TW201917015A - Protection film laminate and functional film - Google Patents

Abstract

The present invention is: an amorphous-film protection film laminate that is a protection film laminate (P) in which a protection film (1) and a protection film (2) are laminated; and a functional film (1) that is a laminate in which an amorphous film is laminated on the protection-film-(2) side of the protection film laminate (P).

Description

Protective film laminate and functional film

The present invention relates to a protective film laminate for an amorphous film and a functional film having the protective film laminate.

In recent years, review of optical films used as components for optical devices such as liquid crystal displays (LCDs) and electroluminescence (EL) displays has used transparent plastic films. As such a plastic film, an amorphous film formed of an amorphous resin is used from the viewpoint of optical characteristics such as transparency and in-plane retardation. Such an amorphous film, because it is brittle and easily scratched, is usually used for protection during transportation steps, processing steps, or storage, at least a laminate in which a protective film is provided on the surface where the amorphous film is in contact with a device, etc. Use or keep it. For example, Patent Document 1 discloses a transparent conductive film having a carrier film having an adhesive layer on at least one side of the protective film and a peelable transparent conductive layer laminated through the adhesive layer, which meets specific requirements of a specific configuration and curl value Film laminate. The carrier film described in Patent Document 1 must be composed of the transparent resin film in the transparent conductive film composed of an amorphous cycloolefin-based resin, and the protective film is a resin different from the amorphous cycloolefin-based resin. Furthermore, an amorphous resin having a glass transition temperature of 130 ° C or higher is formed. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] JP 2016-107503

[Problems to be solved by the invention]

As described above, the amorphous thin film used as a member for an optical device may be formed as a member for an optical device after the amorphous film is further laminated with a layer having various functional layers. When manufacturing the member for an optical device, the aforementioned laminate may be subjected to heat treatment or the like. For example, when an amorphous film is used as a member such as a transparent conductive film, heat treatment in the step of bonding the amorphous film included in the laminate to another member using a thermosetting adhesive, etc., Or, after laminating the transparent conductive film on the amorphous thin film, annealing treatment is performed to crystallize the transparent conductive film. Therefore, when the aforementioned laminate is exposed to a high-temperature environment or used at room temperature after being exposed to a high-temperature environment, unless an appropriate protective film is used to protect the amorphous thin film, there is a problem that the protective film will deform widely . In this way, the protective film itself is deformed, which leads to the undesirable situation that the laminate including the aforementioned amorphous thin film is curled to a large width. If the laminate including the amorphous thin film is curled with a large width, poor transportation or poor processing will occur in the subsequent steps, which will cause troubles in production, lower productivity and lower productivity. Here, the protective film composed of the amorphous resin described in Patent Document 1 may be clogged when used under high temperature conditions. In addition, because the protective film itself is an amorphous resin, the protective film may break due to brittleness. In addition, there are economic disadvantages that the protective film made of amorphous resin is very expensive. The present invention has been made in view of the above circumstances, and aims to provide a functional film capable of suppressing curl even when exposed to a high-temperature environment, and a protective film laminate for an amorphous film used in the functional film. [Means to solve the problem]

The inventors found that by using a laminate (P) in which a protective film (1) and a protective film (2) are laminated as a thin film for protecting an amorphous thin film (hereinafter, also simply referred to as "laminate (P) ".), Can solve the aforementioned problems and complete the present invention. That is, the present invention provides the following [1] to [15]. [1] It is a protective film laminate for an amorphous thin film of a protective film laminate (P) formed by laminating a protective film (1) and a protective film (2). [2] The protective film (1) and the protective film (2) are protective film laminates for amorphous thin films described in [1] above, which are protective films formed of mutually different materials. [3] At least one of the protective film (1) and the protective film (2) is the protective film for an amorphous film described in [1] or [2], which is composed of a base film and an adhesive layer (Y) Laminate. [4] The protective film (1) has a tensile storage elastic modulus E ′ at 23 ° C. that is lower than the protective film (2) at 23 ° C. The tensile storage elastic modulus E ′ is lower than any of the aforementioned [1] to [3]. 1. A laminate of protective films for amorphous thin films. [5] The tensile storage elastic modulus E 'of the protective film (1) at 23 ° C is 1.0 × 10 ⁷ Pa or more and less than 3.0 × 10 ⁹ Pa, and the tensile storage elastic modulus of the protective film (2) at 23 ° C E ′ is 3.0 × 10 ⁹ Pa or more and 1.0 × 10 ¹¹ Pa or less of the protective film laminate for an amorphous thin film according to any one of the above [1] to [4]. [6] The protective film (1) is a protective film laminate for an amorphous film according to any one of the above [1] to [5] of the polyolefin-based protective film. [7] The protective film (2) is a protective film laminate for an amorphous film according to any one of the above [1] to [6] of the polyester-based protective film. [8] The protective film (1) is a polyolefin-based protective film, and the protective film (2) is a polyester-based protective film. The protective film laminate for an amorphous film according to any one of the above [1] to [7] . [9] It is a functional thin film of a laminate in which an amorphous thin film is laminated on the protective film (2) side of the protective film laminate for an amorphous thin film according to any one of the above [1] to [8]. [10] The functional film described in [9] further comprising an adhesive layer (X) between the protective film laminate (P) and the amorphous film. [11] The functional film as described in [9] or [10] whose thickness of the protective film (1) is 0.3 to 1.5 times the thickness of the amorphous film. [12] The functional film according to any one of [9] to [11] described above in which the thickness of the protective film laminate (P) is 2 μm or more and 300 μm or less. [13] The amorphous film is a functional film according to any one of the above [9] to [12] selected from the group consisting of a cycloolefin-based film and a polycarbonate film. [14] The functional thin film according to any one of [9] to [13] described above in which the thickness of the amorphous film is 1 μm or more and 100 μm or less. [15] The functional film according to any one of the above [9] to [14] used in an optical device. [Effect of invention]

According to the present invention, it is possible to provide a functional film capable of suppressing curl even when exposed to a high-temperature environment, and a protective film laminate for an amorphous film used in the functional film.

The present invention will be described in detail in the following embodiments. In this specification, regarding the preferable numerical value range (for example, the range of content, etc.), the lower limit value and the upper limit value described in stages may be independently combined. For example, from the description of "preferably 10 ~ 90, more preferably 30 ~ 60", "better lower limit (10)" and "better upper limit (60)" can also be combined to become "10 ~ 60 ". Similarly, from the description of "preferably 10 or more, more preferably 30 or more" and "preferably 90 or less, more preferably 60 or less" for the same items, the "preferred lower limit value ( 10) "and" Better upper limit (60) "become" 10 or more and 60 or less ". Furthermore, in this specification, "protective film" is the same as described above, and is used as a term for a thin film used for the purpose of protecting an adherend such as an "amorphous thin film". Furthermore, in this specification, "(meth) acrylic acid" is used as a term meaning either "acrylic acid" or "methacrylic acid" or both. Similarly, "(meth) acrylate" is used as a term meaning either or both of "acrylate" or "methacrylate".

[Functional film] The functional film according to one embodiment of the present invention is a protective film laminate (P) formed by laminating a protective film (1) and a protective film (2) according to one embodiment of the present invention And a functional thin film of a laminate in which an amorphous thin film is laminated on the protective film (2) side of the laminate (P). The inventors found that by using the laminate (P) as a film for protecting an amorphous film, a functional film that can suppress curling even when exposed to a high-temperature environment can be provided.

<Structure of Functional Film> The structure of the aforementioned functional film can be exemplified as shown in FIGS. 1 and 2, but it is not limited thereto. 1 is an example of an embodiment of the functional film of the present invention, which is a protective film (2) of a protective film laminate (P) 101 laminated with a protective film (1) 11 and a protective film (2) 12 On the 12 side, a cross-sectional view of the functional film 1 in which a laminate of the amorphous film 10 is laminated. The manufacturing method of the functional thin film 1 of this aspect includes, for example, bonding the protective film (2) 12 to the amorphous thin film 10, and further to the side opposite to the amorphous thin film 10 of the protective film (2) 12 A method of attaching the protective film (1) 11 to the surface. In addition, for example, a protective film laminate (P) 101 in which a protective film (1) 11 is bonded to the protective film (2) 12 is produced, and on the surface side of the protective film (2) 12 of the laminate (P) 101 , The method of bonding the amorphous film 10. In addition, for example, the amorphous film 11 is directly coated and formed on the protective film (2) 12 side of the laminate (P) 101 obtained by bonding the protective film (1) 11 and the protective film (2) 12 in advance. The raw resin is formed after drying. In addition, for example, the protective film (1) 11 and the protective film (2) 12 may be co-extruded to form the protective film (2) 12 side of the laminate (P) 101 that has been pre-formed and directly coated. The method of forming a solution of the raw material resin for forming the amorphous thin film 11 by drying. In addition, for example, after the resin forming the protective film (1) 11, the resin forming the protective film (2) 12, and the resin forming the amorphous film 10 are co-extruded, the laminate (P) 101 and The method of the functional film 1 of the crystalline film 10 and the like. Alternatively, after the protective film (2) 12 and the amorphous film 10 are laminated using the aforementioned method (lamination, co-extrusion molding) or the like, the amorphous film 10 with the protective film (2) 12 A protective film (1) 11 is formed on the surface on the opposite side.

