Laminate, bonded article, image display system, and method for producing bonded article

Abstract

The present invention addresses the problem of providing: a laminate with which it is possible to suppress the generation of a bubble-like defect even if foreign matter is present between an adhesive layer and an object to be bonded; a bonded article which uses this laminate; an image display system which uses this laminate; and a method for producing a bonded article, in which this laminate is bonded to an object to be bonded. A laminate according to the present invention has a base material and an adhesive layer, and the oxygen permeability coefficient of the base material is 300 cc / m2∙day∙atm or less.

Description

Laminate, bonded body, image display system, and method for manufacturing bonded body

[0001] The present invention relates to a laminate having a resin substrate and an adhesive layer, a bonded body obtained by bonding this laminate to an object to be bonded, an image display system using this laminate, and a method for manufacturing the bonded body.

[0002] Currently, there is known a head-up display or head-up display system that projects an image onto the windshield of a vehicle or the like to provide the driver with various information such as a map, driving speed, and vehicle status.

[0003] In a head-up display system, a virtual image containing the above-mentioned various pieces of information is projected onto the windshield glass and observed by the driver or the like. The position of the virtual image is located outside the vehicle and forward of the windshield glass. The position of the virtual image is usually 1000 mm or more forward of the windshield glass, and closer to the outside world than the windshield glass. This allows the driver to obtain the above-mentioned various pieces of information while looking at the outside world ahead, without having to move their line of sight significantly. Therefore, when using a head-up display system, it is expected that the driver will be able to drive more safely while obtaining various pieces of information.

[0004] A head-up display system is constructed by, for example, attaching a light-transmitting reflective film, such as a half-mirror film, to a windshield glass to form a projection image display unit. Various types of such reflective films have been proposed.

[0005] For example, Patent Document 1 proposes an optical film that can be used as a display medium in a head-up display system, which has an optical functional layer and a block layer, and the block layer has a cured product of a resin composition containing a thermoplastic resin and an ultraviolet-curable resin. In this optical film, examples of the optical functional layer include a half-wave plate, a quarter-wave plate, a laminate of a half-wave plate and a circularly polarized light reflective layer, and a laminate of a quarter-wave plate and a circularly polarized light reflective layer. Furthermore, an example of the circularly polarized light reflective layer is a light reflective layer using a cholesteric liquid crystal.

[0006] International Publication No. 2021 / 039394

[0007] As disclosed in Patent Document 1, a reflective film used in a head-up display system is used by being attached to glass such as a windshield glass, etc. As a method for attaching a sheet-like material such as a reflective film to a substrate such as a windshield glass, a method conceptually shown in Fig. 7 is known, which utilizes thermocompression bonding using an adhesive layer.

[0008] In this bonding method, first, as shown in the upper part of FIG. 7 , a laminate 100 such as a reflective film laminated with an adhesive layer (not shown) is placed on a curved substrate 102 such as a windshield glass, and then, as shown in the second part of FIG. 7 , it is placed in a bag 106 such as a rubber bag. Next, the pressure inside the bag 106 is reduced while heating, thereby vacuum-heat-pressing the laminate 100 (adhesive layer) to the substrate 102. After the pressure-pressing using the bag is completed, a bonded body obtained by bonding the laminate 100 to the substrate 102 is removed from the bag, and as shown in the third part of FIG. 7 , the bonded body is heat-pressed using an autoclave, and further, the laminate 100 is heat-pressed to the substrate 102. After the heat-pressing using the autoclave is completed, the bonded body is removed from the autoclave, and a bonded body obtained by bonding the laminate 100 to the substrate 102 is obtained, as shown in the lower part of FIG. 7 .

[0009] That is, according to this lamination method, a laminate such as a reflective film having an adhesive layer can be laminated along the surface of an object to be laminated, such as a glass plate. On the other hand, this lamination method has a problem in that foreign matter such as dust adhering to the adhesive layer or the surface of the object to be laminated becomes trapped between the adhesive layer and the object to be laminated, causing bubble-like defects and reducing visibility, and therefore a laminate and lamination method with fewer bubble-like defects are desired.

[0010] Therefore, the present invention aims to solve the problems of the conventional technology, and to provide a laminate that can suppress the occurrence of bubble-like defects even if foreign matter is present between the adhesive layer and the object to be bonded, a bonded body using this laminate, an image display system using this laminate, and a method for manufacturing a bonded body that bonds this laminate to the object to be bonded.

[0011] As a result of intensive research to achieve the above object, the present inventors have found that when a laminate having a substrate and an adhesive layer satisfying a predetermined oxygen permeability coefficient is used for lamination to an object to be laminated, the occurrence of bubble-like defects can be suppressed even if foreign matter is present between the adhesive layer and the object to be laminated, and have completed the present invention. That is, the present inventors have found that the above object can be achieved by the following configuration.

[0012] [1] A laminate having a substrate and an adhesive layer, wherein the substrate has an oxygen permeability coefficient of 300 cc / m ２ [2] The laminate according to [1], wherein the thickness of the adhesive layer is 0.1 μm or more. [3] The bending stiffness coefficient S represented by the following formula 1 is 0.4 × 10 ６ [GPa·μm ３ The laminate according to [1] or [2], wherein the bending stiffness coefficient S is the average tensile modulus of the laminate [GPa] × (thickness of the laminate [μm]) ３[4] The laminate according to any one of [1] to [3], wherein the substrate comprises a protective film and a transparent resin layer. [5] The laminate according to any one of [1] to [4], wherein the substrate further comprises a reflective layer. [6] The laminate according to any one of [1] to [5], wherein the substrate further comprises a retardation layer. [7] The laminate according to any one of [1] to [6], wherein the substrate further comprises a polarization conversion layer. [8] The laminate according to any one of [1] to [7], wherein the substrate further comprises a hard coat layer. [9] The laminate according to any one of [1] to [4], wherein the substrate further comprises a hard coat layer, a reflective layer, a retardation layer, and a polarization conversion layer.

[10] The laminate according to any one of [1] to [9], wherein the substrate comprises a resin substrate.

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

[10] , wherein the adhesive layer contains an antistatic agent.

[12] The surface resistance of the adhesive layer is 1.0 x 10 １４ The laminate according to

[11] , having a resistivity of Ω / □ or less.

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

[12] , which is attached to glass via an adhesive layer.

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

[12] , which is attached to windshield glass via an adhesive layer.

[15] A bonded body comprising glass and the laminate according to any one of [1] to

[12] attached to the glass.

[16] The bonded body according to

[15] , which further comprises glass on the side of the laminate opposite to the side to which the glass is attached.

[17] A bonded body comprising windshield glass and the laminate according to any one of [1] to

[12] attached to the windshield glass.

[18] The bonded body according to

[17] , which further comprises windshield glass on the side of the laminate opposite to the side to which the windshield glass is attached.

[19] An image display system comprising the laminate according to any one of [1] to

[12] , and an image display device that projects an image onto the laminate.

[20] A method for producing a laminate, comprising: Step 1 of laminating an object to be laminated having a curved surface and the laminate according to any one of [1] to

[12] so that the adhesive layer of the laminate faces the object to be laminated, and placing the laminate in a bag; and reducing the pressure inside the bag to conform the laminate to the curved surface without using a mold having a surface corresponding to the curved surface shape, thereby obtaining a laminate; and Step 2 of heat-pressure-bonding the laminate obtained in Step 1.

[0013] According to the present invention, it is possible to provide a laminate that can be laminated to an object while suppressing the occurrence of bubble defects after lamination.

[0014] Fig. 1 is a diagram conceptually showing an example of a laminate of the present invention. Fig. 2 is a conceptual diagram for explaining a method for producing a bonded body of the present invention. Fig. 3 is a conceptual diagram for explaining a method for producing a bonded body of the present invention. Fig. 4 is a diagram conceptually showing an example of an image display system of the present invention. Fig. 5 is a partially enlarged view of Fig. 4. Fig. 6 is a schematic cross-sectional view showing an example of a bonded body of the present invention. Fig. 7 is a conceptual diagram for explaining a conventional method for producing a bonded body.

[0015] The laminate, bonded body, image display system, and manufacturing method of the bonded body of the present invention will be described in detail below based on preferred embodiments shown in the accompanying drawings. Note that the drawings described below are conceptual for explaining the present invention, and the present invention is not limited to the drawings shown below. Therefore, the size, shape, and positional relationship of each member, as well as the thickness of each layer in the laminate and the thickness relationship between each layer, etc., differ from the actual ones. Furthermore, in the following description, "to" indicating a numerical range includes the values ​​written on both sides. For example, ε １ is the number α １ ~Number β １ That is, ε １ The range of α １ and the number β １ The range includes α １ ≦ε １ ≦β １ In addition, in the present specification, in the numerical ranges described in stages, the upper limit or lower limit value described in a certain numerical range may be replaced with the upper limit or lower limit value of another numerical range described in stages. In addition, in the numerical ranges described in the present specification, the upper limit or lower limit value described in a certain numerical range may be replaced with a value shown in the examples.

[0016] [Laminate] The laminate of the present invention has a substrate and an adhesive layer. FIG. 1 conceptually shows an example of the laminate of the present invention. The laminate 10 of the illustrated example has, from the bottom in the figure, a protective film 12, a hard coat layer 14, a transparent resin layer 16, a retardation layer 18, a reflective layer 20, a polarization conversion layer 24, and an adhesive layer 26. In the figure, the protective film 12 to the polarization conversion layer 24 correspond to the substrate 11 in the laminate 10. In other words, the substrate of the laminate of the present invention refers to all layer structures other than the adhesive layer constituting one surface of the laminate (excluding the substrate to be attached). For example, even if an adhesive layer is present between the retardation layer 18 and the reflective layer 20, this adhesive layer is a layer structure included in the substrate. Furthermore, the substrate of the laminate of the present invention does not include glass, as the laminate of the present invention is suitable for application to glass.

[0017] The laminate of the present invention has an oxygen permeability coefficient of the substrate of 300 cc / m ２ By being 1 / 2 day atm or less, it is possible to suppress the occurrence of bubble-like defects when the laminate is attached to an object to be laminated. Here, the reason why the occurrence of bubble-like defects can be suppressed is not clear in detail, but the present inventors speculate as follows. First, the present inventors investigated the cause of the inability to suppress the occurrence of bubble-like defects in the prior art, and speculated that this is because air penetrates or dissolves from the surface of the substrate opposite the adhesive layer during heat and pressure bonding (for example, autoclave treatment) when producing a laminate, and the amount of air dissolved in the substrate and adhesive layer increases, so that the air around the foreign matter is no longer absorbed by the adhesive layer or substrate. Therefore, in the present invention, an oxygen permeability coefficient of 300 cc / m ２ By using a substrate with an oxygen permeability of 300 cc / m or less, the increase in the amount of dissolved air in the substrate and adhesive layer was suppressed during the heat and pressure bonding process to prepare the laminate, and it was therefore possible to take in the air around the foreign matter into the adhesive layer or substrate, thereby suppressing the occurrence of defects on the air bubbles. ２ ・day・atm or less, 200cc / m ２· day · atm or less is preferable, 150 cc / m ２ ·day·atm or less is more preferable, and 100cc / m ２ More preferably, it is 15 cc / m or less. ２ · day · atm or less is preferable, 10 cc / m ２ ·day·atm or less is more preferable, and 2 cc / m ２ It is more preferable that the oxygen permeability coefficient of the substrate is 1×10 2 × day 2 × atm or less. －１５ cc / m ２ It is preferable to set the temperature at 1×10 －２ cc / m ２ By setting the oxygen permeability coefficient to the above value or more, it is possible to suppress air remaining between the adhesive layer and the object to be pasted after thermocompression bonding.

[0018] The laminate of the present invention has a bending stiffness coefficient S, expressed by the following formula 1, of 0.4×10 ６ [GPa·μm ３ Flexural rigidity coefficient S = average tensile modulus of laminate [GPa] × (thickness of laminate [μm]) Equation 1 ３Here, the average tensile modulus for calculating the bending stiffness coefficient S may be measured by the method described in the Examples below. Specific methods will be described in detail in the Examples. When measuring the average tensile modulus, first, using one in-plane direction of the laminate as a reference, sample pieces of a predetermined size are cut out along the length direction in each direction rotated 45° clockwise from that direction. Next, the cut sample pieces are placed in a tensile tester so that the chuck spacing in the measurement direction is 100 mm, and stretched at a measurement temperature of 25°C and a stretching rate of 300 mm / min so that the chuck spacing increases, to obtain a stress-strain curve. The tensile modulus is calculated by linear regression of the obtained curve. The in-plane direction of the laminate corresponding to the length direction of the test piece showing the maximum tensile modulus of the above sample pieces is defined as the first direction, and the direction perpendicular to the first direction is defined as the second direction. The average value of the tensile modulus in the first direction and the tensile modulus in the second direction is defined as the average tensile modulus of the laminate. The specific method will be described in detail in the Examples. When measuring the average thermal shrinkage, first, using one in-plane direction of the laminate as a reference, a sample piece of a predetermined size is cut out, with its length aligned in each direction rotated 45° clockwise from that direction. Next, two reference lines are marked in the width direction of the cut sample piece at intervals of 100 mm. The sample piece is then placed in a heating oven at 140°C for 45 minutes under no tension, and then cooled to room temperature, and the distance between the two reference lines is measured. The thermal shrinkage of the sample piece is measured from the distance before and after the treatment. The in-plane direction of the laminate corresponding to the length direction of the test piece showing the largest thermal shrinkage among the thermal shrinkages of each sample piece is defined as the first direction, and the direction perpendicular to the first direction is defined as the second direction. The average value of the thermal shrinkage in the first direction and the thermal shrinkage in the second direction is defined as the average thermal shrinkage of the laminate.

[0019] The lower limit of the average tensile elastic modulus is not particularly limited, but is preferably 0.01 GPa or more, more preferably 0.1 GPa or more. The upper limit of the average tensile elastic modulus is not particularly limited, but is preferably 10.0 GPa or less, more preferably 8.0 GPa or less.

[0020] The lower limit of the thickness of the laminate is not particularly limited, but is preferably 100 μm or more, more preferably 150 μm or more. The upper limit of the thickness of the laminate is not particularly limited, but is preferably 1000 μm or less, more preferably 400 μm or less. The thickness (film thickness) of the laminate may be measured by the method described in the examples below.

[0021] [Substrate] The substrate 11 of the laminate of the present invention has an oxygen permeability coefficient of 300 cc / m ２ The substrate is not particularly limited as long as it has a viscosity of 1000 ppm or less, and may be a substrate consisting of only one layer or a substrate consisting of multiple layers. Suitable examples of such substrates include a protective film, a hard coat layer, a transparent resin layer, a retardation layer, a reflective layer, an intermediate layer, and a polarization conversion layer. Among these, it is preferable to use at least a resin substrate (i.e., a film or layer containing 50% by mass or more of a resin material).

[0022] <Protection Film> The substrate 11 included in the laminate of the present invention may include a protection film 12. When the substrate 11 includes the protection film 12, it is preferable that the substrate further includes a transparent resin layer 16.

[0023] 1, the protection film 12 is applied to the surface opposite the adhesive layer 26. The protection film 12 may be laminated when the autoclave treatment is performed, and may be laminated, for example, before thermocompression bonding or after thermocompression bonding but before autoclave treatment. The protection film 12 may be peeled off after autoclave treatment when it is no longer needed.

[0024] Furthermore, the protective film 12 may be peeled off before the heat treatment as long as the oxygen permeability coefficient of the substrate satisfies the above. When the protective film 12 is peeled off before the heat treatment, it is preferable to peel it off after the laminate is placed on the substrate, since this can protect the substrate from adhesion of foreign matter and scratches.

[0025] Examples of materials for the protective film 12 include resins such as polyethylene resins, polypropylene resins, polystyrene resins, and polyethylene terephthalate resins; nitrile rubbers such as acrylonitrile-butadiene rubbers, butyl rubber, acrylic rubbers, thermoplastic elastomers such as thermoplastic polyolefin elastomers (TPO), thermoplastic polyurethane elastomers (TPU), thermoplastic polyester elastomers (TPEE), thermoplastic polyamide elastomers (TPAE), and diene elastomers (1,2-polybutadiene, etc.); silicone elastomers, and fluorine-based elastomers. A film formed from one or more of these materials in a single layer or multilayer configuration can be used as the protective film 12. The material for the protective film is not particularly limited as long as the oxygen permeability coefficient of the substrate satisfies the above criteria; however, polyethylene terephthalate resins are preferred in terms of oxygen permeability coefficient.

[0026] The thickness of the protective film 12 is not particularly limited as long as the oxygen permeability coefficient of the substrate satisfies the above-mentioned range, but is preferably 25 μm or more, more preferably 75 μm or more, and even more preferably 125 μm or more. There is no particular upper limit, but it is often 500 μm or less. Having the protective film 12 with the above-mentioned thickness is preferable because it makes the laminate easier to handle.

[0027] The tensile modulus of the protective film 12 is not particularly limited, but is preferably 0.001 GPa or more, more preferably 0.01 GPa or more, even more preferably 0.1 GPa or more, and particularly preferably 1.0 GPa or more. There is no particular upper limit, but it is often 12.0 GPa or less.

[0028] The tensile modulus of the protective film 12 can be varied, for example, depending on the material constituting the protective film 12. In general, the tensile modulus tends to increase by increasing the molecular weight and / or crystallinity of the resin or elastomer. Furthermore, the tensile modulus of the protective film 12 in the stretching direction can be increased by stretching the protective film 12. Even when the protective film 12 is made up of multiple layers, the tensile modulus refers to the tensile modulus of the protective film as a whole.

