TW202120324A - Laminate and article - Google Patents

Abstract

The present invention pertains to a laminate further comprising an adhesive layer on a first barrier layer-side surface of a laminated film in which a base film, an optical adjustment layer, and a first barrier layer are provided in this order, wherein: the optical adjustment layer contains at least one selected from the group consisting of a metal oxide, a metal nitride, and a metal sulfide and has a refractive index of at least 1.75; the first barrier layer contains a metal oxide and/or a metal nitride; and the moisture permeability of the laminated film at a temperature of 40 DEG C and a relative humidity of 90% is at most 3.5 g/(m2.24h).

Description

Laminated body and articles

The present invention relates to a laminated body and an article.

In recent years, with the development of communication technology and wireless power supply technology, the housing of electronic devices is required to have electromagnetic wave permeability. However, if the housing is made of metal, there is a concern that communication will be hindered due to the reflectivity of radio waves. Therefore, consideration and improve. For example, as a decorative member for electronic devices such as smartphones and other mobile devices, PC (Personal Computer) devices, and home appliances, decorative films with electromagnetic wave permeability have been studied. Such a decorative film is suitable for imparting design or high quality to the appearance of various articles. Moreover, from the viewpoint of high-level appearance or aesthetics, in the design pursuing glossiness, a method of using a transparent compound with a high refractive index instead of a metal with radio wave reflectivity to obtain a glossiness has been studied.

For example, Patent Document 1 discloses a cover glass in which a glass plate and a white resin film containing titanium oxide are fixed via an adhesive layer, and the use of white pigment particles kneaded with titanium oxide or zinc oxide particles has been studied. The diffusion layer is used as a base material to obtain diffused white reflective components, and the two are laminated using an adhesive. Prior art literature Patent literature

Patent Document 1: Japanese Patent Laid-Open No. 2015-145974

[The problem to be solved by the invention]

In such a laminate, an appearance with a sense of depth and gloss or a colored appearance may sometimes be desired. As a method to meet such a demand, a method of further laminating an optical adjustment layer as a layer constituting the laminated body can be considered. Regarding a laminate having an optical adjustment layer, it is sometimes desirable to have a configuration with an adhesive layer on the optical adjustment layer, for example, a configuration with a substrate, an optical adjustment layer, and an adhesive layer in this order. For example, when the adhered member is to be decorated from the inside (the side opposite to the visible surface), a laminate (film) of such a structure is required. If the film of this structure is pasted on the inside of a transparent adhered member and used, the adhered member can be given an appearance colored by the optical adjustment layer. In addition, the film is located inside the adhered member, so it is not easily damaged. Furthermore, the adhered member is located on the outside, so that the texture of the adhered member can be fully displayed in the product.

However, the inventors of the present invention found that such a film has the following problem: various factors such as ultraviolet rays, temperature, humidity, etc., can cause deterioration of the optical adjustment layer, thereby causing its appearance to change.

The present invention was made in view of the above-mentioned problems, and its object is to provide a laminate and an article that can decorate the adhered member to give a gloss and depth appearance or a colored appearance, and further suppress ultraviolet rays, temperature, humidity, etc. Changes in appearance caused by various factors. [Technical means to solve the problem]

In order to solve the above-mentioned problems, the inventors have carried out intensive research and found that by setting the moisture permeability in a specific range in a laminate comprising a base film, an optical adjustment layer, a first barrier layer, and an adhesive layer, it is possible to obtain A laminated body that prevents the optical adjustment layer from deteriorating due to ultraviolet rays, temperature, humidity, etc., and suppresses discoloration, thereby completing the present invention.

That is, the present invention is as follows. [1] A laminated body comprising an adhesive layer on the first barrier layer side of the laminated film having a base film, an optical adjustment layer, and a first barrier layer in this order, and the optical adjustment layer contains an adhesive layer selected from A layer having at least one of the group consisting of a metal oxide, a metal nitride, and a metal sulfide and having a refractive index of 1.75 or more, the first barrier layer is a layer containing a metal oxide and/or a metal nitride, and the laminated film The moisture permeability at a temperature of 40℃ and a relative humidity of 90% is 3.5 g/(m ²・24 h) or less. [2] The laminate according to [1], wherein the laminate film further includes a second barrier layer between the base film and the optical adjustment layer. [3] The laminate according to [1] or [2], wherein the optical adjustment layer contains niobium oxide or titanium oxide. [4] The laminate as described in [2] or [3], wherein the first barrier layer and the second barrier layer contain silicon oxide or silicon nitride. [5] The layered body according to any one of [1] to [4], wherein the thickness of the first barrier layer is 5.0 nm or more. [6] The laminate as described in any one of [1] to [5], which further includes a hard coat layer between the base film and the optical adjustment layer. [7] The laminate as described in any one of [1] to [6], wherein the arithmetic average roughness of the surface of the first barrier layer is 150 nm or less. [8] The laminate according to any one of [1] to [7], wherein the base film contains rutile-type titanium oxide particles. [9] An article obtained by laminating the laminated body described in any one of [1] to [8] to a transparent molded body. [Effects of Invention]

The laminated body of the present invention can decorate the adhered member to give a gloss and depth appearance or a colored appearance, and further can suppress the appearance change caused by various factors such as ultraviolet rays, temperature, and humidity.