FIG. 2 is an example of an embodiment of the functional film of the present invention, which is a sequential direct lamination of a protective film (1) 11, a protective film (2) 12, an adhesive layer (X) 13, and an amorphous film Cross-sectional view of the functional film 2 of the laminate of 10. As shown in FIG. 2, through the adhesive layer (X) 13, the amorphous thin film 10 and the protective film (2) 12 are directly laminated. The manufacturing method of the functional film 2 of this aspect can be exemplified by the manufacturing method example of the functional film 1, using the aforementioned method (lamination, co-extrusion molding), etc., in the laminate (P) 101 prepared in advance An adhesive layer (X) 13 is provided on the side of the protective film (2) 12, and an amorphous film 10 prepared in advance is laminated on the exposed surface of the adhesive layer (X) 13, and a laminating machine or the like is used for bonding. Or, an adhesive layer (X) 13 is provided on the previously prepared amorphous film 10 side, and on the exposed surface of the adhesive layer (X) 13, the protective film (2) 12 of the aforementioned laminate (P) 101 is laminated , The use of laminating machine and other methods of bonding. Alternatively, the monomer of the protective film (2) 12 and the amorphous film 10 may be laminated through the adhesive layer (X) 13 using the aforementioned method (lamination, co-extrusion molding), etc. The protective film (1) 11 is formed on the surface of the protective film (2) 12 opposite to the amorphous thin film 10.

In terms of the configuration of the aforementioned functional film, the protective film laminate (P) formed by laminating the protective film (1) and the protective film (2) is directly or through the adhesive layer (X ) A functional thin film laminated with an amorphous thin film is preferred. That is, in terms of the structure of the aforementioned functional film, a functional film in which a protective film (1) and a protective film (2) and an amorphous film are directly laminated in sequence, or a protective film (1) and The functional film of the protective film (2), the adhesive layer (X) and the amorphous film is preferred.

The thickness of the aforementioned functional film is preferably 10 to 400 μm, more preferably 20 to 300 μm, still more preferably 40 to 200 μm, and still more preferably 50 to 150 μm. The thickness of the functional film can be measured using, for example, the method described in the examples described below. Or it can be calculated as the sum of the thicknesses of the layers described later. In addition, the amount of curl measured by the method described in the below-mentioned examples of the functional film is preferably 10 mm or less, more preferably 8 mm or less, still more preferably 5 mm or less, and still more preferably 3 mm or less. The following is a more detailed description of each member constituting the aforementioned functional film.

<Protective film laminate (P)> The protective film laminate (P) is mainly a laminate for protecting an amorphous thin film, which is a laminate in which protective films (1) and (2) are laminated. For example, even when a protective film as a monomer is used, when the protective film that does not exhibit the aforementioned excellent effect of the present invention is used as the protective film (1) or (2), it can also be used as a laminate (P), and The aforementioned excellent effect of the present invention is exhibited. Therefore, as the laminate (P) used in the present invention, it is possible to use a laminate in which a conventionally used protective film is laminated. In this aspect, the ease of obtaining raw material resins or films and the economics in terms of cost View is also better.

(Protective Films (1) and (2)) As described above, the functional thin film is a laminate in which an amorphous thin film is laminated on the protective film (2) side of the laminate (P). Therefore, the protective film (2) is a protective film laminated on the amorphous thin film side in the laminate (P). The protective film (1) is a protective film laminated on the opposite side of the amorphous film from the protective film (2) in the laminate (P).

The protective films (1) and (2) are not particularly limited as long as they are used to protect the amorphous thin film described later. However, in terms of the protective films (1) and (2), from the viewpoint that the excellent effects of the present invention can be more easily obtained, it is preferable to use protective films having mutually different physical properties (for example, characteristics such as elastic modulus described later). A protective film formed of different materials is better.

Furthermore, at least one of the protective film (1) and the protective film (2) is independent of each other, and may be a laminate of the base film and the adhesive layer (Y). However, when at least one of the protective film (1) and the protective film (2) is composed of a substrate film and an adhesive layer (Y), the substrate film becomes the outermost layer of the laminate (P). In this case, the protective film (1) and the protective film (2) are preferably laminated with each other through at least one adhesive layer (Y), and the protective film (1) and (2) It is more preferable that the laminate is laminated with one adhesive layer (Y). Here, the "adhesive layer" in this specification means not only a layer that can be formed by an adhesive, but also a layer that can be formed by an adhesive, and it is understood as having at least one characteristic of adhesiveness and adhesiveness. In addition, if the "outermost layer of the laminate (P)" is the protective film (1) side, the protective film (2) is the surface layer on the opposite side, and if it is the protective film (2) side, it is amorphous The layer on the surface side where the films are in contact.

The protective films (1) and (2) are independent, and the protective films (1) and (2) having a glass transition temperature (Tg) that does not reach the glass transition temperature (Tg) of an amorphous thin film described later can be used. The glass transition temperatures (Tg) of the protective films (1) and (2) that meet this condition are independent of each other, preferably less than 140 ° C, more preferably less than 130 ° C, even more preferably less than 100 ° C, and then It is preferably 50 ° C or lower, preferably -150 ° C or higher, more preferably -100 ° C or higher, still more preferably -50 ° C or higher, and still more preferably -30 ° C or higher.

As for the protective film (1), a protective film (1) whose glass transition temperature (Tg) does not reach the glass transition temperature (Tg) of the protective film (2) can be used. The glass transition temperature (Tg) of the protective film (1) meeting this condition is preferably 100 ° C. or lower, more preferably 80 ° C. or lower, still more preferably 50 ° C. or lower, still more preferably 30 ° C. or lower, and then It is preferably 10 ° C or lower, further preferably -150 ° C or higher, more preferably -100 ° C or higher, still more preferably -50 ° C or higher, and still more preferably -30 ° C or higher. The glass transition temperature (Tg) of the protective film (2) meeting this condition is preferably less than 140 ° C, more preferably less than 130 ° C, even more preferably 100 ° C or less, and still more preferably 80 ° C or less, Furthermore, it is preferably -100 ° C or higher, more preferably -50 ° C or higher, still more preferably -30 ° C or higher, still more preferably more than 10 ° C, and still more preferably more than 30 ° C.

As for the protective film (2), a protective film (2) having a glass transition temperature (Tg) equal to or higher than the glass transition temperature (Tg) of the amorphous thin film described later can be used. The glass transition temperature (Tg) of the protective film (2) meeting this condition is preferably 140 ° C. or higher, more preferably 160 ° C. or higher, and still more preferably 180 ° C. or higher. In addition, the upper limit of the glass transition temperature (Tg) of the protective film (2) is not particularly limited, but is preferably 400 ° C, more preferably 350 ° C, and still more preferably 300 ° C. The values of the glass transition temperature (Tg) of the protective films (1) and (2) can be measured by the same method as the method for measuring the glass transition temperature (Tg) of the amorphous thin film described later, for example. In addition, when at least one of the protective film (1) and the protective film (2) is a laminate of a base film and an adhesive layer (Y), each glass transition temperature of the protective films (1) and (2) ( The values of Tg) are independent, and refer to the values of the glass transition temperature (Tg) of the aforementioned base film. That is, in this case, the values of the glass transition temperature (Tg) of each base film included in the protective films (1) and (2) are regarded as the respective glass transitions of the protective films (1) and (2). The value of temperature (Tg).

When the aforementioned functional film is used in a high-temperature environment, or when it is used in a room temperature environment after being exposed to a high-temperature environment, from the viewpoint that curling can be more suppressed, the protective films (1) and (2) have mutual phases In the case of a protective film having different physical properties (for example, characteristics such as elastic modulus described later), the elastic modulus of the protective film (1) is preferably lower than the elastic modulus of the protective film (2). Specifically, the tensile storage elastic modulus E 'of the protective film (1) at 23 ° C is better than the tensile storage elastic modulus E' of the protective film (2) at 23 ° C, and the protective film (1) is at 23 The tensile storage elastic modulus E ′ at ℃ is 1.0 × 10 ⁷ Pa or more and less than 3.0 × 10 ⁹ Pa. The protective storage film (2) tensile storage elastic modulus E ′ at 23 ° C. is 3.0 × 10 ⁹ Pa or more 1.0 × 10 ¹¹ Pa or better. In terms of the tensile storage elastic modulus E ′ of the protective film (1) at 23 ° C., it is preferably 1.0 × 10 ⁷ Pa or more, more preferably 1.0 × 10 ⁸ Pa or more, and even more preferably 5.0 × 10 ⁸ Pa or more, Furthermore, it is preferably less than 3.0 × 10 ⁹ Pa, more preferably 2.0 × 10 ⁹ Pa or less, and still more preferably 1.0 × 10 ⁹ Pa or less. In terms of the tensile storage elastic modulus E ′ of the protective film (2) at 23 ° C., it is preferably 3.0 × 10 ⁹ Pa or more, more preferably 4.0 × 10 ⁹ Pa or more, and still more preferably 4.5 × 10 ⁹ Pa or more, Furthermore, it is preferably 1.0 × 10 ¹¹ Pa or less, more preferably 1.0 × 10 ¹⁰ Pa or less, and still more preferably 8.0 × 10 ⁹ Pa or less. Furthermore, when at least one of the protective film (1) and the protective film (2) is a laminate of a base film and an adhesive layer (Y), the respective elastic modulus values of the protective films (1) and (2) are Independent means the value of the elastic modulus of the aforementioned base film. That is, in this case, the values of the modulus of elasticity of each base film included in the protective films (1) and (2) are regarded as the values of the modulus of elasticity of the protective films (1) and (2).

