Method for manufacturing a molded body with a polarizer layer

Abstract

A transfer-medium layered product which includes a hardcoat layer and a resin layer (A) disposed on one surface of the hardcoat layer, wherein the hardcoat layer has stretchability and the resin layer is constituted of a resin having a storage modulus of 1,000 MPa or less. The resin layer (A) preferably contains an ultraviolet absorber. The hardcoat layer is preferably a semicured object obtained from a hardcoat material, and the resin layer (A) is preferably a layer formed on a surface of the semicured object. Also provided are: a polarizing film including the transfer-medium layered product; methods for producing the transfer-medium layered product and the polarizing film; and a method for producing a molded object using the polarizing film.

Description

[Technical Field]

[0001] The present invention relates to a transfer medium laminate, a polarizing film, a method for manufacturing a polarizing film, and a method for manufacturing a molded article using a polarizing film. [Background technology]

[0002] In display devices such as liquid crystal displays and organic electroluminescent displays, films that function as linear polarizers are provided for various purposes. Since such linear polarizers are often thin, layered materials with low mechanical strength, they are generally used as polarizing films comprising a polarizer and a protective film. Polarizing films may also be provided with a hard coat layer for purposes such as improving scratch resistance on the display device surface. In most cases, the hard coat layer is formed by applying a liquid hard coat material to the surface of the molded body to be formed and curing it. However, it is also possible to form a laminate containing the hard coat layer on the surface of a component other than the target and transfer it to the surface of the molded body (for example, Patent Documents 1 and 2). [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2014-130298 [Patent Document 2] International Publication No. 2019 / 087806 (Corresponding publication: U.S. Patent Application Publication No. 2021 / 109268) [Overview of the Initiative] [Problems that the invention aims to solve]

[0004] Traditionally, display surfaces for display devices have only been flat; however, in recent years, there has been a demand for display devices with curved surfaces. If a hard coat layer can be transferred to such curved surfaces, improved manufacturing efficiency can be expected. In particular, if a polarizing film with a hard coat layer can be laminated to the surface, and both the polarizing film and the hard coat layer can be formed simultaneously, further improvements in manufacturing efficiency can be expected.

[0005] However, films with a hard coat layer have the problem of cracking when attempted to bond to curved surfaces. Furthermore, polarizing films with a hard coat layer are prone to curling before bonding, making them difficult to handle. Therefore, the object of the present invention is to provide a polarizing film that conforms well to curved surfaces, is easy to bond to curved surfaces, and suppresses the occurrence of curling, as well as materials constituting the same, a method for manufacturing them, and a method for manufacturing molded articles using them. [Means for solving the problem]

[0006] As a result of investigations to solve the above problems, the inventors of the present invention found that the above problems can be solved by constructing a transfer medium laminate which is a combination of a hard coat layer and a resin layer having specific physical properties, and thus completed the present invention. That is, the present invention provides the following.

[0007] [1] A transfer medium laminate comprising a hard coat layer and a resin layer (A) provided on one surface of the hard coat layer, The hard coat layer has stretchability, The resin constituting the aforementioned resin layer is a transfer medium laminate having a storage modulus of 1000 MPa or less. [2] The transfer medium laminate according to [1], wherein the thickness of the resin layer (A) is 0.1 μm or more and 10 μm or less. [3] The transfer medium laminate according to [1] or [2], wherein the resin layer (A) contains an ultraviolet absorber. [4] The transfer medium laminate according to any one of [1] to [3], wherein the hard coat layer is a semi-cured product of a hard coat material, and the resin layer (A) is a layer formed on the surface of the semi-cured product. [5] The transfer medium laminate according to any one of [1] to [4], wherein the in-plane retardation Re of the resin layer is 0 nm or more and 5 nm or less. [6] The transfer medium laminate according to any one of [1] to [5], further comprising a support provided on the surface of the hard coat layer opposite to the resin layer (A) side. [7] The transfer medium laminate according to [6], wherein the support comprises a release layer provided on the surface on the hard coat layer side. [8] A method for manufacturing a transfer medium laminate according to any one of items [1] to [7], A process of spreading a hard coat material onto the surface of a support, A step of partially curing the hard coat material to form a stretchable hard coat layer, and A step of spreading resin on the hard coat layer to form a resin layer (A) with a storage modulus of 1000 MPa or less. A method for producing a transfer medium laminate, including the following. [9] A transfer medium laminate as described in any one of items [1] to [7], A polarizer layer provided on the resin layer (A) side of the transfer medium laminate, and Adhesive layer interposed between the transfer medium laminate and the polarizer layer A polarizing film equipped with these features.

[10] A transfer medium laminate as described in any one of items [1] to [7], A polarizer layer provided on the resin layer (A) side of the transfer medium laminate, and Adhesive layer interposed between the transfer medium laminate and the polarizer layer A method for manufacturing a polarizing film, comprising: The aforementioned resin layer (A) contains an ultraviolet absorber, A step of bonding the transfer medium laminate and the polarizer layer via an ultraviolet-curing adhesive to form a laminate, and A step of irradiating the laminate with ultraviolet rays from the polarizer layer side of the laminate A method for producing a polarizing film, comprising: 〔11〕 A method for producing a molded body with a polarizer layer, comprising: A step (A) of producing a polarizing film by the production method described in 〔10〕, A step (B) of bonding the polarizing film to a base member, and A step (C) of fully curing the hard coat layer in the polarizing film including The base member used in the step (B) is a member having a curved surface, or further includes a step (Bx) of curving the base member after the step (B) and before the step (C).

Advantages of the Invention

[0008] According to the present invention, there are provided a polarizing film that is easily bonded to a curved surface and has suppressed curl, and a transfer medium laminate constituting the same. According to the present invention, there are also provided a method for producing such a polarizing film, and a method for easily producing a molded body useful as a component of a display device having a curved display surface using such a polarizing film.

Embodiments for Carrying Out the Invention

[0009] Hereinafter, the present invention will be described in detail with reference to embodiments and examples. However, the present invention is not limited to the embodiments and examples shown below, and can be arbitrarily modified and implemented without departing from the scope of the claims of the present invention and its equivalent scope.

[0010] In the following description, the terms "solution" and "solvent" are construed in a broad sense to include not only a solute dissolved in a solvent and the medium therein, but also a liquid medium containing other substances and the medium therein. For example, the "solution" also includes a dispersion in which solid particles are dispersed in a liquid dispersion medium, and an emulsion in which liquid particles are dispersed in a liquid continuous phase.

[0011] In the following explanation, the terms "(meth)acrylate," "(meth)acryloyl," and "(meth)acrylic" refer to acrylic groups, methacrylic groups, and mixtures thereof. For example, "(meth)acrylate" is a term that includes acrylate, methacrylate, and mixtures thereof.

[0012] In the following description, "long-length" film refers to a film having a length of five times or more its width, preferably ten times or more, and specifically, a length sufficient to be wound into a roll for storage or transport. There is no particular upper limit to the ratio of length to width of the film, but it may be, for example, 100,000 times or less.

