH(a) is, respectively, １ It can be determined by 1H-NMR measurement. Specifically, it can be measured by the method described in the examples below.

[0022] EVOH(a) may have structural units other than vinyl alcohol units, ethylene units, and vinyl ester units, to the extent that the objectives of the present invention are not hindered. In particular, by introducing a modified group containing a primary hydroxyl group having a specific structure, it may be possible to achieve a high level of both gas barrier properties and moldability of EVOH(a). The content of other structural units in EVOH(a) is preferably 0 to 10 mol%, more preferably 0 to 5 mol%, even more preferably 0 to 3 mol%, and even more preferably 0 to 1 mol%, out of 100 mol% of the total amount of structural units, and it is even more preferable that they are substantially absent. Specifically, "substantially absent" means that the content of the other structural units in EVOH(a) is 0 to 0.5 mol%, preferably 0 to 0.1 mol%, more preferably 0 to 0.05 mol%, and even more preferably 0 to 0.01 mol%, out of 100 mol% of the total amount of structural units.

[0023] Examples of the other structural units include units derived from monomers other than vinyl alcohol units, ethylene units, and vinyl ester units, and examples of the other monomers include alkenes such as propylene, butylene, pentene, and hexene; 3-acyloxy-1-propene, 3-acyloxy-1-butene, 4-acyloxy-1-butene, 3,4-diasiloxy-1-butene, and 3-acyloxy-4-methyl-1- Butene, 4-acyloxy-1-butene, 3,4-diasiloxy-1-butene, 3-acyloxy-4-methyl-1-butene, 4-acyloxy-2-methyl-1-butene, 4-acyloxy-3-methyl-1-butene, 3,4-diasiloxy-2-methyl-1-butene, 4-acyloxy-1-pentene, 5-acyloxy-1-pentene, 4,5-diasiloxy-1-pentene, 4-acyloxy-1-hexene, 5-acyl Examples include ester group-containing alkenes or saponifies thereof such as xy-1-hexene, 6-acyloxy-1-hexene, 5,6-diasiloxy-1-hexene, and 1,3-diacetoxy-2-methylenepropane; unsaturated acids or their anhydrides, salts, or mono- or dialkyl esters such as acrylic acid, methacrylic acid, crotonic acid, and itaconic acid; nitriles such as acrylonitrile and methacrylonitrile; amides such as acrylamide and methacrylamide; olefin sulfonic acids or their salts such as vinylsulfonic acid, allylsulfonic acid, and methallylsulfonic acid; vinylsilane compounds such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri(β-methoxyethoxy)silane, and γ-methacryloxypropylmethoxysilane; alkyl vinyl ethers, vinyl ketones, N-vinylpyrrolidone, vinyl chloride, and vinylidene chloride.

[0024] EVOH(a) may be modified as needed by urethaneization, cyanoethylation, oxyalkyleneation, etc. Oxyalkyleneation can be carried out using epoxy compounds, for example, epoxyethane (ethylene oxide), epoxypropane, 1,2-epoxybutane, 2,3-epoxybutane, 3-methyl-1,2-epoxybutane, 1,2-epoxypentane, 3-methyl-1,2-epoxypentane, 1,2-epoxyhexane, 2,3-epoxyhexane, 3,4-epoxyhexane, 3-methyl-1,2-epoxyhexane, 3-methyl-1,2-epoxyheptane, 4-methyl-1,2-epoxyheptane, 1, Examples include 2-epoxyoctane, 2,3-epoxyoctane, 1,2-epoxynonane, 2,3-epoxynonane, 1,2-epoxydecane, 1,2-epoxydodecane, epoxyethylbenzene, 1-phenyl-1,2-propane, 3-phenyl-1,2-epoxypropane, various alkyl glycidyl ethers, various alkylene glycol monoglycidyl ethers, various alkenyl glycidyl ethers, various epoxy alkanols such as glycidol, various epoxycycloalkanes, and various epoxycycloalkenes. Among these, 1,2-epoxybutane, 2,3-epoxybutane, epoxypropane, epoxyethane, or glycidol are preferred, and epoxypropane or glycidol are more preferred. However, in one embodiment of the present invention, from the viewpoint of improving adhesion to layer (B), it is preferable that modification by acetalization is not performed.

[0025] The MFR (at 210°C and under a 2.16 kg load) of EVOH(a), measured in accordance with JIS K7210 (2014), is preferably 0.5 g / 10 min or more, more preferably 1.0 g / 10 min or more, and even more preferably 1.5 g / 10 min or more, from the viewpoint of improving the moldability of the resin layer (A), and from the viewpoint of improving the moldability of the resin layer (A) and improving the elastic modulus of the resin layer (A), it is preferably 20 g / 10 min or less, more preferably 15 g / 10 min or less, and even more preferably 10 g / 10 min or less. As described above, these lower and upper limits described in stages can be combined independently. For example, in one embodiment of the structure, the MFR of EVOH(a) is preferably 0.5 to 20 g / 10 min, more preferably 1.0 to 15 g / 10 min, and even more preferably 1.5 to 10 g / 10 min.

[0026] (Alkali Metal Ions) The resin layer (A) preferably contains alkali metal ions, and more preferably contains alkali metal ions at a concentration of 50 ppm or more. A alkali metal ion content of 50 ppm or more is preferable because it tends to result in good interlayer adhesion between the resin layer (A) obtained by molding EVOH(a) and the glass layer (B). From a similar viewpoint, the alkali metal ion content in the resin layer (A) is more preferably 100 ppm or more, and even more preferably 150 ppm or more. On the other hand, a alkali metal ion content of 400 ppm or less is preferable because it tends to suppress discoloration of the resin layer (A). From a similar viewpoint, the alkali metal ion content in the resin layer (A) is more preferably 350 ppm or less, and even more preferably 250 ppm or less. As described above, these lower and upper limits described in stages can be combined independently. For example, in one embodiment of the structure, the content of alkali metal ions in the resin layer (A) is preferably 50 to 400 ppm, more preferably 100 to 350 ppm, and even more preferably 150 to 250 ppm. The content of alkali metal ions can be specifically measured by the method described in the examples below.

[0027] Examples of the alkali metal ions include lithium ions, sodium ions, potassium ions, rubidium ions, and cesium ions, but sodium ions or potassium ions are preferred from the standpoint of industrial availability. These may be used individually or in combination of two or more.

[0028] Examples of alkali metal salts that provide the alkali metal ions include aliphatic carboxylates, aromatic carboxylates, carbonates, hydrochlorides, nitrates, sulfates, phosphates, and metal complexes of alkali metals such as sodium and potassium. Among these, at least one selected from aliphatic carboxylates and phosphates is preferred because it is readily available, and at least one selected from the group consisting of sodium acetate, potassium acetate, sodium phosphate, and potassium phosphate is more preferred because it is readily available.

[0029] (Infrared Absorbing Material) The resin layer (A) may contain an infrared absorbing material. When the infrared absorption capacity of the glass layer (B), described later, is low, it is preferable that the resin layer (A) contains an infrared absorbing material, as this makes it easier to obtain a suitable laminated portion (I) in which at least a portion of the interface between the resin layer (A) and the glass layer (B) is joined by laser welding. The infrared absorbing material that can be used in the resin layer (A) is not particularly limited as long as it is a material that can absorb infrared rays and is dispersible in the resin layer (A). However, it is preferable that it is a material that can absorb wavelengths in the near-infrared region and generate heat, and the wavelength is more preferably 800 to 1,200 nm, even more preferably 900 to 1,100 nm, and even more preferably 1,000 to 1,100 nm. Examples of the infrared absorbing material include: tungsten oxide represented by the general formula WrOs (wherein W is tungsten, O is oxygen, 2.2 ≤ s / r ≤ 2.999); composite tungsten oxide represented by the general formula XaWbOc (wherein X is at least one element selected from the group consisting of H, He, alkali metals, alkaline earth metals and rare earth elements, W is tungsten, O is oxygen, 0.001 ≤ a / b ≤ 1, 2.2 ≤ c / b ≤ 3); and LaM １ O ３(In the formula, La is lanthanum, M １ is at least one metal element selected from the group consisting of Ni, Co, Fe, and Mn, and O is oxygen) a composite oxide represented by; General formula M ２ Bd (where M ２ is at least one metal element selected from the group consisting of Y, Sr, Ca, and lanthanoids, B is boron, and 4.0 ≤ d ≤ 6.2) a boride represented by; Tin-doped indium oxide (ITO); Antimony-doped tin oxide (ATO); Aluminum-doped zinc oxide (AZO); Carbon black; Phthalocyanine compounds, naphthalocyanine compounds, aluminum compounds, anthraquinone compounds, cyanine compounds, squalium compounds, quinone compounds, diimonium compounds, azo compounds, dithiolene compounds, etc. organic compounds and their complexes; etc. are mentioned. Here, the description of the "ZZ-based compound" (in ZZ, for example, a compound name such as phthalocyanine is included) refers to a compound having the skeleton of the compound described in the ZZ part and its complex. Also, as the infrared absorber, an infrared absorber described in the column of the glass layer (B) described later can also be used. Among these, from the viewpoint of low cost, the infrared absorber is more preferably carbon black. In layer (A), the infrared absorber may be used alone or in combination of two or more kinds.

[0030] When the resin layer (A) contains an infrared absorbing material, from the viewpoint of easily obtaining good adhesion by the aforementioned laser welding, the content of the infrared absorbing material in the resin layer (A) is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, even more preferably 0.2% by mass or more, even more preferably 0.3% by mass or more, and even more preferably 0.4% by mass or more, based on 100% by mass of the total amount of the resin layer (A). On the other hand, from the viewpoint of weldability with glass, the content of the infrared absorbing material in the resin layer (A) is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, even more preferably 5% by mass or less, and even more preferably 1% by mass or less, based on 100% by mass of the total amount of the resin layer (A). As described above, these lower and upper limits described in stages can be combined independently. For example, in one embodiment of the structure, the content of the infrared absorbing material in the resin layer (A) is preferably 0.01 to 20% by mass, more preferably 0.01 to 15% by mass, even more preferably 0.01 to 10% by mass, even more preferably 0.1 to 5% by mass, even more preferably 0.2 to 5% by mass, even more preferably 0.2 to 1% by mass, even more preferably 0.3 to 1% by mass, and even more preferably 0.4 to 1% by mass, based on 100% by mass of the total amount of the resin layer (A).

[0031] (Reinforcement) The resin layer (A) may contain a reinforcement. Examples of the reinforcement include clay, talc, wollastonite, silica, alumina, calcium silicate, sodium aluminate, sodium aluminosilicate, magnesium silicate, glass balloons, carbon black, zeolite, montmorillonite, hydrotalcite, fluoromica, metal fibers, metal whiskers, ceramic whiskers, potassium titanate whiskers, boron nitride, graphite, glass fibers, carbon fibers, fullerenes (C60, C70, etc.), carbon nanotubes, etc. Among these, at least one selected from the group consisting of glass fibers and carbon fibers is preferred from the viewpoint of high reinforcement strength, and glass fibers are more preferred.