The protective films (1) and (2) are independent of each other, and for example, a resin film used as an amorphous film used as a device for negative optics can be suitably used. Examples of such films include polyolefin-based protective films, polyester-based protective films, polyimide-based protective films, polyamide-based protective films, and polysulfide-based protective films. Polyolefin-based protective films are more preferred. , Or polyester protective film.

In terms of the structure of the laminate (P), the protective film (1) is preferably a polyolefin-based protective film, or the protective film (2) is a polyester-based protective film, and the protective film (1) is a polyolefin-based protective film. The protective film (2) is preferably a polyester-based protective film. As described later, the polyolefin-based protective film is preferably a polypropylene-based protective film, and the polyester-based protective film is preferably a polyethylene terephthalate-based film. Therefore, in terms of the structure of the laminate (P), the protective film (1) is a polypropylene-based protective film, or the protective film (2) is a polyethylene terephthalate-based protective film. 1) It is a polypropylene-based protective film and the protective film (2) is a polyethylene terephthalate-based protective film.

For the aforementioned polyolefin-based protective film, it is sufficient to use a polyolefin film of 50% by mass or more among 100% by mass of the raw material resin of the protective film. When the protective film is composed of a base film and an adhesive layer (Y), For 100% by mass of the raw material resin of the base film, a polyolefin film of 50% by mass or more may be used. The content of the polyolefin is 100% by mass or more of the raw material resin, preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, still more preferably 98% by mass or more, and even more preferably 100% by mass or less. The aforementioned polyolefin is a resin obtained by polymerizing one kind or two or more kinds of olefin-based monomers. Examples of the olefin-based monomers include ethylene and α-olefins having a carbon number of 3 or more and 8 or less. The selected one or more is preferably selected from the group consisting of ethylene, propylene, 1-butene, isobutene, 1-pentene, 1-hexene, 1-octene and 4-methylpentene-1 One or more is better. With regard to the aforementioned polyolefin, one or more selected from the group consisting of propylene and ethylene, 1-butene, isobutene, 1-pentene, 1-hexene, 1-octene and 4-methylpentene-1 Copolymers or propylene alone polymers are even better. In addition, the aforementioned polyolefin may be a copolymer of a monomer other than the olefin-based monomers such as styrene, vinyl acetate, (meth) acrylate, etc., and the aforementioned olefin-based monomers, as necessary. In addition, this copolymer may be a copolymer having a molecular structure of any one of a random copolymer, a block copolymer, and a graft copolymer. Among these, more preferably, for example, a polyethylene-based protective film, a polypropylene-based protective film, a poly4-methylpentene-1-based protective film, etc., from the viewpoint of more easily obtaining the excellent effects of the present invention and easy to obtain From the viewpoint of versatility such as efficiency and economy, a polypropylene-based protective film is preferred.

Here, the polypropylene-based protective film refers to the use of 50% by mass or more of propylene, preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more as the olefin-based monomer. Preferably, it is a polypropylene-based copolymer polymerized below 100% by mass (hereinafter, also referred to as "propylene copolymer". Examples: ethylene-propylene copolymer, copolymer of α-olefin and propylene, α-olefin and ethylene At least one type of copolymer with propylene, etc.) and propylene alone polymer (homopolymerized polypropylene), in 100% by mass of the raw material resin forming the protective film (the protective film consists of the base film and the adhesive layer (Y) In the case of the constitution, the raw material resin of the base film contains 50% by mass or more of the film in 100% by mass. The content of the propylene copolymer and the propylene individual polymer is 100% by mass of the raw material resin, preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and still more preferably 98 The mass% or more is more preferably 100 mass% or less. In addition, regarding the polyethylene-based protective film and the poly-4-methylpentene-1-based protective film, in the description of the aforementioned polypropylene-based protective film, each of "propylene" was changed to "ethylene" or "4-methyl" The meaning of "pentene-1" is the same. The aforementioned polyolefin-based protective film may use a non-stretched film, a 1-axis stretched film, or a 2-axis stretched film. In this specification, "non-stretched film" refers to a film that is intended to be stretched in a specific direction during the film manufacturing step. For example, the original fabric without a stretched film is used in a transverse stretcher such as a longitudinal stretcher and / or a stretcher, and the film obtained by deliberately stretching is excluded. As an aspect of the non-stretched film, for example, CPP films (Cast Polypropylene Films) may be mentioned. Further, as an aspect of the stretched film, for example, OPP films (Oriented Polypropylene Films) can be mentioned. In addition, in a continuous manufacturing process using a Roll to Roll manufacturing device other than a longitudinal stretching machine (for example, a process using a casting device, a winding device, a slit device, etc.), the film is maintained only in the flow direction due to force majeure When the stress is extended, it is not limited, and it can be regarded as a "non-extension film".

As for the polyester-based protective film, a film of 50% by mass or more of polyester may be used for 100% by mass of the raw resin of the protective film. When the protective film is composed of a base film and an adhesive layer (Y), it is Of 100% by mass of the raw material resin of the base film, a film of 50% by mass or more of polyester may be used. The content of the polyester is 100% by mass of the aforementioned raw resin, preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, still more preferably 98% by mass or more, and still more preferably 100% by mass or less. Examples of the polyester-based protective film include polyethylene terephthalate (PET) -based protective film, polybutylene terephthalate (PBT) -based protective film, and polyethylene naphthalate. From the viewpoint of versatility, a PEN-based protective film, a polyarylate-based protective film, or the like is preferably a polyethylene terephthalate (PET) -based protective film. Here, the PET-based protective film refers to 100% by mass of the raw resin forming the protective film (when the protective film is composed of the base film and the adhesive layer (Y), the raw resin of the base film is 100% by mass ), Containing PET 50% by mass or more of the film. The content is 100% by mass of the raw material resin, preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, still more preferably 98% by mass or more, and still more preferably 100% by mass %the following. In addition, regarding other polyester-based protective films, in the aforementioned description of PET-based protective films, each of which has the same meaning except that "PET" is changed to "PBT", "PEN" or "polyarylate". As for the polyester-based protective film, a uniaxially stretched film or a biaxially stretched product can be used.

For the aforementioned polyimide-based protective film, it is sufficient to use a film of 50% by mass or more of polyimide-based resin in 100% by mass of the raw material resin of the protective film. The protective film is composed of a base film and an adhesive layer (Y ) In the case of the configuration, a film of 50% by mass or more of polyimide-based resin may be used for 100% by mass of the raw material resin of the base film. The content of the polyimide-based resin is 100% by mass of the raw material resin, preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and still more preferably 98% by mass or more It is further preferably 100% by mass or less. For the polyimide-based protective film, for example, a polyimide-based protective film, a polyether amide-based protective film, a polyamide-based imide-based protective film, etc., from the viewpoint of heat resistance and dimensional stability, It is preferably a polyimide-based protective film. In addition, regarding these various polyimide-based protective films, in the aforementioned description of the PET-based protective film, each of the "PET-based" was changed to "polyimide" and "PET" was changed to "polyether-imide" "Amine" or "polyamide imide" have the same meaning.

For the above-mentioned polyamide-based protective film, it is sufficient to use a film of 50% by mass or more of the polyamide-based resin out of 100% by mass of the raw material resin of the protective film. In the case of a configuration, a film of 50% by mass or more of a polyamide-based resin may be used for 100% by mass of the base resin of the base film. The content of the polyamide resin is 100% by mass of the raw material resin, preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and still more preferably 98% by mass or more. Furthermore, it is preferably 100% by mass or less. As for the polyamide-based protective film, for example, an aliphatic polyamide-based protective film, an aromatic polyamide-based protective film, etc. may be mentioned. Furthermore, regarding these various polyamide-based protective films, in the aforementioned description on the PET-based protective films, each of which has the same meaning except that "PET" is changed to "aliphatic polyamide" or "aromatic polyamide". As for the aliphatic polyamide, for example, nylon 6, nylon 66, nylon copolymer, etc. may be mentioned. In addition, the aromatic polyamides include, for example, fully aromatic polyamides such as para-aramid, meta-aramid, etc., monomers used as raw material monomers of aliphatic polyamides and Semi-aromatic polyamido, etc., a copolymer formed by polymerization of a single polymer of the raw material monomer of aromatic polyamidoamine.