[0013] In the following explanation, unless otherwise specified, the term "adhesive" includes not only adhesives in the narrow sense, but also adhesives with a shear storage modulus of less than 1 MPa at 23°C (those that can be used as pressure-sensitive adhesives). Here, adhesives in the narrow sense refer to adhesives whose shear storage modulus at 23°C is between 1 MPa and 500 MPa after energy ray irradiation or heat treatment.

[0014] In the following description, the in-plane retardation Re of a film is given by the value Re = (nx - ny) × d unless otherwise specified. Here, nx represents the refractive index in the direction perpendicular to the thickness direction of the film (in-plane direction) that gives the maximum refractive index. ny represents the refractive index in the direction perpendicular to the direction of nx in the in-plane direction of the film. d represents the thickness of the film. The measurement wavelength is 550 nm unless otherwise specified.

[0015] [1. Overview of the transfer medium laminate and its manufacturing method] In this application, the transfer medium laminate is a laminate including a hard coat layer, and is a laminate for achieving the transfer of a hard coat layer by bonding it to the surface of a solid molded body. The transfer medium laminate of the present invention comprises a hard coat layer and a resin layer (A) provided directly on one surface of the hard coat layer or via another layer. The transfer medium laminate of the present invention may further include, as an optional component, a support provided on the surface of the hard coat layer opposite to the resin layer (A) side.

[0016] The transfer medium laminate of the present invention can be manufactured by any manufacturing method, but a preferred manufacturing method includes the following steps. In the following, this method will be described as a method for manufacturing the transfer medium laminate of the present invention. Step (1): A step of spreading a hard coat material onto the surface of a support. Step (2): A step to partially harden the hard coat material and form a stretchable hard coat layer. Step (3): A step of spreading resin on a hard coat layer to form a resin layer (A) with a storage modulus of 1000 MPa or less.

[0017] [2. Support] Any material having a surface suitable for forming a hard coat layer can be used as the support. In the final product (a display device, or a molded body with a polarizer layer that constitutes it, etc.), the support may remain as part of it, but usually the support can be peeled off and removed in the processes after step (3) until the final product is obtained.

[0018] The support can typically be a resin film. Examples of resins that make up the support include those containing common polymers such as polypropylene (PP) and polyethylene terephthalate (PET) as the main component.

[0019] When the support is to be peeled from the hard coat layer in a step later than step (3), a film with a surface treatment that facilitates such peeling may be preferably used as the support. Specifically, a film whose surface has been peeled with silicone may be used. In addition, biaxially oriented films may have surface properties that are suitable for peeling, so such films are also preferred as supports.

[0020] The surface of the support is usually flat, but is not limited to this; for example, a textured surface formed by shape transfer using an embossing roll may be provided on the surface of the support. By having such a textured surface on the surface of the support, the textured surface on the hard coat layer can be transferred, thereby imparting an anti-glare function and / or reflection reduction function to the surface of the hard coat layer.

[0021] The support may have any layer on its surface, such as an antistatic layer, an antireflective layer, or a release layer. Such any layer may be removed together with the support when the support is peeled off, or it may be left on the product. In particular, if the support has a release layer provided on the surface on the hard coat layer side in addition to the resin layer described above, the support and the hard coat layer can be easily peeled off.

[0022] The thickness of the support can be adjusted as appropriate within the desired range. Specifically, the thickness of the support is preferably 20 μm or more, more preferably 30 μm or more, while preferably 80 μm or less, and more preferably 60 μm or less.

[0023] [3. Hard Court Layer] The hard coat layer in the transfer medium laminate of the present invention is stretchable. In the present invention, the stretchability of the hard coat layer refers to the property that when the hard coat layer is treated as an independent film and uniaxially stretched, it can be stretched by 1.50 times or more without the occurrence of cracks. More specifically, the hard coat layer is treated as an independent film, forming a rectangle with a length of 150 mm and a width of 20 mm, and the presence or absence of stretchability can be determined by freely uniaxially stretching it in the length direction to a magnification of 1.50 times or more and observing whether or not cracks occur. If no cracks occur at a stretching magnification of 1.50 times, it can be determined that the hard coat layer is stretchable. By having such stretchability, the conformability of the transfer medium laminate and the polarizing film to curved surfaces can be improved.

[0024] The hard coat layer in the final product may have a greater hardness than the resin layer (A) and may have the function of suppressing scratches on the surface of the resin layer (A). Preferably, the hard coat layer in the final product exhibits a hardness of "HB" or higher in the pencil hardness test specified in JIS K5600-5-4. Furthermore, it is preferable that the hard coat layer at this stage has high scratch resistance. Specifically, it is preferable that the hard coat layer has sufficient scratch resistance that no scratches can be visually observed when steel wool #0000 is pressed against the hard coat layer under a load of 0.025 MPa and the surface of the hard coat layer is moved back and forth 10 times. The hard coat layer may also have an anti-glare function and / or a reflection reduction function.

[0025] The hard coat layer in a transfer medium laminate may be a semi-cured hard coat material. In this application, "hard coat material" refers to a material that can form a hard coat layer upon curing. Furthermore, a "semi-cured" hard coat material refers to a material that has hardened more than the hard coat material before curing, but which can become a material with even higher hardness through further processing (e.g., ultraviolet irradiation). In contrast, a material whose hardness has been increased to the point where the hardness and other properties required for the final product are obtained is called a "fully cured product."

[0026] The hard coat material may consist of a polymerizable substance (H) as the main component and optional components that may be included as needed. As the polymerizable substance (H), various polymerizable substances that can impart the desired hardness to the hard coat layer in the final product can be used.

[0027] A specific example of a polymerizable substance (H) is a polyfunctional (meth)acrylate. The weight-average molecular weight of the polyfunctional (meth)acrylate is preferably 10,000 or more, and more preferably 100,000 or less. The weight-average molecular weight per (meth)acryloyl group of the polyfunctional (meth)acrylate is preferably 200 or more, and more preferably 400 or less. Having such molecular weights facilitates synthesis, allows for the acquisition of good hard coat layer performance, and facilitates the handling of the hard coat material.

[0028] The polyfunctional (meth)acrylate is preferably a substance having a structure obtained by reacting an α,β-unsaturated carboxylic acid with a polymer of monomer components containing epoxy group-containing (meth)acrylate monomers. By using such a substance as the polyfunctional (meth)acrylate, a hard coat layer with high hardness and excellent scratch resistance can be easily obtained.

[0029] Epoxy group-containing (meth)acrylate monomers are compounds having one or more epoxy groups and one or more unsaturated double bonds in their molecule. Examples of epoxy group-containing (meth)acrylate monomers include glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, vinylcyclohexene monooxide (i.e., 1,2-epoxy-4-vinylcyclohexane), and combinations thereof. Of these, glycidyl (meth)acrylate is preferred from the viewpoint of availability.

[0030] The monomer component may include any monomer copolymerizable with epoxy group-containing (meth)acrylate monomers.

[0031] Examples of arbitrary monomers include (meth)acrylic acid esters, styrene, vinyl acetate, (meth)acrylamide, acrylonitrile, macromonomers having an unsaturated double bond at one of their ends and not containing epoxy or carboxyl groups, and combinations thereof.