[0032] When the resin layer (A) contains a reinforcing material, from the viewpoint of achieving good impact resistance, the reinforcing material content in the resin layer (A) is preferably 1% by mass or more, more preferably 5% by mass or more, even more preferably 10% by mass or more, and even more preferably 15% by mass or more, based on 100% by mass of the total amount of the resin layer (A). On the other hand, from the viewpoint of weldability with glass, the reinforcing material content in the resin layer (A) is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less, based on 100% by mass of the total amount of the resin layer (A). As described above, these lower and upper limits described in stages can be combined independently. For example, in one embodiment of the structure, the reinforcing material content in the resin layer (A) is preferably 1 to 50% by mass, more preferably 5 to 40% by mass, even more preferably 10 to 30% by mass, and even more preferably 15 to 30% by mass, based on 100% by mass of the total amount of the resin layer (A).

[0033] (Resins other than EVOH(a)) The resin layer (A) may further contain resins other than EVOH(a). Examples of resins other than EVOH(a) include EVOH other than EVOH(a), various polyolefins (polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, ethylene-propylene copolymer, copolymer of ethylene and α-olefin having 4 or more carbon atoms, copolymer of polyolefin and maleic anhydride, ethylene-vinyl ester copolymer, ethylene-acrylic acid ester copolymer, or modified polyolefins obtained by grafting these with unsaturated carboxylic acids or their derivatives), various polyamides (nylon 6, nylon 6 / 6, nylon 6 / 66 copolymer, nylon 11, nylon 12, polymetaxylylene adipamide, etc.), various polyesters (polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc.), polyvinyl chloride, polyvinylidene chloride, polystyrene, polyacrylonitrile, polyurethane, polycarbonate, polyacetal, polyacrylate, and modified polyvinyl alcohol resin.

[0034] The content of the resin other than EVOH (a) in the resin layer (A) is preferably 0% by mass or more and less than 50% by mass, more preferably 0 to 30% by mass, still more preferably 0 to 10% by mass, even more preferably 0 to 5% by mass, even more preferably 0 to 3% by mass, and may also be 0 to 1% by mass, based on 100% by mass of the total amount of the resin layer (A).

[0035] Further, the content of EVOH (a) in the resin contained in the resin layer (A) is preferably 60 to 100% by mass, more preferably 80 to 100% by mass, still more preferably 90 to 100% by mass, even more preferably 95 to 100% by mass, even more preferably 97 to 100% by mass, and may also be 99 to 100% by mass, or even 100% by mass, based on 100% by mass of the total amount of the resin contained in the resin layer (A).

[0036] (Other components) The resin layer (A) may contain, within a range not inhibiting the effects of the present invention, EVOH (a), and other components other than the alkali metal ions, the infrared absorber, the reinforcing material, and the resin other than EVOH (a) that may optionally be contained. Examples of the other components include polyvalent metal ions, carboxylic acids, phosphoric acid compounds, boron compounds, oxidation accelerators, antioxidants, plasticizers, heat stabilizers (melt stabilizers), photoinitiators, deodorants, ultraviolet absorbers, antistatic agents, lubricants, colorants, fillers, desiccants, fillers, pigments, dyes, processing aids, flame retardants, and antifogging agents (however, excluding the infrared absorber, the reinforcing material, and the resin other than EVOH (a)). The content of the other components in the resin layer (A) is preferably 0 to 5% by mass, more preferably 0 to 3% by mass, still more preferably 0 to 1% by mass, based on 100% by mass of the total amount of the resin layer (A).

[0037] [Polyvalent Metal Ions] The polyvalent metal ions are preferably at least one selected from the group consisting of magnesium ions, calcium ions, and zinc ions, more preferably at least one selected from the group consisting of magnesium ions and calcium ions, and even more preferably magnesium ions. When the resin layer (A) contains the polyvalent metal ions, it is preferable that they be contained as carboxylate salts. The carboxylic acid in this case may be either an aliphatic carboxylic acid or an aromatic carboxylic acid, but an aliphatic carboxylic acid is preferred. Examples of aliphatic carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, lauric acid, lauric acid, tridecyl acid, myristic acid, pentadecyl acid, palmitic acid, heptadecyl acid, stearic acid, basic stearic acid, hydroxystearic acid, basic hydroxystearic acid, nonadecanoic acid, oleic acid, behenic acid, montanic acid, linoleic acid, etc. The aliphatic carboxylic acid is more preferably a higher fatty acid having 10 to 30 carbon atoms. The number of carbon atoms in the carboxylic acid may be, for example, 10 to 30, 12 to 30, 14 to 26, or 16 to 22. The polyvalent metal ion is preferably present in layer (A) as a cation constituting the salt, and more preferably present in layer (A) as a cation constituting the carboxylate salt. In salts such as carboxylate salts, the polyvalent metal ion and the anion may be bonded or free. From the viewpoint of suppressing discoloration during melt molding, it is also preferable that the polyvalent metal ion be included as a salt of a polyvalent carboxylic acid, as described later.

[0038] When the resin layer (A) contains the polyvalent metal ions, the content of the polyvalent metal ions in the resin layer (A) is preferably 10 ppm or more, more preferably 20 ppm or more in the layer (A), and is preferably 200 ppm or less, more preferably 160 ppm or less, still more preferably 120 ppm or less. As described above, these stepwise-described lower and upper limit values can be combined independently of each other. For example, the content of the polyvalent metal ions in the resin layer (A) is preferably 10 to 200 ppm, more preferably 10 to 160 ppm, still more preferably 20 to 120 ppm in the layer (A). The content of the polyvalent metal ions can be measured in the same manner as the measurement method of the content of the alkali metal ions described above. Specifically, it can be measured by the same method as the measurement method of the content of the alkali metal ions described in the examples described later.

[0039] [Carboxylic Acid] As the carboxylic acid, which is one aspect of the other components, a carboxylic acid having a pKa of 3.5 to 5.5 is preferable. When the pKa of the carboxylic acid is within the above range, the pH buffering ability in the weak acidic range is enhanced, the melt moldability is further improved, and the coloring effect by acidic substances and basic substances can be further reduced. The carboxylic acid may be a monovalent carboxylic acid. The monovalent carboxylic acid is a compound having one carboxy group in the molecule. The monovalent carboxylic acid having a pKa in the range of 3.5 to 5.5 is not particularly limited, and examples thereof include formic acid (pKa = 3.77), acetic acid (pKa = 4.76), propionic acid (pKa = 4.85), acrylic acid (pKa = 4.25), etc. These carboxylic acids may further have substituents such as a hydroxyl group, an amino group, a halogen atom, etc. Among them, acetic acid is preferable because of its high safety and easy availability and handling. These carboxylic acids may be used alone or in combination of two or more.

[0040] The carboxylic acid may be a polycarboxylic acid. If the carboxylic acid is a polycarboxylic acid, the stain resistance of EVOH(a) at high temperatures may be further improved. The polycarboxylic acid is a compound having two or more carboxyl groups in its molecule. In this case, it is preferable that the pKa of at least one carboxyl group is in the range of 3.5 to 5.5, for example, oxalic acid (pKa2 = 4.27), succinic acid (pKa1 = 4.20), fumaric acid (pKa2 = 4.44), malic acid (pKa2 = 5.13), glutaric acid (pKa1 = 4.30, pKa2 = 5.40), adipic acid (pKa1 = 4.43, pKa2 Examples include polycarboxylic acids (pKa1 = 5.41), pimelic acid (pKa2 = 4.71), phthalic acid (pKa2 = 5.41), isophthalic acid (pKa2 = 4.46), terephthalic acid (pKa1 = 3.51, pKa2 = 4.82), citric acid (pKa2 = 4.75), tartaric acid (pKa2 = 4.40), glutamic acid (pKa2 = 4.07), aspartic acid (pKa = 3.90), etc. Furthermore, it is preferable that the polycarboxylic acid has three or more carboxyl groups. In this case, the stain resistance may be improved more effectively.

[0041] When the resin layer (A) contains the carboxylic acid, the content of the carboxylic acid in the resin layer (A) is preferably 50 to 400 ppm, more preferably 100 to 350 ppm. When the content of the carboxylic acid in the resin layer (A) is within this range, deterioration of hue tends to be suppressed. The content of the carboxylic acid is determined by extracting 10 g of the resin composition constituting the resin layer (A) with 50 mL of pure water at 95°C for 8 hours, and then titrating the resulting extract. Note that carboxylic acid present as a salt in the extract is not considered when determining the content of the carboxylic acid in the resin composition. Furthermore, if the resin composition contains acidic compounds other than carboxylic acid, the content of the carboxylic acid in the resin composition can be determined by subtracting the contribution of those acidic compounds from the measured value obtained by titration.

[0042] [Phosphate Compounds] As the phosphate compounds, for example, various acids such as phosphoric acid and phosphorous acid, and their salts can be used. The phosphate may be any of the first, second, or third phosphates. The cation species of the phosphate is not particularly limited, but alkali metals or alkaline earth metals are preferred. Among these, sodium dihydrogen phosphate, potassium dihydrogen phosphate, disodium hydrogen phosphate, and dipotassium hydrogen phosphate are preferred as the phosphate compounds.

[0043] When the resin layer (A) contains the phosphate compound, the content of the phosphate compound is preferably 5 to 100 ppm in the resin layer (A) in terms of phosphate ions. Including the phosphate compound within this range may suppress discoloration of the molten EVOH(a) product and improve its thermal stability.

[0044] [Boron Compounds] Examples of the boron compounds include boric acid, boric acid esters, borate salts, and boron hydride. Specifically, orthoboric acid (H ３ BO ３ Examples include boric acid such as metaboric acid and tetraboric acid; boric acid esters such as trimethyl borate and triethyl borate; alkali metal salts or alkaline earth metal salts of the aforementioned boric acid, and borates such as borax. Among these, orthoboric acid is preferred.

[0045] When the resin layer (A) contains the boron compound, the content of the boron compound is preferably 50 to 400 ppm, more preferably 100 to 200 ppm, in terms of boron element in the resin layer (A). Including the boron compound within this range may improve the thermal stability of EVOH(a) during melt molding and suppress the generation of gel and blemishes. In addition, resistance to drawdown and resistance to neck-in during film formation may be improved. These effects are presumed to be due to chelate interactions occurring between EVOH(a) and the boron compound.

[0046] [Antioxidant] Examples of the antioxidant include hindered phenol compounds having an ester bond or an amide bond. The hindered phenol compound has at least one hindered phenol group. The hindered phenol group refers to a group in which a bulky substituent is bonded to at least one carbon adjacent to the carbon to which the hydroxyl group of phenol is bonded. The bulky substituent is preferably an alkyl group with 1 to 10 carbon atoms, and more preferably a t-butyl group.