The laminated system of the embodiment of the present invention is further provided with an adhesive layer on the side of the first barrier layer side of the laminated film including the base film, the optical adjustment layer, and the first barrier layer in this order, and the optical adjustment layer contains a metal selected from A layer with at least one of the group consisting of oxide, metal nitride, and metal sulfide with a refractive index of 1.75 or more, the first barrier layer is a layer containing metal oxide and/or metal nitride, and the laminated film is The moisture permeability at a temperature of 40℃ and a relative humidity of 90% is 3.5 g/(m ²・24 h) or less.

Hereinafter, the mode for implementing the present invention will be described in detail with reference to the drawings. In addition, the present invention is not limited to the embodiments described below. In addition, in the following drawings, members and parts that perform the same function may be described with the same reference numerals, and repeated descriptions may be omitted or simplified. In addition, the embodiments described in the drawings are modeled in order to clearly explain the present invention, and do not necessarily represent actual dimensions or scales accurately.

[Layered body] Fig. 1 shows a schematic cross-sectional view of a laminate according to an embodiment of the present invention. The laminated body 1 of this embodiment is a laminated body provided with the adhesive layer 15 on the surface of the 1st barrier layer 14a side of the laminated film which sequentially provided the base film 10, the optical adjustment layer 13, and the 1st barrier layer 14a. The hard coat layer 11 can be formed on the base film 10.

<Humidity Permeability> In the laminate of the embodiment of the present invention, the laminate film having the base film 10, the optical adjustment layer 13, and the first barrier layer 14a in this order has a moisture permeability at a temperature of 40°C and a relative humidity of 90% 3.5 g/(m ²・24 h) or less. The moisture permeability is preferably 3.0 g/(m ² ·24 h) or less, more preferably 2.0 g/(m ² ·24 h) or less, and still more preferably 1.0 g/(m ² ·24 h) or less. The lower limit of the moisture permeability is not particularly limited, and it is preferably 0 g/(m ² · 24 h) or more.

The inventors of the present invention have determined through research that when exposed to ultraviolet rays or exposed to a high temperature and high humidity environment, the optical adjustment layer single film will not change color, but it will occur when laminated with an adhesive. Discoloration. It is presumed that the reason is that the components forming the optical adjustment layer and the components forming the adhesive layer have some kind of reaction, and the optical adjustment layer is deteriorated. The factors have not been clarified yet. One of the factors that cause the optical adjustment layer 13 and the adhesive layer 15 to react may be ultraviolet rays, temperature, and humidity.

By providing the layered body 1 of this embodiment with the barrier layer 14a, even when exposed to ultraviolet rays or exposed to a high temperature and high humidity environment, the optical adjustment layer 13 and the adhesive layer 15 can be prevented from reacting. Furthermore, the laminate 1 of the present embodiment can exhibit excellent ultraviolet resistance (difficulty in the reaction of the optical adjustment layer 13 and the adhesive layer 15 when exposed to ultraviolet rays) by setting the moisture permeability of the base film within the above-mentioned range, and High-temperature and high-humidity resistance (difficulty in the reaction between the optical adjustment layer 13 and the adhesive layer 15 when exposed to a high-temperature and high-humidity environment).

Here, the moisture permeability means the moisture permeability measured in accordance with JIS K 7129: 2019 at a temperature of 40°C and a relative humidity of 90%, and specifically means the moisture permeability measured by the method described in the column of Examples .

The laminate 1 of this embodiment has high temperature and high humidity resistance, so it is optically stable and has high reliability, that is, it exhibits excellent optical reliability. Optical reliability can be judged by measuring the spectral transmittance before and after exposing the laminated body 1 of this embodiment to a high-temperature and high-humidity environment. For example, a glass plate can be attached to the adhesive layer of the laminate before and after exposing the laminate 1 to a high-temperature and high-humidity environment to prepare a sample, and use a spectrophotometer to measure the wavelength in the range of 380 nm to 780 nm The spectral transmittance before and after the weathering test is compared with the respective transmittance spectra to judge the optical reliability. Calculate the visual transmittance Y value based on the transmission spectra before and after the weathering test, and set the Y value difference between the samples before and after the weathering test (the initial sample and the sample after the weathering test) as the ΔY value. The ΔY value can be set as an indicator of the change in hue, preferably -1.0% to 1.0%.

In addition, based on the transmission spectra of the initial sample and the sample after the weathering test, the color difference described in the "CIE1994 Color Difference Model", that is, the transmission ΔE ₉₄ value, can be calculated using the method described below, and used as an indicator of the change in hue. The transmittance ΔE ₉₄ value is preferably 0.00 to 0.20.