[0032] Specific examples of macromonomers include macromonomers AA-6, AB-6, AS-6, and AY-707S (manufactured by Toagosei Co., Ltd.); Cyraplane FM-0711 and FM-0721 (manufactured by Chisso Corporation); Praxel FA10L (manufactured by Daicel Chemical Industries, Ltd.); and Bremmer PME-4000 and PSE-1300 (manufactured by NOF Corporation).

[0033] Examples of α,β-unsaturated carboxylic acids include α,β-unsaturated monocarboxylic acids such as (meth)acrylic acid, α,β-unsaturated dicarboxylic acids such as (meth)acrylic acid dimers, and combinations thereof. Of these, (meth)acrylic acid is preferred from the viewpoint of providing the desired hardness to the hard coat layer in the final product.

[0034] An example of an optional component that a hard coat material may contain is a polymerization initiator. Various types of polymerization initiators can be used that can initiate the polymerization of polymerizable substances (H) by irradiation with active energy rays such as ultraviolet light. Specific examples of polymerization initiators include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-cyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)-benzyl]phenyl}-2-methylpropan-1-one, phenylglyoxylic acid methyl ester, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-(dimethylamino Examples include )-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 4-methylbenzophenone, 1-[4-(4-benzoylphenylsulfanyl)phanyl]-2-methyl-2-(4-methylphenylsulfonyl)propan-1-one, 1,2-octanedione, 1-[4-(phenylthio)phenyl,2-(O-benzoyl oxime)], ethanone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-1-(O-acetyloxime), and combinations thereof. An example of a commercially available polymerization initiator is IRGACURE184, manufactured by Ciba Specialty Chemicals.

[0035] The ratio of polymerization initiator in the hard coat material to 100 parts by weight of polymerizable substance (H) is preferably 0.1 parts by weight or more, and preferably 10 parts by weight or less. By setting the ratio of polymerization initiator within the above range, the desired stretchability can be easily imparted to the hard coat layer in the transfer medium laminate and polarizing film, and the desired hardness can be given to the hard coat layer in the final product.

[0036] In addition to the components described above, the hard coat material may contain fine particles. The fine particles can adjust various physical properties of the hard coat layer, such as conductivity and refractive index. Preferably, the fine particles have a refractive index of 1.4 or higher.

[0037] The fine particles may be organic fine particles composed of organic materials, or inorganic fine particles composed of inorganic materials. Preferably, the fine particles are inorganic fine particles, and more preferably, inorganic oxide fine particles. Examples of inorganic oxides that can constitute the fine particles include silica, titania (titanium oxide), zirconia (zirconium oxide), zinc oxide, tin oxide, cerium oxide, antimony pentoxide, titanium dioxide, tin-doped indium oxide (ITO), antimony-doped tin oxide (ATO), phosphorus-doped tin oxide (PTO), zinc-doped indium oxide (IZO), aluminum-doped zinc oxide (AZO), and fluorine-doped tin oxide (FTO).

[0038] As for the fine particles, silica fine particles are preferred because they offer an excellent balance between adhesion to polymers of polymerizable substances (H) and transparency, and allow for easy adjustment of the refractive index of the hard coat layer.

[0039] The hard coat material may contain one type of fine particle alone, or a combination of two or more types.

[0040] The number-average particle size of the fine particles is preferably 1 nm to 1000 nm, more preferably 1 nm to 500 nm, and even more preferably 1 nm to 250 nm. The smaller the number-average particle size of the fine particles, the lower the haze of the hard coat layer can be, and the higher the adhesion between the fine particles and the polymerizable substance (H) polymer can be.

[0041] Haze (%) can be measured in accordance with JIS K-7136 using, for example, a commercially available haze meter (e.g., the "NDH 2000" manufactured by Nippon Denshoku Co., Ltd.).

[0042] In a composition for forming a hard coat layer, the content of fine particles is preferably 10 to 80 parts by weight, more preferably 10 to 50 parts by weight, and even more preferably 20 to 40 parts by weight, per 100 parts by weight of polymerizable substance (H). When the content of fine particles is within the above range, excellent optical properties such as haze value and total light transmittance are obtained.

[0043] The total light transmittance (%) can be measured in accordance with JIS K-7361 using, for example, a commercially available haze meter (such as the "NDH 2000" manufactured by Nippon Denshoku Co., Ltd.).

[0044] Hard coat materials may contain additional optional components in addition to those described above. Examples include polymerization inhibitors, antioxidants, antistatic agents, light stabilizers, solvents, defoamers, and leveling agents.

[0045] In the method for manufacturing a transfer medium laminate of the present invention, the hard coat layer is formed by a process including steps (1) and (2) described above. The hard coat material in step (1) can be applied to the surface of a support by coating the hard coat material or a solution containing the hard coat material to form a coating film. When preparing a solution containing the hard coat material, any liquid capable of dissolving or dispersing the hard coat material therein can be used as the solvent. Examples of such solvents include various organic solvents. Specific examples include alcohols such as methanol, ethanol, isopropanol, n-butanol, and isobutanol; glycols such as ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol acetate monoethyl ether, diethylene glycol, diethylene glycol monobutyl ether, and diacetone glycol; aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as n-hexane and n-heptane; esters such as ethyl acetate and butyl acetate; ketones such as methyl ethyl ketone and methyl isobutyl ketone; oximes such as methyl ethyl ketoxime; and combinations of two or more of these. When a hard coat layer is formed using a hard coat layer material solution, the solvent evaporates as a result of operations such as drying during the formation process, and solid components remain in the hard coat layer. The proportion of solids in the hard coat layer material solution (i.e., the components remaining in the hard coat layer after the hard coat layer has been formed) can be adjusted as appropriate to enable the desired operation, but for example, it can be 5% by weight or more and 40% by weight or less.

[0046] The partial curing of the hard coat material in step (2) can be performed by drying the coating of the hard coat material, irradiating the coating of the hard coat material with active energy rays, or a combination thereof. As the active energy ray, one that is compatible with the polymerization initiator contained in the hard coat material can be selected. Using an ultraviolet polymerization initiator as the polymerization initiator and ultraviolet light as the active energy ray is preferable in terms of the ease of the process, such as adjusting the degree of polymerization. By appropriately adjusting the conditions when partial curing the hard coat material, a stretchable hard coat layer can be formed.

[0047] The semi-cured hard coat layer formed in step (2) preferably has a so-called tack-free surface. A tack-free surface means that when the surface is touched with a finger, the material constituting the hard coat layer does not stick to the finger. A tack-free surface allows the laminate with the hard coat layer exposed to be stored in a film roll or the like, thus increasing the flexibility of the manufacturing method.

[0048] The thickness of the hard coat layer can be adjusted as appropriate within the desired range. Specifically, the thickness of the hard coat layer is preferably 0.5 μm to 20 μm, more preferably 0.5 μm to 10 μm, and even more preferably 0.5 μm to 8 μm.

[0049] [4. Resin layer (A)] The resin layer (A) is a resin layer, and the storage modulus of such resin is 1000 MPa or less. Preferably, the storage modulus is 960 MPa or less, more preferably 920 MPa or less. The lower limit of the storage modulus is not particularly limited, but can be, for example, 200 MPa or more. By having the storage modulus within this range, it is possible to suppress the occurrence of significant curling of the transfer medium laminate and the polarizing film, and to improve the ability to conform to curved surfaces.