[0047] The hindered phenol compound is preferably in a solid state at room temperature (25°C). From the viewpoint of suppressing bleed-out of the hindered phenol compound, the melting point of the hindered phenol compound is preferably 50°C or higher, more preferably 60°C or higher, and even more preferably 70°C or higher. The softening temperature of the hindered phenol compound is preferably 50°C or higher, more preferably 60°C or higher, and even more preferably 70°C or higher. Furthermore, from the viewpoint of facilitating mixing with EVOH(a), the melting point of the hindered phenol compound is preferably 200°C or lower, more preferably 190°C or lower, and even more preferably 180°C or lower. The softening temperature of the hindered phenol compound is preferably 200°C or lower, more preferably 190°C or lower, and even more preferably 180°C or lower. These lower and upper limits described in steps can be combined independently. For example, the melting point and softening temperature of the hindered phenol compound are preferably 50 to 200°C, more preferably 60 to 190°C, and even more preferably 70 to 180°C, respectively. Furthermore, from the viewpoint of suppressing bleed-out, the molecular weight of the hindered phenol compound is preferably 200 or more, more preferably 400 or more, and even more preferably 600 or more. On the other hand, the molecular weight is usually 2,000 or less. In one embodiment of the present invention, the molecular weight of the hindered phenol compound may be, for example, 400 to 2,000 or 400 to 2,000.

[0048] Examples of hindered phenol compounds having an ester bond include esters of an aliphatic carboxylic acid having a hindered phenol group and an aliphatic alcohol. Examples of hindered phenol compounds having an amide include amides of an aliphatic carboxylic acid having a hindered phenol group and an aliphatic amine. In particular, from the viewpoint of facilitating mixing with EVOH(a), it is preferable that the hindered phenol compound has an amide bond.

[0049] Specific structures of the aforementioned hindered phenol compounds include, for example, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], which is marketed by BASF as "Irganox® 1010", stearyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, which is marketed as "Irganox® 1076", 2,2'-thiodiethylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], which is marketed as "Irganox® 1035", and "Irganox® 1135" Examples of commercially available products include octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoate, bis(3-tert-butyl-4-hydroxy-5-methylbenzenepropanoate)ethylenebis(oxyethylene) sold as "Irganox® 245", 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] sold as "Irganox® 259", and N,N'-hexamethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanamide] sold as "Irganox® 1098". In particular, N,N'-hexamethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanamide], which is commercially available as "Irganox® 1098", and pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], which is commercially available as "Irganox® 1010", are preferred, and "Irganox® 1098" is more preferred.

[0050] If the resin layer (A) contains the antioxidant, the content of the antioxidant in the resin layer (A) is preferably 1,000 to 10,000 ppm, more preferably 2,000 to 8,000 ppm.

[0051] Examples of the UV absorbers include ethyl-2-cyano-3,3'-diphenyl acrylate, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3'-t-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, and 2-hydroxy-4-octoxybenzophenone. Examples of the plasticizers include dimethyl phthalate, diethyl phthalate, dioctyl phthalate, wax, liquid paraffin, and phosphate esters. Examples of the antistatic agents include pentaerythritol monostearate, sorbitan monopalmitate, sulfated polyolefins, polyethylene oxide, and polyethylene glycol (trade name: Carbowax®). Examples of the lubricants include ethylene bisstearamide and butyl stearate. Examples of the coloring agents include carbon black, phthalocyanine, quinacridone, indoline, azo pigments, and red iron oxide. Examples of the fillers include glass fiber, wollastonite, calcium silicate, talc, and montmorillonite. Examples of the heat stabilizers include hindered phenol compounds and hindered amine compounds.

[0052] When the resin layer (A) contains components other than EVOH(a), the method for producing the resin composition constituting the resin layer (A) is not particularly limited, but it can be produced by melt-kneading EVOH(a) and, if necessary, the components other than EVOH(a) mentioned above. The components other than EVOH(a) mentioned above may be blended in a solid state such as powder, blended as a molten product, or blended as a solute contained in a solution or a dispersed phase contained in a dispersion. Aqueous solutions and aqueous dispersions are preferred as the solution and dispersion, respectively. For melt-kneading, known mixing or kneading devices such as a kneader-ruder, extruder, mixing roll, or Banbury mixer can be used. The temperature range during melt-kneading can be appropriately adjusted according to the melting point of the EVOH(a) used, for example, 150 to 300°C is used.

[0053] In another embodiment, a masterbatch containing a high concentration of components other than EVOH(a) relative to EVOH(a) can be produced by melt-kneading, and this masterbatch can be dry-blended with EVOH(a) that substantially does not contain the components other than EVOH(a) to produce a resin layer (A). In yet another embodiment, EVOH(a) and the components other than EVOH(a) can be used to produce a resin layer (A) by dry-blending. Dry-blending refers to mechanical mixing in powder or pellet form. Mixing may be carried out using a mixing device such as a tumbler, ribbon mixer, or Henschel mixer, or by manually stirring or shaking in a sealed container. The mixing temperature should be between room temperature (25°C) and below the melting point of EVOH(a), and mixing can be carried out under an air atmosphere or a nitrogen atmosphere.

[0054] In the resin layer (A), the total content of EVOH(a), and optionally the alkali metal ions, infrared absorbers, reinforcing materials, resins other than EVOH(a), and other components shall not exceed 100% by mass of the total amount of resin layer (A). In other words, the total content of EVOH(a), and optionally the alkali metal ions, infrared absorbers, reinforcing materials, resins other than EVOH(a), and other components in the resin layer (A) shall be at most 100% by mass of the total amount of resin layer (A).

[0055] The method for molding the resin layer (A) is not particularly limited, and known methods for molding resin molded products such as extrusion molding, injection molding, blow molding, vacuum molding, and pressure molding can be used. In one embodiment of the present invention, the resin layer (A) is preferably obtained by injection molding. That is, the resin layer (A) is preferably an injection molded product.

[0056] The thickness of the resin layer (A) is not particularly limited as long as the effects of the present invention are achieved, and can be appropriately selected depending on the application of the structure. In one embodiment of the present invention, the thickness of the resin layer (A) is, for example, from the viewpoint of rigidity, preferably 0.5 mm or more, more preferably 1 mm or more, and even more preferably 2 mm or more, in any cross-section obtained by cutting perpendicular to the interface in which layers (A) and (B) are laminated in the laminated portion (I) described later, and, for example, from the viewpoint of facilitating the joining of layers (A) and (B) by laser welding, preferably 10 mm or less, more preferably 8 mm or less, and even more preferably 6 mm or less. These lower and upper limits described in steps can be combined independently. For example, in one embodiment of the structure, the thickness of the resin layer (A) is preferably 0.5 to 10 mm, more preferably 1 to 8 mm, and even more preferably 2 to 6 mm.

[0057] <Glass Layer (B)> The glass layer (B) (hereinafter also referred to as "layer (B)") is not particularly limited as long as the effects of the present invention are achieved, and examples include soda-lime glass, borosilicate glass, lead glass, silica glass, crystallized glass, aluminosilicate glass, borate glass, phosphate glass, fluoride glass, chalcogenide glass, alkali-free glass, etc. These glasses may be physically strengthened or chemically strengthened. The glass layer (B) is preferably infrared absorbing glass. The infrared absorbing glass is more preferably near-infrared absorbing glass, more preferably glass that can absorb near-infrared rays with wavelengths of 800 to 1,200 nm, even more preferably glass that can absorb near-infrared rays with wavelengths of 900 to 1,100 nm, and even more preferably glass that can absorb near-infrared rays with wavelengths of 1,000 to 1,100 nm. In one embodiment of the present invention, the near-infrared absorbing glass is preferably one in which the transmittance T1000 of near-infrared rays at a wavelength of 1,000 nm is 30% or less, more preferably one in which the transmittance T1000 is 20% or less, even more preferably one in which the transmittance T1000 is 15% or less, and still more preferably one in which the transmittance T1000 is 10% or less. The lower limit of the near-infrared transmittance T1000 of the near-infrared absorbing glass at a wavelength of 1,000 nm is not particularly limited, but may be, for example, 0.1% or more, 1% or more, or 5% or more. These lower and upper limits described in steps can be combined independently. In one embodiment of the near-infrared absorbing glass, the near-infrared transmittance T1000 of the infrared absorbing glass at a wavelength of 1,000 nm may be, for example, 0.1 to 30%, 1 to 20%, 1 to 15%, or 5 to 10%. The value of T1000 can be measured using a method described later, for example, by using an instrument such as a spectrophotometer.

[0058] Examples of the infrared absorbing glass include absorbent glass containing copper ions or iron ions, such as phthalate glass or phosphate glass containing copper ions or iron ions. Note that "phosphate glass" refers to glass in which part of the skeleton is SiO２ It also includes silicate glass composed of the following. Furthermore, the copper ions are Cu ２＋ In this state, the iron ion is Fe ２＋ It is preferable that it exists in this state. Examples of infrared absorbing glass include chemically strengthened glass obtained by exchanging alkali metal ions with small ionic radii (e.g., Li ions, Na ions) present on the surface of the glass plate with alkali ions with larger ionic radii (e.g., Na ions or K ions for Li ions, and K ions for Na ions) by ion exchange at a temperature below the glass transition point.

[0059] In one embodiment of the present invention, when the glass layer (B) is infrared absorbing glass, the glass layer (B) may be composed of multiple layers. Examples of infrared absorbing glass composed of multiple layers include infrared absorbing laminated glass having an interlayer containing an infrared absorbing material between the glass layers, or infrared absorbing coated glass having a coating containing an infrared absorbing material on the glass surface. When the glass layer (B) is infrared absorbing laminated glass or infrared absorbing coated glass, it is preferable that each independently satisfies the aforementioned preferred range of absorption wavelengths. Similarly, when the glass layer (B) is infrared absorbing laminated glass or infrared absorbing coated glass, it is preferable that each independently satisfies the aforementioned preferred range of transmittance T1000. The glass used as the glass portion of the infrared absorbing laminated glass or infrared absorbing coated glass is not particularly limited as long as the effects of the present invention are achieved, and various types of glass described above can be used. The infrared absorbing glass described above may be used as the glass portion. In other words, it may be laminated glass having an interlayer containing an infrared absorbing material between two infrared absorbing glasses or other types of glass, or it may be coated glass with a coating containing an infrared absorbing material further applied to the surface of the infrared absorbing glass.

[0060] As described above, when a glass layer (B) is made of glass coated with an infrared-absorbing film, the film is a layer that is provided on the glass in advance to impart infrared absorption properties and constitutes a part of the glass layer (B). In other words, it is a layer that is provided in advance to exhibit the function of infrared-absorbing glass, and it is obvious to those skilled in the art that it is not an adhesive for bonding the resin layer (A) to the glass layer (B). Therefore, one embodiment of the structure is one in which a glass layer (B) is made of glass coated with an infrared-absorbing film, and the resin layer (A) is bonded to the film side.

[0061] In one embodiment of the present invention, it is preferable that the resin layer (A) and the glass surface of the glass layer (B) are directly laminated. In this case, the glass layer (B) may be any of the aforementioned types of glass other than infrared absorbing glass, or, if infrared absorbing glass is used, an infrared absorbing glass other than the aforementioned infrared absorbing coated glass may be used, or the glass surface on the side of the infrared absorbing coated glass that does not have the coating may be directly laminated with the resin layer (A).