＜Calculation method of transmission ΔE ₉₄ value＞ Use the obtained transmission spectrum and the relative spectral distribution of CIE standard illuminant (CIE standard illuminant) D65 to calculate the CIE-L ^* a ^* b ^* color of the initial sample and the sample after the weathering test. L ^* value, a ^* value and b ^* value in the system. ^{The L*} value, a ^* value, and b ^* value of the initial sample are set to L ₁ , a ₁ , and b ₁ , respectively, and the sample after the weathering test is set to L ₂ , a ₂ , and b ₂ .

Use the following formula to calculate the transmission ΔE ₉₄ value.

[Number 1]

Regarding the numerical values included in the above calculation formula, it can be calculated with reference to the following formula.

[Number 2]

The above-mentioned ΔY value and the transmission ΔE ₉₄ value in the laminate 1 of the present embodiment can be specifically measured by the method described in the examples.

＜Base film＞ The base film 10 can be used, for example, including polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate, polyamide, polyvinyl chloride, and polycarbonate. Ester (PC), cyclic olefin polymer (COP), polystyrene, polypropylene (PP), polyethylene, polycyclic olefin, polyurethane, acrylic (PMMA, polymethyl methacrylate) , ABS (acrylonitrile-butadiene-styrene resin) and other homopolymers or copolymers and other resin films. These components will not affect the brilliance or radio wave transmittance described below. However, since various layers will be formed on the substrate film 10 later, it is preferably one that can withstand high temperatures such as evaporation or sputtering. Therefore, among the above materials, for example, polyethylene terephthalate, Polyethylene naphthalate, acrylic, polycarbonate, cyclic olefin polymer, ABS, polypropylene, polyurethane. Among them, in view of a good balance between heat resistance and cost, polyethylene terephthalate, cycloolefin polymer, polycarbonate or acrylic is preferred.

For the base film 10, for the purpose of adjusting optical properties such as refractive index and ultraviolet transmittance, inorganic particles called fillers or fillers may be dispersed in the resin. For example, by dispersing inorganic particles such as titanium oxide particles, zirconium oxide particles, rutile titanium oxide particles, or barium titanate particles in the resin, the refractive index that the resin originally has can be adjusted. As the inorganic particles, rutile-type titanium oxide particles are preferred.

The base film 10 may be a single-layer film or a multilayer film. In terms of ease of processing and the like, the thickness is preferably about 6 μm to 250 μm, for example. In addition, in order to enhance the adhesion with the layer formed on the base film 10, plasma treatment or easy bonding treatment, etc. may also be implemented. In addition, the base film 10 may also have light-shielding properties, and the details will be described below.

The base film 10 may be formed with a smooth or anti-glare hard coat layer as needed. By providing a hard coat layer, scratch resistance can be improved. The hard coat layer can be formed by applying a solution containing a curable resin. Examples of curable resins include thermosetting resins, ultraviolet curing resins, electron beam curing resins, and the like. As the type of curable resin, for example, polyester-based, acrylic-based, urethane-based, acrylic urethane-based, amide-based, silicone-based, silicate-based, epoxy-based, Various resins such as melamine-based, oxetane-based, and acrylic urethane-based resins. One or two or more of these curable resins can be appropriately selected and used. Among them, the self-hardness is high, ultraviolet curing is possible, and the productivity is excellent, and acrylic resins, acrylic urethane resins, and epoxy resins are preferred.

＜Optical adjustment layer＞ The optical adjustment layer 13 is a layer containing at least one selected from the group consisting of metal oxides, metal nitrides, and metal sulfides, and having a refractive index of 1.75 or more. If the refractive index of the optical adjustment layer 13 is 1.75 or more, an appearance with excellent gloss and depth or a colored appearance can be obtained, and excellent design can be imparted. In order to obtain a deeper appearance, the refractive index of the optical adjustment layer 13 is preferably 1.8 or more, more preferably 1.9 or more. In addition, from the viewpoint of thickness controllability, the refractive index of the optical adjustment layer 13 is preferably 3.5 or less, and more preferably 3.0 or less. In addition, the optical adjustment layer 13 may be a laminate of layers with different refractive indexes.

The material constituting the optical adjustment layer 13 is not particularly limited, and at least one selected from the group consisting of metal oxides, metal nitrides, and metal sulfides can be suitably used. Furthermore, the metal elements contained in the metal oxides, metal oxides, and metal sulfides referred to herein include semi-metal elements such as Si. In addition, at least one selected from the group consisting of metal oxides, metal nitrides, and metal sulfides includes metal oxynitride, metal oxysulfide, and metal sulfur nitride. In addition, the metal oxide may be an oxide of a single metal element (single oxide), or an oxide of a plurality of metal elements (complex oxide). Similarly, the metal nitride can be the nitride of a single metal element (single nitride), or the nitride of multiple metal elements (complex nitride), and the metal sulfide can be the sulfide of a single metal element (single sulfide). It can also be a sulfide of a plurality of metal elements (complex sulfide). As a metal element, Ce, Nb, Si, Sb, Ti, Ta, Zr, Zn, etc. are mentioned, for example.