[0029] It is desirable for the protective film 12 to shrink when heated. Generally, the protective film 12 is also stretched during its manufacturing process, and residual stress resulting from the stretching exists. Therefore, this residual stress can be utilized to cause the protective film 12 to shrink thermally by heating during curved surface conforming. The temperature at which the protective film 12 heat shrinks varies depending on the material of the protective film 12, but it is preferable for the protective film 12 to shrink in the range of 80 to 200°C, and more preferably in the range of 90 to 140°C, which is the heating temperature used in typical curved surface conforming processes.

[0030] The protective film 12 may have an adhesive layer on at least one side, or may be a self-adhesive protective film having adhesive properties.

[0031] The protective film 12 may be vapor-deposited with an inorganic material such as silica or alumina in order to reduce the oxygen permeability coefficient of the substrate, and one or more overcoats may be further formed on the vapor-deposited surface.

[0032] <Hard Coat Layer> The substrate 11 included in the laminate of the present invention may include a hard coat layer (HC layer) 14. The inclusion of the HC layer 14 provides abrasion resistance that makes it difficult to scratch even when rubbed with a hard substance, scratch resistance that makes it difficult to scratch even when pressed with a hard substance, and stain resistance that allows stains to be easily wiped off even when stains adhere.

[0033] The HC layer 14 is preferably formed by polymerizing and curing at least one compound selected from the group consisting of polysiloxane-containing compounds having polymerizable groups in their molecules and fluorine-containing compounds having polymerizable groups in their molecules, and a polymerizable compound other than these compounds having polymerizable groups in their molecules, as described below. It is more preferable that these polymerizable groups are radically polymerizable groups. This allows the compound selected from the group consisting of polysiloxane-containing compounds and fluorine-containing compounds to exist in a bonded state with the polymerizable compound forming the HC layer 14, thereby providing better antifouling properties. When the compound selected from the group consisting of polysiloxane-containing compounds and fluorine-containing compounds has a polymerizable group, the polymerizable group in the compound selected from the group consisting of polysiloxane-containing compounds and fluorine-containing compounds described below reacts to form a bond and is present in the HC layer 14.

[0034] In addition, when the HC layer 14 has a laminate structure of two or more layers described below, it is preferable that the compound selected from the group consisting of polysiloxane-containing compounds and fluorine-containing compounds is contained in at least the HC layer farthest from the transparent resin layer 16, and more preferably, only the HC layer farthest from the transparent resin layer 16 contains the compound. When at least one compound selected from the group consisting of polysiloxane-containing compounds having a polymerizable group in the molecule and fluorine-containing compounds having a polymerizable group in the molecule is used, it is preferable that the HC layer 14 farthest from the transparent resin layer 16 is a cured film of at least the above compound, and more preferably, only the HC layer 14 farthest from the transparent resin layer 16 is a cured film of the above compound. Specific embodiments of the HC layer 14 will be described below, but the present invention is not limited to the following embodiments.

[0035] The fluorine-containing compound is not particularly limited, and any compound having a fluorine atom in the molecule can be used as long as it can impart abrasion resistance and antifouling properties to the HC layer 14. As the fluorine-containing compound, a fluorine-containing antifouling agent that exhibits the properties of an antifouling agent is preferably used.

[0036] The fluorine-containing compound may be any of a monomer, an oligomer, and a polymer. The fluorine-containing compound preferably has a substituent that contributes to bond formation or compatibility with other components in the HC layer 14 (for example, a polysiloxane-containing compound, a polymerizable monomer that is a component of the resin, or a resin). The substituents may be the same or different, and it is preferable that there are multiple substituents. The substituent is preferably a polymerizable group, and may be any polymerizable reactive group that exhibits any of radical polymerization, cationic polymerization, anionic polymerization, condensation polymerization, and addition polymerization. Preferred examples of the substituent include an acryloyl group, a methacryloyl group, a vinyl group, an allyl group, a cinnamoyl group, an epoxy group, an oxetanyl group, a hydroxyl group, a polyoxyalkylene group, a carboxyl group, and an amino group. Among them, a radical polymerizable group is preferred, and an acryloyl group or a methacryloyl group is more preferred. The fluorine-containing compound may be a polymer or an oligomer with a compound that does not contain a fluorine atom.

[0037] The polysiloxane-containing compound in the present invention is not particularly limited, and examples thereof include compounds having a polysiloxane structure in the molecule. The polysiloxane structure of the polysiloxane-containing compound may be any of linear, branched, and cyclic. As the polysiloxane-containing compound, a polysiloxane antifouling agent exhibiting the properties of an antifouling agent is preferably used.

[0038] The content of the polysiloxane-containing compound in the HC layer-forming curable composition used to form the HC layer 14 is preferably 0.01 to 5 mass%, more preferably 0.1 to 5 mass%, still more preferably 0.5 to 5 mass%, and particularly preferably 0.5 to 2 mass%, relative to the total solid content in the HC layer-forming curable composition. When the HC layer 14 has a laminate structure of two or more layers, as described below, the content refers to the amount added in the HC layer-forming curable composition that forms the HC layer 14 containing the polysiloxane compound.

[0039] The HC layer 14 can be obtained by irradiating an HC layer-forming curable composition with active energy rays to cure it. In this specification, the term "active energy rays" refers to ionizing radiation, and includes X-rays, ultraviolet rays, visible light, infrared rays, electron beams, α rays, β rays, γ rays, etc.

[0040] The curable composition for forming the HC layer 14 contains at least one component that has the property of being cured by irradiation with active energy rays (hereinafter also referred to as the "active energy ray-curable component"). The active energy ray-curable component is preferably at least one polymerizable compound selected from the group consisting of radically polymerizable compounds and cationically polymerizable compounds. In this specification, the term "polymerizable compound" refers to a compound having a polymerizable group in its molecule, and there may be at least one polymerizable group per molecule. The polymerizable group is a group that can participate in a polymerization reaction, and specific examples include groups contained in the various polymerizable compounds described below. Examples of polymerization reactions include various polymerization reactions such as radical polymerization, cationic polymerization, and anionic polymerization. The HC layer 14 is preferably obtained by irradiating a curable composition for forming the HC layer, which contains at least one compound selected from the group consisting of polysiloxane-containing compounds having a polymerizable group in their molecules and fluorine-containing compounds having a polymerizable group in their molecules, and a polymerizable compound other than these compounds having a polymerizable group in their molecules, with active energy rays to polymerize and cure the composition. In this case, the polymerizable groups of the polysiloxane-containing compound, the fluorine-containing compound, and the polymerizable compound are preferably radically polymerizable groups. The HC layer 14 may have a single-layer structure or a laminated structure of two or more layers, and an HC layer having a single-layer structure or a laminated structure of two or more layers, which will be described in detail below, is preferred.

[0041] As a preferred embodiment of the curable composition for forming a single-layer HC layer, a first embodiment includes a curable composition for forming a HC layer containing at least one polymerizable compound having two or more ethylenically unsaturated groups in one molecule. The ethylenically unsaturated group refers to a functional group containing an ethylenically unsaturated double bond. A second embodiment includes a curable composition for forming a HC layer containing at least one radically polymerizable compound and at least one cationically polymerizable compound.

[0042] The curable composition for forming an HC layer preferably contains a polymerization initiator, and more preferably contains a photopolymerization initiator. The curable composition for forming an HC layer containing a radical polymerizable compound preferably contains a radical photopolymerization initiator, and the curable composition for forming an HC layer containing a cationic polymerizable compound preferably contains a cationic photopolymerization initiator. Only one type of radical photopolymerization initiator may be used, or two or more types with different structures may be used in combination. This also applies to cationic photopolymerization initiators. Each photopolymerization initiator will be explained in turn below.

[0043] The radical photopolymerization initiator may be any one that can generate radicals as active species upon irradiation with light, and known radical photopolymerization initiators can be used without any limitations. The radical photopolymerization initiator and auxiliary agent can be synthesized by known methods and are also available as commercially available products. Preferred examples of commercially available radical photopolymerization initiators include Irgacure (127, 651, 184, 819, 907, 1870 (CGI-403 / Irg184=7 / 3 mixed initiator, 500, 369, 1173, 2959, 4265, 4263, etc.), OXE01) manufactured by BASF, KAYACURE (DETX-S, BP-100, BDMK, CTX, BMS, 2-EAQ, ABQ, CPTX, EPD, ITX, QTX, BTC, MCA, etc.) manufactured by Nippon Kayaku, and Esacure (KIP100F, KB1, EB3, BP, X33, KT046, KT37, KIP150, TZT) manufactured by Sartomer.

[0044] The content of the radical photopolymerization initiator in the curable composition for forming an HC layer is not particularly limited, and may be appropriately adjusted within a range in which the polymerization reaction (radical polymerization) of the radical polymerizable compound proceeds satisfactorily. The content is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, and even more preferably 1 to 10 parts by mass, relative to 100 parts by mass of the radical polymerizable compound contained in the curable composition for forming an HC layer.

[0045] The cationic photopolymerization initiator may be any one that can generate cations as active species upon irradiation with light, and known cationic photopolymerization initiators can be used without any restrictions.

[0046] As the cationic photopolymerization initiator, a diazonium salt, an iodonium salt, a sulfonium salt, or an iminium salt is preferred from the viewpoint of the sensitivity of the photopolymerization initiator to light, the stability of the compound, etc. Furthermore, an iodonium salt is preferred from the viewpoint of weather resistance.

[0047] Specific commercially available examples of iodonium salt-based cationic photopolymerization initiators include B2380 manufactured by Tokyo Chemical Industry Co., Ltd., BBI-102 manufactured by Midori Chemical Industry Co., Ltd., WPI-113 manufactured by Wako Pure Chemical Industries, Ltd., WPI-124 manufactured by Wako Pure Chemical Industries, Ltd., WPI-169 manufactured by Wako Pure Chemical Industries, Ltd., WPI-170 manufactured by Wako Pure Chemical Industries, Ltd., and DTBPI-PFBS manufactured by Toyo Synthetic Chemical Industry Co., Ltd.

[0048] Specific examples of iodonium salt compounds that can be used as cationic photopolymerization initiators include the following compounds PAG-1 and PAG-2.

[0049]

[0050]

[0051] The content of the cationic photopolymerization initiator in the curable composition for forming the HC layer is not particularly limited, and may be appropriately adjusted within a range in which the polymerization reaction (cationic polymerization) of the cationic polymerizable compound proceeds satisfactorily. The content is preferably 0.1 to 200 parts by mass, more preferably 1 to 150 parts by mass, and even more preferably 2 to 100 parts by mass, relative to 100 parts by mass of the cationic polymerizable compound.

[0052] Other photopolymerization initiators include those described in paragraphs 0052 to 0055 of JP-A-2009-204725, the contents of which are incorporated herein by reference.

[0053] -Components that can be optionally contained in the curable composition for forming an HC layer- The curable composition for forming an HC layer contains at least one component that has the property of being cured by irradiation with active energy rays and a compound selected from the group consisting of polysiloxane-containing compounds and fluorine-containing compounds, and can optionally contain, and preferably contains, at least one polymerization initiator. The details of these are as described above.

[0054] The curable composition for forming an HC layer preferably contains a solvent. The solvent is preferably an organic solvent, and one or more organic solvents can be mixed in any desired ratio. Specific examples of organic solvents include alcohols such as methanol, ethanol, propanol, n-butanol, and i-butanol; ketones such as acetone, methyl isobutyl ketone, methyl ethyl ketone, and cyclohexanone; cellosolves such as ethyl cellosolve; aromatics such as toluene and xylene; glycol ethers such as propylene glycol monomethyl ether; acetate esters such as methyl acetate, ethyl acetate, and butyl acetate; and diacetone alcohol. Among these, it is preferable to use a mixture of cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, butyl acetate, isopropyl acetate, and methyl acetate in any desired ratio.

[0055] The amount of solvent in the HC layer-forming curable composition can be adjusted as appropriate within a range that ensures the coating suitability of the composition. The solvent content is preferably 50 to 500 parts by mass, more preferably 80 to 200 parts by mass, relative to 100 parts by mass of the total amount of the polymerizable compound and the photopolymerization initiator. The solid content of the HC-forming curable composition is preferably 10 to 90% by mass, more preferably 50 to 80% by mass, and even more preferably 65 to 75% by mass, relative to the total mass of the HC-forming curable composition.

[0056] In addition to the above components, the curable composition for forming an HC layer can contain any amount of one or more known additives. Examples of additives include surface conditioners, polymerization inhibitors, polyrotaxanes, etc. For details, see, for example, paragraphs 0032 to 0034 of JP 2012-229412 A. However, the additives are not limited to these, and various additives that can generally be added to curable compositions for forming an HC layer can be used.

[0057] The curable composition for forming the HC layer can be prepared by mixing the above-described various components simultaneously or sequentially in any order. The preparation method is not particularly limited, and a known mixer or the like can be used for preparation.

[0058] The thickness of the HC layer 14 is preferably 1 μm or more, more preferably 1 to 100 μm, even more preferably 1 to 20 μm, particularly preferably 3 to 20 μm, and most preferably 5 to 20 μm. The thickness of the HC layer 14 is measured by cutting the HC layer 14 with a microtome to cut out a cross section, staining it overnight with an approximately 3% by mass aqueous solution of osmium tetroxide, cutting out the surface again, and observing the cross section using a scanning electron microscope (SEM).

[0059] An HC layer can be formed by applying a curable composition for forming an HC layer and irradiating it with active energy rays. Coating can be performed by known coating methods such as dip coating, air knife coating, curtain coating, roller coating, die coating, wire bar coating, and gravure coating. The HC layer can also be formed as an HC layer having a laminate structure of two or more layers (e.g., about two to five layers) by simultaneously or sequentially applying two or more compositions having different compositions.

[0060] The HC layer can be formed by irradiating the applied HC layer-forming curable composition with active energy rays. For example, when the HC layer-forming curable composition contains a radical polymerizable compound, a cationic polymerizable compound, a radical photopolymerization initiator, and a cationic photopolymerization initiator, the polymerization reactions of the radical polymerizable compound and the cationic polymerizable compound can be initiated and progressed by the action of the radical photopolymerization initiator and the cationic photopolymerization initiator, respectively. The wavelength of the irradiated light can be determined depending on the type of polymerizable compound and polymerization initiator used. Examples of light sources for light irradiation include high-pressure mercury lamps, ultra-high-pressure mercury lamps, carbon arc lamps, metal halide lamps, xenon lamps, chemical lamps, electrodeless discharge lamps, and LEDs (light-emitting diodes), all of which emit light in the 150 to 450 nm wavelength range. The light irradiation dose is 30 to 3,000 mJ / cm. ２ is preferred, and 100 to 1500 mJ / cm ２ is more preferable. A drying treatment may be carried out as necessary either before or after light irradiation, or both. The drying treatment can be carried out by blowing hot air, placing the composition in a heating furnace, transporting the composition in the heating furnace, or the like. When the curable composition for forming an HC layer contains a solvent, the heating temperature is not particularly limited as long as it is set to a temperature at which the solvent can be dried and removed. Here, the heating temperature refers to the temperature of the hot air or the atmospheric temperature in the heating furnace.

[0061] When the substrate 11 has an HC layer, it is desirable that the HC layer be provided between the protective film 12 and the transparent resin layer 16 .

[0062] <Transparent Resin Layer> As described above, the substrate 11 of the laminate of the present invention may include the transparent resin layer 16. The material of the transparent resin layer 16 is not particularly limited as long as the oxygen permeability coefficient of the laminate 10 satisfies the specified range. The transparent resin layer 16 is preferably transparent in the visible light region.

[0063] There are no particular limitations on the material of the transparent resin layer 16. Examples of the transparent resin layer 16 include plastic films such as polyesters such as polyethylene terephthalate (PET), polycarbonates, acrylic resins such as polymethyl methacrylate (PMMA) and styrene-methacrylic acid copolymers, epoxy resins, polyurethanes, polyamides, polyimides, polyolefins, cellulose derivatives, and silicones. Preferred examples of the transparent resin layer 16 include cellulose acylate films and polyethylene terephthalate films.

[0064] The thickness of the transparent resin layer 16 is not particularly limited as long as the laminate satisfies the above oxygen permeability coefficient, but is preferably 25 μm or more, more preferably 40 μm or more. There is no particular upper limit, but it is often 500 μm or less.

[0065] The tensile modulus of the transparent resin layer 16 is not particularly limited, but is preferably 1.0 GPa or more, more preferably 2.5 GPa or more, even more preferably 3.0 GPa or more, particularly preferably 3.5 GPa or more, and most preferably 4.0 GPa or more. There is no particular upper limit, but it is often 12.0 GPa or less.

[0066] The tensile modulus of the transparent resin layer 16 can be varied, for example, depending on the type of resin constituting the transparent resin layer 16. In general, the tensile modulus tends to increase by increasing the molecular weight and / or crystallinity of the resin. Furthermore, the tensile modulus of the transparent resin layer 16 in the stretching direction can be increased by stretching the transparent resin layer 16. Even when the transparent resin layer 16 is made up of multiple layers, the tensile modulus refers to the tensile modulus of the transparent resin layer 16 as a whole.

[0067] The transparent resin layer 16 may be formed by any method, for example, a melt casting method or a solution casting method.

[0068] (Melt film-forming method) When the transparent resin layer 16 is formed by the melt film-forming method, the melt film-forming method preferably includes a melting step of melting the resin in an extruder, a step of extruding the molten resin into a sheet from a die, and a step of forming it into a film. Depending on the resin material, a filtering step of the molten resin may be provided after the melting step, or the molten resin may be cooled when extruded into a sheet. Specific melt film-forming methods will be described below, but the present invention is not limited thereto.

[0069] The method for producing the transparent resin layer preferably includes a melting step in which the resin is melted in an extruder, a filtration step in which the molten resin is filtered through a filtration device equipped with a filter, a film forming step in which the filtered resin is extruded into a sheet form through a die and brought into close contact with a cooling drum to be cooled and solidified to form an unstretched transparent resin layer, and a stretching step in which the unstretched transparent resin layer is stretched uniaxially or biaxially. This configuration allows the transparent resin layer to be produced. If the pore size of the filter used in the filtration step of the molten resin is 1 μm or less, foreign matter can be sufficiently removed. As a result, the surface roughness of the resulting transparent resin layer in the film width direction can be controlled. Specifically, the method for forming the transparent resin layer includes the following steps.