As for the above-mentioned poly-cement-based protective film, it is sufficient to use a film of 50% by mass or more of poly-cement-based resin for 100% by mass of the raw resin of the protective film, and the protective film is composed of a base film and an adhesive layer (Y) , For 100% by mass of the raw material resin of the base film, a film of 50% by mass or more of poly-resin-based resin may be used. The content of the polyphenol resin is 100% by mass of the aforementioned raw resin, preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and still more preferably 98% by mass or more, and It is preferably 100% by mass or less. As for the above-mentioned poly-ballast protective film, for example, poly-ballast protective film, polyether-ballast protective film, etc. may be mentioned. In addition to the above-mentioned PET-based protective films, the various PET-based protective films mentioned above have the same meaning except that "PET-based" is changed to "poly-based" and "PET" is changed to "polyether-based".

In addition, from the viewpoint of suppressing the adhesion of the aforementioned functional film, it is preferable that the protective film (1) is a protective film other than the amorphous protective film, and from the viewpoint of suppressing cracking of the protective film itself, the protective film (1) and the protective film (2) A protective film other than an amorphous protective film is more preferable. The amorphous protective film refers to a protective film formed of an amorphous resin. Here, the amorphous resin refers to a resin having a crystallinity of less than 25% as measured by X-ray diffraction (XRD). On the other hand, crystalline resin refers to a resin having a crystallinity of 25% or more.

{Base film} As mentioned above, when at least one of the protective film (1) and the protective film (2) is composed of a base film and an adhesive layer (Y), it can be used as a film for the base film and The suitable state is mentioned in the columns of protective films (1) and (2), and the detailed description is omitted.

{Adhesive layer (Y)} At least one of the adhesive and the adhesive constituting the adhesive layer (Y) can be appropriately selected according to the application of the aforementioned functional film. In addition, the adhesive layer (Y) can be appropriately selected to have a layer having re-peelability, permanent adhesion, or permanent adhesiveness according to the application. As mentioned above, the adhesive layer (Y) exists as an inner layer of the laminate (P) and is used for laminating the protective films (1) and (2), so it has re-peelability, permanent adhesion or permanent adhesion Better. When it is not necessary to peel off the protective film (1) from the protective film (2), the adhesive layer (Y) may have permanent adhesion.

Examples of the aforementioned adhesives include acrylic adhesives, urethane adhesives, silicone adhesives, rubber adhesives, polyester adhesives, and hardened adhesives that are hardened by energy rays such as ultraviolet rays. Agent. Among these, acrylic adhesives, rubber adhesives or silicone adhesives are preferred. These adhesives can be used alone or in combination of two or more.

As for the aforementioned adhesive, for example, an active energy ray hardening type adhesive or a thermosetting type adhesive may be mentioned. The active energy ray hardening type adhesive has the property of being hardened by irradiation with active energy rays such as ultraviolet rays or electron rays. In terms of active energy ray-curable adhesives, the so-called solventless adhesives are preferably free of organic solvents. (Meth) acrylate adhesive, olefin / thiol adhesive, epoxy adhesive, oxetane adhesive, epoxy / oxetane adhesive, unsaturated polyester adhesive Adhesives utilizing photo-radical polymerization reaction; epoxy-based, vinyl ether-based, oxetane-based adhesives utilizing photo-cation polymerization; etc. The thermosetting adhesive has the property of being hardened by heating. In terms of thermosetting adhesives, the so-called solventless adhesives preferably contain no organic solvents. The thermosetting adhesives include adhesives that harden at room temperature or higher, such as epoxy adhesives, polyurethane adhesives, (meth) acrylate adhesives, and ene / thiol adhesives. Agent, silicone adhesive, polyester adhesive, unsaturated polyester adhesive, cyanoacrylate adhesive, nylon adhesive, modified olefin adhesive, etc.

In addition, other adhesives include, for example, water-based adhesives such as polyvinyl alcohol-based resin aqueous solutions and water-based two-component urethane-based emulsified adhesives. Among these, the aqueous solution of polyvinyl alcohol-based resin is preferred. The polyvinyl alcohol-based resin includes, for example, a vinyl alcohol homopolymer obtained by saponifying polyvinyl acetate, which is a separate polymer of vinyl acetate; vinyl acetate and vinyl acetate are copolymerized with other monomers A vinyl alcohol-based copolymer obtained by saponification of a copolymer of a polymer; a modified polyvinyl alcohol-based polymer in which the hydroxyl group of the vinyl alcohol homopolymer or the vinyl alcohol-based copolymer is partially modified; Wait. As the water-based adhesive, polyvalent aldehydes, water-soluble epoxy compounds, melamine-based compounds, zirconia compounds, zinc compounds, and the like can be added as additives. These adhesives can be used alone or in combination of two or more.

The manufacturing method of the laminate (P) may be, for example, a protective film composed of a base film and an adhesive layer (Y) by using either or both of the protective films (1) or (2) to make the protective film (1) and (2) The method of bonding together to obtain a laminate (P). In addition, in the case where the protective film (1) and the protective film (2) composed only of the base film are bonded to each other, an adhesive layer can be used by forming an adhesive layer on the surface side of either or both base films. The adhesive layer is also regarded as the adhesive layer (Y) of the protective film (1) or (2). In addition, if necessary, in addition to the adhesive layer (Y) included in the protective film, a novel adhesive layer (Y) can be formed, and the protective films (1) and (2) can be bonded to each other to obtain a laminate (P) . That is, the adhesive layer existing in the inner layer of the laminate (P) is regarded as the adhesive layer (Y) included in the protective film (1) or (2). In addition, for example, a method of co-extrusion of the resin forming the protective film (1) and the resin forming the protective film (2) to directly form the laminate (P), etc. may be mentioned.

The thickness of the protective film (1) is preferably 1 μm or more, more preferably 3 μm or more, still more preferably 10 μm or more, still more preferably 30 μm or more, and yet more preferably 35 μm or more from the viewpoint of curling of the functional film obtained easily. . In addition, when the obtained functional film is wound up or the laminate (P) is peeled off from the functional film, the protective film (1) is protected from the viewpoint of operability and economy of the functional film in the subsequent step. The thickness is preferably 200 μm or less, more preferably 150 μm or less, still more preferably 100 μm or less, still more preferably 80 μm or less, and still more preferably 60 μm or less. In addition, from the viewpoint of easily suppressing the curl of the obtained functional film, the thickness of the protective film (1) is preferably 0.3 to 1.5 times, 0.4 to 1.5 times, and 0.4 to 1.3 times the thickness of the amorphous film described later. , 0.4 ~ 1.2 times better, 0.4 ~ 1.0 times better, 0.4 ~ 0.8 times better.

When the protective film (1) is a laminate composed of the base film and the adhesive layer (Y), the thickness of the base film is easily suppressed from the viewpoint of curling of the obtained functional film, and is preferably 1 μm or more, more preferably It is 2 μm or more, preferably 10 μm or more, still more preferably 25 μm or more, and still more preferably 30 μm or more. In addition, when the obtained functional film is taken up or the laminate (P) is peeled off from the functional film and used, the thickness of the base film is from the viewpoints of operability and economy of the functional film in the subsequent step, etc. It is preferably 150 μm or less, more preferably 100 μm or less, still more preferably 80 μm or less, still more preferably 60 μm or less, and still more preferably 50 μm or less. Further, the thickness of the adhesive layer (Y) is preferably 1 to 100 μm, more preferably 2 to 50 μm, still more preferably 3 to 30 μm, and still more preferably 5 to 20 μm. In addition, when the protective film (1) is a laminate composed of the base film and the adhesive layer (Y), from the viewpoint of easily suppressing curling of the obtained functional film, the thickness of the base film is described later as an amorphous film The thickness of 0.2 to 1.5 times is better, 0.3 to 1.3 times better, 0.3 to 1.2 times better, 0.3 to 1.0 times better.

The thickness of the protective film (2) is preferably 1 μm or more, more preferably 3 μm or more, still more preferably 10 μm or more, still more preferably 20 μm or more, and still more preferably 25 μm or more from the viewpoint of curling of the obtained functional film. . In addition, when the obtained functional film is wound up or when the laminate (P) is peeled off from the functional film, the protective film (2) is protected from the viewpoint of operability and economy of the functional film in the subsequent step. The thickness is preferably 200 μm or less, more preferably 150 μm or less, still more preferably 100 μm or less, still more preferably 80 μm or less, yet more preferably 60 μm or less, yet more preferably 50 μm or less, and yet more preferably 40 μm or less. In addition, from the viewpoint of easily suppressing the curl of the obtained functional film, the thickness of the protective film (2) is preferably 0.2 to 1.5 times, 0.3 to 1.3 times, and 0.3 to 1.2 times the thickness of the amorphous film described later. , 0.3 ~ 1.0 times better, 0.3 ~ 0.5 times better.