As the material of the optical adjustment layer 13, more specifically, for example, CeO ₂ (2.30), Nb ₂ O ₃ (2.15), Nb ₂ O ₅ (2.20), SiN _x (2.03), Sb ₂ O ₃ (2.10), TiO ₂ (2.35), Ta ₂ O ₅ (2.10), ZrO ₂ (2.05), ZnO (2.10), ZnS (2.30), etc. [The values in parentheses for the above materials are the refractive index]. In particular, the optical adjustment layer 13 preferably contains Si and/or Nb, for example, preferably contains Nb ₂ O ₅ and/or SiN _x , and more preferably is composed of Nb ₂ O ₅ and/or SiN _x .

The thickness of the optical adjustment layer 13 is preferably 10 nm to 1000 nm. From the viewpoint of cost, it is more preferably 800 nm or less, and still more preferably 500 nm or less. Moreover, from the viewpoint of the hue, it is preferably 15 nm or more, more preferably 20 nm or more, and still more preferably 30 nm or more. The thickness of the optical function layer 13 may be exposed in a direction perpendicular to the surface (thickness direction), for example, and then measured using a transmission electron microscope.

＜The first barrier layer＞ The first barrier layer 14a is a barrier layer containing metal oxide and/or metal nitride. Furthermore, the term “metal oxide” and the metal element contained in the metal oxide include semi-metal elements such as Si. In addition, the metal oxide and/or metal nitride include metal oxynitride. In addition, the metal oxide may be an oxide of a single metal element (single oxide), or an oxide of a plurality of metal elements (complex oxide). Similarly, the metal nitride can be a nitride of a single metal element (single nitride), or a nitride of a plurality of metal elements (complex nitride). The present inventors found that the appearance change of the laminate 1 is caused by the following reasons. That is, when the laminate 1 is exposed to ultraviolet rays (UV rays) or placed in a high-temperature and high-humidity environment, the optical adjustment layer 13 and the adhesive layer 15 responses. Therefore, by disposing the first barrier layer 14a between the optical adjustment layer 13 and the adhesive layer 15 to suppress their reaction, high temperature and humidity resistance can be exhibited, and excellent optical reliability can be exhibited. The appearance change of the laminated body 1 can be suppressed.

The material for forming the first barrier layer 14a is not particularly limited, and is preferably transparent, as long as it is a material that does not react with the adhesive layer 15 and the optical adjustment layer 13. It is preferably, for example, _{SiO 2, Al 2 O 3,} AZO and the like, preferably containing SiO _2, more preferably constituted by SiO _2.

In addition, the first barrier layer 14a is preferably a highly crystalline and dense film. By setting the first barrier layer 14a as a highly crystalline and dense film, it is easy to set the moisture permeability of the laminated film to 3.5 g/(m ² · 24 h) or less. The crystallinity of the components constituting the first barrier layer 14a can be controlled by adjusting the sputtering conditions (for example, the gas pressure of the inert gas, the gas pressure of the reactive gas, and the film forming temperature) during film formation.

In order to impart gloss, the arithmetic average roughness of the surface of the first barrier layer is preferably 150 nm or less, more preferably 120 nm or less, further preferably 100 nm or less, and particularly preferably 70 nm or less. By reducing the surface roughness of the first barrier layer, the light component scattered at the interface between the first adhesive layer and the first barrier layer can be suppressed. As a result, the regular reflection component is increased and the glossiness is improved. The arithmetic average roughness of the surface of the first barrier layer can be measured by an atomic force microscope (AFM).

In order to suppress the reaction between the optical adjustment layer 13 and the adhesive layer 15, the thickness of the first barrier layer is preferably 5 nm or more, more preferably 10 nm or more, further preferably 20 nm or more, and particularly preferably 40 nm or more. On the other hand, from the viewpoint of flexibility, it is preferably 300 nm or less, more preferably 200 nm or less, and particularly preferably 100 nm or less.

In addition, the laminated body 1 may include a plurality of barrier layers. For example, as shown in FIG. 2, a second barrier layer 14 b may be provided between the base film (in the case of the hard coating layer 11) and the optical adjustment layer 13. When the second barrier layer 14b is provided between the base film and the optical adjustment layer 13, effects such as improved adhesion and relaxation of stress applied to the optical adjustment layer can be obtained. When the second barrier layer is provided, the thickness of the second barrier layer is preferably 5 nm or more, more preferably 10 nm or more, still more preferably 20 nm or more, and particularly preferably 40 nm or more. On the other hand, in terms of flexibility, it is preferably 300 nm or less, more preferably 200 nm or less, and particularly preferably 100 nm or less.

＜Adhesive layer＞ The adhesive layer 15 is preferably a layer containing a transparent adhesive. The laminated body 1 of the present embodiment can be used, for example, by being stuck on the inner side (the side opposite to the visible side) of a transparent adhered member via an adhesive layer 15 to decorate the adhered member from the inner side.