[0070] The method for producing the transparent resin layer includes a melting step in which the resin is melted in an extruder. Preferably, the resin or a mixture of the resin and additives is dried to a moisture content of 200 ppm or less and then introduced into a single-screw (single-screw) or twin-screw extruder and melted. To suppress decomposition of the resin, it is also preferable to melt the resin in nitrogen or vacuum. Detailed conditions can be found in Japanese Patent No. 4,962,661, paragraphs 0051-0052 (US 2013 / 0100378, paragraphs 0085-0086), and the details of these publications are incorporated herein by reference. The extruder is preferably a single-screw kneading extruder. Furthermore, it is also preferable to use a gear pump to increase the delivery accuracy of the molten resin (melt).

[0071] The method for producing the transparent resin layer includes a filtration step of filtering the molten resin through a filtration device equipped with a filter, and the pore size of the filter used in the filtration step is preferably 1 μm or less. Only one set of filtration devices having filters with such pore sizes may be installed in the filtration step, or two or more sets of filtration devices may be installed.

[0072] The method for producing the transparent resin layer includes a film forming step in which the filtered resin is extruded through a die into a sheet, which is then brought into close contact with a cooling drum and cooled and solidified to form an unstretched transparent resin layer.

[0073] When the melted (and kneaded) and filtered resin (melt containing the resin) is extruded through a die into a sheet, it may be extruded as a single layer or as a multilayer. When extruding a multilayer, for example, a layer containing an ultraviolet absorber and a layer not containing an ultraviolet absorber may be laminated. A three-layer structure with an ultraviolet absorber-containing layer as the inner layer is more preferable because it can suppress deterioration of the polarizer due to ultraviolet rays and suppress bleed-out of the ultraviolet absorber. When a transparent resin layer is produced by extruding a multilayer, the thickness of the inner layer of the resulting transparent resin layer relative to the thickness of all layers is preferably 50 to 99%, more preferably 60 to 99%, and even more preferably 70 to 99%. Such lamination can be performed using a feedblock die and a multi-manifold die.

[0074] According to paragraph 0059 of JP 2009-269301 A, it is preferable to extrude a resin (a melt containing a resin) extruded into a sheet form from a die onto a cooling drum (a casting drum), cool and solidify it, and obtain an unstretched transparent resin layer (raw sheet).

[0075] In the above-mentioned method for producing a transparent resin layer, the temperature of the resin extruded from the die is preferably 280 to 320°C, more preferably 285 to 310°C. It is preferable that the temperature of the resin extruded from the die in the melting step is 280°C or higher, since this reduces the amount of unmelted raw resin and suppresses the generation of foreign matter. It is preferable that the temperature of the resin extruded from the die in the melting step is 320°C or lower, since this reduces the decomposition of the resin and suppresses the generation of foreign matter. The temperature of the resin extruded from the die can be measured non-contact on the surface of the resin using a radiation thermometer (manufactured by Hayashi Denko, model number: RT61-2, emissivity 0.95).

[0076] In the method for producing the transparent resin layer, it is preferable to use an electrostatically applied electrode when the resin is brought into close contact with the cooling drum in the film forming step, which allows the resin to be tightly adhered to the cooling drum without roughening the film surface.

[0077] In the method for producing the transparent resin layer, the temperature of the resin when it is brought into close contact with the cooling drum (the point where the molten resin extruded from the die first comes into contact with the cooling drum) is preferably 280°C or higher. This increases the electrical conductivity of the resin, allowing it to be tightly adhered to the cooling drum by applying static electricity, and suppressing roughness of the film surface. The temperature of the resin when it is brought into close contact with the cooling drum can be measured by contactless measurement of the resin surface using a radiation thermometer (manufactured by Hayashi Denko, model number: RT61-2, emissivity 0.95).

[0078] The method for producing the transparent resin layer includes a stretching step of uniaxially or biaxially stretching the unstretched transparent resin layer. In the longitudinal stretching step (stretching in the same direction as the film transport direction), the transparent resin layer is preheated and then stretched in the transport direction with a group of rollers having different peripheral speeds (i.e., different transport speeds) while the transparent resin layer is still heated.

[0079] The preheating temperature in the longitudinal stretching step is preferably Tg-40°C or higher and Tg+60°C or lower, more preferably Tg-20°C or higher and Tg+40°C or lower, and even more preferably Tg or higher and Tg+30°C or lower, relative to the glass transition temperature (Tg) of the transparent resin layer. The stretching temperature in the longitudinal stretching step is preferably Tg or higher and Tg+60°C or lower, more preferably Tg+2°C or higher and Tg+40°C or lower, and even more preferably Tg+5°C or higher and Tg+30°C or lower. The stretching ratio in the longitudinal direction is preferably 1.0 to 2.5 times, and more preferably 1.1 to 2 times.

[0080] In addition to or instead of the longitudinal stretching step, the transparent resin layer is stretched transversely in the width direction by a transverse stretching step (a step of stretching in a direction perpendicular to the film conveying direction). In the transverse stretching step, for example, a tenter can be suitably used, and the transparent resin layer is stretched transversely by this tenter while holding both ends in the width direction with clips. This transverse stretching can increase the tensile modulus of the transparent resin layer.

[0081] The transverse stretching is preferably carried out using a tenter, and the preferred stretching temperature is preferably from Tg to Tg + 60°C, more preferably from Tg + 2°C to Tg + 40°C, and even more preferably from Tg + 4°C to Tg + 30°C, relative to the glass transition temperature (Tg) of the transparent resin layer. The stretching ratio is preferably 1.0 to 5.0 times, more preferably 1.1 to 4.0 times. It is also preferable to relax the transparent resin layer in either or both the longitudinal and transverse directions after the transverse stretching.

[0082] Furthermore, it is preferable that the variation in thickness in both the width direction and the length direction depending on the location be 10% or less, more preferably 8% or less, even more preferably 6% or less, particularly preferably 4% or less, and most preferably 2% or less.

[0083] The thickness variation can be calculated as follows.

[0084] A 10 m (meter) sample of the stretched transparent resin layer is taken, and 20% of each end in the width direction of the film is removed. 50 samples are taken at equal intervals in both the width direction and the length direction from the center of the film, and the thickness is measured.

[0085] Average thickness in the width direction Th ＴＤ－ａｖ , maximum value Th ＴＤ－ｍａｘ , and the minimum value Th ＴＤ－ｍｉｎ , (Th ＴＤ－ｍａｘ -Th ＴＤ－ｍｉｎ ) ÷ Th ＴＤ－ａｖ ×100 [%] is the thickness variation in the width direction.

[0086] In addition, the average thickness in the longitudinal direction Th ＭＤ－ａｖ , maximum value Th ＭＤ－ｍａｘ , and the minimum value Th ＭＤ－ｍｉｎ , (Th ＭＤ－ｍａｘ -Th ＭＤ－ｍｉｎ ) ÷ Th ＭＤ－ａｖ ×100 [%] is the thickness variation in the longitudinal direction.

[0087] The stretching step can improve the thickness accuracy of the transparent resin layer.

[0088] The stretched transparent resin layer can be wound into a roll in a winding step. At this time, the winding tension of the transparent resin layer is 0.02 kg / mm ２ It is preferable to do the following:

[0089] Regarding other detailed conditions, the contents described in paragraphs 0134 to 0148 of JP 2015-224267 A regarding the melt film-forming process and the contents described in JP 2007-137028 A regarding the stretching process can be incorporated into this specification in accordance with the present invention.

[0090] (Solution Casting Method) When the transparent resin layer is formed by the solution casting method, it is preferable to include the steps of casting a dope solution on a casting band to form a cast film, drying the cast film, and stretching the cast film. Specifically, it is preferable to form the film by the method described in Japanese Patent No. 4,889,335. In the present invention, it is preferable to adopt the following method. For example, there is a method described in Japanese Patent Laid-Open No. 11-123732, in which the drying speed of the cast film is set to 300% by mass / min (=5% by mass / s) or less in terms of the solvent content on a dry basis, and gentle drying is performed. Furthermore, there is a method described in Japanese Patent Laid-Open No. 2003-276037, in which a multilayered cast film having a core layer as an intermediate layer and skin layers (outer layers) on both surfaces thereof is cast by increasing the viscosity of the dope forming the core layer to ensure the strength of the cast film and decreasing the viscosity of the dope forming the outer layer. Furthermore, there are also preferred methods such as a method in which the casting film is rapidly dried to form a film on the surface of the casting film, and the surface condition is smoothed by the leveling effect of the formed film, and a method in which the casting film is stretched.

[0091] It is desirable that the transparent resin layer 16 shrinks due to heat. When the laminate is made to conform to a curved glass surface, excess portions of the flat laminate are generated relative to the curved glass, which presumably makes it difficult to conform to the curved surface. However, heat shrinkage of the transparent resin layer 16 is preferable because the excess portions of the laminate shrink and allow it to conform to the curved surface.

[0092] Generally, transparent resin layers are stretched during their manufacturing process, and residual stress resulting from the stretching remains. Therefore, this residual stress can be utilized to cause thermal shrinkage by heating during curved surface conforming. It is presumed that this thermal shrinkage allows the layer to conform to the curved glass. Furthermore, insufficient conforming is likely to occur in areas of greater curvature near the periphery of the curved glass, but is unlikely to occur in areas of lesser curvature. In contrast, a laminate using a thermally shrinkable transparent resin layer effectively suppresses insufficient conforming in areas of greater curvature. In areas of greater curvature, the laminate has the freedom to expand in the thickness direction, resulting in shrinkage in the planar direction. In areas of lesser curvature, the laminate has the freedom to expand in the thickness direction, resulting in almost no shrinkage in the planar direction. This is thought to be the mechanism of action. The temperature at which the transparent resin layer 16 thermally shrinks varies depending on the material from which the transparent resin layer 16 is formed, but shrinkage is preferably in the range of 80 to 200° C., and more preferably in the range of 90 to 140° C., which is the heat treatment temperature in a typical curved surface conforming process. Heating to shrink the transparent resin layer 16 may be applied to the entire curved glass, or may be applied locally to a portion with a high curvature where insufficient conforming is likely to occur.

[0093] The amount of shrinkage of the transparent resin layer 16 required to suppress insufficient conformance varies depending on the curvature and dimensions of the glass. The thermal shrinkage of the transparent resin layer 16 is not particularly limited as long as the above thermal shrinkage is satisfied when the layer is formed into a laminate, but at 140°C, the average thermal shrinkage in the direction in which the thermal shrinkage is greatest and in the direction perpendicular to that direction is preferably 0.3 to 5.0%, more preferably 0.3 to 3.0%, and even more preferably 0.3 to 2.0%. The thermal shrinkage can be adjusted as appropriate by the stretching conditions when producing the transparent resin layer.

[0094] <Retardation Layer> The substrate 11 included in the laminate of the present invention may include a retardation layer 18. The retardation layer 18 imparts a phase difference (optical path difference) to two orthogonal polarized light components, thereby changing the state of incident polarized light.

[0095] When the retardation layer 18 is disposed on the glass plate side facing the vehicle interior and provides optical compensation, the front retardation of the retardation layer may be a retardation that can provide optical compensation. In this case, the front retardation of the retardation layer 18 at a wavelength of 550 nm is preferably 50 to 160 nm. Furthermore, when the direction corresponding to the vertically upward direction of the surface of the glass plate when the windshield glass having the laminate is mounted on a vehicle is defined as 0°, the angle of the slow axis is preferably 10 to 50° or −50 to −10°.

[0096] In addition, when the retardation layer 18 converts linearly polarized light into circularly polarized light, the retardation layer 18 is preferably configured to give a front retardation of λ / 4, or may be configured to give a front retardation of 3λ / 4. The angle of the slow axis may be set so as to be oriented in a direction that converts incident linearly polarized light into circularly polarized light.

[0097] In this case, the retardation layer 18 preferably has a front retardation at a wavelength of 550 nm in the range of 100 to 450 nm, more preferably in the range of 120 to 200 nm or 300 to 400 nm, for example. In addition, the direction of the slow axis of the retardation layer 18 is preferably determined depending on the incident direction of projection light for projecting an image when the laminate is used in a head-up display system and the sense of the helix of the cholesteric liquid crystal layer constituting the reflective layer.

[0098] The retardation layer 18 is not particularly limited and can be appropriately selected depending on the purpose. Examples of the retardation layer 18 include a stretched polycarbonate film, a stretched norbornene-based polymer film, a transparent film containing and oriented inorganic particles having birefringence such as strontium carbonate, a thin film obtained by obliquely depositing an inorganic dielectric on a support, a film in which a polymerizable liquid crystal compound is uniaxially oriented and fixed in orientation, and a film in which a liquid crystal compound is uniaxially oriented and fixed in orientation.

[0099] Among these, a film in which a polymerizable liquid crystal compound is uniaxially aligned and fixed is a suitable example of the retardation layer 18. As an example, such a retardation layer 18 can be formed by applying a liquid crystal composition containing a polymerizable liquid crystal compound to a transparent substrate, a temporary support, or the surface of an alignment layer, forming the polymerizable liquid crystal compound in the liquid crystal composition into a nematic alignment in a liquid crystal state, and then fixing the alignment by curing.

[0100] The retardation layer 18 may be a layer obtained by applying a composition containing a polymer liquid crystal compound to the surface of a transparent substrate, a temporary support, an alignment layer, or the like, forming a nematic alignment in a liquid crystal state, and then fixing the alignment by cooling.

[0101] The thickness of the retardation layer 18 is not particularly limited, but is preferably 0.2 to 300 μm, more preferably 0.5 to 150 μm, and even more preferably 1.0 to 80 μm. The thickness of the retardation layer 18 formed from a liquid crystal composition is not particularly limited, but is preferably 0.2 to 10 μm, more preferably 0.5 to 5.0 μm, and even more preferably 0.7 to 2.0 μm.

[0102] <Reflective Layer> The substrate 11 of the laminate of the present invention may include a reflective layer 20. The reflective layer 20 reflects part or all of visible light and is not particularly limited. Examples include a layer containing a metal, a layer in which a dielectric is laminated, and a layer containing a liquid crystal. The reflective layer 20 preferably includes a cholesteric liquid crystal layer having a selective reflection center wavelength in the red wavelength region, a cholesteric liquid crystal layer having a selective reflection center wavelength in the green wavelength region, and a cholesteric liquid crystal layer having a selective reflection center wavelength in the blue wavelength region. The three cholesteric liquid crystal layers have mutually different selective reflection center wavelengths. Each cholesteric liquid crystal layer may be in direct contact with any of the other cholesteric liquid crystal layers.

[0103] As is well known, a cholesteric liquid crystal layer is a layer in which liquid crystal compounds are fixed in a helical oriented state of a cholesteric liquid crystal phase, and reflects light with a selective reflection center wavelength corresponding to the pitch of the helical structure and transmits light in other wavelength ranges. Furthermore, a cholesteric liquid crystal layer exhibits selective reflection for either left- or right-handed circularly polarized light at a specific wavelength.

[0104] Here, from the viewpoint of visibility, it is preferable that the reflective layer 20 satisfy the following requirements (i) to (iii): (i) in the wavelength range of 400 nm or more and less than 500 nm, the maximum value of natural light reflectance is more than 7% (preferably more than 20%), the difference between the maximum and minimum values ​​of natural light reflectance is 3% or more, and the total value of the wavelength bandwidth of the region higher than the average value of the maximum and minimum values ​​of natural light reflectance is 20 to 80 nm; (ii) in the wavelength range of 500 nm or more and less than 600 nm, the maximum value of natural light reflectance is more than 7% (preferably more than 20%), the difference between the maximum and minimum values ​​of natural light reflectance is 3% or more, and the total value of the wavelength bandwidth of the region higher than the average value of the maximum and minimum values ​​of natural light reflectance is 20 to 80 nm. (iii) In the wavelength range of 600 to 800 nm, the maximum value of the natural light reflectance is more than 7% (preferably, 20% or more), and the total value of the wavelength bandwidth of the region higher than the average value of the maximum and minimum values ​​of the natural light reflectance is 120 nm or more.

[0105] In a reflective layer having a cholesteric liquid crystal layer, the reflected wavelength and reflectance can be adjusted by the selective reflection center wavelength and thickness (helical pitch number) of the cholesteric liquid crystal layer, etc. A reflection that satisfies requirement (i) can be realized mainly by a cholesteric liquid crystal layer that reflects light in the blue wavelength region, a reflection that satisfies requirement (ii) can be realized by a cholesteric liquid crystal layer that reflects light in the green wavelength region, and a reflection that satisfies requirement (iii) can be realized by a cholesteric liquid crystal layer that reflects light in the red wavelength region.

[0106] From the viewpoint of being able to increase transmittance while improving reflected color, the maximum natural light reflectance at 400 nm or more and less than 500 nm is preferably more than 7%, more preferably 20% or more. The upper limit is not particularly limited, but is often, for example, 35% or less. Similarly, from the viewpoint of being able to increase transmittance while improving reflected color, the maximum natural light reflectance at 500 nm or more and less than 600 nm is preferably more than 7%, more preferably 20% or more. The upper limit is not particularly limited, but is often, for example, 35% or less. From the viewpoint of being able to increase the brightness of a displayed image while improving reflected color, the maximum natural light reflectance at 600 to 800 nm is preferably more than 7%, more preferably 20% or more. The upper limit is not particularly limited, but is often, for example, 35% or less.