[0050] The storage modulus of the resin constituting the resin layer (A) can be determined by forming the resin into a 1 mm thick measuring film and measuring its storage modulus at 23°C using a dynamic viscoelasticity measuring device (for example, "ARES" manufactured by T.A. Instruments Japan).

[0051] The resin constituting the resin layer (A) preferably has a low water vapor permeability measured as a 100 μm thick film at 40°C and 90% RH. Such water vapor permeability is preferably 5 g / (m²). 2 Less than 4g / (m³) per day, more preferably 4g / (m³) 2 It is less than or equal to (day). The lower limit of water vapor transmission is ideally 0 g / (m³). 2·day) and 0.1g / (m 2 It may also be set to (day). By keeping the water vapor transmission rate below the upper limit, the low moisture permeability of the resin layer (A) can be made sufficiently excellent, suppressing water vapor from reaching the polarizer layer and improving the reliability of the polarizing film. The water vapor transmission rate can be measured using a commercially available water vapor transmission rate measuring device, and specifically can be measured as described in the evaluation items section of the examples.

[0052] The resin that constitutes the resin layer (A) typically contains a polymer as its main component. Examples of polymers include polyester, acrylic polymers, and polymers having an alicyclic structure.

[0053] The resin forming the resin layer (A) preferably contains a polymer having an alicyclic structure. A polymer having an alicyclic structure is a polymer whose structural units have an alicyclic structure. Polymers having an alicyclic structure typically have low water vapor permeability. Therefore, by forming a resin layer (A) with a resin containing a polymer having an alicyclic structure, it is possible to suppress the reach of water vapor to the polarizer layer and improve the moisture resistance of the polarizing film.

[0054] The resin forming the resin layer (A) may contain one polymer having an alicyclic structure by itself, or it may contain a combination of two or more polymers.

[0055] A polymer having an alicyclic structure may have an alicyclic structure in its main chain, in its side chains, or in both its main chain and side chains. Among these, polymers having an alicyclic structure in at least the main chain are preferred from the viewpoint of mechanical strength and heat resistance.

[0056] Examples of alicyclic structures include saturated alicyclic hydrocarbon (cycloalkane) structures and unsaturated alicyclic hydrocarbon (cycloalkene, cycloalkyne) structures. Among these, cycloalkane and cycloalkene structures are preferred from the viewpoint of mechanical strength and heat resistance, and cycloalkane structures are particularly preferred.

[0057] The number of carbon atoms constituting an alicyclic structure is preferably 4 or more, more preferably 5 or more, preferably 30 or less, more preferably 20 or less, and particularly preferably 15 or less per alicyclic structure. By setting the number of carbon atoms constituting an alicyclic structure within this range, the mechanical strength, heat resistance, and moldability of the resin containing the polymer having an alicyclic structure are highly balanced.

[0058] In polymers having an alicyclic structure, the proportion of structural units having an alicyclic structure can be appropriately selected depending on the intended use. The proportion of structural units having an alicyclic structure in a polymer having an alicyclic structure is preferably 55% by weight or more, more preferably 70% by weight or more, particularly preferably 90% by weight or more, and may be 100% by weight or less. When the proportion of structural units having an alicyclic structure in a polymer having an alicyclic structure is within this range, the transparency and heat resistance of the resin containing the polymer having an alicyclic structure are good.

[0059] Examples of polymers having an alicyclic structure include norbornene polymers, monocyclic olefin polymers, cyclic conjugated diene polymers, vinyl alicyclic hydrocarbon polymers, and their hydrides, as well as hydrides of vinyl aromatic hydrocarbon polymers. Among these, one or more selected from the group consisting of norbornene polymers and hydrides of vinyl aromatic hydrocarbon polymers are more preferred because they have good transparency and moldability.

[0060] Examples of norbornene polymers include ring-opening polymers of monomers having a norbornene structure and their hydrides; addition polymers of monomers having a norbornene structure and their hydrides. Furthermore, examples of ring-opening polymers of monomers having a norbornene structure include ring-opening homopolymers of one type of monomer having a norbornene structure, ring-opening copolymers of two or more types of monomers having a norbornene structure, and ring-opening copolymers of a monomer having a norbornene structure and any monomer copolymerizable therewith.In addition, examples of addition polymers of monomers having a norbornene structure include addition homopolymers of one type of monomer having a norbornene structure, addition copolymers of two or more types of monomers having a norbornene structure, and addition copolymers of a monomer having a norbornene structure and any monomer copolymerizable therewith. Among these, hydrides of ring-opening polymers of monomers having a norbornene structure, addition copolymers of monomers having a norbornene structure and α-olefins, and hydrides of addition copolymers of monomers having a norbornene structure and α-olefins are preferred, and hydrides of ring-opening copolymers of two or more monomers having a norbornene structure, addition copolymers of monomers having a norbornene structure and α-olefins, and hydrides of addition copolymers of monomers having a norbornene structure and α-olefins are more preferred.

[0061] Examples of monomers having a norbornene structure include bicyclo[2.2.1]hepto-2-ene (common name: norbornene), tricyclo[4.3.0.1 2,5 Deca-3,7-diene (common name: dicyclopentadiene), 7,8-benzotricyclo[4.3.0.1 2,5 Deca-3-ene (common name: methanotetrahydrofluorene), tetracyclo[4.4.0.1 2,5 .1 7,10Examples include dodeca-3-ene (common name: tetracyclododecene) and derivatives of these compounds (for example, those having substituents on the ring). Here, examples of substituents include alkyl groups, alkylene groups, polar groups, etc. Multiple substituents may be bonded to the ring, either identical or different in nature. Monomers having a norbornene structure may be used individually or in combination of two or more types in any ratio.

[0062] Examples of polar groups include heteroatoms or groups of atoms containing heteroatoms. Examples of heteroatoms include oxygen atoms, nitrogen atoms, sulfur atoms, silicon atoms, and halogen atoms. Specific examples of polar groups include carboxyl groups, carbonyloxycarbonyl groups, epoxy groups, hydroxyl groups, oxy groups, ester groups, silanol groups, silyl groups, amino groups, nitrile groups, and sulfonic acid groups.

[0063] Examples of monomers copolymerizable with a monomer having a norbornene structure include monocyclic olefins such as cyclohexene, cycloheptene, and cyclooctene, and their derivatives; and cyclic conjugated dienes such as cyclohexadiene and cycloheptadiene, and their derivatives. A single monomer copolymerizable with a monomer having a norbornene structure may be used alone, or two or more types may be used in any ratio.

[0064] Ring-opening polymers of monomers having a norbornene structure can be produced, for example, by polymerizing or copolymerizing monomers in the presence of a ring-opening polymerization catalyst.

[0065] In addition copolymers of monomers having a norbornene structure and α-olefins, examples of α-olefins include α-olefins having 2 to 20 carbon atoms, such as ethylene, propylene, and 1-butene, and their derivatives. Among these, ethylene is preferred. One type of α-olefin may be used alone, or two or more types may be used in any ratio.

[0066] Addition polymers of monomers having a norbornene structure can be produced, for example, by polymerizing or copolymerizing monomers in the presence of an addition polymerization catalyst.