The adhesive for forming the adhesive layer 15 is not particularly limited, but a transparent adhesive is preferred. For example, acrylic adhesives, rubber adhesives, silicone adhesives, polyester adhesives, and urethanes can be used alone. Any one of an ester-based adhesive, an epoxy-based adhesive, and a polyether-based adhesive, or a combination of two or more of them can be used. From the viewpoints of transparency, processability, durability, etc., it is preferable to use an acrylic adhesive.

Although the thickness of the adhesive layer 15 is not particularly limited, the visible light transmittance, film thickness accuracy, and flatness can be improved by making it thinner. Therefore, it is preferably 100 μm or less, more preferably 75 μm or less, and more It is preferably 50 μm or less.

The total light transmittance of the adhesive layer 15 as a whole is not particularly limited, but it is preferably 10% or more, more preferably 30% or more, and still more preferably 50 as measured at any visible light wavelength according to JIS K7361. %the above. The higher the total light transmittance of the adhesive layer 15 is, the better.

The adhesive layer 15 is preferably protected by a release liner before being attached to the adhered member.

＜Other floors＞ In addition to the base film 10, the optical adjustment layer 13, the first barrier layer 14a, and the adhesive layer 15, the laminate 1 of the present embodiment may be provided with other layers depending on the application, as long as the effects of the present invention are exhibited. For example, the laminate 1 of the present embodiment may be provided with a light-shielding layer that does not have visible light transmittance on the surface of the base film 10 opposite to the side on which the optical adjustment layer 13 is formed. By providing a light-shielding layer, for example, when the laminate 1 of the present embodiment is used to decorate the casing of an electronic device, it is possible to prevent the laminate 1 from visually recognizing the circuits inside the casing. The material of the light-shielding layer is not particularly limited. For example, the material exemplified as the material that can be used for the base film 10 can be colored black and used. Moreover, in the laminated body which does not have a light-shielding layer, by making the base film 10 light-shielding, the same effect as the case where a light-shielding layer is provided can also be exhibited.

[Manufacturing of laminated body] The formation method in the case of forming the hard coat layer 11 on the base film 10 is not particularly limited. For example, it can be formed by coating the hard coat composition on the base film 10 and drying and removing the solvent or the like.

As a coating method of the hard coating composition, various methods can be used. Specifically, for example, roll coating, touch roll coating, gravure coating, reverse coating, roll brushing, spray coating, dip roll coating, bar coating, knife coating, air knife coating Cloth, curtain coating, die lip coating, extrusion coating using die nozzle coater, etc.

The method for forming the optical adjustment layer 13 on the base film 10 (on the hard coating layer 11 when the hard coating layer 11 is formed) is not particularly limited, and examples include: vacuum evaporation method, sputtering method, ionization Plating method, coating method, etc.

The method of forming the first barrier layer 14a on the optical adjustment layer 13 is also not particularly limited. For example, it may be a vacuum evaporation method, a sputtering method, an ion plating method, a coating method, etc. The dense film is preferably sputtered. For example, when the first barrier layer 14a is formed by the sputtering method, it can be configured by adjusting the sputtering conditions during film formation (for example, the pressure of the inert gas, the pressure of the reactive gas, the film formation temperature), etc. By controlling the crystallinity of the components of the first barrier layer 14a, it becomes easy to control the moisture permeability of the laminated film.

The adhesive layer 15 can be formed by transferring the adhesive layer formed on the separator after the peeling process to the surface of the barrier layer 14a side of the laminated film including the base film, the optical adjustment layer, and the first barrier layer in this order. In addition, the adhesive layer 15 can also be directly coated with the adhesive composition for the adhesive layer on the side of the first barrier layer of the laminated film including the base film, the optical adjustment layer, and the first barrier layer in this order, and It is formed by removing the solvent by heat drying or the like.

The adhesive composition can be coated with a conventional coater, such as a gravure roll coater, a reverse roll coater, a touch roll coater, a dip roll coater, a bar coater, and a knife coater. Machine, spray coating machine, etc. The drying temperature is not particularly limited, but is preferably 40°C to 200°C, more preferably 50°C to 180°C, and particularly preferably 70°C to 120°C. The drying time is also not particularly limited, and is preferably 5 seconds to 20 minutes, more preferably 5 seconds to 10 minutes, and particularly preferably 10 seconds to 5 minutes.

The laminated body 1 of this embodiment is used by sticking, for example, on the inner side (the side opposite to the visible side) of a transparent adhered member.

＜Item＞ The article of this embodiment is obtained by bonding the laminated body of this embodiment to a transparent molded body. When the laminated body is attached to the surface of the transparent member on the opposite side (hereinafter, also called the inner side) to the visible side (hereinafter also called the outer side) via the adhesive layer, the transparent member can be used for adhesion. The agent layer and the first barrier layer visualize the optical function layer. That is, the laminated body of this embodiment can decorate a transparent member from the inside. The article of this embodiment is obtained by attaching the laminate to the inner side of the transparent member, so it is not easy to be damaged. In addition, the texture of the transparent member can be fully exhibited, and the transparent member can be decorated.