[0107] From the viewpoint of being able to increase transmittance while improving reflected color, the difference between the maximum and minimum natural light reflectance values ​​at wavelengths of 400 nm or more and less than 500 nm is preferably 4 to 20%, more preferably 4 to 12%. Similarly, from the viewpoint of being able to increase transmittance while improving reflected color, the difference between the maximum and minimum natural light reflectance values ​​at wavelengths of 500 nm or more and less than 600 nm is preferably 4 to 20%, more preferably 4 to 12%.

[0108] From the viewpoint of improving the reflected color and increasing the transmittance, the wavelength bandwidth of the region where the reflectance is higher than the average of the maximum and minimum values ​​of the reflectance between 400 nm and less than 500 nm is preferably 30 to 78 nm, more preferably 35 to 75 nm. Similarly, from the viewpoint of improving the reflected color and increasing the transmittance, the wavelength bandwidth of the region where the reflectance is higher than the average of the maximum and minimum values ​​of the reflectance between 500 nm and less than 600 nm is preferably 30 to 78 nm, more preferably 35 to 75 nm. The narrower the wavelength bandwidth between 400 nm and less than 500 nm and the narrower the wavelength bandwidth between 500 nm and less than 600 nm, the more advantageous the transmittance is. However, since the wavelength bandwidth between 600 and 800 nm is wide, if the wavelength bandwidth between 400 nm and less than 500 nm and / or the wavelength bandwidth between 500 nm and less than 600 nm is too narrow, the reflected color may deteriorate. From this point of view, it is preferable that the wavelength bandwidth from 400 nm to less than 500 nm and the wavelength bandwidth from 500 nm to less than 600 nm are within the above ranges. Furthermore, the wavelength bandwidth from 500 nm to less than 600 nm has a greater effect on the transmittance.

[0109] From the viewpoint of improving the reflected color and the front brightness of the displayed image, the wavelength bandwidth of the region where the reflectance is higher than the average value of the maximum and minimum reflectance values ​​from 600 to 800 nm is preferably 120 to 200 nm.

[0110] The reflective layer 20 preferably has two or more cholesteric liquid crystal layers with different selective reflection center wavelengths, and each cholesteric liquid crystal layer is preferably in direct contact with any other cholesteric liquid crystal layer.

[0111] If the cholesteric liquid crystal layers are spaced apart, the thickness between the layers becomes thicker, making it difficult to obtain the effect of interference of light reflected by each cholesteric liquid crystal layer. In contrast, a configuration in which the cholesteric liquid crystal layers are in contact with each other is preferable because the wavelength band width can be narrowed by the effect of interference of light reflected by each cholesteric liquid crystal layer. In particular, if the thickness of each cholesteric liquid crystal layer is thinner than the wavelength of light (visible light 380 to 780 nm), the effect of interference becomes more pronounced, which is preferable.

[0112] When the reflective layer 20 has two or more cholesteric liquid crystal layers, the cholesteric liquid crystal layers are not limited to being in direct contact with each other, but may be stacked via an adhesive layer or the like.

[0113] Here, each cholesteric liquid crystal layer may have at least one selective reflection center wavelength, but at least one of the cholesteric liquid crystal layers may have two or more selective reflection center wavelengths. A cholesteric liquid crystal layer having two or more selective reflection center wavelengths is achieved by a helical structure in which the helical pitch changes in the thickness direction.

[0114] The total thickness of the reflective layer 20 is preferably 0.4 to 2.0 μm, more preferably 0.6 to 1.8 μm, and even more preferably 0.8 to 1.4 μm.

[0115] <Intermediate layer> The substrate 11 of the laminate of the present invention may include an intermediate layer. This intermediate layer is preferably used in the embodiment of the bonded body shown in Fig. 6, for example, in the embodiment in which the laminate of the present invention is applied to laminated glass.

[0116] For example, a resin film containing a resin selected from the group consisting of polyvinyl butyral (PVB), ethylene-vinyl acetate copolymer, and chlorine-containing resins can be used as the intermediate layer. The resin is preferably the main component of the intermediate layer. The term "main component" refers to a component that accounts for 50% or more by mass of the intermediate layer. Of the above resins, polyvinyl butyral or ethylene-vinyl acetate copolymer is preferred, with polyvinyl butyral being more preferred. The resin is preferably a synthetic resin.

[0117] Here, polyvinyl butyral can be obtained by acetalizing polyvinyl alcohol with butyraldehyde. The degree of acetalization of the polyvinyl butyral is preferably 40 to 85%, more preferably 60 to 75%. The polyvinyl butyral can also be prepared by acetalizing polyvinyl alcohol with butyraldehyde. Polyvinyl alcohol is usually obtained by saponifying polyvinyl acetate, and polyvinyl alcohol with a saponification degree of 80 to 99.8 mol% is generally used.

[0118] <Polarization Conversion Layer> The substrate 11 of the laminate of the present invention may include a polarization conversion layer 24. The polarization conversion layer 24 is a layer in which a helical orientation structure of a liquid crystal compound is fixed, and it is preferable that the pitch number x of the helical orientation structure and the film thickness y (unit: μm) of the polarization conversion layer satisfy all of the following relational expressions (a) to (c): 0.1≦x≦1.0 (formula (a)) 0.5≦y≦3.0 (formula (b)) 3000≦(1560×y) / x≦50000 (formula (c)) Note that one pitch of the helical structure of the liquid crystal compound corresponds to one turn of the helix of the liquid crystal compound. In other words, a pitch number of 1 is defined as a state in which the director of the helically oriented liquid crystal compound (the long axis direction in the case of rod-shaped liquid crystals) has rotated 360°.

[0119] When the polarization conversion layer 24 has a helical structure of a liquid crystal compound, it exhibits optical rotation and birefringence for visible light, which has a wavelength shorter than the reflection peak wavelength in the infrared range. Therefore, it is possible to control polarization in the visible range. By setting the pitch number x of the helical orientation structure of the polarization conversion layer 24 and the thickness y of the polarization conversion layer within the above-mentioned ranges, it is possible to provide the polarization conversion layer with the function of optically compensating for visible light, or the function of converting linearly polarized light (p-polarized light) incident on the laminate to circularly polarized light.

[0120] The polarization conversion layer 24 exhibits optical rotation and birefringence for visible light because the liquid crystal compound has a helical structure that satisfies the relational expressions (a) to (c). In particular, by setting the pitch P of the helical structure of the polarization conversion layer 24 to a length that corresponds to the pitch P of the cholesteric liquid crystal layer whose selective reflection center wavelength is in the long-wavelength infrared region, the polarization conversion layer 24 exhibits high optical rotation and birefringence for short-wavelength visible light.

[0121] The relational expression (a) satisfies "0.1≦x≦1.0." When the pitch number x of the helical structure is 0.1 or more, sufficient optical rotation and birefringence are obtained, which is preferable. When the pitch number x of the helical structure is 1.0 or less, sufficient optical rotation and birefringence are obtained, making it easy to obtain the desired elliptically polarized light.

[0122] The relational expression (b) is "0.5≦y≦3.0". When the thickness y of the polarization conversion layer is 0.5 μm or more, sufficient optical rotation and birefringence are obtained. When the thickness y of the polarization conversion layer is 3.0 μm or less, the optical rotation and birefringence are sufficient, making it easy to obtain the desired circularly polarized light.

[0123] The relational expression (c) is "3000≦(1560×y) / x≦50000". When "(1560×y) / x" is 3000 or more, the desired polarization is easily obtained. When "(1560×y) / x" is 50000 or less, the desired polarization is easily obtained.

[0124] In the present invention, the pitch number x of the helical structure of the polarization conversion layer 24 is more preferably 0.1 to 0.8, and the film thickness y is more preferably 0.6 to 2.6 μm. Also, "(1560×y) / x" is more preferably 5000 to 13000.

[0125] That is, it is preferable that the polarization conversion layer 24 has a long helical pitch P and a small pitch number x. Specifically, it is preferable that the polarization conversion layer 24 has a helical pitch P equivalent to the pitch P of a cholesteric liquid crystal layer having a selective reflection center wavelength in the long-wavelength infrared region and a small pitch number x. More specifically, it is preferable that the polarization conversion layer 24 has a helical pitch P equivalent to the pitch P of a cholesteric liquid crystal layer having a selective reflection center wavelength of 3,000 to 10,000 nm and a small pitch number x. Since the selective reflection center wavelength corresponding to the pitch P is much longer than that of visible light, such a polarization conversion layer 24 more suitably exhibits the optical rotation and birefringence for visible light described above.

[0126] Such a polarization conversion layer 24 can be formed basically in the same way as a known cholesteric liquid crystal layer. However, when forming the polarization conversion layer 24, it is preferable to adjust the liquid crystal compound to be used, the chiral agent to be used, the amount of chiral agent added, the film thickness, etc. so that the pitch number x of the helical structure and the film thickness y [μm] of the polarization conversion layer 24 satisfy all of the relational expressions (a) to (c).

[0127] In the laminate of the present invention, the substrate preferably includes all of the above-mentioned hard coat layer, reflective layer, retardation layer, and polarization conversion layer, and more preferably includes all of the above-mentioned protective film, transparent resin layer, hard coat layer, reflective layer, retardation layer, and polarization conversion layer.

[0128] [Adhesive Layer] The laminate of the present invention has an adhesive layer 26. The adhesive layer 26 is a layer for physically bonding the laminate and the object to be pasted, and air contained in defects dissolves in the adhesive layer, thereby eliminating the air bubbles and reducing the visibility of the defects.

[0129] The adhesive layer is not particularly limited in material as long as it has transparency that ensures visibility of the display content when attached to the substrate and can bond the substrate to the substrate, and may be made of a resin or an elastomer (including oil-extended rubber). Furthermore, it may be a layer that plasticizes and develops adhesiveness due to heat when attached to the substrate (heat seal layer), or a layer that has adhesiveness at room temperature and can be attached (adhesive layer).

[0130] The adhesive layer 26 preferably contains a thermoplastic resin or elastomer. Thermoplastic resins with good affinity and adhesion to the substrate (e.g., a glass substrate) are preferred. Examples of suitable thermoplastic resins include 1,2-polybutadiene resin, ethylene-vinyl acetate copolymer (abbreviated as "EVA," which typically contains 3% or more by mass of vinyl acetate structural units), polyolefin resins such as polyethylene, polyvinyl chloride resin, polystyrene resin, vinyl ester resin (excluding EVA), saturated polyester resin, polyamide resin, fluororesin (e.g., polyvinylidene fluoride), polycarbonate resin, polyacetal resin, urethane resin, epoxy resin, (meth)acrylate resin (also referred to as (meth)acrylic resin, meaning (meth)acrylic acid ester resin, etc.), unsaturated polyester resin, silicone resin, and modified versions of these resins. Urethane resins include urethane-modified polyester resins and urethane resins. Thermoplastic resins include (meth)acrylate resin, polyvinyl butyral, and ethylene-vinyl acetate copolymer.

[0131] Polyvinyl butyral can be obtained by acetalizing polyvinyl alcohol with butyraldehyde. The degree of acetalization of polyvinyl butyral is not particularly limited, but is preferably 40% or more, more preferably 60% or more. The upper limit is not particularly limited, but is preferably 85% or less, more preferably 75% or less. Polyvinyl alcohol used in the synthesis of polyvinyl butyral is usually obtained by saponifying polyvinyl acetate, and polyvinyl alcohol with a saponification degree of 80 to 99.8 mol% is generally used. The degree of polymerization of the polyvinyl alcohol is preferably 200 to 3000.

[0132] Examples of the elastomer include block (co)polymers of conjugated dienes, acrylic block (co)polymers, styrene block (co)polymers, block copolymers of aromatic vinyl compounds and conjugated dienes, hydrogenated products of block (co)polymers of conjugated dienes, hydrogenated products of block copolymers of aromatic vinyl compounds and conjugated dienes, ethylene-α-olefin copolymers, polar group-modified olefin copolymers, elastomers composed of polar group-modified olefin copolymers and metal ions and / or metal compounds, nitrile rubbers such as acrylonitrile-butadiene rubbers, butyl rubber, acrylic rubbers, thermoplastic elastomers such as thermoplastic polyolefin elastomers (TPO), thermoplastic polyurethane elastomers (TPU), thermoplastic polyester elastomers (TPEE), thermoplastic polyamide elastomers (TPAE), diene elastomers (1,2-polybutadiene, etc.), silicone elastomers, and fluorine-based elastomers.

[0133] The thermoplastic resin or elastomer may be synthesized by a known method, or a commercially available product may be used. Examples of commercially available elastomers include Kuralyte LA1114, Kuralyte LA2140, Kuralyte LA2250, Kuralyte LA2330, Kuralyte LA4285, Hybrar 5127, Hybrar 7311F, Septon 2104, and Septon 2063 (trade names, manufactured by Kuraray Co., Ltd.). As the elastomer, an acrylic block (co)polymer or a styrene block (co)polymer is preferred in terms of oxygen solubility.

[0134] The weight average molecular weight of the thermoplastic resin and elastomer is preferably 10,000 to 1,000,000, more preferably 50,000 to 500,000, from the viewpoint of the balance between solubility in a solvent and storage modulus.

[0135] The adhesive layer 26 is preferably formed using a composition (adhesive layer-forming composition) containing a polymerizable compound for chemically bonding to the reflective layer or the polarization conversion layer. The polymerizable compound is preferably one that can chemically bond with the polymerizable liquid crystal compound used to form the base material (particularly the reflective layer or the polarization conversion layer). For example, if the polymerizable liquid crystal compound has an ethylenically unsaturated polymerizable group, the polymerizable compound also preferably has an ethylenically unsaturated polymerizable group.

[0136] Examples of the ethylenically unsaturated polymerizable group-containing compound include the following. However, the present invention is not limited to the following exemplified compounds. For example, polyethylene glycol 200 di(meth)acrylate, polyethylene glycol 300 di(meth)acrylate, polyethylene glycol 400 di(meth)acrylate, polyethylene glycol 600 di(meth)acrylate, triethylene glycol di(meth)acrylate, epichlorohydrin-modified ethylene glycol di(meth)acrylate (commercially available products include Denacol DA-811 manufactured by Nagase & Co., Ltd.), polypropylene glycol 200 di(meth)acrylate, polypropylene glycol 400 di(meth)acrylate, polypropylene glycol 700 di(meth)acrylate, ethylene oxide (EO), propylene oxide (PO),propylene oxide) block polyether di(meth)acrylate (commercially available products, such as the Blemmer PET series manufactured by Nippon Oil & Fats Co., Ltd.), dipropylene glycol di(meth)acrylate, bisphenol A EO addition type di(meth)acrylate (commercially available products, such as M-210 manufactured by Toagosei Co., Ltd. and NK Ester A-BPE-20 manufactured by Shin-Nakamura Chemical Co., Ltd.), hydrogenated bisphenol A EO addition type di(meth)acrylate (NK Ester A-HPE-4 manufactured by Shin-Nakamura Chemical Co., Ltd.), bisphenol A PO addition type di(meth)acrylate (commercially available products, such as Light Acrylate BP-4PA manufactured by Kyoeisha Chemical Co., Ltd.), bisphenol A epichlorohydrin addition type di(meth)acrylate (commercially available products, such as Ebecryl 150 manufactured by Daicel UCB Co., Ltd.), bisphenol A EO·PO addition type di(meth)acrylate (commercially available products include BP-023-PE manufactured by Toho Chemical Industry Co., Ltd.), bisphenol F Examples of bifunctional (meth)acrylate compounds include EO-added di(meth)acrylate (commercially available products include Aronix M-208 manufactured by Toagosei Co., Ltd.), 1,6-hexanediol di(meth)acrylate and its epichlorohydrin-modified products, neopentyl glycol di(meth)acrylate, hydroxypivalic acid neopentyl glycol di(meth)acrylate and its caprolactone-modified products, 1,4-butanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, trimethylolpropane di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, pentaerythritol di(meth)acrylate monostearate, trimethylolpropane acrylic acid benzoate, and isocyanuric acid EO-modified di(meth)acrylate (commercially available products include Aronix M-215 manufactured by Toagosei Co., Ltd.);

[0137] Further, trifunctional (meth)acrylate compounds such as trimethylolpropane tri(meth)acrylate (commercially available products include, for example, TPMTA manufactured by Nippon Kayaku Co., Ltd.) and its EO, PO, or epichlorohydrin-modified products, pentaerythritol tri(meth)acrylate, glycerol tri(meth)acrylate and its EO, PO, or epichlorohydrin-modified products, isocyanuric acid EO-modified tri(meth)acrylate (commercially available products include, for example, Aronix M-315 manufactured by Toagosei Co., Ltd.), tris(meth)acryloyloxyethyl phosphate, hydrogen phthalate-(2,2,2-tri-(meth)acryloyloxymethyl)ethyl, glycerol tri(meth)acrylate and its EO, PO, or epichlorohydrin-modified products; Examples of such compounds include tetrafunctional (meth)acrylate compounds such as tetraerythritol tetra(meth)acrylate (commercially available products include TPMTA manufactured by Shin-Nakamura Chemical Co., Ltd.), EO, PO, and epichlorohydrin-modified products thereof, and ditrimethylolpropane tetra(meth)acrylate; pentafunctional (meth)acrylate compounds such as dipentaerythritol penta(meth)acrylate and EO, PO, epichlorohydrin, fatty acid, and alkyl-modified products thereof; and hexafunctional (meth)acrylate compounds such as dipentaerythritol hexa(meth)acrylate and EO, PO, epichlorohydrin, fatty acid, and alkyl-modified products thereof, and sorbitol hexa(meth)acrylate and EO, PO, epichlorohydrin, fatty acid, and alkyl-modified products thereof. Two or more ethylenically unsaturated polymerizable group-containing compounds may be used in combination. In this case, a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, "DPHA" (manufactured by Nippon Kayaku Co., Ltd.), or the like can be preferably used.