[0062] As long as the effects of the present invention are achieved, there are no particular limitations on the infrared absorbing material used in the interlayer of the laminated glass or the coating formed on the glass surface of the coated glass (hereinafter also referred to as "infrared absorbing material used in the glass layer (B)"), but for example, tin-doped indium oxide (ITO), antimond-doped tin oxide (ATO), aluminum-doped zinc oxide (AZO), and general formula M ３ mWOn(M ３ Metal-doped oxides such as metal-doped tungsten oxide (where m represents a metal element, and m is 0.001 to 1.0, and n is 2.2 to 3.0); zinc antimonate (ZnSb ２ O ５ ), lanthanum hexaboride (LaB ６Examples include inorganic fine particles such as ) or organic materials such as phthalocyanine compounds (NIOBP), naphthalocyanine compounds, or compounds having an anthracianine skeleton. Examples of the metal element represented by M in the metal-doped tungsten oxide include Cs, Tl, Rb, Na, Ba, K, and in particular Cs-based CWO (cesium-doped tungsten oxide; "CWO" is a registered trademark). The value of m is preferably 0.01 or more, more preferably 0.1 or more, even more preferably 0.2 or more, even more preferably 0.3 or more, and preferably 0.5 or less, more preferably 0.4 or less. These stepwise lower and upper limits can be combined independently of each other. For example, m may be 0.1 to 1.0, 0.2 to 1.0, 0.3 to 1.0, 0.01 to 0.5, 0.1 to 0.5, 0.2 to 0.5, 0.3 to 0.5, 0.01 to 0.4, 0.1 to 0.4, 0.2 to 0.4, or 0.3 to 0.4. From the viewpoint of infrared absorption, the phthalocyanine compound is preferably a compound coordinated to nickel(II).

[0063] The infrared absorbing material used in the glass layer (B) is preferably used in the form of fine particles. From the viewpoint of easily achieving good transparency of the glass layer (B), the average particle size of the infrared absorbing material used in the glass layer (B) is preferably 100 nm or less, and more preferably 50 nm or less. The average particle size referred to here is the one measured by a laser diffraction device. The lower limit of the average particle size is not particularly limited as long as the effects of the present invention are achieved, but it may be, for example, 1 nm. In one embodiment of the present invention, the average particle size of the infrared absorbing material used in the glass layer (B) may be, for example, 1 to 100 nm, or 1 to 50 nm. The infrared absorbing material used in the glass layer (B) may be used alone or two or more types may be used in combination. As described above, each infrared absorbing material described as an infrared absorbing material used in the glass layer (B) can also be used as an infrared absorbing material that may be contained in the resin layer (A).

[0064] The main component of the interlayer of the laminated glass is not particularly limited as long as the effects of the present invention are achieved, and for example, thermoplastic resins, thermoplastic elastomers, thermosetting resins, silicon oxide components, etc., can be used. Similarly, the main component of the coating formed on the glass surface of the coated glass is not particularly limited as long as the effects of the present invention are achieved, and for example, thermoplastic resins, thermosetting resins, silicon oxide components, etc., can be used. Examples of the silicon oxide component include 2- to 4-functional hydrolyzable silane compounds.

[0065] The thickness of the glass layer (B) is not particularly limited as long as the effects of the present invention are achieved, and can be appropriately selected depending on the application of the structure. In one embodiment of the present invention, the thickness of the glass layer (B) is not particularly limited as long as the effects of the present invention are achieved, but for example, in any cross-section obtained by cutting perpendicular to the interface in which layers (A) and (B) are laminated in the laminated portion (I) described later, it is preferably 0.5 mm or more, more preferably 1 mm or more, and even more preferably 2 mm or more, and, for example, from the viewpoint of facilitating the joining of layers (A) and (B) by laser welding, it is preferably 20 mm or less, more preferably 10 mm or less, and even more preferably 5 mm or less. These lower and upper limits described in steps can be combined independently. For example, in one embodiment of the structure, the thickness of the glass layer (B) is preferably 0.5 to 20 mm, more preferably 1 to 10 mm, and even more preferably 2 to 5 mm.

[0066] <Laminated portion (I)> The laminated portion (I) refers to a laminated portion in the structure in which at least one surface part or all of the resin layer (A) and at least one surface part or all of the glass layer (B) are laminated without an adhesive layer in between. Therefore, the entire structure may be composed of the laminated portion (I), or a part of the structure may be composed of the laminated portion (I). It is preferable that the laminated portion (I) includes a portion in which at least a part or all of the interface between the resin layer (A) and the glass layer (B) is joined by laser welding. For example, an example of the structure will be explained using Figure 5, a schematic diagram showing Figure 1 above. Figure 5 is a schematic plan view of the structure 10 according to Figure 1 above, and is a schematic plan view in which only the resin layer (A) 1 is viewed through and the portion 7 joined by laser welding on the interface between the resin layer (A) 1 and the glass layer (B) 2 is shown by a dashed line. As shown in Figure 5, the entire interface between the resin layer (A) 1 and the glass layer (B) 2 may be laser-welded, or the laser may be scanned intermittently or continuously along the dashed line in Figure 5, welding only the interface along the dashed line. In other words, the structure 30 shown in Figure 5 is a schematic plan view of a structure in which at least a portion 7 of the interface between the resin layer (A) 1 and the glass layer (B) 2 in the laminated portion (I) 3 is joined by laser welding.

[0067] In the laminated portion (I), it is preferable that at least one of the resin layer (A) and the glass layer (B) is a layer capable of generating heat by laser absorption, and it is more preferable that in the laminated portion (I), one of the resin layer (A) or the glass layer (B) is a layer capable of generating heat by laser absorption, and the other is a layer that can transmit laser light. For example, if the resin layer (A) is the laser-transmitting layer and the glass layer (B) is the laser-absorbing layer, a method can be used to join the two layers by irradiating a laser from the resin layer (A) side to generate heat at the interface between the resin layer (A) and the glass layer (B), and welding the two layers at the interface.

[0068] In one embodiment of the present invention, a molten pool may be formed in at least a part or all of the joint portion at the interface between the resin layer (A) and the glass layer (B) in the laminated portion (I). The molten pool is formed when the resin layer (A) and the glass layer (B) are laminated and a laser is irradiated from the laser-transmitting layer side, causing the laser-absorbing layer to expand with heat generation, and heat is transferred to the laser-transmitting layer side, resulting in the melting of at least one layer selected from layers (A) and (B).

[0069] In one embodiment of the present invention, from the viewpoint of facilitating the joining of layer (A) and layer (B) by laser welding, the near-infrared transmittance T1000 at a wavelength of 1,000 nm of either the resin layer (A) or the glass layer (B) is preferably 30% or less, more preferably 20% or less, even more preferably 15% or less, and even more preferably 10% or less. The lower limit of the near-infrared transmittance T1000 at a wavelength of 1,000 nm is not particularly limited, but may be, for example, 0.1% or more, 1% or more, or 5% or more. In one embodiment of the structure, the near-infrared transmittance T1000 at a wavelength of 1,000 nm of either the resin layer (A) or the glass layer (B) may be 0.1 to 30%, 1 to 20%, 1 to 15%, or 5 to 10%. In one embodiment of the present invention, from the viewpoint of facilitating the joining of layer (A) and layer (B) by laser welding, the difference between the value of the near-infrared transmittance T1000 (%) of the resin layer (A) at a wavelength of 1,000 nm and the value of the near-infrared transmittance T1000 (%) of the glass layer (B) at a wavelength of 1,000 nm is preferably 30 or more, more preferably 50 or more, even more preferably 70 or more, and even more preferably 80 or more. In one embodiment of the present invention, the upper limit of the difference between the value of the near-infrared transmittance T1000 (%) of the resin layer (A) at a wavelength of 1,000 nm and the value of the near-infrared transmittance T1000 (%) of the glass layer (B) at a wavelength of 1,000 nm is not particularly limited as long as the effects of the present invention are achieved, but for example it may be 99.9. In one embodiment of the present invention, the difference between the value (%) of the near-infrared transmittance T1000 at a wavelength of 1,000 nm of the resin layer (A) and the value (%) of the near-infrared transmittance T1000 at a wavelength of 1,000 nm of the glass layer (B) may be, for example, 30 to 99.9, 50 to 99.9, 70 to 99.9, or 80 to 99.9. The value (%) of the near-infrared transmittance T1000 at a wavelength of 1,000 nm can be confirmed using an instrument such as a spectrophotometer capable of measuring and calculating the near-infrared transmittance at a wavelength of 1,000 nm. Examples of such spectrophotometers include various spectrophotometers manufactured by Hitachi High-Tech Corporation (e.g., "U-4100", "UH4150", etc.).

[0070] The laser welding method described above is not particularly limited as long as it is possible to join at least a portion of the interface between the resin layer (A) and the glass layer (B), and any known laser welding apparatus can be used. For example, a galvanoscanning type laser welding machine can be suitably used. The laser is not particularly limited as long as the effects of the present invention are achieved, but a laser having a wavelength in the near-infrared region is preferred, a laser with a wavelength of 800 to 1,200 nm is more preferred, a laser with a wavelength of 900 to 1,100 nm is even more preferred, and a laser with a wavelength of 1,000 to 1,100 nm is even more preferred.

[0071] While there are no particular limitations as long as the effects of the present invention are achieved, the ratio of the area of ​​the portion joined by laser welding (hereinafter also referred to as the "area of ​​the laser-welded portion") to the total area of ​​the interface between the resin layer (A) and the glass layer (B), that is, the area of ​​the contact portion between the resin layer (A) and the glass layer (B), is preferably 5% or more, more preferably 10% or more, and even more preferably 20% or more, of 100% of the total area of ​​the contact portion between the resin layer (A) and the glass layer (B). Furthermore, there are no particular upper limits on the area of ​​the laser-welded portion, and it may be 100% of the total area of ​​the contact portion between the resin layer (A) and the glass layer (B). Also, from the viewpoint of work efficiency, the area of ​​the laser-welded portion may be 80% or less, or 60% or less, of 100% of the total area of ​​the contact portion between the resin layer (A) and the glass layer (B). As described above, these progressively defined lower and upper limits can be combined independently. For example, in one embodiment of the structure, the area of ​​the laser-welded portion is preferably 5 to 100%, more preferably 10 to 100%, and even more preferably 20 to 100%, of 100% of the total area of ​​contact between the resin layer (A) and the glass layer (B). For example, it may be 20 to 80%, or 20 to 60%.

[0072] In one embodiment of the above structure, both sides of the glass layer (B) in the laminated portion (I) do not need to be directly sandwiched between the resin layer (A). That is, the laminated portion (I) may not have a multilayer structure of resin layer (A) / glass layer (B) / resin layer (A). In one embodiment of the above structure, it is preferable that both sides of the resin layer (A) in the laminated portion (I) do not have to be directly sandwiched between the glass layer (B). That is, it is preferable that the laminated portion (I) does not have a multilayer structure of glass layer (B) / resin layer (A) / glass layer (B). For example, the structure 10 shown in Figures 1 to 3, or the structure 20 shown in Figure 4, are examples of embodiments in which the laminated portion (I) does not have a multilayer structure of glass layer (B) / resin layer (A) / glass layer (B).