As a transparent member, from the viewpoint of transparency, a member including glass or plastic can be used.

The thickness of the transparent member is appropriately selected according to its use, and is preferably 100 μm to 2000 μm.

The method of attaching the laminate to the transparent member is not particularly limited, and it can be attached by vacuum forming, for example. Vacuum forming refers to heating and softening one side of the laminated body 1 and flattening the other side, depressurizing the space on the transparent member side of the laminated body, and pressurizing the space on the opposite side as necessary, thereby moving the laminated body along the side of the transparent member. The three-dimensional shape of the surface is formed, and the layer is attached to one side. As the laminate, the above description can be directly cited.

＜Use of laminated body and articles＞ As the application of the laminated body and articles of the present embodiment, for example, housings of electronic equipment, structural parts for vehicles, equipment for vehicles, housings for household appliances, structural parts, mechanical parts, various automobile parts, Parts for electronic equipment, furniture, kitchen supplies, etc. for personal use, medical equipment, parts for construction materials, other structural parts or exterior parts, etc. Examples of electronic equipment and home appliances include more specifically: refrigerators, washing machines, vacuum cleaners, microwave ovens, air conditioners, lighting equipment, electric water heaters, televisions, clocks, exhaust fans, projectors, speakers and other home appliances, computers, mobile phones , Smart phones, digital cameras, tablet PCs (Personal Computers), walkmans, handheld game consoles, chargers, batteries and other electronic information equipment. Examples of vehicle-related: dashboards, console boxes, door handles, door trims, gear levers, pedals, glove boxes, bumpers, hoods, mudguards, trunks, doors, sunroofs, pillars, seats , Steering wheel, ECU (electronic control unit, electronic control unit) box, electrical parts, engine peripheral parts, drive system/gear peripheral parts, intake/exhaust system parts, cooling system parts, etc. [Example]

Hereinafter, the present invention will be specifically described using examples, but the present invention is not limited in any way by these examples.

[Example 1] (Preparation of hard coating composition) The ultraviolet curable acrylic urethane resin ("AICAAITRON Z844-22HL" manufactured by AICA Industries) was dissolved in methyl isobutyl ketone to prepare a hard coating composition with a solid content ratio of 25%.

(Production of base film with hard coating) As a substrate film, the hard coating composition was applied to one side of a polyethylene terephthalate substrate (manufactured by Mitsubishi Chemical Co., Ltd.) with a thickness of 50 μm, and dried at 100° C. for 1 minute. After that, curing treatment was performed by ultraviolet irradiation to form a hard coat layer with a thickness of 1.5 μm, thereby obtaining a base film with a hard coat layer.

(Formation of the optical adjustment layer and the first barrier layer) A pure Nb target (manufactured by Datong Special Steel Co., Ltd.) and a pure Si target (manufactured by Datong Special Steel Co., Ltd.) are installed in an AC (alternating current, AC): 40 kHz), while introducing Ar gas and O ₂ gas, and performing reactive sputtering on the other side, 63 nm niobium oxide ( The Nb ₂ O ₅ ) film was used as the optical adjustment layer, and a 20 nm silicon _{oxide (SiO 2} ) film was formed on the optical adjustment layer as the first barrier layer to obtain the laminated film of Example 1. The film forming conditions of each layer are as follows.

(Conditions for forming niobium oxide film) Ultimate vacuum: 1.0×10 ^-4 Pa Sputtering gas: adjusted to O ₂ /(Ar+O ₂ ) to become 0.25 Film forming pressure: 0.15 Pa

(Conditions for silicon oxide film formation) Ultimate vacuum: 1.0×10 ^-4 Pa Sputtering gas: adjusted to O ₂ /(Ar+O ₂ ) to become 0.30 Film formation pressure: 0.07 Pa

Next, an adhesive layer (optical transparent adhesive sheet, thickness 25 μm, a product named "CS9861UAS" manufactured by Nitto Denko Co., Ltd.) is attached to the silicon oxide film of the laminated film to obtain the laminated layer of Example 1 body.

[Example 2] Except that the film thickness of the silicon oxide film in Example 1 was changed to 10 nm, in the same manner as in Example 1, the laminated film and laminated body of Example 2 were obtained.

[Example 3] In the same manner as in Example 1, a base film with a hard coat layer was obtained. A pure Nb target (manufactured by Datong Special Steel Co., Ltd.) and a pure Si target (manufactured by Datong Special Steel Co., Ltd.) are installed in an AC sputtering device (AC: 40 kHz), and Ar gas and O ₂ gas are introduced while performing Reactive sputtering, by which a 20 nm silicon oxide film is continuously formed on the hard coat side of the hard-coated substrate film as the second barrier layer, and a 63 nm niobium oxide film is formed for optical adjustment Layer, a 20 nm silicon oxide film was formed as the first barrier layer to obtain the build-up film of Example 3. The film forming conditions of each layer are the same as in Example 1.