When the protective film (2) is a laminate composed of the base film and the adhesive layer (Y), the thickness of the base film is easily suppressed from the viewpoint of curling of the obtained functional film, and is preferably 1 μm or more, more preferably It is 2 μm or more, more preferably 10 μm or more, still more preferably 20 μm or more, and still more preferably 25 μm or more. In addition, when the obtained functional film is taken up or the laminate (P) is peeled off from the functional film and used, the thickness of the base film is from the viewpoints of operability and economy of the functional film in the subsequent step, etc. It is preferably 150 μm or less, more preferably 100 μm or less, still more preferably 80 μm or less, still more preferably 60 μm or less, yet more preferably 50 μm or less, and yet more preferably 40 μm or less. Further, the thickness of the adhesive layer (Y) is preferably 1 to 100 μm, more preferably 2 to 50 μm, still more preferably 3 to 30 μm, and still more preferably 5 to 20 μm. In addition, when the protective film (2) is a laminate composed of the base film and the adhesive layer (Y), from the viewpoint of easily suppressing curling of the obtained functional film, the thickness of the base film is described later as an amorphous film The thickness of 0.2 to 1.5 times is better, 0.3 to 1.3 times better, 0.3 to 1.2 times better, 0.3 to 1.0 times better, 0.3 to 0.5 times better.

Furthermore, by using the laminate (P), the thickness of each layer of the protective films (1) and (2), etc., can be appropriately adjusted independently of each other. This makes it easy to adjust and suppress the curl amount of the functional film including the laminate (P). From such a viewpoint, the ratio of the thickness of the protective film (1) to the thickness of the protective film (2) [thickness (t1) / thickness (t2)] is preferably 0.5 to 1.5, more preferably 0.7 to 1.3, and even more preferably 0.7 ~ 1.2. The thickness of the protective film (1), the thickness of the protective film (2), the thickness of the base material film, and the thickness of the adhesive layer (Y) can be measured by, for example, methods described in Examples described later.

The thickness of the laminate (P) is preferably 2 to 300 μm, more preferably 10 to 250 μm, still more preferably 20 to 200 μm, still more preferably 30 to 150 μm, and still more preferably 40 to 100 μm. The thickness of the laminate (P) can be measured using, for example, the method described in Examples described later. Alternatively, the total thickness of the protective films (1) and (2) described below may be calculated. In addition, from the viewpoint of easily suppressing the curl of the obtained functional film, the thickness of the laminate (P) is preferably 0.5 to 3.0 times, preferably 0.6 to 2.4 times, and 0.7 to 2.0 times the thickness of the amorphous film described later. , 0.7 ~ 1.5 times better.

In addition, at least one surface of the protective film (1) and the protective film (2) may be subjected to etching treatment such as sputtering, corona discharge, flame, ultraviolet irradiation, electron beam irradiation, formation, oxidation, etc. in advance as necessary. Surface treatment such as primer treatment.

<Amorphous film> The aforementioned amorphous film is a film formed of an amorphous resin, and is excellent in transparency and dimensional stability, and is preferably selected from the group consisting of cycloolefin-based films and polycarbonate films One or more types, and from the viewpoint of low water absorption and excellent heat resistance, is more preferably a cycloolefin-based film.

The aforementioned cycloolefin-based film refers to a film formed of cycloolefin-based resin. The cycloolefin-based resin is a resin obtained by polymerizing an alicyclic olefin, that is, a cycloolefin as a monomer, and has a structural unit derived from a cycloolefin as a repeating unit in the molecule.

As for the aforementioned cyclic olefin, for example, norbornene or its substitutes (hereinafter, these are also collectively referred to as "norbornene-based monomers."), Etc. may be mentioned. Norbornene refers to a compound in which one carbon-carbon bond of norbornane becomes a double bond, and is named bicyclo [2,2,1] hept-2-ene according to the IUPAC nomenclature. Examples of the norbornene substitutes include, for example, a 3-substituent substituted with a double bond position of norbornene at the 1,2-position and substituted with a substituent such as methyl, ethyl, butyl, or phenyl. 4-Substitution, and 4,5-disubstitution, 5-ethylidene-2-norbornene, etc. Also, dicyclopentadiene, dihydrodicyclopentadiene, methyldicyclopentadiene, dimethyldicyclopentadiene, tetracyclododecene, methyltetracyclododecene, dimethyl Polycyclic cyclic olefins such as cyclododecene, tricyclopentadiene, tetracyclopentadiene, and dimethyl octahydronaphthalene; and cyclobutene, cyclopentene, cyclooctene, cyclooctene Monocyclic cyclic olefins such as diene, cyclooctatriene, and cyclododecatriene can also be used as monomers constituting the cycloolefin-based resin.

The cycloolefin-based resin may or may not have a norbornane ring in its constituent unit. Examples of the norbornene-based monomer that forms a cycloolefin-based resin that does not have a norbornene ring in the constituent unit include, for example, a monomer that becomes a 5-membered ring through ring opening. Examples of the monomer that becomes a 5-membered ring through ring opening include norbornene, dicyclopentadiene, 1- or 4-methylnorbornene, 4-phenylnorbornene, and the like. Here, for example, a method of ring-opening norbornene to make a resin having a 5-membered ring structure includes, for example, ring-opening metathesis polymerization using a Grubb catalyst. As described above, norbornene has a double bond in the norbornane ring. For example, when addition polymerization is performed using a metallocene catalyst, a cycloolefin-based resin having a norbornene ring in its constituent unit can also be synthesized.

More specific examples of cycloolefin-based resins include, for example, ring-opening polymers of norbornene-based monomers; ring-opening copolymers of norbornene-based monomers and other monomers; addition of maleic acid to them And modified polymers of at least one kind of cyclopentadiene; and polymers or copolymers of hydrogenation of these polymers; addition polymers of norbornene-based monomers; norbornene-based Addition copolymer of monomer and other monomers; etc. Examples of other monomers in the case of copolymers include ethylene; α-olefins such as propylene; cycloolefins; non-conjugated dienes. In addition, the cycloolefin-based resin may be a copolymer using one or more types of norbornene-based monomers and other alicyclic olefins. Furthermore, when the cycloolefin-based resin is a copolymer, the arrangement state of its molecules is not particularly limited, and it may be a random copolymer, a block copolymer, or a graft copolymer.

The aforementioned cyclic olefin resins can also be obtained from commercially available products, such as "ZEONEX" and "ZEONOR" (both registered trademarks) sold by Zeon Corporation of Japan, and "ARTON (registered trademark) sold by JSR Corporation. ) ";" TOPAS (registered trademark) "sold by Polyplastics;" APEL (registered trademark) "sold by Mitsui Chemicals; etc. In addition, commercially available products of these cyclic olefin resin films or stretched films are available, such as "ZEONORFILM (registered trademark)" sold by Zeon Corporation of Japan under the trade name; Gunze is sold by the company. "F film"; "ARTON (registered trademark) film" sold by JSR; "Esushina (registered trademark)" sold by Sekisui Chemical Industries, etc.

The aforementioned cycloolefin-based resin can be formed into a film by a casting method from a solution or a melt extrusion method. When making a film from two or more kinds of mixed resins, the film forming method is not particularly limited. For example, a uniform solution obtained by stirring and mixing a resin component with a solvent at a specified ratio is used to produce a film by a casting method. The resin component is melt-mixed at a specified ratio, and the method of making a film by the melt extrusion method, etc.

The aforementioned polycarbonate film refers to a film formed of polycarbonate resin. Polycarbonate resin has a carbonate group in the main chain. The polycarbonate resin is not particularly limited, and known ones can be used. Examples of polycarbonates include aromatic polycarbonates, aliphatic polycarbonates, and aromatic-aliphatic polycarbonates. Among these, from the viewpoint of excellent heat resistance, mechanical strength, transparency, and the like, it is preferably one or more selected from the group consisting of aromatic-aliphatic polycarbonate and aromatic polycarbonate And more preferably aromatic polycarbonate. Aromatic polycarbonate can be obtained by the method of reacting aromatic diol and carbonate precursor by interfacial polycondensation method or molten transesterification method, the method of polymerizing carbonate prepolymer by solid phase transesterification method, Or it can be obtained by a method of polymerization through a ring-opening polymerization method of a cyclic carbonate compound. As for the aromatic polycarbonate, for example, bisphenol-based polycarbonate can be used. Examples of the polycarbonate using bisphenols include bisphenol A polycarbonate, branched bisphenol A polycarbonate, expanded polycarbonate, copolycarbonate, block copolycarbonate, and polyester carbonate. , Polyphosphate carbonate, diethylene glycol bisallyl carbonate (CR-39) and so on. In addition, the polycarbonate resin also includes a polycarbonate resin composition mixed with other components such as a bisphenol A polycarbonate mixture, a polyester mixture, an ABS mixture, a polyolefin mixture, and a styrene-maleic anhydride copolymer mixture. . The aforementioned polycarbonate resins can also be obtained from commercially available products, such as "Panlite (registered trademark)" sold by Teijin Corporation; "Iupilon (registered trademark)" sold by Mitsubishi Gas Chemical Company; etc. In addition, these polycarbonate resin films or stretched films can also be obtained from commercially available products, such as "PureAce (registered trademark)" sold by Teijin Company under the trade name; sold by Mitsubishi Gas Chemical Company. "Iupilon (registered trademark) ･ sheet"; etc.

The aforementioned amorphous film may contain other ingredients such as stabilizers, plasticizers, aging inhibitors, antistatic agents, flattening agents and ultraviolet absorbers as necessary. Furthermore, surface treatment such as sputtering, corona discharge, flame, ultraviolet irradiation, electron beam irradiation, formation, oxidation, etc., or primer treatment may be applied in advance on the surface of the amorphous film.