[0073] In one embodiment of the above structure, a glass layer (B) may be laminated on both sides of the resin layer (A) in the laminated portion (I) without an adhesive layer in between. That is, the laminated portion (I) may include a multilayer structure of glass layer (B) / resin layer (A) / glass layer (B). In one embodiment of the above structure, it is preferable that a resin layer (A) is laminated on both sides of the glass layer (B) in the laminated portion (I) without an adhesive layer in between. That is, it is preferable that the laminated portion (I) includes a multilayer structure of resin layer (A) / glass layer (B) / resin layer (A). For example, the structure 10 shown in Figures 1 to 3, or the structure 20 shown in Figure 4, are examples of embodiments in which the laminated portion (I) includes a multilayer structure of resin layer (A) / glass layer (B) / resin layer (A).

[0074] One embodiment of the structure in which a part of it consists of a laminated portion (I) is, for example, a configuration in which the entire structure is a multilayer structure, and two of the multilayers correspond to the laminated portion (I). Another embodiment of the structure in which a part of it consists of a laminated portion (I) is, for example, a configuration in which, within the structure, the total area of ​​at least one surface on the side where the resin layer (A) is laminated to the glass layer (B) is larger than the area of ​​the contact portion with the resin layer (A) on the surface, that is, a configuration in which only a part of the surface of the glass layer (B) is in contact with the resin layer (A), and the portion where the resin layer (A) and the glass layer (B) are laminated corresponds to the laminated portion (I). Therefore, one embodiment of the structure is, for example, a configuration in which the resin layer (A) is laminated to a part of the side of the glass layer (B) where the resin layer (A) is laminated, without an adhesive layer in between, and the resin layer (A) is not laminated to the remaining part of the surface of the glass layer (B) where the resin layer (A) is laminated. Examples of such embodiments include the structure 10 shown in Figures 1 to 3, or the structure 20 shown in Figure 4.

[0075] As described above, in the laminated portion (I), when the resin layer (A) is directly laminated on both sides of the glass layer (B), the resin layer (A) may be laminated on a part of one of the surfaces of the glass layer (B) without an adhesive layer in between, and the resin layer (A) may not be laminated on the remaining part of the surface of the glass layer (B) on which the resin layer (A) is laminated, or the resin layer (A) may be laminated on a part of each surface of both sides of the glass layer (B) without an adhesive layer in between, and the resin layer (A) may not be laminated on the remaining part of the surface of the glass layer (B) on which the resin layer (A) is laminated. Examples of such embodiments include, for example, the structure 10 shown in Figures 1 to 3, or the structure 20 shown in Figure 4.

[0076] One embodiment of the structure in which a part of the structure is composed of a laminated portion (I) is, for example, a configuration in which, within the structure, the total area of ​​at least one surface on the side where the glass layer (B) is laminated is larger than the area of ​​the contact portion with the glass layer (B) on the surface, that is, a configuration in which only a part of the surface of the resin layer (A) is in contact with the glass layer (B), and the portion where the resin layer (A) and the glass layer (B) are laminated corresponds to the laminated portion (I). Therefore, one embodiment of the structure is, for example, a configuration in which the glass layer (B) is laminated on a part of the side of the resin layer (A) where the glass layer (B) is laminated, without an adhesive layer in between, and the glass layer (B) is not laminated on the remaining part of the surface of the resin layer (A) where the glass layer (B) is laminated.

[0077] As described above, in the laminated portion (I), if the glass layer (B) is laminated on both sides of the resin layer (A) without an adhesive layer in between, the resin layer (A) may be laminated on a part of one of the surfaces of the glass layer (B) without an adhesive layer in between, and the resin layer (A) may not be laminated on the remaining part of the surface of the glass layer (B) on which the resin layer (A) is laminated, or the resin layer (A) may be laminated on a part of each surface of both sides of the glass layer (B) without an adhesive layer in between, and the resin layer (A) may not be laminated on the remaining part of the surface of the glass layer (B) on which the resin layer (A) is laminated. Examples of such embodiments include, for example, the structure 10 shown in Figures 1 to 3 or the structure 20 shown in Figure 4.

[0078] In each of the embodiments relating to the laminated portion (I) described above, in the portion where the resin layer (A) and the glass layer (B) are laminated without an adhesive layer in between, it is preferable, as described above, that the surface of the glass contained in the glass layer (B) and the resin layer (A) are directly laminated.

[0079] In one embodiment of the present invention, the structure may include only one laminated portion (I), or it may include multiple laminated portions (I). When the structure includes multiple laminated portions (I), the configuration and shape of the multiple laminated portions (I) may be the same or different. Furthermore, when the structure includes multiple laminated portions (I), it is preferable that at least one of the multiple laminated portions (I) is a preferred embodiment among the embodiments described above. However, when the entire structure is a laminated portion (I), the laminated portion (I) will not have a multilayer structure of glass layer (B) / resin layer (A) / glass layer (B). In other words, the structure is not laminated glass.

[0080] <Thermoplastic Resin Layer (C)> The structure may further include a thermoplastic resin layer (C) as needed. The thermoplastic resin layer (C) (hereinafter also referred to as "layer (C)") is a resin layer other than resin layer (A), and preferably contains thermoplastic resin (c) as its main component. Examples of thermoplastic resin (c) included in layer (C) include EVOH other than EVOH (a), polyolefin resins, various polyamides (nylon 6, nylon 6・6, nylon 6 / 66 copolymer, nylon 11, nylon 12, polymetaxylylene adipamide, etc.), various polyesters (polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc.), polyvinyl chloride, polyvinylidene chloride, polystyrene, polyacrylonitrile, polyurethane, polycarbonate, polyacetal, polyacrylate, and modified polyvinyl alcohol resin.

[0081] The content of the thermoplastic resin (c) in layer (C) is preferably 60 to 100% by mass, more preferably 80 to 100% by mass, even more preferably 90 to 100% by mass, even more preferably 95 to 100% by mass, and even more preferably 97 to 100% by mass, out of 100% by mass of the total amount of resin in layer (C), and may also be 99 to 100% by mass, or even 100% by mass. The content of the thermoplastic resin (c) in layer (C) is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, even more preferably 90 to 100% by mass, and even more preferably 95 to 100% by mass, out of 100% by mass of the total amount of layer (C), and may also be, for example, 50 to 99.99% by mass, 70 to 99.9% by mass, 90 to 99.8% by mass, or 95 to 99.5% by mass. In layer (C), the thermoplastic resin (c) may be used alone or in combination of two or more types. When two or more types of thermoplastic resin (c) are included in the resin layer (C), the content of the thermoplastic resin (c) is the total content of the two or more types of thermoplastic resin (c).

[0082] Furthermore, in one embodiment of the layer (C) included in the structure, it is preferable that the thermoplastic resin (c) contains a polyolefin resin as its main component, and it is more preferable that the layer (C) used in the laminated portion (II) described later contains a polyolefin resin as its main component. When the layer (C) contains a polyolefin resin as its main component, the proportion of the resin constituting the layer (C) is preferably 60 to 100% by mass, more preferably 80 to 100% by mass, even more preferably 90 to 100% by mass, even more preferably 95 to 100% by mass, even more preferably 97 to 100% by mass, even more preferably 99 to 100% by mass, and may also be 100% by mass, out of 100% by mass of the total amount of the resin constituting the layer (C). The polyolefin resin is preferably at least one selected from polyethylene resin and polypropylene resin.

[0083] The type of polyethylene resin is not particularly limited, and examples include high-density polyethylene, low-density polyethylene, linear low-density polyethylene, etc. Linear low-density polyethylene is a resin obtained by polymerizing ethylene with an α-olefin having 3 or more carbon atoms. Examples of α-olefins having 3 or more carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 4-methyl-1-pentene, 4-methyl-hexene-1, 4,4-dimethylpentene-1, etc. The number of carbon atoms in the α-olefin having 3 or more carbon atoms may be, for example, 3 to 20, 3 to 14, or 3 to 10. The polyethylene resin may be used alone or in combination of two or more types.

[0084] There are no particular restrictions on the polymerization catalyst used when polymerizing the polyethylene resin, and examples include catalysts such as Ziegler-Natta catalysts, Phillips catalysts, metallocene catalysts, and post-metallocene catalysts. For example, linear low-density polyethylene polymerized using a metallocene catalyst is produced by copolymerizing ethylene and α-olefin in the presence of a catalyst formed from a compound having at least one ligand having a cyclopentadienyl skeleton and a transition metal of Group 4 of the periodic table as the central metal atom (preferably a compound having zirconium as the central metal atom), an organoaluminum oxy compound, and various components added as needed. Linear low-density polyethylene polymerized using a metallocene catalyst has excellent melt-molding properties, and the resulting layer (C) tends to have an excellent balance of heat resistance, flexibility, and mechanical strength, which is preferable.

[0085] The MFR (190°C, 2.16 kg load) of the polyethylene resin, measured in accordance with ISO 1133-1:2011, is not particularly limited, but is preferably 0.5 to 12.0 g / 10 min, more preferably 0.5 to 10.0 g / 10 min, and even more preferably 0.5 to 8.0 g / 10 min.

[0086] The type of polypropylene resin is not particularly limited, and examples include propylene homopolymers and copolymers of propylene and at least one selected from the group consisting of ethylene and α-olefin monomers having 4 or more carbon atoms. Examples of the α-olefins having 4 or more carbon atoms include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 4-methyl-1-pentene, 4-methyl-hexene-1, and 4,4-dimethylpentene-1. The copolymer may be a random copolymer, a block copolymer, or a random block copolymer. The number of carbon atoms in the α-olefins having 4 or more carbon atoms may be, for example, 4 to 20, 4 to 14, or 4 to 10.

[0087] Specific examples of the copolymer include propylene-ethylene random copolymer, propylene-ethylene block copolymer, propylene-1-butene random copolymer, propylene-1-butene block copolymer, propylene-ethylene-1-butene random copolymer, propylene-ethylene-1-butene block copolymer, propylene-ethylene random block copolymer, and propylene-ethylene-1-butene random block copolymer. The polypropylene resin may be used alone or in combination of two or more types.

[0088] The content of structural units derived from propylene (hereinafter also referred to as "propylene units") in the polypropylene resin is not particularly limited, but for example, it may be 8 to 100 mol%, 10 to 100 mol%, 40 to 100 mol%, 50 to 100 mol%, or 60 to 100 mol% of the total amount of structural units constituting the polypropylene resin.

[0089] The aforementioned polypropylene resin can be produced by known manufacturing methods. While there are no particular limitations on the polymerization catalyst that can be used when polymerizing the polypropylene resin, as long as the effects of the present invention are achieved, examples of such catalysts include Ziegler-Natta catalysts, Phillips catalysts, metallocene catalysts, and post-metallocene catalysts.