[0138] Also preferred as the ethylenically unsaturated polymerizable group-containing compound are polyester(meth)acrylates and epoxy(meth)acrylates having a weight-average molecular weight of 200 or more and less than 1,000. Commercially available polyester(meth)acrylates include those manufactured by Arakawa Chemical Industries Co., Ltd. under the trade name of the Beamset 700 series, such as Beamset 700 (hexafunctional), Beamset 710 (tetrafunctional), and Beamset 720 (trifunctional). Epoxy(meth)acrylates include those manufactured by Showa Polymer Co., Ltd. under the trade name of the SP series, such as SP-1506, 500, SP-1507, and 480, and those manufactured by VR series, such as VR-77, and those manufactured by Shin-Nakamura Chemical Co., Ltd. under the trade names of EA-1010 / ECA, EA-11020, EA-1025, and EA-6310 / ECA.

[0139] The I / O ratio (ratio of inorganic value (I value) to organic value (O value)) of the polymerizable compound (particularly, an ethylenically unsaturated polymerizable group-containing compound) is preferably 0.40 or more, more preferably 0.60 or more, and even more preferably 1.2 or more, from the viewpoint of adhesion to a glass substrate. There is no particular upper limit to the I / O ratio, but it is preferably less than 3.0 from the viewpoint of compatibility with a thermoplastic resin.

[0140] The I / O ratio is calculated using the calculation method in the organic conceptual diagram. The organic conceptual diagram was proposed by Fujita et al. and is an effective method for predicting various physicochemical properties from the chemical structure of an organic compound (see Koda Yoshio, Organic Conceptual Diagram - Fundamentals and Applications, Sankyo Publishing (1984)). Since the polarity of an organic compound depends on the number of carbon atoms and substituents, the inorganic and organic values ​​of other substituents are determined based on the organic value of the methylene group being 20 and the inorganic value of the hydroxyl group being 100, and the inorganic and organic values ​​of the organic compound are then calculated. Organic compounds with a high inorganic value have high polarity, and organic compounds with a high organic value have low polarity.

[0141] Specific methods for calculating the I value, O value, and I / O ratio have been published as an organic conceptual diagram calculation sheet for Excel by Homma et al., co-authors of "New Edition Organic Conceptual Diagram: Fundamentals and Applications" (http: / / www.ecosci.jp / sheet / orgs_help.html), and these calculations can be performed using this.

[0142] When the composition used to form the adhesive layer 26 contains a polymerizable compound, the content of the polymerizable compound is preferably 5 to 80 mass %, more preferably 10 to 60 mass %, and even more preferably 15 to 50 mass %, based on the solid content of the composition. The solid content of the composition refers to the other components in the composition excluding the solvent. Even if the other components are in a liquid state, they are counted as solids.

[0143] The composition used to form the adhesive layer 26 (adhesive layer-forming composition) preferably contains a polymerization initiator from the viewpoint of adhesion to glass. Examples of the polymerization initiator include a photopolymerization initiator. The photopolymerization initiator may be any one that can generate radicals as active species upon light irradiation, and known photopolymerization initiators can be used without any restrictions. Specific examples include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-morpholino(4-thiomethylphenyl)propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone oligomer, and 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one and other acetophenones; 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyloxime)], and Oxime esters such as ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(0-acetyloxime); benzoins such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenones such as benzophenone, methyl ortho-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, 4-benzoyl-N,N-dimethyl-N-[2-(1-oxo-2-propenyloxy)ethyl]benzenemethanaminium bromide, and (4-benzoylbenzyl)trimethylammonium chloride;Thioxanthones such as 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and 2-(3-dimethylamino-2-hydroxy)-3,4-dimethyl-9H-thioxanthone-9-one mesochloride; and acylphosphine oxides such as 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide, and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide. Furthermore, as an auxiliary agent for the polymerization initiator, triethanolamine, triisopropanolamine, 4,4'-dimethylaminobenzophenone (Michler's ketone), 4,4'-diethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid, ethyl 4-dimethylaminobenzoate, (n-butoxy)ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, etc. may be used in combination. The above polymerization initiators and auxiliary agents can be synthesized by known methods or are commercially available. Commercially available radical photopolymerization initiators include Irgacure (127, 651, 184, 819, 907, 1870 (CGI-403 / Irg184=7 / 3 mixed initiator, 500, 369, 1173, 2959, 4265, 4263, etc.), OXE01) manufactured by BASF, KAYACURE (DETX-S, BP-100, BDMK, CTX, BMS, 2-EAQ, ABQ, CPTX, EPD, ITX, QTX, BTC, MCA, etc.) manufactured by Nippon Kayaku, and Esacure (KIP100F, KB1, EB3, BP, X33, KT046, KT37, KIP150, TZT) manufactured by Sartomer, and the like;

[0144] The content of the polymerization initiator contained in the composition used to form the adhesive layer 26 is not particularly limited, and may be appropriately adjusted within a range that allows the polymerization reaction of the polymerizable compound to proceed smoothly. When the composition used to form the adhesive layer contains a polymerization initiator, the content of the polymerization initiator is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, and even more preferably 1 to 10 parts by mass, relative to 100 parts by mass of the polymerizable compound contained in the composition.

[0145] The adhesive layer 26 may contain inorganic particles or resin particles. The inclusion of inorganic particles or resin particles in the adhesive layer 26 creates an uneven surface on the adhesive layer 26. This reduces friction between the adhesive layer 26 and the HC layer 14 when the adhesive layer 26 is rolled up in a state where the adhesive layer 26 and the HC layer 14 are in direct contact with each other, thereby enabling the adhesive layer 26 to be rolled up without wrinkles. This is also preferable because it reduces friction between the adhesive layer 26 and the substrate and suppresses air retention during pressure bonding. The inorganic particles contained in the adhesive layer 26 are preferably inorganic oxide particles, with silica (silicon dioxide) particles, aluminum oxide particles, titanium dioxide particles, or zirconium oxide particles being more preferred, and silica particles being even more preferred. The resin particles contained in the adhesive layer 26 are preferably crosslinked acrylic particles, crosslinked acrylic-styrene particles, or crosslinked styrene particles. The resin particles may be spherical or irregular in shape. Two or more different types of matte particles may also be used in combination. The average primary particle diameter of the resin particles is preferably 20% to 300% of the thickness of the adhesive layer, more preferably 50% to 200%, and particularly preferably 100% to 200 μm. By setting the average primary particle diameter of the resin particles within the above range, it is possible to impart unevenness to the adhesive layer 26 while preventing the resin particles from falling off.

[0146] Resin particles are also commercially available, and examples thereof include cross-linked acrylic resins MX-40T, MX-80H3wT, MX-150, MX-180TA, MX-300, MX-500, MX-1000, MX-1500H, MR-2HG, MR-7HG, MR-10HG, MR-3GSN, MR-5GSN, MR-7G, MR-10G, MR-5C, and MR-7GC manufactured by Soken Chemical & Engineering Co., Ltd., and styryl resin-based SX-350H and SX-500H, and acrylic resins MBX-5, MBX-8, and MBX-12MBX manufactured by Sekisui Plastics Co., Ltd. -15, MBX-20, MB20X-5, MB30X-5, MB30X-8, MB30X-20, SBX-6, SBX-8, SBX-12, SBX-17, SSX-101, SSX-102, SSX-103, SSX-105, SSX-108, SSX-110, polyolefin resins manufactured by Mitsui Chemicals, Inc., Chemipearl W100, W200, W300, W308, W310, W400, W401, W405, W410, W500, WF640, W700, W800, W900, W950, WP100, and the like.

[0147] The content of the resin particles in the adhesive layer 26 is not particularly limited, but is preferably 0.1% by mass or more, and more preferably 0.5% by mass or more, relative to the total mass of the adhesive layer 26. The upper limit is not particularly limited, but is preferably 10% by mass or less, and more preferably 3% by mass or less.

[0148] The inorganic particles preferably consist of primary particles, with secondary particles formed by aggregation of the primary particles. The average primary particle size of the inorganic particles is not particularly limited, but is preferably 5 to 50 nm, more preferably 5 to 15 nm. The average secondary particle size of the inorganic particles is not particularly limited, but is preferably 100 to 500 nm.

[0149] The content of the inorganic particles in the adhesive layer 26 is not particularly limited, but is preferably 1% by mass or more, and more preferably 9% by mass or more, relative to the total mass of the adhesive layer 26. The upper limit is not particularly limited, but is preferably 40% by mass or less, and more preferably 30% by mass or less.

[0150] The average primary particle diameter of inorganic particles and resin particles is measured by observation with a transmission electron microscope. Specifically, the diameter of the circle circumscribing the primary particles is determined for 50 randomly selected primary particles, and the arithmetic mean is taken as the average primary particle diameter. The magnification of the transmission electron microscope is set to any magnification between 500,000 and 5,000,000 that allows the primary particle diameter to be determined. The average secondary particle diameter is measured using a laser diffraction / scattering particle size distribution analyzer with spherical fitting (refractive index 1.46). A MicroTrac MT3000 manufactured by Microtrac-Bell, for example, can be used as the measuring device.

[0151] The adhesive layer 26 may contain a leveling agent. Known leveling agents can be used as the leveling agent, and examples thereof include surfactants. Of these, fluorine-based surfactants or silicone-based surfactants are preferred. The fluorine content of the fluorine-based surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and even more preferably 7 to 25% by mass. Fluorine-based surfactants with a fluorine content within this range are effective in terms of the uniformity of the thickness of the coating film and the liquid saving.

[0152] The content of the leveling agent in the adhesive layer 26 is not particularly limited, but is preferably 0.005 to 0.5 mass % relative to the total mass of the adhesive layer 26, and more preferably 0.01 to 0.1 mass %.

[0153] The adhesive layer 26 may contain an antistatic agent. When the adhesive layer 26 contains an antistatic agent, the generation of static electricity caused by friction between the adhesive layer 26 and hands, air, or the like when handling the laminate can be suppressed, preventing adhesion of environmental dust to the surface of the adhesive layer 26 due to static electricity and reducing the occurrence of bubble-like defects caused by dust.

[0154] As the antistatic agent, known antistatic agents can be used, and examples thereof include ionic liquids, ion-conductive polymers, ion-conductive fillers, and electrically conductive polymers.

[0155] <Ionic Liquid> Any known ionic liquid can be used as the ionic liquid as long as it does not impair the effects of the adhesive layer 26. Here, the term "ionic liquid" refers to a molten salt (i.e., an ionic compound) that is liquid at 25°C.

[0156] The ionic liquid is preferably an ionic liquid composed of a fluoroorganic anion and an onium cation, which can further suppress charging that may occur due to friction with other objects.

[0157] Specific examples of the ionic liquid include 1-hexylpyridinium bis(fluorosulfonyl)imide, 1-ethyl-3-methylpyridinium trifluoromethanesulfonate, 1-ethyl-3-methylpyridinium pentafluoroethanesulfonate, 1-ethyl-3-methylpyridinium heptafluoropropanesulfonate, 1-ethyl-3-methylpyridinium nonafluorobutanesulfonate, 1-butyl-3-methylpyridinium trifluoromethanesulfonate, 1-butyl-3-methylpyridinium bis(trifluoromethanesulfonyl)imide, 1-octyl-4-methylpyridinium bis(fluorosulfonyl)imide, 1-methyl-1-propylpyrrolidinium bis(trifluoromethanesulfonyl)imide, and 1-methyl-1-propylpyrrolidinium bis(fluorosulfonyl). propyl)imide, 1-methyl-1-propylpiperidinium bis(trifluoromethanesulfonyl)imide, 1-methyl-1-propylpiperidinium bis(fluorosulfonyl)imide, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium heptafluoropropanesulfonate, 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide, 1-hexyl-3-methylimidazolium bis(fluorosulfonyl)imide, trimethylpropylammonium bis(trifluoromethanesulfonyl)imide, lithium bis(trifluoromethanesulfonyl)imide, and lithium bis(fluorosulfonyl)imide.

[0158] The ionic liquid is available, for example, as IL-AP3 (Hiroe Chemical Industry Co., Ltd.).

[0159] <Ion Conductive Polymer> As the ion conductive polymer, known ion conductive polymers can be used as long as the effect of the adhesive layer 26 is not impaired.

[0160] Examples of the ion-conductive polymer include ion-conductive polymers obtained by polymerizing or copolymerizing a monomer having a quaternary ammonium salt group.

[0161] Ion-conductive polymers are available, for example, as the Acrit 1SX series (for example, trade name 1SX-1055F, Taisei Fine Chemical Co., Ltd.).

[0162] <Ion-Conductive Filler> As the ion-conductive filler, known ion-conductive fillers can be used as long as the effect of the adhesive layer 26 is not impaired.

[0163] Examples of ion conductive fillers include tin oxide, antimony oxide, indium oxide, cadmium oxide, titanium oxide, zinc oxide, indium, tin, antimony, gold, silver, copper, aluminum, nickel, chromium, titanium, iron, cobalt, copper iodide, ITO (indium oxide / tin oxide), and ATO (antimony oxide / tin oxide).

[0164] The ion-conductive filler is available, for example, as the FS series (for example, trade name FS-10D, Ishihara Sangyo Kaisha, Ltd.).

[0165] <Electrically Conductive Polymer> As the electrically conductive polymer, known electrically conductive polymers can be used as long as the effect of the adhesive layer 26 is not impaired.

[0166] Examples of electrically conductive polymers include polythiophene, polyaniline, polypyrrole, polyethyleneimine, and allylamine polymers.Specific examples of electrically conductive polymers include (3,4-ethylenedioxythiophene)-poly(styrenesulfonic acid).

[0167] As the polythiophene, a polymer compound containing PEDOT (poly(3,4-ethylenedioxythiophene)) is preferred, and a conductive polymer compound consisting of poly(3,4-ethylenedioxythiophene) and polystyrene sulfonic acid (hereinafter abbreviated as "PEDOT / PSS") is particularly preferred. Commercially available polythiophenes include, for example, the Clevios series (Hereos Co., Ltd.), the ORGACON series (Agfa Materials Japan), Denatron P-502RG (Nagase ChemteX Corporation), Denatron PT-432ME, Denatron N8-2-1, Sepulgida AS-X (Shin-Etsu Polymer Co., Ltd.), Sepulgida AS-D, Sepulgida AS-H, Sepulgida AS-F, Sepulgida HC-R, Sepulgida HC-A, Sepulgida SAS-P, Sepulgida SAS-M, and Sepulgida SAS-F.

[0168] Examples of polyaniline include the ORMECON series (Nissan Chemical Industries, Ltd.). Examples of polypyrrole include 482552 (Aldrich Corporation) and 735817. In the present disclosure, the above commercially available products can be preferably used as the electrically conductive polymer.

[0169] The adhesive layer 26 may contain one type of antistatic agent alone, or may contain two or more types of antistatic agents.

[0170] From the viewpoint of antistatic properties, the content of the antistatic agent is preferably 0.1% by mass to 20% by mass, more preferably 1% by mass to 10% by mass, and particularly preferably 3% by mass to 10% by mass, relative to the total mass of the adhesive layer 26.

[0171] When the adhesive layer 26 contains an antistatic agent, the surface resistance of the adhesive layer 26 is 1.0×10 １４ It is preferably 1.0×10 Ω / □ or less, １１ It is more preferable that the surface resistance value of the adhesive layer 26 is Ω / □ or less. When the surface resistance value of the adhesive layer 26 is equal to or less than the above value, the generation of static electricity due to friction between the adhesive layer 26 and an object can be further suppressed.

[0172] The lower limit of the surface resistance of the antistatic layer is not particularly limited, but is 1.0×10 ６ It is preferably Ω / □ or more, and 1.0×10 ７It is more preferable that the resistance is Ω / □ or more.

[0173] The adhesive layer 26 is preferably formed by applying an adhesive layer-forming composition. The adhesive layer-forming composition contains the above-mentioned components and is used to form the adhesive layer 26. From the viewpoint of coatability, the adhesive layer-forming composition preferably contains a solvent. The type of solvent is not particularly limited, and examples include water and organic solvents, with organic solvents being preferred. Examples of organic solvents include ketones, alkyl halides, amides, sulfoxides, heterocyclic compounds, hydrocarbons, esters, and ethers.

[0174] The method for applying the adhesive layer-forming composition is not particularly limited, and examples thereof include wire bar coating, curtain coating, extrusion coating, direct gravure coating, reverse gravure coating, die coating, spin coating, dip coating, spray coating, and slide coating.

[0175] The coating film obtained by coating may be subjected to a drying treatment, if necessary. Examples of the drying treatment include a heat treatment. The heating temperature in the heat treatment is not particularly limited, but is preferably 50 to 150°C, and more preferably 60 to 140°C. The heating time is not particularly limited, but is preferably 0.5 to 20 minutes, and more preferably 0.5 to 10 minutes.

[0176] The surface of the formed adhesive layer 26 (the surface opposite the reflective layer or polarization conversion layer) may be subjected to a surface treatment as needed. For example, in order to reduce the water contact angle of the surface of the adhesive layer 26, the surface of the adhesive layer 26 may be subjected to a hydrophilization treatment. Examples of hydrophilization treatments include plasma treatment, ultraviolet irradiation treatment, corona treatment, and electron beam irradiation treatment, with corona treatment being preferred. The conditions for the hydrophilization treatment are appropriately selected depending on the type of treatment to be performed, and are preferably adjusted so that the water contact angle of the surface of the adhesive layer 26 falls within the range described above.

[0177] The average thickness (film thickness) of the adhesive layer 26 is preferably 0.1 μm or more, more preferably 0.2 μm or more, even more preferably 0.5 μm or more, and particularly preferably 1 μm or more, from the viewpoints of bubble solubility and adhesion to the substrate, reflective layer, or polarization conversion layer. There is no particular upper limit, but from the viewpoint of thinning, it is preferably 100 μm or less, more preferably 50 μm or less, and even more preferably 20 μm or less. The average thickness is measured by cutting the adhesive layer 26 with a microtome to extract a cross section, observing the cross section with a scanning electron microscope (SEM), measuring the thickness at three different positions on the adhesive layer 26, and calculating the average (arithmetic mean) of the measured values.