[0067] The hydrides of the ring-opening polymers and addition polymers described above can be produced, for example, by hydrogenating the carbon-carbon unsaturated bonds by preferably 90% or more in a solution of the ring-opening polymer or addition polymer in the presence of a hydrogenation catalyst containing a transition metal such as nickel or palladium.

[0068] A hydride of a vinyl aromatic hydrocarbon polymer means a hydride of a polymer containing repeating units [I] derived from an aromatic vinyl compound. A repeating unit derived from an aromatic vinyl compound means a repeating unit having a structure obtained by polymerizing an aromatic vinyl compound. However, the hydride and its constituent units are not limited by the manufacturing method.

[0069] Examples of aromatic vinyl compounds corresponding to the repeating unit [I] include styrene; styrenes having C1-C6 alkyl groups as substituents, such as α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 4-t-butylstyrene, and 5-t-butyl-2-methylstyrene; styrenes having halogen atoms as substituents, such as 4-chlorostyrene, dichlorostyrene, and 4-monofluorostyrene; styrenes having C1-C6 alkoxy groups as substituents, such as 4-methoxystyrene; styrenes having aryl groups as substituents, such as 4-phenylstyrene; vinylnaphthalenes such as 1-vinylnaphthalene and 2-vinylnaphthalene; and the like. These may be used individually or in combination of two or more in any ratio. Among these, aromatic vinyl compounds that do not contain polar groups, such as styrene and styrenes having C1-C6 alkyl groups as substituents, are preferred because they can reduce hygroscopicity, and styrene is particularly preferred due to its ease of industrial availability.

[0070] The hydride of a polymer containing repeating units [I] derived from an aromatic vinyl compound is preferably a specific block copolymer hydride [E]. The block copolymer hydride [E] is a hydride of block copolymer [D]. Block copolymer [D] is a polymer block consisting of polymer block [A] and polymer block [B] or polymer block [C]. Polymer block [A] is a polymer block mainly composed of repeating units [I] derived from an aromatic vinyl compound. Polymer block [B] is a polymer block mainly composed of repeating units [I] derived from an aromatic vinyl compound and repeating units [II] derived from a chain-like conjugated diene compound. Polymer block [C] is a polymer block mainly composed of repeating units [II] derived from a chain-like conjugated diene compound. Here, "main component" refers to a component that makes up 50% by weight or more of the polymer block. Repeating units derived from a chain-like conjugated diene compound mean repeating units having a structure obtained by polymerizing a chain-like conjugated diene compound.

[0071] Examples of chain-like conjugated diene compounds corresponding to the repeating unit [II] include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and 1,3-pentadiene. These may be used individually or in combination of two or more in any ratio. The chain-like conjugated diene compounds may be linear or branched.

[0072] Hydrogenated vinyl aromatic hydrocarbon polymers are substances obtained by hydrogenating the unsaturated bonds of the vinyl aromatic hydrocarbon polymer. Here, the unsaturated bonds of the vinyl aromatic hydrocarbon polymer to be hydrogenated include both the carbon-carbon unsaturated bonds of the main chain and side chains of the polymer, as well as the carbon-carbon unsaturated bonds of the aromatic ring.

[0073] Hydrides can be produced, for example, by hydrogenating 90% or more of the unsaturated bonds of a vinyl aromatic hydrocarbon polymer in a solution of the polymer in the presence of a hydrogenation catalyst containing a transition metal such as nickel or palladium.

[0074] The weight-average molecular weight Mw of the polymer contained in the resin forming the resin layer (A) is preferably 10,000 or more, more preferably 15,000 or more, particularly preferably 20,000 or more, preferably 100,000 or less, more preferably 80,000 or less, and particularly preferably 50,000 or less. When the weight-average molecular weight is within this range, the mechanical strength and moldability of the resin layer (A) are highly balanced.

[0075] The molecular weight distribution (Mw / Mn) of the polymer contained in the resin forming the resin layer (A) is preferably 1.2 or higher, more preferably 1.5 or higher, particularly preferably 1.8 or higher, preferably 3.5 or lower, more preferably 3.0 or lower, and particularly preferably 2.7 or lower. Here, Mn represents the number-average molecular weight. By setting the molecular weight distribution above the lower limit of the above range, the productivity of the polymer can be increased and manufacturing costs can be suppressed. Furthermore, by setting it below the upper limit, the amount of low-molecular-weight components is reduced. As a result, relaxation of the resin layer (A) when exposed to high temperatures can be suppressed, and the stability of the resin layer (A) can be increased.

[0076] The weight-average molecular weight (Mw) and number-average molecular weight (Mn) mentioned above can be measured using gel permeation chromatography (GPC). Examples of solvents used in GPC include cyclohexane, toluene, and tetrahydrofuran. When using GPC, the weight-average molecular weight is measured as a relative molecular weight, for example, on a polyisoprene or polystyrene basis.

[0077] The resin forming the resin layer (A) preferably further contains a plasticizer and / or a softener (plasticizer or softener, or both) in addition to the polymer. The further inclusion of a plasticizer and / or a softener in the resin improves the moldability (e.g., extensibility) of the resin forming the resin layer (A).

[0078] Examples of plasticizers and / or softeners include compounds having an ester structure and aliphatic hydrocarbon polymers. The resin forming the resin layer (A) preferably contains one or more selected from the group consisting of compounds having an ester structure and aliphatic hydrocarbon polymers as a plasticizer and / or softener, and more preferably contains an aliphatic hydrocarbon polymer.

[0079] Examples of compounds having an ester structure include phosphate ester compounds such as triphenyl phosphate, tricresyl phosphate, and phenyldiphenyl phosphate; aliphatic carboxylic acid esters such as oxalic acid ester, malonic acid ester, succinic acid ester, glutaric acid ester, adipic acid ester, pimelic acid ester, suberic acid ester, azelaic acid ester, sebaciate ester, and stearic acid ester; and aromatic carboxylic acid ester compounds such as benzoic acid ester, phthalic acid ester, isophthalic acid ester, terephthalic acid ester, trimellitic acid ester, and pyromellitic acid ester.

[0080] Examples of aliphatic hydrocarbon polymers include polyisobutene, hydrogenated polyisobutene, hydrogenated polyisoprene, hydrogenated 1,3-pentadiene petroleum resins, hydrogenated cyclopentadiene petroleum resins, and hydrogenated styrene-indene petroleum resins.

[0081] The total amount of plasticizer and softener in the resin forming the resin layer (A) is preferably 5 parts by weight or more, more preferably 10 parts by weight or more, even more preferably 20 parts by weight or more, preferably 100 parts by weight or less, more preferably 70 parts by weight or less, and even more preferably 50 parts by weight or less, relative to 100 parts by weight or less of polymer. By keeping the total ratio of plasticizer and softener in the resin within the above range, the moldability of the resin can be improved.