Next, stick an adhesive layer (optical transparent adhesive sheet, thickness 25 μm, a product named "CS9861UAS" manufactured by Nitto Denko Co., Ltd.) on the silicon oxide film (first barrier layer) of the laminated film. The laminate of Example 3 was obtained.

[Comparative Example 1] In the same manner as in Example 1, a base film with a hard coat layer was obtained. A pure Nb target (manufactured by Datong Special Steel Co., Ltd.) was installed in an AC sputtering device (AC: 40 kHz), and Ar gas and O ₂ gas were introduced on one side, and reactive sputtering was performed on the other side. A 63 nm niobium oxide film was made on the hard coat side of the substrate film as an optical adjustment layer. The film formation conditions of the niobium oxide film are the same as in Example 1.

Next, an adhesive layer (optical transparent adhesive sheet, thickness 25 μm, a product named "CS9861UAS" manufactured by Nitto Denko Co., Ltd.) is attached to the niobium oxide film of the laminated film to obtain the laminated layer of Comparative Example 1 body.

[Comparative Example 2] In the same manner as in Example 1, a base film with a hard coat layer was obtained. A pure Nb target (manufactured by Datong Special Steel Co., Ltd.) and a pure Si target (manufactured by Datong Special Steel Co., Ltd.) are installed in an AC sputtering device (AC: 40 kHz), and Ar gas and O ₂ gas are introduced while performing Reactive sputtering is used to continuously form a 63 nm niobium oxide film as the optical adjustment layer on the hard coat side of the base film with a hard coat layer, and a 20 nm silicon oxide film as the first barrier Layer to obtain the laminated film of Comparative Example 2. The film forming conditions of each layer are as follows.

(Conditions for forming niobium oxide film) Ultimate vacuum: 1.0×10 ^-4 Pa Sputtering gas: adjusted to O ₂ /(Ar+O ₂ ) to become 0.25 Film forming pressure: 0.15 Pa

(Conditions for silicon oxide film formation) Ultimate vacuum: 1.0×10 ^-4 Pa Sputtering gas: adjusted to O ₂ /(Ar+O ₂ ) to become 0.15 Film formation pressure: 0.15 Pa

Next, an adhesive layer (optical transparent adhesive sheet, thickness 25 μm, a product named "CS9861UAS" manufactured by Nitto Denko Co., Ltd.) is attached to the niobium oxide film of the laminated film to obtain the laminated layer of Comparative Example 2 body.

<Measurement of moisture permeability> Based on JISK-7129-2: 2019, the water vapor permeability (g/(m ²・24 h)) of the laminated film obtained by Examples 1 to 3 and Comparative Examples 1 to 2 was measured And set the moisture permeability. For the measurement, "PERMATRAN-W Model 3/33" manufactured by MOCON was used, and the measurement environment was set to a temperature of 40°C and a relative humidity of 90%.

＜Evaluation of durability of temperature and humidity＞ A glass plate (glass slide "S200200" manufactured by Matsuba Glass Co., Ltd.) was bonded to the surface of the adhesive sheet of each laminated film obtained in Examples 1 to 3 and Comparative Examples 1 and 2 to obtain durability Evaluation sample (initial sample). Regarding the prepared sample, use a spectrophotometer ("U-4100" manufactured by Hitachi High-Technology Co., Ltd.) to irradiate visible light with a wavelength of 380 nm to 780 nm at 5 nm intervals to measure the light transmitted through the sample and set it as the initial Spectral transmittance.

The sample whose initial spectral transmittance was evaluated was put into a weather resistance tester ("Super Xenon Weather Meter SX120" manufactured by Suga Testing Machine Co., Ltd.) for 120 hours, and a sample after the weather test (sample after the weather test) was obtained. The test conditions are shown below.

Irradiance: 120 W/m ² @300～400 nm Black panel temperature: 55℃ Relative humidity: 55%

Regarding the sample after the weathering test, similar to the evaluation of the initial spectral transmittance, use a spectrophotometer to measure the spectral transmittance after the weathering tester with a wavelength in the range of 380 nm to 780 nm. With the above method, the transmission spectrum of the initial sample and the sample after the weathering test were obtained in the range of 380 nm to 780 nm. The visual transmittance Y value was calculated from each transmission spectrum, and the difference between the Y value of the initial sample and the sample after the weathering test was set as the ΔY value. In addition, from the transmission spectra of the initial sample and the sample after the weathering test, the color difference described in the "CIE1994 Color Difference Model" was calculated using the method described below _{, that is, the transmission ΔE 94} value, and this value was used as an indicator of the change in hue.

＜Calculation method of transmission ΔE ₉₄ value＞ Use the obtained transmission spectrum and the relative spectral distribution of CIE standard illuminant (CIE standard illuminant) D65 to calculate the CIE-L ^* a ^* b ^* color of the initial sample and the sample after the weathering test. L ^* value, a ^* value and b ^* value in the system. The initial sample of the L ^* value, a ^* value and b ^* values are set to _{L 1, a 1, a 2} , the L ^* values for the sample after the weathering test, a ^* value and b ^* value is set to L ₂ , a ₂ , b ₂ .