[0178] The adhesive layer 26 may have a single layer structure or a multi-layer structure of two or more layers. When the adhesive layer 26 has a multi-layer structure, it is sufficient that the average value of the total thickness of the adhesive layer 26 is within the above range.

[0179] The surface of the adhesive layer 26 may also be roughened. By roughening the surface of the adhesive layer 26, it is possible to impart irregularities to the surface and suppress air remaining during compression bonding. Examples of roughening processes include sanding, embossing, and blasting. Sanding is a process in which an irregular shape is formed on the surface of the object to be polished using a substrate such as a disk or belt that holds abrasive grains. Embossing is a process in which a mold having a predetermined irregular shape is pressed against the object at high temperature and pressure to transfer the shape and form an irregular shape. Blasting is a process in which an irregular shape is formed on the surface of the object to be polished by spraying abrasive grains.

[0180] The laminate of the present invention is preferably used in applications in which it is attached to glass via the above-mentioned adhesive layer 26, and more preferably used in applications in which it is attached to windshield glass via the above-mentioned adhesive layer 26.

[0181] [Laminated body] The laminated body of the present invention has an object to be laminated and the laminated body of the present invention laminated to the object to be laminated. The object to be laminated may have a curved surface, and various known objects can be used. Examples include window glass, glass used for the interior and exterior of buildings, and curved glass used for lenses.

[0182] In the present invention, because wrinkles occurring between the adhesive layer and the substrate (glass) can be suppressed, a bonded structure having another glass on the side opposite to the side where the glass in the laminate of the present invention is bonded, i.e., an embodiment in which the laminate of the present invention is applied to laminated glass, is preferred. Figure 6 shows a schematic cross-sectional view of an example of the bonded structure of the present invention. The bonded structure in the illustrated example has glass 27A and laminate 10B bonded to glass 27A, and further has glass 27B on the side opposite to the side where glass 27A is bonded in laminate 10B. The layer structure of laminate 10B includes, from the glass 27A side, adhesive layer 26, transparent resin layer 16, reflective layer 20, and intermediate layer 19, in this order. Note that, as described above, bonding to glass is preferably performed via an adhesive layer. However, in an embodiment in which bonding to laminated glass is performed, as shown in Figure 6, bonding to at least one of the glasses may be performed via an adhesive layer.

[0183] Another embodiment of the laminate of the present invention comprises a windshield glass and the laminate of the present invention bonded to the windshield glass. There are no limitations on the windshield glass, and various types of windshield glass (windshield glass) used in vehicles such as automobiles, ships, aircraft, trains, motorcycles, etc. can be used. Therefore, the windshield glass may be a single sheet of glass or a laminated glass in which multiple sheets of glass are laminated. Furthermore, the laminated glass may have an interlayer film such as polyvinyl butyral between the sheets, or may not have an interlayer film.

[0184] In the present invention, because it is possible to suppress wrinkles that occur between the adhesive layer and the object to be bonded (windshield glass), a preferred embodiment is one in which the laminate of the present invention is bonded to a windshield glass on the side opposite to the side to which the windshield glass is bonded, i.e., the laminate of the present invention is applied to a windshield glass made of laminated glass.

[0185] Such a bonded body of the present invention is preferably produced by the bonded body production method of the present invention shown below. Figures 2 and 3 conceptually show an example of a method for producing a bonded body of the present invention. The following explanation will be given, as an example, of a case where the laminate of the present invention is bonded to a windshield glass. However, the present invention is not limited thereto, and various known bonded objects can be used. Examples of bonded objects other than windshield glass include the various types of glass and resin substrates mentioned above.

[0186] In the manufacturing method of the bonded body of the present invention, first, as shown in the upper part of Fig. 2, a windshield glass 28 and the laminate 10 of the present invention are laminated. At this time, lamination is performed so that the adhesive layer 26 of the laminate 10 faces the windshield glass 28. Next, as shown in the second part of Fig. 2, the laminate is placed in a bag 106 such as a rubber bag similar to the example shown in Fig. 7. Here, depending on the curvature of the windshield, when laminating the laminate 10 of the present invention, wrinkles may occur in the laminate 10 as shown in the upper part of Fig. 3 by making the laminate 10 follow the curved shape of the windshield glass 28.

[0187] In order to suppress the above-mentioned wrinkles, the laminate 10 of the present invention has a bending stiffness coefficient S of 0.4×10 ６ [GPa·μm ３ ] or more, and ６ [GPa·μm ３ When the laminate 10 has the above-described bending stiffness coefficient, large localized wrinkles are not generated by the pressure applied by the bag 106, and the laminate 10 is pressed by the bag 106 in a state in which small wrinkles are generated all over the surface, as shown in the middle part of FIG.

[0188] Further, similarly to the above, heat bonding is performed. That is, by heating while reducing the pressure inside the bag 106, the laminate 10 is pressed by the bag 106, and as a result, the laminate 10 is pressed against the windshield glass 28 and heat bonded thereto.

[0189] A sheet of film, rubber, cloth, or the like may be sandwiched between the laminate 10 and the bag 106 and then heat-pressed. By sandwiching the sheet and then heat-pressing the laminate 10, it is possible to suppress indentations caused by dust that has become mixed in between the laminate 10 and the bag 106 being pressed against the laminate 10. Furthermore, if the slipperiness between the laminate 10 and the bag 106 is poor, it is possible to reduce uneven deaeration by sandwiching a sheet with good slipperiness between both the laminate 10 and the bag 106.

[0190] The material of the film is not particularly limited, but examples thereof include acrylic resin films, polycarbonate (PC) resin films, cellulose ester resin films such as triacetyl cellulose (TAC) resin films, polyethylene terephthalate (PET) resin films, polyolefin resin films, polyester resin films, and acrylonitrile-butadiene-styrene copolymer films, and from the viewpoint of heat resistance, polycarbonate resin films, cellulose ester resin films, and polyethylene terephthalate resin films are preferred.

[0191] The film may have a surface irregularity from the viewpoint of improving the slipperiness. The surface irregularity can be imparted by a known method such as adding a matting agent to the film or embossing the film.

[0192] The surface of the film is preferably subjected to an antistatic treatment in order to reduce adhesion of foreign matter during thermocompression bonding. The antistatic treatment can be carried out by a known method such as adding an antistatic agent.

[0193] The rubber is not particularly limited in terms of material, but examples thereof include butadiene rubber (BR), styrene-butadiene rubber (SBR), chloroprene rubber (CR), isoprene rubber (IR), acrylonitrile-butadiene rubber (NBR), ethylene-propylene-diene rubber (EPDM), butyl rubber (IIR), chloroprene rubber (CR), silicone rubber, and fluororubber, with EPDM rubber, silicone rubber, and fluororubber being preferred from the viewpoint of heat resistance. These may be used alone or in combination of two or more.

[0194] The rubber may have an uneven surface from the viewpoint of improving the slipperiness. The uneven surface can be imparted by a known method such as adding a matting agent to the rubber or embossing the rubber.

[0195] The rubber is preferably subjected to an antistatic treatment on its surface in order to reduce adhesion of foreign matter during heat and pressure bonding. The antistatic treatment can be carried out by a known method such as adding an antistatic agent.

[0196] The rubber may be formed into a film by a known method, or a commercially available product may be used. Examples of commercially available rubbers include EB240N, EB250N, EB260N, EB270N, EB280W, EB265N, EB565N, and EB360E2 (EPDM rubbers, manufactured by Maxell Kureha Co., Ltd.), SW940D, SW950D, SW960D, SW970D, SR950D, SR930T, SR940T, SH950T, and SW955T (silicone rubbers, manufactured by Maxell Kureha Co., Ltd.), and FB750N, FB760N, FB770N, FB780N, FB880N, and FB970N (fluororubbers, manufactured by Maxell Kureha Co., Ltd.).

[0197] The cloth is preferably made of a dust-free material in order to reduce the generation and adhesion of foreign matter during heat and pressure bonding, and is preferably sewn with conductive carbon yarn in order to prevent static electricity.

[0198] The fabric may be prepared by a known method, or a commercially available product such as HM-CLC (manufactured by Tanimura Co., Ltd.) may be used.

[0199] The above-mentioned film, rubber, cloth, etc. are preferably the same size as or larger than the laminate 10 so that the pressure from the bag 106 can be transmitted to the laminate 10 evenly.

[0200] The above-mentioned film, rubber, cloth, etc. may be the same size as the windshield glass 28 or may be larger in size.

[0201] In addition, the thermocompression bonding may be vacuum thermocompression bonding, and conditions such as the degree of vacuum and heating temperature may be set appropriately depending on the material forming the adhesive layer 26, the heat resistance of the other materials forming the laminate 10, and the thickness of the laminate 10, etc.

[0202] After completion of the thermocompression bonding, the laminate 10 and the windshield glass 28 are removed from the bag, and the laminate 10 and the windshield glass 28 are further thermocompression bonded in an autoclave in the same manner as above, as shown in the third row of Fig. 2. After completion of the thermocompression bonding in the autoclave, the laminate is removed from the autoclave and cooled, as shown in the lower row of Fig. 2.

[0203] Here, as described above, the laminate 10 of the present invention has a substrate with an oxygen permeability coefficient of 300 cc / m ２ Therefore, as shown in the lower part of Figure 3, the bubble defects are eliminated by heating and pressurizing in the autoclave.

[0204] The conditions of the autoclave, such as the pressure and heating temperature, may be set appropriately depending on the material forming the adhesive layer 26, the heat resistance of the other materials forming the laminate 10, the thickness of the laminate 10, etc.

[0205] The image display system of the present invention includes the laminate of the present invention and an image display device that projects an image onto the laminate of the present invention. Figure 4 conceptually shows an example in which the image display system of the present invention is used in a head-up display system. In the following description, the head-up display system is also referred to as HUD.

[0206] The HUD 30 shown in Fig. 4 includes a laminate 10A of the present invention and a projector 32. As conceptually shown in Fig. 5, the laminate 10A is attached to a windshield glass 28 with the adhesive layer 26 facing the windshield glass 28. The laminate 10A is obtained by attaching the laminate 10 shown in Fig. 1 to the windshield glass 28 and then peeling off the protective film 12.

[0207] The projector 32 shown in FIG. 4 includes an image forming section 34 , an intermediate image screen 36 , a mirror 38 , and a concave mirror 40 .

[0208] 4, the projection light projected by the projector 32 passes through a transparent window 46 provided on a dashboard 42 of a vehicle equipped with the HUD 30, as indicated by the dashed-dotted line, enters the laminate 10A bonded to the windshield glass 28, is reflected by the reflective layer 20, and is observed by the driver D (also indicated by the dashed-dotted line). As with known HUDs, in the illustrated HUD 30, the driver D observes a virtual image of the image projected on the windshield glass 28.

[0209] The image forming unit 34 has an LCD (Liquid Crystal Display) 50 and a projection lens 52. Both the LCD 50 and the projection lens 52 are well-known devices used in HUD projectors. The image forming unit 34 projects the image displayed by the LCD 50 onto the intermediate image screen 36 using the projection lens 52. In the projector 32, the intermediate image screen 36 converts the projected image into a real image, which is then reflected along a predetermined optical path by the mirror 38 and the concave mirror 40. As described above, this reflected light passes through the transmission window 46 provided in the dashboard 42, enters the laminate 10A, and is reflected, allowing the projected image to be observed by the driver D.

[0210] In a preferred embodiment, the LCD 50 displays a p-polarized image (projected image). That is, in a preferred embodiment of the HUD 30 of the present invention, the projector 32 emits p-polarized projection light. Therefore, if the LCD 50 does not display p-polarized projection light, it is preferable to provide a polarizer that converts the projection light from the LCD 50 to p-polarized light, for example, somewhere along the optical path of the projection light from the LCD 50 to the concave mirror 40. Any known polarizer can be used. Alternatively, a polarizer that converts the projection light from the LCD 50 to p-polarized light may be provided outside the projector 32, i.e., somewhere along the optical path of the projection light from the concave mirror 40 to the windshield glass 28.

[0211] The illustrated laminate 10A uses a cholesteric liquid crystal layer as the reflective layer 20, for example. In the illustrated laminate 10A, the retardation layer 18 is a quarter-wave plate, for example. This quarter-wave plate converts incident p-polarized light into circularly polarized light with a rotational direction that is selectively reflected by the reflective layer 20, i.e., the cholesteric liquid crystal layer. Therefore, the laminate 10A converts p-polarized light into circularly polarized light using the retardation layer 18, reflects this circularly polarized light using the reflective layer 20, and converts the circularly polarized light back to p-polarized light using the retardation layer 18. This allows the laminate 10A to selectively reflect p-polarized light. As is well known, polarized sunglasses selectively block S-polarized light. Therefore, by emitting p-polarized projection light from the projector 32, a p-polarized image can be projected, allowing the driver D to view the image projected by the HUD 30 even when wearing polarized sunglasses.

[0212] In the projector constituting the HUD of the present invention, the image forming unit 34 is not limited to one using the LCD 50, and various known image forming means used in HUD projectors can be used. Examples of such known image forming means used in HUD projectors (imagers) include a fluorescent display tube, a liquid crystal on silicon (LCOS) display using liquid crystal, an organic electroluminescence (organic EL) display, and a digital light processing (DLP) display using a digital micromirror device (DMD). In these image forming means, similar to the LCD 50, a projection lens projects a projected image onto the intermediate image screen 36. Furthermore, the image forming means of the image forming unit 34 can also be an image forming means using light beam scanning.

[0213] The projection light emitted from the image forming unit 34 is then converted into a real image (visible image) by the intermediate image screen 36. There are no limitations on the intermediate image screen 36, and various known intermediate image screens that convert the projected image into a real image in the HUD projector can be used. Specific examples of the intermediate image screen 36 include a scattering film, a microlens array, and a screen for rear projection.

[0214] As described above, the projected light that has been formed into a real image on the intermediate image screen 36 is reflected along a predetermined optical path by the mirror 38 and the concave mirror 40, passes through the transparent window 46 provided in the dashboard 42, and is projected onto the laminate 10A bonded to the windshield glass 28, where it is observed by the driver D (see the dotted line).

[0215] The mirror 38 is a known mirror used in a projector to adjust the optical path of the projection light. The mirror 38 may also be a so-called cold mirror that reflects visible light and transmits infrared light, thereby preventing heating of the components of the projector 32 due to sunlight entering through the windshield glass. On the other hand, the concave mirror 40 is a known concave mirror that enlarges and projects the projection light and is used in a HUD projector.

[0216] Although the projector 32 in the illustrated example uses a mirror 38 and a concave mirror 40 as components that change the optical path of the projected light, the present invention is not limited to this. For example, the projector 32 may have only one of the mirror 38 and the concave mirror 40, or may have one or more other light-reflecting elements, such as a free-form mirror, in addition to or instead of the mirror 38 and / or the concave mirror 40. In other words, the projector that constitutes the HUD of the present invention can be configured using various light-reflecting elements.

[0217] As described above, the projector 32 emits p-polarized projection light. The p-polarized projection light projected by the projector 32 and transmitted through the transmission window 46 then passes through the hard coat layer 14 and the transparent resin layer 16 and enters the retardation layer 18. As described above, the retardation layer 18 is a quarter-wave plate that converts the incident p-polarized projection light into circularly polarized light with a rotation direction that is selectively reflected by the reflective layer 20 (cholesteric liquid crystal layer). The circularly polarized projection light converted by the retardation layer 18 is reflected by the reflective layer 20 and re-enters the retardation layer 18, where it is converted back to p-polarized light by the retardation layer 18. The projection light converted to p-polarized light by the polarization conversion layer 24 is irradiated onto the viewing position of the driver D. Here, because the projected image is p-polarized, the driver D can properly view the projected image even when wearing polarized sunglasses, as described above. Furthermore, as described above, the laminate of the present invention can be attached to a curved substrate such as windshield glass 28 without causing wrinkles, etc. Therefore, HUD 30, which reflects projected light from projector 32 using laminate 10A, which is the laminate of the present invention, can project high-quality images without image distortion caused by wrinkles, etc. in laminate 10A, regardless of whether polarized sunglasses are worn or not.

[0218] On the other hand, when glare-causing s-polarized light, such as light reflected from a puddle or the hood, enters from outside the vehicle, this s-polarized light passes through windshield glass 28 and enters laminate 10A, and then passes through adhesive layer 26 and enters polarization conversion layer 24. The s-polarized light that enters polarization conversion layer 24 is converted into elliptically polarized light with a rotation direction corresponding to the s-polarized light, for example, by the helical structure of the liquid crystal compound in polarization conversion layer 24.

[0219] The elliptically polarized light that has passed through the polarization conversion layer 24 then enters the reflective layer 20. As described above, the reflective layer 20 is a cholesteric liquid crystal layer that selectively reflects circularly polarized light converted from p-polarized light by the retardation layer 18. Therefore, elliptically polarized light with a rotation direction corresponding to s-polarized light passes through the reflective layer 20. Furthermore, by passing through the reflective layer 20 (cholesteric liquid crystal layer), the elliptically polarized light with a rotation direction corresponding to s-polarized light is converted to circularly polarized light with a rotation direction corresponding to s-polarized light. The circularly polarized light that has passed through the reflective layer 20 enters the retardation layer 18. As described above, the retardation layer 18 is a quarter-wave plate that converts p-polarized light into circularly polarized light that is selectively reflected by the cholesteric liquid crystal layer that constitutes the reflective layer 20. Therefore, the circularly polarized light with a rotation direction corresponding to s-polarized light that has entered the retardation layer 18 passes through the retardation layer 18 and is converted to s-polarized light. In this way, s-polarized light that causes glare and enters from outside the vehicle passes through the laminate 10A as s-polarized light. Therefore, this s-polarized light is blocked by polarized sunglasses even when it reaches the driver D. That is, when the laminate of the present invention is used in a HUD, it has a polarization conversion layer, and thus compensates for the change in polarization of external light caused by the retardation layer and the reflective layer, and s-polarized light that enters from outside the vehicle and causes glare can be transmitted as s-polarized light, making it possible to block the light with polarized sunglasses.