[0082] The resin forming the resin layer (A) preferably contains an ultraviolet absorber. By including an ultraviolet absorber in the resin, a resin layer (A) containing an ultraviolet absorber can be formed. The inclusion of an ultraviolet absorber in the resin layer (A) has the effect of making it easier to perform the step of bonding the transfer medium laminate and the polarizer layer via an ultraviolet-curing adhesive during the manufacturing process of the polarizing film while maintaining the stretchability of the hard coat layer. It also has the effect of reducing the degradation of the final product due to irradiation with ultraviolet rays contained in ambient light.

[0083] Specific examples of UV absorbers include benzotriazole-based UV absorbers and triazine-based UV absorbers. Examples of commercially available UV absorbers include the brand names "Tinuvin326," "Tinuvin329," and "Tinuvin234" (all manufactured by BASF and are benzotriazole-based UV absorbers), as well as the brand name "ADEKA Stab LA-70" (manufactured by ADEKA and is a triazine-based UV absorber).

[0084] The resin forming the resin layer (A) may contain various additives in addition to the components described above. Examples of additives include antioxidants and light stabilizers.

[0085] The thickness of the resin layer (A) is preferably 0.5 μm or more, more preferably 0.8 μm or more, preferably 9 μm or less, and more preferably 8 μm or less. By setting the thickness of the resin layer (A) to be above the lower limit, the reliability of the polarizing film in high temperature and high humidity environments can be further improved, and the polarizer layer contained in the polarizing film can be better protected. By setting the thickness of the resin layer (A) to be below the upper limit, the thickness of the polarizing film can be reduced, and the effect of suppressing curl can be enhanced.

[0086] The resin layer (A) is preferably optically substantially isotropic. Here, "optically substantially isotropic" means that the in-plane retardation Re is preferably 0 nm to 5 nm, more preferably 0 nm to 2 nm.

[0087] In the method for manufacturing a transfer medium laminate of the present invention, the resin layer (A) is formed by a process including the above step (3). The resin application in step (3) can be carried out by applying the resin or a resin-containing solution to the surface of the hard coat layer to form a coating film. When preparing a resin-containing solution, any liquid capable of dissolving or dispersing the resin therein can be used as the solvent. Examples of such solvents include various organic solvents. Specific examples are similar to those of the solvents that can be used in step (1).

[0088] After step (3), if necessary, the spread resin or its solution may be subjected to drying or other operations to harden the coating film and form a resin layer (A).

[0089] After forming the resin layer (A), the surface of the resin layer (A) may be subjected to treatment such as corona treatment. Such treatment can enable the resin layer (A) to exhibit properties such as improved adhesion to the adhesive layer.

[0090] By performing the process of forming the resin layer (A), which includes step (3), a transfer medium laminate having a layer structure of (support) / (hard coat layer) / (resin layer (A)) can be obtained. Here, by performing step (3) when the hard coat layer is in a semi-cured state, a transfer medium laminate having a structure in which the resin layer (A) is formed on the surface of the semi-cured material can be obtained. Having such a structure provides various advantages. Specifically, at this point, the hard coat layer, which has relatively low hardness, is protected by the resin layer (A) and the support, so that mechanical damage to the hard coat layer caused by subsequent operations can be reduced. In addition, because the hard coat layer is in a semi-cured state, the conformability of the hard coat layer to curved surfaces is maintained.

[0091] [5. Overview of Polarizing Films] The polarizing film of the present invention comprises the transfer medium laminate, the polarizer layer, and the adhesive layer interposed between the transfer medium laminate and the polarizer layer. The polarizer layer is provided on the resin layer (A) side of the transfer medium laminate (i.e., the side opposite to the hard coat layer; if a support is present, the side opposite to the support).

[0092] The polarizing film comprises a transfer medium laminate, and as described above, the transfer medium laminate includes a stretchable layer as a hard coat layer; therefore, the hard coat layer in the polarizing film is also a stretchable layer. Generally, polarizing films having a polarizer layer and a hard coat layer have poor conformability to curved surfaces when laminated to them due to the brittleness of the hard coat layer. However, the polarizing film of the present invention, having the configuration described above, can be made into a film with high conformability to curved surfaces. Furthermore, due to the low tendency of the transfer medium laminate to curl, the polarizing film also has a low tendency to curl. Therefore, handling of the polarizing film when laminating it to a substrate member having a curved or other shape becomes easier.

[0093] [6. Polarizer layer] As the polarizer layer, a film capable of transmitting one of two perpendicularly intersecting linearly polarized rays and absorbing or reflecting the other may be used. Specific examples of the polarizer layer include a polyvinyl alcohol resin film containing a vinyl alcohol polymer such as polyvinyl alcohol or partially formalized polyvinyl alcohol, subjected to appropriate treatments such as dyeing with a dichroic substance like iodine or a dichroic dye, stretching, and crosslinking in an appropriate order and manner. It is preferable that the polarizer layer contains polyvinyl alcohol resin.

[0094] The thickness of the polarizer layer is preferably 1 μm or more, more preferably 2 μm or more, even more preferably 4 μm or more, preferably 25 μm or less, and more preferably 23 μm or less.

[0095] [7. Adhesive layer] The adhesive layer is typically the layer that bonds the polarizer layer and the resin layer (A). Examples of adhesives used to form the adhesive layer include acrylic adhesives, epoxy adhesives, urethane adhesives, polyester adhesives, polyvinyl alcohol adhesives, polyolefin adhesives, modified polyolefin adhesives, polyvinyl alkyl ether adhesives, rubber adhesives, vinyl chloride-vinyl acetate adhesives, ethylene-based adhesives such as SEBS (styrene-ethylene-butylene-styrene copolymer) adhesives and ethylene-styrene copolymers, and acrylic ester adhesives such as ethylene-(meth)acrylate methyl copolymer and ethylene-(meth)acrylate ethyl copolymer.

[0096] The adhesive is preferably an ultraviolet-curing adhesive. By using an ultraviolet-curing adhesive, the method for manufacturing the polarizing film described later can be easily carried out. A specific example of an ultraviolet-curing adhesive is "Arkles KRX-7007" (product name, manufactured by ADEKA).

[0097] The thickness of the adhesive layer is usually greater than 0 μm, preferably 0.1 μm or more, more preferably 1 μm or more, preferably 5 μm or less, and more preferably 3 μm or less. Having the adhesive layer thickness within this range allows the adhesive layer to bond more strongly to the polarizer layer and the resin layer (A), improving the bending recovery of the polarizing film and allowing the polarizing film to be made thinner.

[0098] [8. Any layer] The polarizing film may include any layer other than those described above. An example of an arbitrary layer is an adhesive layer provided on the side of the polarizer layer opposite to the resin layer (A). The thickness of such an adhesive layer is preferably 2 μm or more, more preferably 5 μm or more, preferably 25 μm or less, and more preferably 20 μm or less.

[0099] [9. Method for manufacturing polarizing film] The polarizing film of the present invention can be manufactured by any manufacturing method, but a preferred manufacturing method is one in which a resin layer (A) containing an ultraviolet absorber is used, an ultraviolet-curing adhesive is used as the adhesive for forming the adhesive layer, and the manufacturing method includes the following steps. In the following, this method will be described as the manufacturing method for the polarizing film of the present invention. Step (4): A step of bonding the transfer medium laminate and the polarizer layer via an ultraviolet-curing adhesive to form a laminated product. Step (5): A step of irradiating the laminate with ultraviolet light from the polarizer layer side of the laminate.