The thickness of the aforementioned amorphous film is preferably 1 to 100 μm, more preferably 10 to 90 μm, still more preferably 10 to 80 μm, still more preferably 30 to 80 μm, and yet more preferably 45 to 80 μm. The value of the thickness of the amorphous thin film can be measured using, for example, the method described in Examples described later. The glass transition temperature (Tg) of the amorphous resin forming the amorphous thin film is preferably 130 ° C or higher, more preferably 140 ° C or higher, and still more preferably 150 ° C or higher. In addition, the upper limit of the glass transition temperature (Tg) is not particularly limited, but is preferably 250 ° C, more preferably 200 ° C, and still more preferably 180 ° C. The value of the glass transition temperature (Tg) of the amorphous thin film can be measured using, for example, the following method. The amorphous thin film was cut into strips with a width (TD direction) of 5 mm × length (MD direction) of 15 mm to prepare test pieces. After that, using a viscoelasticity measuring device ("DMA Q800" manufactured by TA Instruments), the tan δ (ratio of loss elasticity ratio and storage elasticity ratio) of the test piece at a frequency of 10 Hz, a heating rate of 5 ° C./min, atmosphere in the tensile mode Measure at 0 ~ 350 ℃ under the environment. In this temperature range, the temperature at which tan δ is the maximum value is read as the glass transition temperature (Tg) of the amorphous thin film. Furthermore, MD in the MD direction refers to the abbreviation of Machine Direction, and the MD direction is the long direction during film formation. In addition, TD in the TD direction refers to the abbreviation of Transverse Direction, and TD direction refers to the width direction at the time of film formation.

<Adhesive layer (X)> The functional film of the laminate is preferably a laminate having an adhesive layer (X) between the amorphous film and the laminate (P). When the functional film of the present invention has an adhesive layer (X), at least one of the adhesive and the adhesive constituting the adhesive layer (X) can be appropriately selected according to the use of the functional film. Furthermore, the adhesive layer (X) can be suitably selected to have a re-peelable, permanently adhesive or permanently adhesive layer according to the application, preferably having re-peelability.

Examples of the aforementioned adhesives include acrylic adhesives, urethane adhesives, silicone adhesives, rubber adhesives, polyester adhesives, and hardened adhesives that are hardened by energy rays such as ultraviolet rays. Agent. Among these, acrylic adhesives are preferred, and acrylic adhesives are not particularly limited. For example, it is preferable to use 100% by mass relative to the total amount of raw material monomers, and use 50% by mass or more of alkyl groups to have a carbon number of 4 The acrylic resin obtained by polymerizing alkyl (meth) acrylate of ~ 10 contains 50% by mass or more of acrylic adhesive in 100% by mass of the total resin used to use 2-ethylhexyl acrylate described later (2EHA) 2EHA adhesives are preferred. Examples of alkyl (meth) acrylates having 4 to 10 carbon atoms in the alkyl group include, for example, butyl (meth) acrylate, octyl (meth) acrylate, and isooctyl (meth) acrylate. , 2-ethylhexyl (meth) acrylate, etc., preferably (meth) acrylic acid alkyl esters having 6 to 10 carbon atoms in the alkyl group and (meth) acrylic acid alkyl esters having 8 carbon atoms in the alkyl group The more preferred is an ester, and even better is 2-ethylhexyl acrylate (2EHA). These adhesives can be used alone or in combination of two or more.

In addition, as for the adhesive, the adhesive exemplified in the adhesive layer (Y) can be used, and the suitable aspects are the same. These adhesives can be used alone or in combination of two or more.

The thickness of the adhesive layer (X) is not particularly limited, but it is preferably 1 to 100 μm, more preferably 3 to 50 μm, and still more preferably 5 to 30 μm. The thickness of the adhesive layer (X) can be measured using, for example, the method described in Examples described later.

<Other Layers> The functional film of the aforementioned laminate may have other layers in addition to the aforementioned laminate (P), amorphous film and adhesive layer (X), without impairing the effect of the present invention. For other layers, for example, it may be laminated between at least one layer of the laminate (P) and the amorphous film and the adhesive layer (X), or may be laminated on the opposite side of the laminate (P) of the amorphous film. For this other layer, for example, one or more than one protective film, an undercoat layer, and an adhesive layer (X) formed of the same or different materials as the protective film (1) or (2) Adhesive layer, refractive index adjustment layer, adhesion-resistant layer, hard coat layer, gas barrier layer, etc.

In addition, in the configuration of the aforementioned functional film, the adhesive layer (X) is transmitted through the protective film (2) side of the protective film laminate (P) formed by laminating the protective film (1) and the protective film (2). ) Or a functional film of a laminate in which an amorphous film is directly laminated. That is, in terms of the structure of the aforementioned functional film, a functional film in which a protective film (1) and a protective film (2) and an amorphous film are directly laminated in sequence, or a protective film (1) and The functional film of the protective film (2), the adhesive layer (X) and the amorphous film is preferred.

[Protective film laminate for amorphous thin film] A protective film laminate for amorphous thin film according to another embodiment of the present invention is a protective film layer formed by laminating a protective film (1) and a protective film (2) Fit (P). Here, the protective film laminate (P), the protective film (1) and the protective film (2) of the protective film laminate for an amorphous thin film, and their suitable aspects are respectively in the column of the aforementioned functional thin film As already explained, the detailed description is omitted.

[Use of Functional Film] The functional film according to one embodiment of the present invention is a functional film having the aforementioned amorphous film, and is therefore suitable as a functional film used in the manufacture of optical devices. For example, when it is used as a functional film for an optical device, various functional layers such as a transparent conductive film, an optical adjustment layer, and a polarizing plate can be laminated on the amorphous film side, and used for manufacturing a member for an optical device. In addition, for example, the aforementioned amorphous film itself may be used as a substrate for a retardation film, a liquid crystal cell substrate, etc., or a polarizing plate protective film. In such a manufacturing process, the aforementioned laminate (P) is for protecting the amorphous thin film. Furthermore, the functional film of the present invention can suppress curling even when used in a high-temperature environment. Therefore, for example, the manufacturing process of components used in optical devices is more suitable as a functional film for high-temperature processes. That is, it is more preferable as a functional film for optical devices manufactured through this process. In terms of use examples of this process, for example, when the amorphous film is used as one of the members of the transparent conductive film as described above, the amorphous film and other members are used with an adhesive such as the thermosetting adhesive. Use of a heating step such as a step of performing a bonding step, or a step of performing an annealing treatment to crystallize the transparent conductive film after laminating a transparent conductive film on the amorphous film. Furthermore, the functional film according to an embodiment of the present invention can suppress curling even when a load is applied in a high-temperature environment. Therefore, the manufacturing process of the optical member used in the optical device is, for example, more suitable as a functional film used in a high-temperature and load-bearing process such as the Roll to Roll process. That is, it is more suitable as a functional film for optical devices manufactured by this process. Moreover, the protective film laminate for an amorphous film according to an embodiment of the present invention can be used for the functional film according to an embodiment of the present invention described above. The functional film has the protective film laminate to achieve the foregoing Excellent effect. Therefore, the suitable use of the protective film laminate for an amorphous film according to an embodiment of the present invention is also the same as the use of the aforementioned functional film.

For the aforementioned optical device, in order to manufacture the optical device, the aforementioned functional film of the present invention is not particularly limited, and examples thereof include light emitting diodes (LEDs); liquid crystal displays (LCDs); organic electricity Electroluminescence (EL) such as electroluminescence (organic EL), inorganic electroluminescence (inorganic EL); plasma display panel (PDP); touch panel; cathode ray tube (CRT); electronic paper, solar cells, etc. Optical devices, etc. Among these, the aforementioned functional thin film is preferably suitable for EL, and more preferably suitable for organic EL. [Example]

Next, the present invention will be described in more detail with examples. However, the present invention is not limited to the following embodiments.

Regarding the characteristics of each amorphous film, each protective film (base material film and adhesive layer (Y)), and adhesive layer (X) used in each example and each comparative example, and the obtained functional film, Use the following method to evaluate.结果 结果 如 表 1。 The results are shown in Table 1.

<Amorphous film, adhesive layer (X), protective film, substrate film, adhesive layer (Y), laminate (P), thickness of hard coat layer> each used in each example and each comparative example For the thickness of the amorphous film and each protective film, use a constant pressure thickness measuring device (model: "PG-02J", based on standard specifications: JIS K6783: 1994, JIS Z1702: 1994, JIS Z1709: 1995) manufactured by TECLOCK Perform the measurement. The thickness of the base film in each protective film was used as the measured value of the thickness of the protective film where the adhesive layer (Y) was not applied. For the thickness of the adhesive layer (Y) in each protective film, the thickness of both the laminated base film and the adhesive layer (Y) (that is, the thickness of the protective film) minus the thickness of the base film is used The value of thickness. In addition, the thickness of the dried adhesive layer (X) was measured using the same method using the thickness of the laminate (P) with the adhesive layer (X) obtained in each example and each comparative example, minus the advance The value of the measured thickness of the laminate (P) (the total thickness of the protective films (1) and (2)). For the thickness of the hard coat layer, the measured value of the thickness of the hard-coated amorphous film obtained in each example and each comparative example was measured using the same method, minus the previously measured amorphous film The measured value of the thickness.