[0220] The image display system of the present invention is not limited to the HUD shown in the figure, and can be used in various known image display systems as long as it includes the laminate of the present invention and an image display device that projects an image onto the laminate of the present invention.

[0221] The laminate, the bonded body, the image display system, and the method for manufacturing the bonded body of the present invention have been described in detail above, but the present invention is not limited to the above-mentioned embodiments, and various improvements or modifications may be made within the scope of the present invention.

[0222] The features of the present invention will be explained in more detail below with reference to examples. The materials, reagents, amounts and proportions of substances, and procedures shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the following examples.

[0223] <Preparation of Transparent Resin Layer 1> A cellulose acylate film having a thickness of 40 μm was prepared by the same preparation method as in Example 20 of WO 2014 / 112575, except that UV-531 manufactured by Teisei Chemical Industry Co., Ltd. was used as the ultraviolet absorber and the amount added was 3 phr (per hundred resin). The prepared cellulose acylate film was passed through a dielectric heating roll at a temperature of 60° C. to raise the surface temperature of the film to 40° C., and then an alkaline solution having the composition shown below was applied to one side of the film using a bar coater in an amount of 14 mL / m ２ The coating was then allowed to stand for 10 seconds under a steam-type far-infrared heater (manufactured by Noritake Co., Ltd.) heated to 110°C. Next, pure water was applied at a rate of 3 mL / m using the same bar coater. ２ Next, the coating was washed with water using a fountain coater and then drained with an air knife three times, and then allowed to stay in a drying zone at 70° C. for 5 seconds to dry, thereby preparing a transparent resin layer 1.

[0224] --------------------------------------------------- Composition of alkaline solution --------------------------------------------------- Potassium hydroxide 4.7 parts by mass Water 15.7 parts by mass Isopropanol 64.8 parts by mass Surfactant (C １６ H ３３ O (CH ２ CH ２ O) １０ H) 1.0 part by mass Propylene glycol 14.9 parts by mass

[0225] <Preparation of Protective Film P-1> Novatec HF560 (manufactured by Japan Polyethylene Co., Ltd.) was prepared as the resin constituting the base layer. Ultrathene (registered trademark) 750 (manufactured by Tosoh Corporation) was prepared as the ethylene-vinyl acetate copolymer constituting the adhesive layer. Novatec (registered trademark) LC522 (manufactured by Japan Polyethylene Co., Ltd.) was also used as the polyethylene resin constituting the adhesive layer. Next, a resin mixture for the adhesive layer was prepared by blending the ethylene-vinyl acetate copolymer and the polyethylene resin at a mass ratio of 50:50. Next, using a T-die type composite film-forming machine having two extruders, the resin constituting the base layer and the resin mixture for the adhesive layer were charged into each extruder, and the discharge rate of each extruder was adjusted (220 ° C) so that the base layer thickness ratio was 96% and the adhesive thickness ratio was 4%, resulting in a film thickness of 300 μm. Protective film P-1, a two-layer laminate film (polyethylene film / adhesive layer), was prepared.

[0226] <Preparation of Protective Film P-2> A 16 μm thick PET film (16KS40, manufactured by Toray Industries, Inc.) was prepared as the base layer, and MF-58 (adhesive layer thickness: 12 μm, manufactured by Tomoegawa Paper Co., Ltd.) was prepared as the adhesive layer. After peeling off the light release film of MF-58, the exposed adhesive layer was brought into contact with the surface of the PET film, and the PET film was laminated with a rubber roller under a load of 2 kg, to prepare a protective film P-2 having a configuration of PET film / adhesive layer / heavy release film.

[0227] <Preparation of Protective Film P-3> Protective film P-3 was prepared in the same manner as protective film P-2, except that a 75 μm thick PET film (Lumirror T60, manufactured by Toray Industries, Inc.) was used as the substrate layer.

[0228] <Preparation of Protective Film P-4> Protective film P-4 was prepared in the same manner as protective film P-2, except that a 125 μm thick PET film (Lumirror T60, manufactured by Toray Industries, Inc.) was used as the substrate layer.

[0229] <Preparation of Protective Film P-5> Protective film P-5 was prepared in the same manner as protective film P-2, except that a 250 μm thick PET film (Lumirror T60, manufactured by Toray Industries, Inc.) was used as the substrate layer.

[0230] <Preparation of Protective Film P-6> Protective film P-6 was prepared in the same manner as protective film P-2, except that a 12 μm thick PET film with an alumina layer (Barrierox 1011SBR2, manufactured by Toray Advanced Film Co., Ltd.) was used as the substrate layer.

[0231] <Preparation of Protective Film P-7> Protective film P-7 was prepared in the same manner as protective film P-1, except that the film thickness was changed to 200 μm.

[0232] [Preparation of substrate]

[0233] <Preparation of Substrate 1> The adhesive layer of the above-mentioned protective film P-1 was attached to the surface of the above-mentioned transparent resin layer 1 opposite to the surface treated with the alkaline solution, with the surface in contact with the adhesive layer, while applying a load of 2 kg with a rubber roller, to prepare a substrate 1 having a polyethylene film / adhesive layer / transparent resin layer 1 configuration.

[0234] <Preparation of Substrate 2> After peeling off the heavy release film of the above-mentioned protective film P-2, the exposed adhesive layer was attached to the surface of the above-mentioned transparent resin layer 1 opposite to the surface treated with the alkaline solution, with the surface in contact with the surface, while applying a load of 2 kg with a rubber roller, to prepare a substrate 2 having a configuration of PET film / adhesive layer / transparent resin layer 1.

[0235] <Preparation of Substrate 3> Substrate 3 was prepared in the same manner as substrate 2, except that protect film P-3 was used instead of protect film P-2.

[0236] <Preparation of Substrate 4> Substrate 4 was prepared in the same manner as substrate 2, except that protect film P-4 was used instead of protect film P-2.

[0237] <Preparation of Substrate 5> Substrate 5 was prepared in the same manner as substrate 2, except that protect film P-5 was used instead of protect film P-2.

[0238] <Preparation of Substrate 6> Substrate 6 was prepared in the same manner as substrate 2, except that protect film P-6 was used instead of protect film P-2.

[0239] <Preparation of substrate 7>

[0240] (Preparation of curable composition for forming hard coat layer (HC layer)) The components were mixed according to the formulation shown in Table 1 below, and filtered through a polypropylene filter having a pore size of 10 μm to prepare curable composition HC-1 for forming a HC layer. The blending amount of each component shown in Table 2 is expressed in parts by mass.

[0241]

[0242] PAG-1 is the following compound:

[0243]

[0244] (Formation of Hard Coat Layer) An HC layer-forming curable composition HC-1 was applied to the surface of the transparent resin layer 1 prepared above opposite to the surface treated with the alkaline solution, and cured to form an HC1 layer with a film thickness of 6 μm. Specifically, the application and curing methods were as follows. The HC layer-forming curable composition HC-1 was applied at a conveying speed of 30 m / min by the die coating method using a slot die described in Example 1 of JP-A-2006-122889, and dried at an atmospheric temperature of 60°C for 60 seconds to obtain a coating film. Thereafter, under a nitrogen purge, an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) with an oxygen concentration of about 0.1% by volume and an illuminance of 150 mW / cm was applied to the coating film. ２ , irradiation amount 600mJ / cm ２ The coating film was cured by irradiating it with ultraviolet light of 1000 kJ / cm 2 to form an HC layer, thereby obtaining a film HC1 having a structure of HC layer / transparent resin layer 1.

[0245] After peeling off the heavy release film of the above-mentioned protective film P-4, the exposed adhesive layer was attached to the HC layer side of the above-mentioned film HC1 with the surface in contact with it while applying a load of 2 kg with a rubber roller, thereby producing a substrate 7 having a configuration of PET film / adhesive layer / HC layer / transparent resin layer 1.

[0246] <Preparation of substrate 8>

[0247] (Preparation of reflective layer-forming composition, retardation layer-forming composition, and polarization conversion layer-forming composition) The components were mixed according to the formulations shown in Table 2 below and filtered through a polypropylene filter with a pore size of 10 μm to prepare reflective layer-forming compositions BG1, R1, and IR1, retardation layer-forming composition A1, and polarization conversion layer-forming composition TW1. The blending amount of each component shown in Table 2 is expressed in parts by mass. Note that mixture 1, alignment control agent 1, and alignment control agent 2 are the following compounds.

[0248]

[0249]

[0250]

[0251]

[0252] (Formation of Alignment Film) A coating solution for forming an alignment film having the composition shown below was applied to the surface of the transparent resin layer 1 obtained above, which had been treated with the alkaline solution, at a rate of 24 mL / m using a wire bar coater. ２ The coating was dried with hot air at 100° C. for 120 seconds to obtain an alignment film having a thickness of 0.5 μm.

[0253] ------------------------------------------------------------------ Composition of coating liquid for forming alignment film -------------------------------------------------- 28 parts by mass of modified polyvinyl alcohol shown below 1.2 parts by mass of citric acid ester (AS3, manufactured by Sankyo Chemical Co., Ltd.) 0.84 parts by mass of photopolymerization initiator (Irgacure 2959, manufactured by BASF) 2.8 parts by mass of glutaraldehyde 699 parts by mass of water 226 parts by mass of methanol ------------------------------------------------------------------

[0254] (Modified polyvinyl alcohol)

[0255] (Preparation of Reflective Film) The alignment film prepared above was subjected to a rubbing treatment (rayon cloth, pressure: 0.1 kgf (0.98 N), rotation speed: 1000 rpm (revolutions per minute), conveying speed: 10 m / min, number of strokes: 1 round trip) in a direction rotated 45° clockwise from the long side direction of the substrate.

[0256] The reflective layer-forming composition IR1 was applied to the rubbed alignment film surface at room temperature using a wire bar to obtain a coating film with a dry film thickness of 0.4 μm. The coating film was dried at room temperature for 30 seconds and then heated in an 85°C atmosphere for 2 minutes. The coating film was then irradiated with ultraviolet light at 60% output for 6 to 12 seconds using a Fusion D-bulb (90 mW / cm lamp) at 60°C in an environment with an oxygen concentration of 1000 ppm or less, thereby fixing the cholesteric liquid crystal phase and obtaining a 0.4 μm-thick cholesteric liquid crystal layer IR1. Next, the same process was repeated using the reflective layer-forming composition BG1 on the surface of the obtained cholesteric liquid crystal layer IR1, resulting in a 0.84 μm-thick cholesteric liquid crystal layer BG1. Next, the same process was repeated using the reflective layer-forming composition R1 on the surface of the obtained cholesteric liquid crystal layer BG1, resulting in a 0.36 μm-thick cholesteric liquid crystal layer R1. In this way, a film A1 was obtained having a structure of R1 / BG1 / IR1 / transparent resin layer 1. When the transmission spectrum of film A1 was measured with a spectrophotometer (manufactured by JASCO Corporation, V-670), a transmission spectrum having selective reflection center wavelengths at 515 nm, 685 nm, and 775 nm was obtained.

[0257] (Formation of hard coat layer) On the surface of the above film A1 opposite to the liquid crystal layer, the curable composition HC-1 for forming an HC layer was applied in the same manner as for the substrate 7, and cured to form an HC1 layer with a thickness of 6 μm, thereby obtaining a film HC2 having a structure of HC layer / transparent resin layer 1 / IR1 / BG1 / R1.

[0258] After peeling off the heavy release film of the above-mentioned protect film P-4, the exposed adhesive layer was attached to the HC layer side of the above-mentioned film HC2 with the surface in contact with it while applying a load of 2 kg with a rubber roller, thereby producing a substrate 8 having a configuration of PET film / adhesive layer / HC layer / transparent resin layer 1 / IR1 / BG1 / R1.

[0259] <Preparation of Substrate 9> A substrate 9 having a structure of PET film / adhesive layer / HC layer / transparent resin layer 1 / A1 / IR1 / BG1 / R1 was prepared in the same manner as the substrate 8, except that a composition A1 for forming a retardation layer was applied to a rubbed alignment film surface using a wire bar, dried, and then cured under the following conditions, and a composition IR1 for forming a reflective layer was applied onto the cured retardation layer A1.

[0260] (Curing Conditions for Composition A1 for Forming Retardation Layer) After the composition A1 for forming a retardation layer was applied and dried to obtain a coating film, the coating film was placed on a hot plate at 50°C and cured with an electrodeless lamp "D Bulb" (60 mW / cm) manufactured by Fusion UV Systems in an environment with an oxygen concentration of 1000 ppm or less. 2 The coating film was irradiated with ultraviolet light for 6 seconds using a UV ray irradiator (UV irradiator) to form a retardation layer. This resulted in a retardation layer having a thickness adjusted to achieve a desired front retardation, i.e., a desired retardation. The retardation of the prepared retardation layer at 550 nm was measured using an AxoScan manufactured by Axometrics, and was found to be 126 nm.

[0261] <Preparation of substrate 10> A polarization conversion layer TW1 was applied to the cholesteric liquid crystal layer R1 to a thickness of 1.5 μm in the same manner as the substrate 9, except that a laminate of a substrate 11 having a structure of PET film / adhesive layer / HC layer / transparent resin layer 1 / A1 / IR1 / BG1 / R1 / TW1 was prepared. The polarization conversion layer TW1 was prepared by applying the polarization conversion layer-forming composition TW1 to the cholesteric liquid crystal layer R1 at room temperature using a wire bar, and then drying the coating at room temperature for 30 seconds and heating it in an 85 ° C. atmosphere for 2 minutes. Then, in an environment with an oxygen concentration of 1000 ppm or less, the coating was irradiated with ultraviolet light at 60% output for 6 to 12 seconds using a Fusion D bulb (90 mW / cm lamp) at 60 ° C. to form a polarization conversion layer.

[0262] <Preparation of Substrate 11> Based on the method described in JP-A-9-506837, the substrate 11 was prepared as follows.

[0263] 2,6-Polyethylene naphthalate (PEN) and a 70% naphthalate / 30% terephthalate copolyester (coPEN) were synthesized in a standard polyester resin synthesis reactor using ethylene glycol as the diol. Monolayer films of PEN and coPEN were extruded, stretched at approximately 150°C with a 5:1 draw ratio, and heat-treated at approximately 230°C for 30 seconds. The refractive index of the PEN film along the slow axis (orientation axis) was found to be approximately 1.86, the refractive index along the transverse axis was found to be 1.64, and the refractive index of the coPEN film was found to be approximately 1.64.

[0264] By adjusting the stretch ratio, the refractive index of the PEN film along the slow axis was found to be about 1.71, that along the transverse axis was found to be 1.64, and that of the coPEN film was found to be about 1.64. That is, the difference Δn between the refractive index of the optically anisotropic layer along the slow axis and that of the isotropic layer was found to be 0.07.

[0265] Next, PEN and coPEN were coextruded using a 25-slot feed block equipped with a standard extrusion die to form 16 alternating layers of PEN and coPEN with the thicknesses shown in (1) of Table 3. The same procedure was repeated to form 16 alternating layers of PEN and coPEN in order with the thicknesses shown in (2) to (6) of Table 3, thereby producing a laminate having a total of 96 layers.

[0266]

[0267] Next, the stretched laminate was heat-treated in an air oven at about 230°C for 30 seconds to produce a substrate 11. The thickness of the produced substrate 11 was 50 µm. When the reflection spectrum of this substrate 11 was measured using a spectrophotometer (V-670, manufactured by JASCO Corporation), a reflection spectrum with reflectance peaks in the reflection bands of 450 nm, 550 nm, 650 nm, 700 nm, 750 nm, and 800 nm was obtained.

[0268] <Preparation of Substrate 12> Substrate 12 was prepared in the same manner as substrate 11, except that the thickness was set to 100 μm.

[0269] <Preparation of Substrate 13> Substrate 13 was prepared in the same manner as substrate 1, except that protect film P-7 was used instead of protect film P-1.

[0270] [Example 1]

[0271] <Preparation of adhesive layer-forming compositions> The components were mixed according to the formulations shown in Table 4 below, and filtered through a polypropylene filter with a pore size of 10 μm to prepare adhesive layer-forming compositions HS1 to HS5. The blending amount of each component shown in Table 4 below is expressed in parts by mass.

[0272]

[0273] [Preparation of Laminate] <Formation of Adhesive Layer> The adhesive layer-forming composition HS1 was applied to the surface of the substrate 1 (polyethylene film / adhesive layer / transparent resin layer 1) opposite the protective film P-1 (polyethylene film / adhesive layer) using a wire bar so that the film thickness after drying would be 0.5 μm, and then the coating was dried at 120° C. for 1 minute to form a coating. Thereafter, the coating was further purged with nitrogen and exposed to an illuminance of 150 mW / cm using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) at an oxygen concentration of about 0.1% by volume and a power of 160 W / cm. ２ , irradiation amount 300mJ / cm ２ The coating film was cured by irradiating it with ultraviolet light of 1000 kJ / cm 2 , thereby preparing a laminate of Example 1 having a structure of protective film P-1 / transparent resin layer / adhesive layer.

[0274] Examples 2 to 6 and 13 to 16 Laminates of Examples 2 to 6 and 13 to 16 were prepared in the same manner as in Example 1, except that substrates 2 to 10 were used instead of substrate 1.

[0275] Example 7 A laminate of Example 7 was produced in the same manner as in Example 1, except that the adhesive layer was applied so as to have a thickness of 1.0 μm.

[0276] Example 8 A laminate of Example 8 was produced in the same manner as in Example 1, except that the adhesive layer was applied so as to have a thickness of 5.0 μm.

[0277] Example 9 A laminate of Example 9 was produced in the same manner as in Example 1, except that the adhesive layer was applied so as to have a thickness of 10.0 μm.