[0100] [9.1. Process (4)] In step (4), the transfer medium laminate and the polarizer layer are bonded together via an ultraviolet-curable adhesive. At the time this bonding is completed, the adhesive has not yet undergone curing treatment. Therefore, for example, if a transfer medium laminate having a layer structure of (support) / (hard coat layer) / (resin layer (A)) is used, the laminate obtained in step (4) will have a layer structure of (support) / (hard coat layer) / (resin layer (A)) / (adhesive layer (uncured)) / (polarizer layer).

[0101] [9.2. Process (5)] In step (5), ultraviolet light is irradiated onto the laminate from the polarizer layer side of the laminate. As a result, the irradiated ultraviolet light passes through the polarizer layer and reaches the adhesive layer (uncured), thereby curing the adhesive and forming the adhesive layer. As a result, a polarizing film of the present invention can be obtained having a layer structure such as (support) / (hard coat layer) / (resin layer (A)) / (adhesive layer (cured adhesive layer)) / (polarizer layer).

[0102] In step (5), some of the ultraviolet light irradiated may penetrate the adhesive layer or bonding layer and reach the resin layer (A). If the resin layer (A) is a layer with high ultraviolet transmittance, the ultraviolet light may further penetrate the resin layer (A) and reach the hard coat layer. However, in the method for manufacturing a polarizing film of the present invention, a resin layer (A) containing an ultraviolet absorber is used, so the amount of ultraviolet light reaching the hard coat layer can be reduced. Therefore, even when an ultraviolet-curable material is used as the hard coat layer, the manufacturing of the polarizing film can be completed while maintaining the properties of the hard coat layer, such as stretchability and semi-cured state. With ultraviolet-curable materials, the degree of curing can be easily adjusted by adjusting the irradiation amount. Therefore, the manufacturing method of the present invention can conveniently enjoy all of these benefits.

[0103] [9.3. Optional Steps] The method for manufacturing a polarizing film of the present invention may include any steps in addition to those described above. For example, it may include a step of forming any layer that the polarizing film may have. Specifically, it may include a step of providing an adhesive layer as an arbitrary layer on the surface of the polarizer layer opposite to the adhesive layer. The formation of such an adhesive layer is preferably carried out by applying an adhesive composition onto a suitable release film to form a layer of the adhesive composition, and then laminating this to the surface of the polarizer layer. The step of providing the adhesive layer can be carried out at any stage from before step (4) to after step (5), but it is preferable to carry it out after step (5) from the viewpoint of ease of work. As a result of carrying out such an arbitrary step, a polarizing film with an adhesive layer and a release film can be obtained, for example, having a layer structure of (support) / (hard coat layer) / (resin layer (A)) / (adhesive layer (cured adhesive layer)) / (polarizer layer) / (adhesive layer) / (release film). Furthermore, when a transfer medium laminate including a support is used, the support may be peeled off at any stage of the method for manufacturing the polarizing film, or it may be left on without being peeled off.

[0104] [10. Method for manufacturing a molded body with a polarizer layer] The method for manufacturing a molded article with a polarizer layer according to the present invention includes the following steps. Step (A): A step of manufacturing a polarizing film using the polarizing film manufacturing method of the present invention. Process (B): The process of laminating the polarizing film to the base material. Process (C): A process for fully curing the hard coat layer in the polarizing film.

[0105] A molded article produced by the method for manufacturing a polarizer layer of the present invention may be a molded article comprising a base member having a curved surface, a polarizer layer formed on the curved surface, a resin layer (A) formed on the polarizer layer and capable of functioning as a protective film for protecting the polarizer, and a hard coat layer formed on the resin layer (A). The hard coat layer in such a molded article can have sufficient hardness and scratch resistance as a hard coat layer to protect the outermost surface of the molded article, and can be a layer that conforms well to the shape of the curved surface.

[0106] The base material used in process (B) can be a component of a display device such as a liquid crystal display device or an organic electroluminescent display device. As an example, the base material can be a liquid crystal panel of a liquid crystal display device. Here, a liquid crystal panel is a component having a pair of substrates and a number of display cells that enclose liquid crystal material, provided between them. A liquid crystal display device usually comprises a liquid crystal panel and a pair of polarizer layers provided on the viewing side and the back side thereof. The method for manufacturing a molded body with a polarizer layer of the present invention can be preferably applied to the manufacture of a liquid crystal display device having a curved display surface, or to the manufacture of its components, which comprises a liquid crystal panel as a base material, a polarizer layer on its viewing side, and a hard coat layer protecting the outermost surface on the viewing side of the display device.

[0107] As another example, the base material can be a display element of an organic electroluminescent display device. Here, the display element is a material that includes a substrate, a layered first electrode formed on the substrate, a light-emitting layer formed on the first electrode, a second electrode formed on the light-emitting layer, and a sealing layer that seals the electrodes and the light-emitting layer. In organic electroluminescent display devices, a material containing a polarizer layer may be provided on the viewing side of the display element for purposes such as preventing reflection of ambient light and improving display quality when the display surface is observed through polarized sunglasses. The method for manufacturing a molded body with a polarizer layer of the present invention can be preferably applied to the manufacture of an organic electroluminescent display device having a curved display surface, or to the manufacture of its components, which comprises a display element as a base material, a polarizer layer on its viewing side, and a hard coat layer protecting the outermost surface on the viewing side of the display device.

[0108] The bonding in process (B) can be performed by bonding the polarizing film and the substrate member with an appropriate adhesive. Any of the adhesive components described above, such as the adhesive layer, can be used. For example, if a polarizing film with an adhesive layer and a release film is used, having a layer structure of (support) / (hard coat layer) / (resin layer (A)) / (adhesive layer) / (polarizer layer) / (adhesive layer) / (release film), the release film can be peeled off to expose the adhesive layer, and bonding with the substrate member can be achieved via this adhesive layer.

[0109] In one embodiment of the method for manufacturing a polarizer-coated molded article of the present invention, the base material used in step (B) is a curved material. In another embodiment of the method for manufacturing a polarizer-coated molded article of the present invention, a step (Bx) of curving the base material is further included after step (B) and before step (C). Hereinafter, the former manufacturing method will be referred to as "manufacturing method 1," and the latter manufacturing method will be referred to as "manufacturing method 2."

[0110] In manufacturing method 1, in step (B), the polarizing film is laminated to a base material having a curved surface. Specifically, the polarizing film is laminated to such a curved surface. Since polarizing films are usually manufactured as flat films, when performing such lamination, the polarizing film needs to conform to the curved surface. In the method for manufacturing a molded body with a polarizer layer of the present invention, a polarizing film with high conformability to curved surfaces, manufactured by the polarizing film manufacturing method of the present invention, is used as the polarizing film, so this process can be easily carried out. In addition, the tendency of the polarizing film to curl is low, which makes lamination easier.