<Amorphous film, protective film (1) and protective film (2) tensile storage elastic modulus E 'at 23 ° C> Each protective film and each amorphous film used in each example and each comparative example The test pieces were prepared by cutting into strips with a width of 5 mm (TD direction) and a length of 20 mm (MD direction). After that, using a dynamic viscoelasticity measuring device (manufactured by Netz Japan Co., Ltd., product name "DMA 242E Artemis"), the measurement was carried out under the conditions of stretching mode, frequency 10 Hz, heating rate 3 ° C / min, temperature range 0 ° C to 200 ° C The tensile storage elastic modulus E 'is calculated as the tensile storage elastic modulus E' at 23 ° C.

<Glass transition temperature (Tg) of amorphous film> The glass transition temperature of the amorphous film used in each example and each comparative example was measured using the method described in the specification.

<Evaluation of curling of functional film 1> The functional films 1 to 18 produced in each example and each comparative example were cut to a size of 100 mm × 100 mm, and a test piece was produced. This test piece was heated at 150 ° C for 60 minutes using an oven "SPHH-202" manufactured by Espek. After heating for 60 minutes, the test piece was taken out of the oven and allowed to cool naturally. It was confirmed that the temperature of the test piece was reduced to room temperature (25 ° C), and the test piece was placed on a horizontal tabletop. The floating height (height from the table top) of the four corners (four vertices) of the test piece was measured with a ruler, and the average value of the four heights was calculated, and the value was used as the curling amount. The value of the curl amount is "good" when it is less than 10 mm, and it is "bad" when it exceeds 10 mm, and the quality of the curl suppression effect of each test piece is judged. The results obtained are shown in Tables 1 and 2 below. In addition, the value of the curl amount is described as a positive value when the amorphous film side floats, and as a negative value when the protective film (1) side floats.

<Evaluation of curling of functional film 2> The functional films 1 to 18 produced in each example and each comparative example were cut to a size of 200 mm × 100 mm to prepare test pieces. The tension of 20 N / 100 mm is applied to one short side of the test piece in such a manner as to apply tension to the long side of the test piece. With this tension applied, the test piece was heated at 100 ° C. for 5 minutes using an oven “SPHH-202” manufactured by Espek. After heating for 5 minutes, the test piece was taken out of the oven, while applying tension, it was allowed to cool naturally. It was confirmed that the temperature of the test piece was reduced to room temperature (25 ° C), the central part of the test piece was cut, and 100 mm × 100mm test piece. The test piece cut into 100 mm × 100 mm was placed on a horizontal tabletop. The floating height (height from the table top) of the four corners (four vertices) of the test piece was measured with a ruler, and the average value of the four heights was calculated, and the value was used as the curling amount. The value of the curl amount is "good" when it is less than 10 mm, and it is "bad" when it exceeds 10 mm. The curl suppression effect of each test piece is judged as good or bad. The results obtained are shown in Tables 1 and 2 below. In addition, the value of the curl amount is described as a positive value when the amorphous film side floats, and as a negative value when the protective film (1) side floats.

[Example 1] As a protective film (1), a non-stretching polypropylene-based protective film (manufactured by Sumiron Corporation, model "EC7507"), consisting of an adhesive layer (Y) formed of a base film and an acrylic adhesive The thickness of the thin film and the base film is 30 μm, and the thickness of the adhesive layer (Y1) is 7 μm). As a protective film (2), a polyethylene terephthalate film (manufactured by Mitsubishi Chemical Corporation, model "NW07T600E", thickness 25 μm) was prepared. Lay the protective film (1) and the protective film (2) through the adhesive layer (Y) using a roll laminator "RSL-380S" manufactured by JOL Corporation to produce a laminate (P). Next, on the protective film (2) side of the laminate (P), a 2EHA-based adhesive was applied so that the thickness of the dried adhesive layer (X) became 7 μm to form a coating film. This coating film was heated at 100 ° C. for 1 minute to form an adhesive layer (X). As the amorphous film, a cycloolefin polymer film (1) (manufactured by Zeon Corporation of Japan, ZEONOR film (registered trademark), model "ZF16-080", thickness 80 μm) was used, and the exposed surface of the adhesive layer (X) was exposed The surface of this amorphous film was bonded using a roll laminator "RSH-380SL" manufactured by JOL Corporation to obtain a functional film 1 of a laminate.

[Example 2] Functionality was obtained in the same manner as in Example 1, except that the amorphous film used in Example 1 was changed to a polycarbonate film (manufactured by Teijin Corporation, model "C110-40", thickness 40 μm) Film 2.

[Example 3] The function was obtained in the same manner as in Example 1, except that the amorphous film used in Example 1 was changed to a cycloolefin copolymer film (manufactured by Gunes Co., Ltd., model "F1 film", thickness 80 μm).性 膜 3。 Sex film 3.

[Example 4] In addition to changing the amorphous film used in Example 1 to a cycloolefin polymer film (manufactured by Zeon Corporation of Japan, ZEONOR film (registered trademark), model "ZF16-040", thickness 40 μm), and A functional thin film 4 was obtained in the same manner as in Example 1 except that a hard coat layer having a thickness of 1 μm was provided on the side opposite to the surface of the protective film laminate provided with this amorphous thin film. The aforementioned hard coat layer is an ultraviolet (UV) hardening acrylate resin composition (manufactured by Arakawa Chemical Industry Co., Ltd., trade name "OPSTAR (registered trademark) Z7530") using MEYER BAR so that the resulting coating film is at 70 ° Dry for 1 minute. Thereafter, using a high-pressure mercury lamp (manufactured by Heraeus Corporation), the coating film was irradiated with ultraviolet light at a linear speed of 20 m / min at an illuminance of 250 mW / cm ² and a light amount of 170 mJ / cm ² , and ultraviolet (UV) hardening acrylate The resin composition is hardened to form a hard coating layer with a thickness of 1 μm.

[Example 5] except that the protective film (2) used in Example 4 was changed to a polyethylene terephthalate film (manufactured by Toyobo Cosmoshine (registered trademark), model "PET50A4300", thickness 50 μm) In the same manner as in Example 4, a functional film 5 was obtained.

[Example 6] The protective film (1) used in Example 4 was changed to a 2-axis stretch polypropylene protective film (manufactured by Futamura Chemical Co., model "150M") and formed of a base film and an acrylic adhesive The functional film 6 was obtained in the same manner as in Example 4 except that the film composed of the adhesive layer (Y2) and the thickness of the base film (30 μm) and the thickness of the adhesive layer (Y2) were 7 μm).

[Example 7] In addition to the functional film 1 described in Example 1, the hard coat layer described in Example 4 is provided on the side opposite to the surface of the protective film laminate provided with an amorphous film, and Example 1 Similarly, the functional film 7 is obtained.

[Example 8] In addition to the functional film 2 described in Example 2, the hard coating layer described in Example 4 was provided on the surface opposite to the surface of the protective film laminate provided with the amorphous film, and Example 2 was used. Similarly, the functional film 8 is obtained.

[Example 9] The function was obtained in the same manner as in Example 4 except that the amorphous film used in Example 4 was changed to a cycloolefin copolymer film (manufactured by Gunes Co., Ltd., model "FX film", thickness 40 μm).性 膜 9。 Sex film 9.

[Comparative Example 1] Except that the protective film (1) was not used in Example 1, and the protective film (2) was a polyethylene terephthalate film (manufactured by Toyobo Co., Cosmoshine (registered trademark), model "PET50A4300" , Except for the thickness of 50 μm), in the same manner as in Example 1, a functional film 10 was obtained.

[Comparative Example 2] In addition to changing the amorphous film used in Comparative Example 1 to a cycloolefin polymer film (manufactured by Zeon Corporation of Japan, ZEONOR film (registered trademark), model "ZF16-040", thickness 40 μm), In Comparative Example 1, the functional film 11 was obtained in the same manner.

[Comparative Example 3] Functionality was obtained in the same manner as Comparative Example 1, except that the amorphous film used in Comparative Example 1 was changed to a polycarbonate film (manufactured by Teijin Corporation, model "C110-40", thickness 40 μm)膜 12。 Film 12.

[Comparative Example 4] The function was obtained in the same manner as in Comparative Example 1 except that the amorphous film used in Comparative Example 1 was changed to a cycloolefin copolymer film (manufactured by Gunze Corporation, model "FX film", thickness 40 μm)性 膜 13。 Sex film 13.

[Comparative Example 5] In addition to the functional film 11 described in Comparative Example 2, a hard coat layer described in Example 4 was provided on the surface opposite to the surface of the protective film laminate provided with an amorphous film, as compared with Comparative Example 2 Similarly, the functional film 14 is obtained.

[Comparative Example 6] Except that the protective film (2) used in Comparative Example 5 was changed to a polyethylene terephthalate film (manufactured by Mitsubishi Chemical Corporation, model "NW07T600E", thickness 25 μm), the same as Comparative Example 5 Similarly, the functional film 15 is obtained.