[0090] The MFR (at 230°C, 2.16 kg load) of the polypropylene resin, as measured in accordance with ISO 1133-1:2011, is preferably 0.2 to 12.0 g / 10 min, more preferably 0.5 to 10.0 g / 10 min, and even more preferably 1.0 to 8.0 g / 10 min.

[0091] Layer (C) may contain other components besides the thermoplastic resin (c), as long as the effects of the present invention are not hindered. Examples of such other components include resins other than the thermoplastic resin (c), monovalent or polyvalent metal ions, carboxylic acids, phosphoric acid compounds, boron compounds, oxidation accelerators, antioxidants, plasticizers, heat stabilizers (melt stabilizers), photoinitiators, deodorizers, ultraviolet absorbers, antistatic agents, lubricants, colorants, fillers, desiccants, fillers, pigments, dyes, processing aids, flame retardants, and antifogging agents. Specific examples of such other components include, for example, those similar to the corresponding agents described above in the section for resin layer (A). The content of the other components in layer (C) is preferably 0 to 50% by mass, more preferably 0 to 30% by mass, even more preferably 0 to 10% by mass, and even more preferably 0 to 5% by mass, based on 100% by mass of the total amount of layer (C). Alternatively, it may be, for example, 0.01 to 50% by mass, 0.1 to 30% by mass, 0.2 to 10% by mass, or 0.5 to 5% by mass.

[0092] In layer (C), the total content of the thermoplastic resin (c) and the other components as needed does not exceed 100% by mass of the total amount of layer (C). In other words, the total content of the thermoplastic resin (c) and the other components as needed in the resin layer (C) is at most 100% by mass of the total amount of layer (C).

[0093] The thickness of layer (C) is not particularly limited as long as the effects of the present invention are achieved, and can be appropriately selected depending on the application of the structure. In one embodiment of the present invention, the thickness of layer (C) is not particularly limited as long as the effects of the present invention are achieved, but for example, from the viewpoint of rigidity, in any cross section obtained by cutting perpendicular to the interface between layer (A) and layer (C) or the interface between layer (C) and layer (D) in the laminated portion (II) described later, it is preferably 0.1 mm or more, more preferably 0.5 mm or more, even more preferably 1 mm or more, and also preferably 10 mm or less, more preferably 5 mm or less, and even more preferably 3 mm or less. As described above, these lower and upper limits described in stages can be combined independently. For example, in one embodiment of the structure, the thickness of layer (C) is preferably 0.1 to 10 mm, more preferably 0.5 to 5 mm, and even more preferably 1 to 3 mm.

[0094] The method for molding the thermoplastic resin layer (C) is not particularly limited, and known methods for molding resin molded articles such as extrusion molding, injection molding, blow molding, vacuum molding, and pressure molding can be used. In one embodiment of the present invention, the laminated portion (II) described below may be an in-mold molded article in which the thermoplastic resin layer (C) is laminated by injection molding on one surface of the resin layer (A) or on the surface of the adhesive layer (D) opposite to the resin layer (A).

[0095] <Laminated portion (II)> If the structure includes the thermoplastic resin layer (C), the structure may include a laminated portion (II) in which part or all of the thermoplastic resin layer (C) and the resin layer (A) are directly laminated, or in which part or all of the thermoplastic resin layer (C) and the resin layer (A) are laminated via an adhesive layer (D). Here, as stated above, "part or all of the thermoplastic resin layer (C) and the resin layer (A) are directly laminated" means that part or all of layer (C) and layer (A) are laminated without any other layers in between.

[0096] <Adhesive layer (D)> The adhesive layer (D) (hereinafter also referred to as "layer (D)") is a layer that adheres layer (A) to other layers, and preferably a layer that adheres layer (A) to layer (C). In one embodiment of the structure, it is more preferable that part or all of the adhesive layer (D) and resin layer (A) are directly laminated. Here, as stated above, "part or all of the adhesive layer (D) and resin layer (A) are directly laminated" means that part or all of layer (D) and layer (A) are laminated without other layers in between. In one embodiment of the structure, it is even more preferable that part or all of the adhesive layer (D) and resin layer (A) are directly laminated, and that part or all of the adhesive layer (D) and thermoplastic resin layer (C) are directly laminated. Here, as stated above, "part or all of the adhesive layer (D) and thermoplastic resin layer (C) are directly laminated" means that part or all of layer (D) and layer (C) are laminated without other layers in between.

[0097] The layer (D) preferably contains a thermoplastic adhesive resin (d) as its main component. The proportion of the adhesive resin (d) in the resin constituting the layer (D) is preferably 80 to 100% by mass, more preferably 90 to 100% by mass, even more preferably 97 to 100% by mass, even more preferably 99 to 100% by mass, and may also be 100% by mass, based on 100% by mass of the total amount of the resin constituting the layer (D). The content of the adhesive resin (d) in the layer (D) is preferably 60 to 100% by mass, more preferably 80 to 100% by mass, even more preferably 90 to 100% by mass, even more preferably 95 to 100% by mass, even more preferably 97 to 100% by mass, and may also be 99 to 100% by mass, and may also be 100% by mass, based on 100% by mass of the total amount of the resin contained in the layer (D). In layer (D), the content of the adhesive resin (d) is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, even more preferably 90 to 100% by mass, and even more preferably 95 to 100% by mass, of 100% by mass of the total amount of layer (D). Alternatively, it may be, for example, 50 to 99.99% by mass, 70 to 99.9% by mass, 90 to 99.8% by mass, or 95 to 99.5% by mass. In layer (D), one type of adhesive resin (d) may be used alone, or two or more types may be used in combination. When two or more types of adhesive resin (d) are included in layer (D), the content of the adhesive resin (d) is the total content of the two or more types of adhesive resin (d).

[0098] The adhesive resin (d) is preferably a thermoplastic resin that is adhesive to both layer (A) and layer (C), and examples include acid-modified polyolefin resins (carboxylic acid-modified polyolefin resins, sulfonic acid-modified polyolefin resins, etc.) and epoxy-modified polyolefin resins. The adhesive resin (d) is preferably an acid-modified polyolefin resin (acid-modified polyethylene resin, acid-modified polypropylene resin, etc.), and more preferably at least one selected from acid-modified polyethylene resin and acid-modified polypropylene resin. Furthermore, from the viewpoint of further improving adhesion, if the thermoplastic resin layer (C) contains polyethylene resin as the main component of thermoplastic resin (c), it is even more preferable that the adhesive layer (D) contains acid-modified polyethylene resin as the main component. Similarly, if the thermoplastic resin layer (C) contains polypropylene resin as the main component of thermoplastic resin (c), it is even more preferable that the adhesive layer (D) contains acid-modified polypropylene resin as the main component.

[0099] The adhesive resin (d) is preferably a carboxylic acid-modified polyolefin resin (a polyolefin resin having a carboxyl group or an anhydride group thereof), and more preferably at least one selected from carboxylic acid-modified polyethylene resin and carboxylic acid-modified polypropylene resin.

[0100] The carboxylic acid-modified polyolefin resin may be a polyolefin resin having a carboxyl group or its anhydride group. The carboxylic acid-modified polyolefin resin can be obtained, for example, by chemically bonding an ethylenically unsaturated carboxylic acid or its anhydride to an unmodified polyolefin resin through an addition reaction, graft reaction, or the like. As the unmodified polyolefin resin used in the production of the carboxylic acid-modified polyolefin resin, at least one selected from polyethylene resin and polypropylene resin is preferred.

[0101] Examples of the ethylenically unsaturated carboxylic acids and their anhydrides include monocarboxylic acids, monocarboxylic acid esters, dicarboxylic acids, dicarboxylic acid monoesters, dicarboxylic acid diesters, and dicarboxylic acid anhydrides. Specifically, examples include maleic acid, fumaric acid, itaconic acid, maleic anhydride, itaconic anhydride, monomethyl maleic acid, monoethyl maleic acid, diethyl maleic acid, and monomethyl fumaric acid. Of these, dicarboxylic acid anhydrides such as maleic anhydride and itaconic anhydride are preferred, and maleic anhydride is more preferred. That is, the adhesive resin (d) is preferably a maleic anhydride-modified polyolefin resin, and more preferably at least one selected from maleic anhydride-modified polyethylene resin and maleic anhydride-modified polypropylene resin. Therefore, in one embodiment of the adhesive resin (d), the acid-modified polyethylene resin is preferably a carboxylic acid-modified polyethylene resin, more preferably a maleic anhydride-modified polyethylene resin, and the acid-modified polypropylene resin is preferably a carboxylic acid-modified polypropylene resin, and more preferably a maleic anhydride-modified polypropylene resin.

[0102] Carboxylic acid-modified polyolefin resins are obtained, for example, by introducing an ethylenically unsaturated carboxylic acid or its anhydride into an unmodified polyolefin resin by an addition reaction or graft reaction in the presence of a solvent such as xylene and a catalyst such as a peroxide. The amount of carboxylic acid or its anhydride added or grafted (degree of modification) to the unmodified polyolefin resin is preferably 0.01 to 15% by mass, more preferably 0.02 to 10% by mass, based on 100% by mass of the unmodified polyolefin resin.

[0103] The MFR (190°C, 2.16 kg load) of the adhesive resin (d), measured in accordance with ISO 1133-1:2011, may be, for example, 0.2 to 12 g / 10 min or 0.5 to 8.0 g / 10 min. In one embodiment of the structure, when the adhesive resin (d) is an acid-modified polyethylene resin, the MFR (190°C, 2.16 kg load) of the acid-modified polyethylene resin is preferably 0.2 to 12.0 g / 10 min, more preferably 0.5 to 8.0 g / 10 min, and even more preferably 1.0 to 5.0 g / 10 min. In one embodiment of the above structure, when the adhesive resin (d) is an acid-modified polypropylene resin, the MFR (at 230°C, with a 2.16 kg load) of the acid-modified polypropylene resin is preferably 0.2 to 12.0 g / 10 min, more preferably 0.5 to 8.0 g / 10 min, and even more preferably 1.0 to 5.0 g / 10 min.

[0104] Layer (D) may contain other components besides the adhesive resin (d), as long as the effects of the present invention are not hindered. Examples of such other components include resins other than the adhesive resin (d), monovalent or polyvalent metal ions, carboxylic acids, phosphoric acid compounds, boron compounds, oxidation accelerators, antioxidants, plasticizers, heat stabilizers (melt stabilizers), photoinitiators, deodorizers, ultraviolet absorbers, antistatic agents, lubricants, colorants, fillers, drying agents, fillers, pigments, dyes, processing aids, flame retardants, and antifogging agents. Specific examples of such other components include, for example, those similar to the corresponding agents described above in the section for resin layer (A).

[0105] The content of the other components in layer (D) is preferably 0 to 50% by mass, more preferably 0 to 30% by mass, even more preferably 0 to 10% by mass, and even more preferably 0 to 5% by mass, based on 100% by mass of the total amount of layer (D). Alternatively, it may be, for example, 0.01 to 50% by mass, 0.1 to 30% by mass, 0.2 to 10% by mass, or 0.5 to 5% by mass.