[0278] Example 10 A laminate of Example 10 was produced in the same manner as in Example 1, except that the adhesive layer was applied so that the thickness was 20.0 μm.

[0279] Example 11 A laminate of Example 11 was produced in the same manner as in Example 4, except that the adhesive layer was applied so as to have a thickness of 10.0 μm.

[0280] Example 12 A laminate of Example 12 was produced in the same manner as in Example 5, except that the adhesive layer was applied so that the thickness was 20.0 μm.

[0281] Example 17 A laminate of Example 17 having a structure of substrate 11 / adhesive layer was produced in the same manner as in Example 9, except that substrate 11 was used instead of substrate 1.

[0282] Example 18 A laminate of Example 18 was produced in the same manner as in Example 17, except that the adhesive layer was coated so as to have a thickness of 50.0 μm.

[0283] Example 19 A laminate of Example 19 having a structure of substrate 12 / adhesive layer was produced in the same manner as in Example 18, except that substrate 12 was used instead of substrate 11 .

[0284] Comparative Example 1 A laminate of Comparative Example 1 was produced in the same manner as in Example 1, except that the substrate 13 was used instead of the substrate 1.

[0285] [Evaluation] [Measurement of oxygen permeability coefficient] The oxygen permeability coefficient was measured based on ISO 15105-2 (isobaric method) as follows. The substrates of the examples and comparative examples were attached to the electrodes of a tester (oxygen concentration meter model 3600 manufactured by Hack Ultra Analytical) at 25°C and 50% RH with silicone grease. ２After purging for 2 hours at 100°C, the electrode was opened to the atmosphere and allowed to stand for 90 minutes until the oxygen concentration reached a steady state. If the electrode did not reach a steady state within 90 minutes, the electrode was allowed to stand for another 90 minutes. The oxygen permeability coefficient of the substrate was calculated from the amount of oxygen that reached the electrode at a steady state. The results are shown in Table 5 below.

[0286] [Measurement of Tensile Modulus] The tensile modulus was measured and calculated by the following method in accordance with the method described in JIS K7127. The results are shown in Table 5 below. For the laminates of the Examples and Comparative Examples, a width of 10 mm and a length of 150 mm were cut out, with the length aligned in each direction rotated 45° clockwise from one in-plane direction as a reference. The cut-out sample pieces were placed in a tensile tester (manufactured by Toyo Seiki Seisakusho, trade name "Strograph-R2") so that the chuck spacing in the measurement direction was 100 mm, and stretched at a stretching rate of 300 mm / min at a measurement temperature of 25°C so that the chuck spacing increased, to obtain a stress-strain curve. The tensile modulus was calculated by linear regression of the curve between the two specified strains ε1 = 0.0005 and ε2 = 0.0025. The in-plane direction of the laminate corresponding to the length direction of the test piece showing the maximum tensile modulus of elasticity among the tensile moduli of the above sample pieces was defined as the first direction, and the direction perpendicular to the first direction was defined as the second direction.The average value of the tensile modulus of elasticity in the first direction and the tensile modulus of elasticity in the second direction was defined as the average tensile modulus of elasticity of the laminate.

[0287] [Film Thickness Measurement] The film thickness was measured by observation with a scanning electron microscope (SEM) using the following method. The cross sections of the laminates of the Examples and Comparative Examples were exposed using a standard method such as an ion beam or a microtome, and the exposed cross sections were then observed using an SEM. In the cross-sectional observation, the laminate was divided into four equal parts in the width direction, and the film thickness of the laminate was determined as the arithmetic mean of the film thicknesses at three equal division points excluding both ends. The results are shown in Table 5 below.

[0288] [Evaluation of bubble defects] The bubble defects were evaluated as follows. In an environment with a cleanliness level of 1000, the laminates of the examples and comparative examples, each measuring 90 mm long and 90 mm wide, were placed on a 100 mm wide and 100 mm long flat glass plate at the center of the glass substrate, with the adhesive layer facing the contact surface. The front and back of the laminate and glass were cleaned with an adhesive roller to remove only dust adhering to the adhesive roller, while dust not adhering to the adhesive roller was left unremoved. This was placed in a rubber bag and the pressure was reduced to 10 kPa (0.1 atmospheres) using a vacuum pump. The temperature was then increased to 95°C under reduced pressure, held for 20 minutes, and then temporarily returned to room temperature and pressure. The laminate and glass substrate were then held at 130°C and 1.1 MPa (11 atmospheres) for 20 minutes in an autoclave (manufactured by Kurihara Seisakusho) to bond the adhesive layer to each other, thereby obtaining a glass sample. For laminates with a protective film laminated thereon, the protective film was peeled off after autoclaving. A central 5 cm square portion of the glass sample was observed with an optical microscope for bubble defects caused by dust, and evaluated according to the following criteria. The results are shown in Table 5 below. A: No bubble defects with a diameter of 100 μm or more were present. B: 1 to 5 bubble defects with a diameter of 100 μm or more. C: 6 to 15 bubble defects with a diameter of 100 μm or more. D: 16 to 30 bubble defects with a diameter of 100 μm or more. E: 31 or more bubble defects with a diameter of 100 μm or more.

[0289] [Evaluation of Wrinkles] Wrinkles were evaluated as follows. A 260mm long x 330mm wide laminate of each of the Examples and Comparative Examples was placed on the concave side of a curved glass substrate with a curvature of 330mm long x 1750mm R in the longitudinal direction and 260mm short x 1250mm R in the transverse direction, with the adhesive layer surface in contact with the glass substrate. This was placed in a rubber bag and the pressure was reduced to 10 kPa (0.1 atmospheres) using a vacuum pump. The bag was then heated to 115°C under reduced pressure, held for 60 minutes, and then returned to room temperature and pressure. The bag was then held in an autoclave (manufactured by Kurihara Seisakusho) at 140°C and 1.3 MPa (13 atmospheres) for 60 minutes to remove air bubbles, resulting in a glass sample in which the laminate and glass substrate were bonded together with the adhesive layer. The glass sample was evaluated according to the following criteria. The results are shown in Table 5 below. A: No wrinkles were present. B: There were wrinkles, but not more than two. C: There were more than two wrinkles.

[0290]

[0291] Example 101 A laminate of Example 101 was obtained in the same manner as in Example 16, except that the adhesive layer-forming composition HS2 was used instead of the adhesive layer-forming composition HS1 when forming the adhesive layer.

[0292] Example 102 The adhesive layer side of the laminate of Example 16 was subjected to blasting (time: 1 second) to obtain a laminate of Example 102.

[0293] [Example 103] The laminate of Example 16 was laminated on a 4 mm thick flat glass plate with the protective film side facing the glass, and an embossed paper release liner (manufactured by Loparex LLC, Hammond, WI) was laminated on the adhesive layer side of the laminate of Example 16 with the embossed surface facing the adhesive layer side. A 4 mm thick flat glass plate was then laminated on the opposite side of the embossed surface of the paper release liner. This was placed in a rubber bag and the pressure was reduced to 10 kPa (0.1 atmospheres) using a pump. The temperature was then increased to 100 ° C under reduced pressure, maintained for 10 minutes, and then returned to room temperature and pressure. The flat glass plate and paper release liner were then removed, yielding the laminate of Example 103. The surface structure of the embossed surface of the paper release liner was transferred to the adhesive layer of the laminate of Example 103.

[0294] [Evaluation of Remaining Air Bubbles] The evaluation of remaining air bubbles was as follows. A 260 mm long x 330 mm wide laminate of each of the Examples and Comparative Examples was placed on the concave side of a curved glass substrate with a curvature of 330 mm in the longitudinal direction (R1750 mm) and 260 mm in the transverse direction (R1250 mm), with the adhesive layer surface serving as the contact surface, at the center of the glass substrate. This was placed in a rubber bag and the pressure was reduced to 10 kPa (0.1 atm) using a vacuum pump. The temperature was then increased to 95°C under reduced pressure, held for 20 minutes, and then temporarily returned to room temperature and atmospheric pressure. The autoclave (manufactured by Kurihara Seisakusho) was then held at 130°C and 1.1 MPa (11 atm) for 20 minutes, after which the pressure was rapidly reduced to 100°C and returned to room temperature and atmospheric pressure. The laminate and glass substrate were bonded together with the adhesive layer to obtain a glass sample. The glass sample was evaluated according to the following criteria. The results are shown in Table 6 below. A: No bubbles with a diameter of 1 mm or more exist. B: One or more bubble-like defects with a diameter of 1 mm or more exist.

[0295]

[0296] [Example 201] [Preparation of Laminated Glass] A laminate was prepared using a 125 μm thick PET film (Lumirror T60, manufactured by Toray Industries, Inc.) as the substrate layer, with the following structure: adhesive layer (heat seal layer) / substrate layer / A1 (retardation layer) / IR1 / BG1 / R1 / TW1 (polarization conversion layer). That is, a laminate was prepared in the same manner as in Example 16, except that the position of the adhesive layer was changed. It was confirmed that the prepared laminate had the same effect as in Example 16. Next, the laminate (220 mm long x 290 mm wide) prepared above was placed on a convex curved glass substrate with a layer structure of 260 mm long x 330 mm wide and 2 mm thick, in the center of the glass substrate, with the surface on the adhesive layer (heat seal layer) side as the contact surface. This formed a laminate having, in this order, a first glass substrate, a heat seal layer, a substrate layer, a retardation layer, a selective reflection layer, and a polarization conversion layer. A 260 mm long x 330 mm wide x 0.76 mm thick PVB film (interlayer) manufactured by Sekisui Chemical Co., Ltd. was placed on this laminate, and a 260 mm long x 330 mm wide x 2 mm thick convex curved glass substrate (second glass substrate) was placed on top of that. This was held at 115°C and 10 kPa (0.1 atmospheres) for 1 hour, and then evaluated for air release as described below. The glass was then heated in an autoclave (manufactured by Kurihara Seisakusho) at 140°C and 1.3 MPa (13 atmospheres) for 60 minutes to remove air bubbles, producing a laminated glass.

[0297] Examples 202 to 205 and Comparative Example 301 Laminated glass was produced in the same manner as in Example 201, except that the substrate layer in the laminate produced in Example 201 was changed to the substrate shown in Table 7 below. It was confirmed that the laminates produced in Examples 202 to 205 had the same effects as in Example 16.

[0298] [Example 206] Toretec 7832C (manufactured by Toray Film Processing Co., Ltd.) was attached to the TW1 (polarization conversion layer) side of the laminate of Example 201, with the adhesive layer of Toretec 7832C being attached to the TW1 side, and a laminate having the following order was produced: adhesive layer (heat seal layer) / base layer / A1 (retardation layer) / IR1 / BG1 / R1 / TW1 (polarization conversion layer) / Toretec 7832C. It was confirmed that the produced laminate had the same effect as in Example 16. Next, the laminate (220mm long x 290mm wide) produced above was placed on a convex curved glass substrate with a layer structure of 260mm long x 330mm wide and 2mm thick, with the surface of the adhesive layer (heat seal layer) side as the contact surface, at the center of the glass substrate. Then, Toretec 7832C was peeled off from the laminate, and a laminate having, in this order, a first glass substrate, a heat seal layer, a base layer, a retardation layer, a selective reflection layer, and a polarization conversion layer was formed. On this laminate, a PVB film (interlayer) manufactured by Sekisui Chemical Co., Ltd., measuring 260 mm in length x 330 mm in width and 0.76 mm in thickness was placed, and a convex curved glass substrate (second glass substrate) measuring 260 mm in length x 330 mm in width and 2 mm in thickness was placed on top of that. After holding this at 115 ° C. and 10 kPa (0.1 atmosphere) for 1 hour, the air release evaluation described below was performed, and then heated in an autoclave (manufactured by Kurihara Seisakusho) at 140 ° C. and 1.3 MPa (13 atmospheres) for 60 minutes to remove air bubbles, and a laminated glass was produced.

[0299] The produced laminated glass was heated at 140°C and 1.3 MPa (13 atmospheres) for 60 minutes during the production of the laminated glass, and then the size and number of marks (streaks) formed by crushing bubbles larger than 1 mm in the laminated glass were visually measured and evaluated according to the following criteria. The results are shown in Table 7 below. A rating of C or higher was considered acceptable. A higher rating indicates better air release. A: No marks formed by crushing bubbles larger than 1 mm exist. B: 1 to 5 marks formed by crushing bubbles larger than 1 mm exist. C: 6 to 20 marks formed by crushing bubbles larger than 1 mm exist. D: 21 or more marks formed by crushing bubbles larger than 1 mm exist.

[0300]

[0301] Examples 401 to 403 Laminates of Examples 401 to 403 were obtained in the same manner as in Example 101, except that the adhesive layer-forming composition HS2 was replaced with HS3 to HS5 when forming the adhesive layer.

[0302] [Measurement of Surface Resistivity of Adhesive Layer] The surface resistance of the adhesive layer was evaluated as follows. For the laminates of Examples 101 and 401 to 403, the humidity was conditioned for 24 hours under conditions of a temperature of 23°C and a humidity of 55%, and then the surface resistance of the adhesive layer was measured using a resistivity meter (Hiresta-UX MCP-HT800 manufactured by Mitsubishi Chemical Analytech Co., Ltd.) at an applied voltage of 1000 V. The results are shown in Table 8 below.

[0303] [Evaluation of bubble defects in a non-clean environment] The bubble defects were evaluated as follows. In an environment with a cleanliness level of 10,000, a 90 mm x 90 mm laminate of Examples 101 and 401-403 was placed on a 100 mm wide x 100 mm long flat glass plate at the center of the glass substrate, with the adhesive layer facing the contact surface. The front and back of the glass were cleaned with an adhesive roller to remove only dust adhering to the adhesive roller, while dust not adhering to the adhesive roller was left unremoved. This was placed in a rubber bag and the pressure was reduced to 10 kPa (0.1 atm) using a vacuum pump. The temperature was then increased to 95°C under reduced pressure, held for 20 minutes, and then temporarily returned to room temperature and pressure. The laminate and glass substrate were then held at 130°C and 1.1 MPa (11 atm) for 20 minutes in an autoclave (manufactured by Kurihara Seisakusho) to bond the adhesive layer to each other, thereby obtaining a glass sample. For laminates with a protective film laminated thereon, the protective film was peeled off after autoclaving. A central 5 cm square portion of the glass sample was observed with an optical microscope for bubble defects caused by dust, and evaluated according to the following criteria. The results are shown in Table 8 below. A: No bubble defects with a diameter of 100 μm or more were present. B: 1 to 15 bubble defects with a diameter of 100 μm or more. C: 16 or more bubble defects with a diameter of 100 μm or more.

[0304]

[0305] REFERENCE SIGNS LIST 10, 10A, 10B, 100 Laminate 11 Substrate 12 Protective film 14 Hard coat layer 16 Transparent resin layer 18 Retardation layer 19 Intermediate layer 20 Reflective layer 24 Polarization conversion layer 26 Adhesive layer 27A, 27B Glass 28 Windshield glass 30 HUD (Head-up display system) 32 Projector 34 Image forming unit 36 ​​Intermediate image screen 38 Mirror 40 Concave mirror 42 Dashboard 46 Transmitting window 50 LCD (Liquid crystal display) 52 Projection lens 102 Bonded object 104 Mold 106 Bag D Driver

Claims

1. A laminate having a substrate and an adhesive layer, wherein the substrate has an oxygen permeability coefficient of 300 cc / m ２ .day.atm or less.

2. The laminate according to claim 1, wherein the adhesive layer has a thickness of 0.1 μm or more.

3. The bending stiffness coefficient S expressed by the following formula 1 is 0.4 x 10 ６ [GPa·μm ３ The laminate according to claim 1, wherein the bending stiffness coefficient S is equal to or greater than the average tensile modulus of the laminate [GPa] × (thickness of the laminate [μm]) ３ 4. The laminate according to claim 1, wherein the substrate comprises a protective film and a transparent resin layer.

5. The laminate of claim 1, wherein the substrate further comprises a reflective layer.

6. The laminate according to claim 1, wherein the substrate further comprises a retardation layer.

7. The laminate of claim 1, wherein the substrate further comprises a polarization conversion layer.

8. The laminate according to claim 1, wherein the substrate further comprises a hard coat layer.

9. The laminate according to claim 4, wherein the substrate further comprises a hard coat layer, a reflective layer, a retardation layer, and a polarization conversion layer.

10. The laminate of claim 1, wherein the adhesive layer comprises an antistatic agent.

11. The surface resistance of the adhesive layer is 1.0 x 10 １４ The laminate according to claim 10, having a resistance of Ω / □ or less.

12. The laminate according to claim 1, wherein the substrate comprises at least a resin substrate.

13. The laminate according to any one of claims 1 to 12, which is attached to glass via the adhesive layer.

14. The laminate according to any one of claims 1 to 12, which is attached to a windshield glass via the adhesive layer.

15. A laminate comprising glass and the laminate according to any one of claims 1 to 12 laminated to the glass.

16. The laminate according to claim 15, further comprising glass on the side of the laminate opposite to the side to which the glass is attached.

17. A laminate comprising a windshield glass and the laminate according to any one of claims 1 to 12 attached to the windshield glass.

18. The laminate according to claim 17, further comprising a windshield glass on the side of the laminate opposite to the side to which the windshield glass is attached.

19. An image display system comprising the laminate according to any one of claims 1 to 12 and an image display device that projects an image onto the laminate.

20. A method for manufacturing a laminate, comprising: Step 1: laminating a curved object to be laminated and the laminate according to any one of claims 1 to 12 with the adhesive layer of the laminate facing the object to be laminated, and placing the laminate in a bag; and, without using a mold having a surface corresponding to the curved shape, reducing the pressure inside the bag to align the laminate with the curved shape to obtain a laminate; and Step 2: heat-pressing the laminate obtained in Step 1.

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