[Comparative Example 7] except that the protective film (2) used in Comparative Example 5 was changed to polyethylene terephthalate film (manufactured by Toray, model "U48", thickness 125 μm), and Comparative Example 5 Similarly, the functional film 16 is obtained.

[Comparative Example 8] In Example 4, a functional film 17 was obtained in the same manner as in Example 4 except that the protective film (2) and the adhesive layer (X) were not used. (The protective film (1) of Example 4 is directly laminated with the amorphous thin film with a hard coat layer.)

[Comparative Example 9] In Example 6, a functional film 18 was obtained in the same manner as in Example 6, except that the protective film (2) and the adhesive layer (X) were not used. (The protective film (1) of Example 6 is directly laminated with the amorphous thin film with a hard coat layer.)

From Table 1, it was confirmed that even when the functional films 1 to 9 of Examples 1 to 9 were exposed to a high-temperature environment, the amount of curl was small, and curl was suppressed. Further, it was confirmed that the functional films 1 to 9 of Examples 1 to 9 had a small amount of curl and suppressed curl even when a load was applied in a high-temperature environment. On the other hand, from Table 2, it was confirmed that the functional films 10 to 18 of Comparative Examples 1 to 9 had a large amount of curl when exposed to a high-temperature environment, and it was difficult to suppress curling. Further, it was confirmed that the functional films 10 to 18 of Comparative Examples 1 to 9 have a larger amount of curl when a load is applied in a high-temperature environment, and it is difficult to suppress curling.

<Curly Evaluation of Functional Film 3> The functional films 19 to 22 produced in Examples 10 and 11 and Comparative Examples 10 and 11 described below were cut to a size of 100 mm × 100 mm to prepare test pieces. The test piece was heated in an oven "SPHH-202" manufactured by ESPEC at 150 ° C for 5 minutes. After heating for 5 minutes, the test piece was taken out of the oven and allowed to cool naturally. It was confirmed that the temperature of the test piece was lowered to room temperature (25 ° C), and the test piece was allowed to stand on a horizontal table. The floating height (height from the table top) of the four corners (four vertices) of the test piece was measured with a ruler, and the average value of the four heights obtained was calculated, and the value was used as the curling amount. The value of the curl amount is "good" when it is less than 10 mm, and it is "bad" when it exceeds 10 mm. The curl suppression effect of each test piece is judged as good or bad. The results obtained are shown in Table 1 below. Furthermore, the value of the curl amount is described as a positive value when the amorphous thin film side floats, and is described as a negative value when the protective film (1) side floats.

[Example 10] As a protective film (1), a polypropylene-based protective film (manufactured by Sumiron Corporation, model "EC-430") and an adhesive layer (Y3) formed of a base film and an acrylic adhesive were prepared. The thickness of the thin film and the base film is 40 μm, and the thickness of the adhesive layer (Y3) is 5 μm). As a protective film (2), a polyethylene terephthalate film (made by Toyobo Cosmoshine (registered trademark), model "PET38A4300", thickness 38 μm) was prepared. The protective film (1) and the protective film (2) are laminated through the adhesive layer (Y3) using a roll laminator "RSL-380S" manufactured by JOL Corporation to produce a laminate (P). Next, on the protective film (2) side of the laminate (P), a 2EHA-based adhesive was applied so that the thickness of the dried adhesive layer (X) became 10 μm to form a coating film. This coating film was heated at 100 ° C. for 1 minute to form an adhesive layer (X). As an amorphous film, a cycloolefin polymer film (1) (manufactured by Zeon Corporation of Japan, ZEONOR film (registered trademark), model "ZF16-040", thickness 40 μm) was used to expose the exposed surface of the adhesive layer (X) The surface of this amorphous film was bonded using a roll laminator "RSH-380SL" manufactured by JOL Corporation to obtain a functional film 19 of a laminate.

[Example 11] Except that the protective film (1) used in Example 10 was changed to a polypropylene-based protective film (manufactured by Hitachi Chemical Co., Ltd., model "P-5310") and formed of a base film and an acrylic adhesive A functional film 20 was obtained in the same manner as in Example 10 except that the film composed of the adhesive layer (Y) and the base film had a thickness of 30 μm and the adhesive layer (Y) had a thickness of 5 μm).

[Comparative Example 10] In Example 10, a functional film 21 was obtained in the same manner as in Example 10 except that the protective film (1) was not used, and only the protective film (2) was used.

[Comparative Example 11] A functional film 22 was obtained in the same manner as in Example 10, except that the protective film (2) was not used in Example 10, and only the protective film (1) was used.

From Table 3, it was confirmed that the functional films 19 and 20 of Examples 10 and 11 had a small amount of curl and suppressed curl even when exposed to a high-temperature environment. On the other hand, it was confirmed that the functional films 21 and 22 of Comparative Examples 10 and 11 had a large amount of curl when exposed to a high-temperature environment, and it was difficult to suppress curling. [Industrial utility]

The functional film using a protective film laminate according to an embodiment of the present invention can suppress curling in a high-temperature environment. The aforementioned functional film is a functional film having an amorphous film, so it is suitable as a protective film laminate for a functional film used in the manufacture of optical devices. The protective film laminate is preferably used in the manufacturing process of components used in optical devices, such as functional films used in processes used at high temperatures. That is, it is more suitable as a protective film laminate for a functional thin film for optical devices manufactured by this process. In terms of use examples of this process, for example, when an amorphous film is used as a member of a transparent conductive film, etc., the amorphous film and other members are carried out using an adhesive such as the thermosetting adhesive. The use of the step of bonding, or the heating step such as the annealing treatment step performed to crystallize the transparent conductive film after laminating the transparent conductive film on the amorphous film. Furthermore, the functional film using a protective film laminate according to an embodiment of the present invention can suppress curling even when a load is applied at a high temperature. Therefore, in the manufacturing process of the optical member used in the optical device, for example, a protective film laminate for a functional thin film used in a process that applies a high temperature such as a roll to roll process and the like is preferably used. That is, it is more suitable as a protective film laminate used as a functional film for optical devices manufactured by this process. Furthermore, the functional film according to an embodiment of the present invention, as described above, is a functional film using a protective film laminate according to an embodiment of the present invention, so it can be suitably used for the aforementioned uses.

1, 2‧‧‧ Functional film

10‧‧‧Amorphous film

11‧‧‧Protection film (1)

12‧‧‧Protection film (2)

101‧‧‧Protective film laminate (P)

13‧‧‧Adhesive layer (X)

[FIG. 1] A cross-sectional view of a functional film 1 as an example of the functional film of the present invention. [FIG. 2] A cross-sectional view of the functional film 2 which is an example of the functional film of the present invention.

Claims (15)

A protective film laminate for an amorphous thin film, characterized in that it is a protective film laminate (P) formed by laminating a protective film (1) and a protective film (2). The protective film laminate for an amorphous thin film according to claim 1, wherein the protective film (1) and the protective film (2) are protective films formed of mutually different materials. In the protective film laminate for an amorphous film according to claim 1 or 2, at least one of the protective film (1) and the protective film (2) is composed of a base film and an adhesive layer (Y). The protective film laminate for an amorphous film according to any one of claims 1 to 3, wherein the protective film (1) has a tensile storage elastic modulus E 'at 23 ° C which is 23 ° C higher than that of the protective film (2) The tensile storage elastic modulus E 'is low. The protective film laminate for an amorphous film according to any one of claims 1 to 4, wherein the tensile storage elastic modulus E 'of the protective film (1) at 23 ° C. is not more than 1.0 × 10 ⁷ Pa 3.0 × 10 ⁹ Pa, the tensile storage elastic modulus E ′ of the protective film (2) at 23 ° C. is 3.0 × 10 ⁹ Pa or more and 1.0 × 10 ¹¹ Pa or less. The protective film laminate for an amorphous film according to any one of claims 1 to 5, wherein the protective film (1) is a polyolefin-based protective film. The protective film laminate for an amorphous film according to any one of claims 1 to 6, wherein the protective film (2) is a polyester-based protective film. The protective film laminate for an amorphous film according to any one of claims 1 to 7, wherein the protective film (1) is a polyolefin-based protective film, and the protective film (2) is a polyester-based protective film. A functional thin film, characterized in that it is a laminate in which an amorphous thin film is laminated on the protective film (2) side of the protective film laminate for an amorphous thin film according to any one of claims 1 to 8. The functional film according to claim 9, which further has an adhesive layer (X) between the protective film laminate (P) and the aforementioned amorphous film. The functional film according to claim 9 or 10, wherein the thickness of the protective film (1) is 0.3 to 1.5 times the thickness of the aforementioned amorphous film. The functional film according to any one of claims 9 to 11, wherein the thickness of the protective film laminate (P) is 2 μm or more and 300 μm or less. The functional film according to any one of claims 9 to 12, wherein the amorphous film is one or more types selected from the group consisting of cycloolefin-based films and polycarbonate films. The functional film according to any one of claims 9 to 13, wherein the thickness of the amorphous film is 1 μm or more and 100 μm or less. The functional film described in any one of claims 9 to 14 is used for optical devices.