[0106] In layer (D), the total content of the adhesive resin (d) and the other components as needed does not exceed 100% by mass of the total amount of layer (D). In other words, the total content of the adhesive resin (d) and the other components as needed in layer (D) is at most 100% by mass of the total amount of layer (D).

[0107] The thickness of layer (D) is not particularly limited as long as the effects of the present invention are achieved, and can be appropriately selected depending on the application of the structure. In one embodiment of the present invention, the thickness of layer (D) is not particularly limited as long as the effects of the present invention are achieved, but for example, from the viewpoint of rigidity, in any cross section obtained by cutting perpendicular to the interface between layer (A) and layer (C) or the interface between layer (C) and layer (D) in the laminated portion (II), it is preferably 0.1 mm or more, more preferably 0.5 mm or more, even more preferably 1 mm or more, and preferably 10 mm or less, more preferably 5 mm or less, and even more preferably 3 mm or less. As described above, these lower and upper limits described in stages can be combined independently. For example, in one embodiment of the structure, the thickness of layer (D) is preferably 0.1 to 10 mm, more preferably 0.5 to 5 mm, and even more preferably 1 to 3 mm.

[0108] There are no particular restrictions on the molding method of the adhesive layer (D), and known methods for molding resin molded products such as extrusion molding, injection molding, blow molding, vacuum molding, and pressure molding can be used.

[0109] <Other Layers> The structure may have layers other than the resin layer (A), glass layer (B), thermoplastic resin layer (C), and adhesive layer (D) described above (hereinafter also referred to as "other layers"). Examples of other layers that the structure may have include other thermoplastic resin layers, printed layers, metal layers, adhesive layers present in areas other than between layers (A) and (B), and in areas other than layer (D), etc.

[0110] [Method for Manufacturing a Structure] Another embodiment of the present invention provides a method for manufacturing a structure, which includes a step of laminating a part or all of at least one surface of a resin layer (X) containing an ethylene-vinyl alcohol copolymer with a part or all of at least one surface of a glass layer (Y) without an adhesive layer in between, and laser welding at least part or all of the interface of the laminated portion (Iz) of the layers (X) and (Y). The method includes a step of laminating a part or all of at least one surface of the resin layer (X) and a part or all of at least one surface of the glass layer (Y) without an adhesive layer in between, thereby manufacturing a structure (Z) in which a part or all of at least one surface of the resin layer (X) and a part or all of at least one surface of the glass layer (Y) are laminated without an adhesive layer in between. As will be described later, in the method for manufacturing the structure (Z), it is preferable to use the resin layer (A) as the resin layer (X) and the glass layer (B) as the glass layer (Y). The preferred method for manufacturing the structure (Z) in which the resin layer (A) is used as the resin layer (X) and the glass layer (B) is used as the glass layer (Y) corresponds to the method for manufacturing a structure according to the embodiment of the present invention described above.

[0111] <Resin layer (X)> The resin layer (X) (hereinafter also referred to as "layer (X)") contains an ethylene-vinyl alcohol copolymer, preferably the ethylene-vinyl alcohol copolymer (a). That is, the resin layer (X) is preferably the resin layer (A). The resin layer (A) is as described above, and the preferred embodiments thereof are also as described above.

[0112] <Glass layer (Y)> The glass layer (Y) (hereinafter also referred to as "layer (Y)") is preferably the glass layer (B). The glass layer (B) is as described above, and the preferred embodiments thereof are also as described above.

[0113] As described above, the manufacturing method of the structure (Z) includes a step of laminating at least one part or all of the surface of the resin layer (X) and at least one part or all of the surface of the glass layer (Y) without an adhesive layer in between, and laser welding at least a part of the interface of the laminated portion (Iz) of the layers (X) and (Y). The laser welding used in this step is also as described above, and the preferred embodiment is the same. By laser welding, a laminated portion (Iz) is formed in which at least one part or all of the surface of the resin layer (X) and at least one part or all of the surface of the glass layer (Y) are welded together. The laminated portion (Iz) is preferably the laminated portion (I) described above. The details of the laminated portion (I) are as described above, and the preferred embodiment is the same.

[0114] The method for molding the resin layer (X) is not particularly limited, and known methods for molding resin molded products such as extrusion molding, injection molding, blow molding, vacuum molding, and pressure molding can be used. In one embodiment of the present invention, the resin layer (X) is preferably obtained by injection molding. That is, the resin layer (X) is preferably an injection molded body. In one embodiment of the manufacturing method, the resin layer (X) is preferably obtained by injection molding before laminating the resin layer (X) and the glass layer (B) and performing laser welding.

[0115] The structure (Z) may further include a thermoplastic resin layer (C), and if it includes a thermoplastic resin layer (C), the structure (Z) may include a laminated portion (IIz) in which part or all of the thermoplastic resin layer (C) and part or all of the resin layer (X) are directly laminated, or in which part or all of the thermoplastic resin layer (C) and part or all of the resin layer (X) are laminated via an adhesive layer (D). Here, the laminated portion (IIz) is preferably the laminated portion (II) described above. The details of the laminated portion (II) are as described above, and the preferred embodiments thereof are the same. The thermoplastic resin layer (C) is as described above, and the preferred embodiments thereof are the same. The adhesive layer (D) is as described above, and the preferred embodiments thereof are the same. The molding method for the thermoplastic resin layer (C) and the molding method for the adhesive layer (D) are as described above, and the preferred embodiments thereof are the same.

[0116] In one embodiment of the above manufacturing method, a thermoplastic resin layer (C), or an adhesive layer (D) and a thermoplastic resin layer (C), may be formed on the resin layer (X), and then at least a part or all of the exposed surface of the resin layer (X) and at least a part or all of the glass layer (Y) may be laminated without an adhesive layer in between, and at least a part of the interface of the laminated portion may be welded by laser welding. In this case, if the resin layer (X) is the layer through which the laser used for laser welding passes, it is preferable that the thermoplastic resin layer (C), or the adhesive layer (D) and thermoplastic resin layer (C) formed on the resin layer (X) in advance, are both layers through which the laser used for laser welding passes. This is to prevent deformation or defects due to heat generation from occurring at locations other than the interface between layer (X) and layer (Y) during laser welding. The same applies when layer (X) is layer (A) and layer (Y) is layer (B), or when layer (X) is layer (A) and layer (Y) is layer (B).

[0117] On the other hand, if the resin layer (X) is the layer that absorbs the laser used for laser welding, it is preferable to irradiate it with laser from the glass layer (Y) side. This is to prevent deformation or defects due to heat generation from occurring at locations other than the interface between layers (X) and (Y) during laser welding. In this case, the thermoplastic resin layer (C) formed on the resin layer (X) beforehand, or the adhesive layer (D) and the thermoplastic resin layer (C), may each be independently a layer through which the laser used for laser welding passes, or a layer that absorbs the laser used for laser welding. However, from the viewpoint of avoiding unintended heat generation and deformation as much as possible, it is preferable that the layer be one through which the laser used for laser welding passes. The same applies when layer (X) is layer (A) and layer (Y) is layer (B), or when layer (X) is layer (A) and layer (Y) is layer (B).

[0118] In each embodiment relating to the laminated portion (Iz) described above, in the portion where the resin layer (X) and the glass layer (Y) are laminated without an adhesive layer in between, it is preferable, as described above, that the glass surface contained in the glass layer (Y) and the resin layer (X) are directly laminated, similar to layers (A) and (B) described above.

[0119] [Applications of the Structure] There are no particular limitations on the applications of the structure, but it can be suitably used as part or component of products that require a structure in which glass and resin are bonded together. Examples include automotive parts, electronic equipment parts, and building materials. Among these, it can be suitably used as an automotive part. That is, one aspect of the present invention is an automotive part having the structure. The applications of the structure obtained by the manufacturing method of the structure according to one aspect of the present invention are similar. Examples of automotive parts include various glass windows (power windows, front windows, roof windows, rear windows, quarter windows, etc.) that include a portion in which a resin member is bonded to a glass member, and the window itself. Examples include a glass window part equipped with a resin bracket used for mounting various in-vehicle equipment (in-vehicle cameras, in-vehicle sensors, mirrors, etc.) and a glass window that includes the part as part thereof; a power window part equipped with a resin glass holder etc. on the door glass and the power window itself; and so on. The structure according to one aspect of the present invention can be suitably used as a power window part and a power window that includes the part as part thereof. However, as mentioned above, laminated glass is not included as an application of the aforementioned structure.

[0120] The embodiments of this model will be described in more detail below with reference to examples, but the embodiments are not limited to these examples.

[0121] The physical properties of the components used in the examples and comparative examples were measured or evaluated by the following methods.

[0122] [Vinyl alcohol unit content, ethylene unit content, and degree of saponification] Dry pellets of EVOH were dissolved in didimethyl sulfoxide (DMSO-d6) containing tetramethylsilane (TMS) as an internal standard and trifluoroacetic acid (TFA) as an additive, and heated at 500 MHz. １Measurements were taken at 80°C using 1H-NMR (JEOL Ltd.: "GX-500"). From the obtained NMR spectrum, the vinyl alcohol unit content, vinyl alcohol unit content, and degree of saponification were determined from the peak intensity ratios of ethylene units, vinyl alcohol units, and vinyl ester units.

[0123] [MFR] The MFR (g / 10min) was measured at 210°C and a 2.16 kg load in accordance with JIS K7210 (2014).

[0124] [Quantitative Determination of Alkali Metals] 0.5 g of the resin layer (A) obtained in each example and comparative example was placed in a Teflon® pressure vessel, and 5 mL of concentrated nitric acid was added to decompose the resin layer (A) at room temperature (25°C) for 30 minutes. After 30 minutes, the pressure vessel was covered, and the resin layer (A) was further decomposed by heating at 150°C for 10 minutes, then at 180°C for 5 minutes, using a wet decomposition apparatus (MWS-2, manufactured by Actac Co., Ltd.). The solution was then allowed to cool naturally to room temperature (25°C) to obtain the processed solution. This processed solution was transferred to a 50 mL volumetric flask (TPX®) and diluted with pure water. The metal content of this solution was analyzed using an ICP emission spectrometer (OPTIMA4300DV, manufactured by PerkinElmer), and the amount of metal (element) was calculated. Calibration curves prepared using commercially available standard solutions were used for quantitative determination.

[0125] The components used in the examples and comparative examples are shown below. [EVOH(a)] ・EVOH(a-1): Vinyl alcohol unit content 76 mol%, degree of saponification 99.9 mol%, ethylene unit content 24 mol%, MFR (210°C, 2.16 kg load) 2.2 g / 10 min, contains sodium acetate equivalent to 200 ppm of sodium ions) ・EVOH(a-2): Vinyl alcohol unit content 68 mol%, degree of saponification 99.9 mol%, ethylene unit content 32 mol%, MFR (210°C, 2.16 kg load) 3.8 g / 10 min, contains sodium acetate equivalent to 180 ppm of sodium ions) ・EVOH(a-3): Vinyl alcohol unit content 52 mol%, degree of saponification 99.9 mol%, ethylene unit content 48 mol%, MFR (210°C, 2.16 kg load) 13.2 g / 10 min, contains sodium acetate equivalent to 5 ppm of sodium ions) EVOH (a-4): Vinyl alcohol unit content 76 mol%, degree of saponification 99.9 mol%, ethylene unit content 24 mol%, MFR (210°C, 2.16 kg load) 2.2 g / 10 min, contains 100 ppm sodium acetate in terms of sodium ions.