Use the following formula to calculate the transmission ΔE ₉₄ value.

[Number 3]

For each value included in the above calculation formula, refer to the following formula for calculation.

[Number 4]

As far as the ΔY value is concerned, for samples of -1% to 1%, no significant apparent change is recognized between the initial sample and the sample after the weathering test. Regarding the transmittance ΔE ₉₄ value, with respect to Examples 1 to 3 whose values are 0.2 or less, no apparent change caused by the weathering test was recognized.

The film formation conditions and evaluation results are shown in Table 1 below.

[Table 1] Table 1 Example 1 Example 2 Example 3 Comparative example 1 Comparative example 2 Film forming conditions The first barrier layer (SiO ₂ ) 200 sccm/ 0.07 Pa 200 sccm/ 0.07 Pa 200 sccm/ 0.07 Pa - 400 sccm/ 0.15 Pa Optical adjustment layer (Nb ₂ O ₅ ) 250 sccm/ 0.10 Pa 250 sccm/ 0.10 Pa 250 sccm/ 0.10 Pa 250 sccm/ 0.10 Pa 250 sccm/ 0.10 Pa The second barrier layer (SiO ₂ ) - - 400 sccm/ 0.15 Pa - - Through ∆E ₉₄ 0.12 0.13 0.09 0.87 0.28 ∆Y -0.30% -0.51% -0.30% -3.60% -1.10% Moisture permeability 2.7 3.3 0.15 5.5 4.3

The moisture permeability of the laminated film of Comparative Example 1 and Comparative Example 2 exceeded 3.5 g/(m ² · 24 h). Among them, Comparative Example 1 had a _{larger transmittance ΔE 94} after being irradiated with ultraviolet light for 24 hours, and Comparative Example 2 had a value of ΔY Larger and greater degree of discoloration, impaired gloss. On the other hand, even after the laminates of Examples 1 to 3 are irradiated with ultraviolet light for 24 hours, the transmittance ΔE _{94 of the} laminate film is small, and the value of ΔY is in the range of -1% to 1%, discoloration is suppressed, and optically reliable The sex is excellent.

The present invention is not limited by the above-mentioned embodiments, and can be implemented with appropriate changes within the scope not departing from the spirit of the invention. [Industrial availability]

According to the present invention, it is possible to provide a laminate that can decorate the adhered member to give an excellent appearance, and further suppress the appearance change caused by various factors such as ultraviolet rays, temperature, and humidity. In addition, the decorative member provided with the laminate or article of the present invention can be used for various devices or parts. For example, it can be used for housings of electronic devices such as mobile phones, smartphones, computers, structural parts for vehicles, automotive supplies, housings for home appliances, structural parts, mechanical parts, various automotive parts, electronic equipment parts, and furniture , Kitchen supplies and other household movable property uses, medical equipment, parts of building materials, and other structural parts or exterior parts, etc., which require design and cost control.

The present invention has been described in detail with reference to specific embodiments, but those skilled in the art should know that various changes or modifications can be made without departing from the spirit and scope of the present invention. This application is based on a Japanese patent application (Japanese Patent Application 2019-179322) filed on September 30, 2019, and the content is incorporated herein by reference.

1: Layered body 10: Substrate film 11: Hard coating 13: Optical adjustment layer 14a: The first barrier layer 14b: The second barrier layer 15: Adhesive layer

Fig. 1 is a schematic cross-sectional view of a laminate according to an embodiment of the present invention. Fig. 2 is a schematic cross-sectional view of a laminate according to an embodiment of the present invention.

Claims (9)

A laminate having an adhesive layer on the side of the first barrier layer of the laminate film including a base film, an optical adjustment layer, and a first barrier layer in this order, the optical adjustment layer containing a metal oxide , A layer with at least one of the group consisting of metal nitride and metal sulfide and a refractive index of 1.75 or more, the first barrier layer is a layer containing metal oxide and/or metal nitride, and the laminated film is at a temperature of 40 The moisture permeability at ℃ and 90% relative humidity is 3.5 g/(m ²・24 h) or less. The laminate of claim 1, wherein the laminate film further includes a second barrier layer between the base film and the optical adjustment layer. The laminate of claim 1 or 2, wherein the optical adjustment layer contains niobium oxide or titanium oxide. The laminate of claim 2 or 3, wherein the first barrier layer and the second barrier layer contain silicon oxide or silicon nitride. The laminate according to any one of claims 1 to 4, wherein the thickness of the first barrier layer is 5.0 nm or more. The laminate according to any one of claims 1 to 5, wherein a hard coat layer is further provided between the base film and the optical adjustment layer. The laminate according to any one of claims 1 to 6, wherein the arithmetic average roughness of the surface of the first barrier layer is 150 nm or less. The laminate according to any one of claims 1 to 7, wherein the base film contains rutile-type titanium oxide particles. An article which is formed by attaching the laminated body of any one of claims 1 to 8 to a transparent molded body.

Images