[0126] [Glass] ・Glass plate B-1: Infrared absorbing glass (thickness 3 mm, width 25 mm, length 50 mm) ・Glass plate B-2: Silica glass (microscope slide (manufactured by Matsunami Glass Industry Co., Ltd.), thickness 1.5 mm, width 26 mm, length 50 mm)

[0127] [Infrared absorbing material] ・Carbon black: "CB-980B" (manufactured by Mitsubishi Chemical Corporation)

[0128] [Resins other than EVOH] ・Polyamide: "Trepearl (registered trademark) PA6" (manufactured by Toray Industries, Inc.)

[0129] [Example 1] (Molding of resin layer (A)) EVOH (a-1) was molded into a resin plate A-1 with a thickness of 3 mm, a width of 100 mm, and a length of 100 mm using an injection molding machine (Japan Steel Works Ltd. "J85AD") under the following injection molding conditions: ・Cylinder temperature: HP / H1 / H2 / H3 / H4 / NH1 / NH2 = 45°C / 175°C / 245°C / 245°C / 245°C / 230°C / 230°C ・Mold temperature: 50°C (Fabrication of structure) The resin plate A-1 obtained by the injection molding described above was cut into strips measuring 25 mm in width and 50 mm in length. The ends of the cut resin plate A-1 and the ends of the glass plate B-1 were then laminated so that they overlapped by a range of 25 mm horizontally and 30 mm vertically. A laser welding machine (Panasonic Industries, Ltd. "Galvanoscanning Laser Welding Machine VL-W1A00", wavelength λ = 1,070 nm) was used to irradiate the center of the laminated area in a circle with a radius of 1 cm under the conditions of irradiation beam diameter φ2 mm, laser power 70 W, scan speed 10 mm / second, and number of repetitions 1, thereby creating a structure including a laminated section in which a portion of the resin plate A-1 and glass plate B-1 are directly laminated.

[0130] [Example 2] (Preparation of EVOH(a)-containing resin composition) 99.5 parts by mass of EVOH(a-1) and 0.5 parts by mass of carbon black (CB) were melt-kneaded and pelletized to obtain a resin composition pellet for resin layer (A) with a CB content of 0.5% by mass. The extruder used for melt-kneading was a twin-screw extruder with D (mm) = 25, and a fully meshed co-direction screw with L / D = 25 was used. The resin temperature was set to 220°C. (Molding of resin layer (A)) Resin plate A-2 was molded by injection molding in the same manner as in Example 1, except that a resin composition pellet containing EVOH(a-1) and carbon black was used instead of using EVOH(a-1) alone. (Fabrication of the structure) Except for using resin plate A-2 instead of resin plate A-1 and glass plate B-2 instead of glass plate B-1, a structure including a laminated section in which resin plate A-2 and a part of glass plate B-2 are directly laminated was fabricated by laser welding in the same manner as in Example 1.

[0131] [Example 3] (Molding of resin layer (A)) Resin plate A-3 was molded by injection molding in the same manner as in Example 1, except that EVOH (a-2) was used instead of EVOH (a-1). (Fabrication of structure) A structure including a laminated portion in which resin plate A-3 and a part of glass plate B-1 are directly laminated was fabricated by laser welding in the same manner as in Example 1, except that resin plate A-3 was used instead of resin plate A-1.

[0132] [Example 4] (Molding of resin layer (A)) Resin plate A-4 was molded by injection molding in the same manner as in Example 1, except that EVOH (a-3) was used instead of EVOH (a-1). (Fabrication of structure) A structure including a laminated portion in which resin plate A-4 and a part of glass plate B-1 are directly laminated was fabricated by laser welding in the same manner as in Example 1, except that resin plate A-4 was used instead of resin plate A-1.

[0133] [Example 5] (Preparation of EVOH(a)-containing resin composition) 99.5 parts by mass of EVOH(a-4) and 0.5 parts by mass of carbon black (CB) were melt-kneaded and pelletized to obtain a resin composition pellet for resin layer (A) with a CB content of 0.5% by mass. The extruder used for melt-kneading was a twin-screw extruder with D (mm) = 25, and a fully meshed co-direction screw with L / D = 25 was used. The resin temperature was set to 220°C. (Molding of resin layer (A)) Resin plate A-5 was molded by injection molding in the same manner as in Example 1, except that the resin composition pellet containing EVOH(a-4) and carbon black was used instead of using EVOH(a-1) alone. (Fabrication of the structure) Except for using resin plate A-5 instead of resin plate A-1 and glass plate B-2 instead of glass plate B-1, a structure including a laminated section in which resin plate A-5 and a part of glass plate B-2 are directly laminated was fabricated by laser welding in the same manner as in Example 1.

[0134] [Comparative Example 1] (Molding of resin layer (A)) Resin plate CA-1 was molded by injection molding in the same manner as in Example 1, except that the polyamide was used instead of EVOH (a-1). (Fabrication of structure) A structure including a laminated portion in which resin plate CA-1 and a part of glass plate B-1 are directly laminated was fabricated by laser welding in the same manner as in Example 1, except that resin plate CA-1 was used instead of resin plate A-1.

[0135] The structures obtained in each example and comparative example were measured or evaluated by the following methods. The results are shown in Table 1 below.

[0136] [Thickness] The thickness of each layer was measured using a digital micrometer "293-421" manufactured by Mitutoyo Corporation.

[0137] [Elastic Modulus of Resin Layer (A)] The resin layer (A) obtained in each example and comparative example was cut into strips measuring 15 mm (width) x 50 mm (length), and the elastic modulus in the length direction was measured using an Autograph® (AGS-H, manufactured by Shimadzu Corporation) in accordance with ASTM-638 at a test speed of 5 mm / min. Measurements were performed on five strip-shaped samples, and the average value was used for evaluation.

[0138] [Peel Strength] The structures obtained in each example and comparative example (width 25 mm or 26 mm, length 70 mm) were conditioned in an atmosphere of 23°C and 50% RH. Then, using the Instron Japan Company Limited "Universal Material Tester 3367," the ends of the resin plate and the ends of the glass plate were clamped in the tester's chucks under conditions of 23°C and 50% RH, with a chuck distance of 3 cm and a tensile speed of 10 mm / min. The peel strength of the joint between the resin plate and the glass plate was measured and judged according to the following criteria. A D judgment indicates insufficient peel strength, i.e., insufficient bonding between the resin plate and the glass plate. [Judgment Criteria] A: Over 500 N B: 400 N or more, 500 N or less C: 350 N or more, less than 400 N D: Less than 350 N

[0139]

[0140] In Table 1, CB is an abbreviation for carbon black, and PA6 is an abbreviation for polyamide.

[0141] From the results in Table 1, it was confirmed that the structures of Examples 1 to 5 exhibited good peel strength, and that the resin plate and glass plate were well joined by laser welding without the use of adhesive.

[0142] 10, 20, 30 Structure 1 Resin layer (A) 2 Glass layer (B) 3 Laminated section (I) 4 Thermoplastic resin layer (C) 5 Adhesive layer (D) 6 Laminated section (II) 7 Section joined by laser welding

Claims

1. A structure comprising a resin layer (A) and a glass layer (B) containing an ethylene-vinyl alcohol copolymer (a) in which the vinyl alcohol unit content is 50 mol% or more of the total amount of structural units constituting the ethylene-vinyl alcohol copolymer (a), and a laminated portion (I) in which at least one surface of the resin layer (A) and at least one surface of the glass layer (B) are laminated without an adhesive layer in between.

2. The structure according to claim 1, wherein the resin layer (A) contains alkali metal ions at a concentration of 50 ppm or more in the resin layer (A).

3. The structure according to claim 1, wherein the vinyl alcohol unit content is 65 mol% or more of the total amount of structural units constituting the ethylene-vinyl alcohol copolymer (a) (100 mol%).

4. The structure according to claim 1, wherein the resin layer (A) includes an infrared absorbing material.

5. The structure according to claim 4, wherein the infrared absorbing material is carbon black.

6. The structure according to claim 1, wherein the resin layer (A) includes a reinforcing material.

7. The structure according to claim 6, wherein the reinforcing material is glass fiber.

8. The structure according to claim 1, wherein the content of the ethylene-vinyl alcohol copolymer (a) in the resin layer (A) is 50% by mass or more of the total amount of the resin layer (A) by 100% by mass.

9. The structure according to claim 1, wherein the resin layer (A) is an injection-molded body.

10. The structure according to claim 1, wherein the glass layer (B) is infrared absorbing glass.

11. The structure according to claim 1, further comprising a thermoplastic resin layer (C).

12. The structure according to claim 11, having a laminated portion (II) in which part or all of the thermoplastic resin layer (C) and part or all of the resin layer (A) are directly laminated, or in which part or all of the thermoplastic resin layer (C) and part or all of the resin layer (A) are laminated via an adhesive layer (D).

13. The structure according to claim 12, wherein the laminated portion (II) is an in-mold molded article in which a thermoplastic resin layer (C) is laminated by injection molding on one surface of the resin layer (A) or on the surface of the adhesive layer (D) opposite to the resin layer (A).

14. The structure according to claim 1, wherein the laminated portion (I) includes a portion in which at least a part or all of the interface between the resin layer (A) and the glass layer (B) is joined by laser welding.

15. The structure according to claim 1, wherein in the laminated portion (I), both sides of the resin layer (A) are not directly sandwiched between the glass layer (B).

16. The structure according to claim 1, wherein in the laminated portion (I), resin layers (A) are laminated on both sides of a glass layer (B) without an adhesive layer in between.

17. The structure according to claim 1, wherein the resin layer (A) is laminated on a portion of the surface of the glass layer (B) without an adhesive layer in between, and the resin layer (A) is not laminated on the remaining portion of the surface of the glass layer (B) with the resin layer (A) laminated.

18. The structure according to claim 1, wherein the glass layer (B) is laminated on a portion of the side of the resin layer (A) on which the glass layer (B) is laminated, without an adhesive layer in between, and the glass layer (B) is not laminated on the remaining portion of the side of the resin layer (A) on which the glass layer (B) is laminated.

19. An automotive part comprising the structure described in any one of claims 1 to 18.

20. A method for manufacturing a structure (Z) including a laminated portion (Iz) in which at least one surface of a resin layer (X) containing an ethylene-vinyl alcohol copolymer and at least one surface of a glass layer (Y) are laminated without an adhesive layer, comprising the step of laminating a part or all of at least one surface of a resin layer (X) containing an ethylene-vinyl alcohol copolymer and at least one surface of a glass layer (Y) without an adhesive layer, and laser welding at least a part or all of the interface of the laminated portion (Iz) of the layers (X) and (Y).

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