[0111] In manufacturing method 2, as step (Bx), the base member is curved after step (B). The surface of the base member before curving may be a flat surface. Alternatively, an already curved surface may be further deformed in step (Bx) to change the degree of curvature. Even when the base member is curved after bonding, the polarizing film needs to follow the curved surface after step (Bx). In the method for manufacturing a molded article with a polarizer layer of the present invention, a polarizing film with high conformability to curved surfaces, manufactured by the polarizing film manufacturing method of the present invention, is used as the polarizing film, so such a step can be easily performed. In addition, because the polarizing film has a low tendency to curl, bonding in step (B) can be easily performed.

[0112] In process (C), the hard coat layer in the polarizing film is fully cured. This curing process causes the hard coat layer to become a fully cured product, losing its stretchability, but acquiring the hardness and other properties required for the hard coat layer in the final product. This process is carried out while the polarizing film maintains a state of conforming to the curved surface. Therefore, after going through such a process, the molded article with a polarizer layer, which is the product, can be a molded article having a curved surface shape, comprising a polarizer layer, a resin layer (A) protecting it, and a hard coat layer that has sufficient hardness and scratch resistance to protect the resin layer (A) and the outer surface of the product, and that conforms well to the curved shape. [Examples]

[0113] The present invention will be specifically described below with reference to examples. However, the present invention is not limited to the examples shown below, and can be modified and implemented as appropriate without departing from the scope of the claims and equivalents of the present invention. In the following explanation, "%" and "parts" refer to weight unless otherwise specified. Furthermore, the operations described below were performed under normal temperature and pressure conditions unless otherwise specified.

[0114] [Evaluation Method] (Storage modulus) A 1 mm thick measurement film was obtained by heat-melting and molding the resin to be measured using a heat-melting press under the conditions of a clearance of 1 mm, 250°C, and 30 MPa. The storage modulus of this measurement film at 23°C was measured using a dynamic viscoelasticity measuring device (ARES, manufactured by T.A. Instruments Japan).

[0115] (Water vapor transmission rate) A 100 μm thick measurement film was obtained by heat-melting and molding the resin to be measured using a heat-melting press under the conditions of a clearance of 100 μm, 250°C, and 30 MPa. For this measurement film, the water vapor transmission rate was measured using a water vapor transmission rate measuring device ("PERMATRAN-W" manufactured by MOCON Corporation) in accordance with JIS K 7129 B method, under conditions of a temperature of 40°C and a humidity of 90% RH.

[0116] (Curling) The film to be measured was cut into 10cm x 10cm square sections. The sections were left in an environment of 23°C and 55% RH for 24 hours to regulate humidity. Then, the sections were placed on the surface of a horizontal surface plate with the hard coat layer facing upwards. The height of each of the four vertices of the section (the vertical distance from the surface plate to the vertex of the section) was measured, and the maximum value h1 was determined, and the curling properties were evaluated according to the following criteria. AA (The curl is very small and the mountability to the panel is very good): h1 ≤ 10 mm A (The curl is small and the mountability to the panel is good): 10 mm < h1 ≤ 25 mm B (The curl is large, the mountability to the panel is poor, and the yield of the panel decreases): 25 mm < h1 ≤ 40 mm C (The curl is very large and it is difficult to mount to the panel): 40 mm < h1

[0117] (Bending test) The bending test laminate containing an aluminum plate and other layers obtained in the examples and comparative examples was bent at 90° so that the aluminum plate was on the inside. From the hard coat layer side, ultraviolet rays were irradiated on the laminate under the condition of 750 mJ / cm 2 Thereafter, the bending test laminate was placed under the conditions of 85°C and 85% for 120 hours, and then the state of the bent portion was observed and evaluated according to the following criteria. The bent portion to be observed was a strip-shaped region with a width of 20 mm centered on the straight line at the position where the plate was bent. A: There is no discoloration. B: Discoloration is observed in less than 40% of the region of the bent portion. C: Discoloration is observed in 40% or more of the region of the bent portion.

[0118] [Example 1] (1-1. Hard coat material solution) Ethyl acetate, which is a diluent, was added to a solution containing a polymerizable substance (H) for the hard coat material (trade name "Lucidia V-6850", manufactured by DIC Corporation, solid content ratio: 50% by weight) to obtain a solution (i) with a solid content ratio of 20% by weight. Further, a photoinitiator (manufactured by Ciba Specialty Chemicals, trade name "IRGACURE184") was added to this solution (i) at a ratio of 3 parts per 100 parts by weight of the solid content of the solution (i), and the mixture was stirred for 10 minutes. By such an operation, a hard coat material solution (ii) was obtained.

[0119] (1-2. Hard coat layer) A biaxially oriented polypropylene film support (product name "Trefan BO40-2500", manufactured by Toray) was prepared. The hard coat material solution (ii) obtained in (1-1) was applied to one surface of the support using gravure coating and dried (90°C for 2 minutes). This operation formed a hard coat layer with a thickness of 7 μm, and a laminate (i) having a layer structure of (support) / (hard coat layer) was obtained.

[0120] (1-3. Resin A1) Referring to the manufacturing example described in Japanese Patent Publication No. 2002-105151, 25 parts of styrene monomer were polymerized in the first step, followed by polymerization of 30 parts of styrene monomer and 25 parts of isoprene monomer in the second step, and then polymerization of 20 parts of styrene monomer in the third step to obtain a block copolymer [D1]. Block copolymer [D1] was further hydrogenated to synthesize block copolymer hydride [E1]. The Mw of block copolymer hydride [E1] was 84,500, the Mw / Mn ratio was 1.20, and the hydrogenation rate of the main chain and aromatic rings was approximately 100%.

[0121] 100 parts of block copolymer hydride [E1] were mixed with 0.1 parts of pentaerythrityl tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] (manufactured by Matsubara Sangyo Co., Ltd., product name "Songnox1010") as an antioxidant, and the mixture was melt-kneaded and formed into pellets to obtain resin A1 for molding. The storage modulus of resin A1 was measured to be 720 MPa. The water vapor permeability of resin A1 was measured to be 4.0 g / (m³). 2 It was (day).

[0122] (1-4. Transfer medium laminate) The resin A1 obtained in (1-3) was dissolved in cyclohexane, and 7 parts by weight of an ultraviolet absorber (product name "ADEKA Stab LA-70", manufactured by ADEKA Corporation) was added per 100 parts by weight of resin A1 to obtain a solution (iii) with a solid content of 15% by weight.

[0123] Solution (iii) was applied to the hard coat layer side surface of the laminate (i) obtained in (1-2) using a gravure coater and dried (90°C for 2 minutes). This operation formed a resin layer (A) with a thickness of 5 μm, and a transfer medium laminate having a layer structure of (support) / (hard coat layer) / (resin layer (A)) was obtained.

[0124] A portion of the obtained transfer medium laminate was used in the following steps (1-6) and beyond. Another portion was used for measuring the in-plane retardation Re. Specifically, the resin layer (A) was peeled off from the transfer medium laminate and Re was measured.

[0125] (1-5. Polarizers) As the raw material, an unstretched polyvinyl alcohol film (vinylon film, average degree of polymerization approximately 2400, degree of saponification 99.9 mol%) with a thickness of 20 μm was prepared. The film was continuously conveyed longitudinally via guide rolls, and then subjected to swelling and dyeing treatments to adsorb iodine onto the film. In the swelling treatment, the film was immersed in pure water at 30°C for 1 minute. In the dyeing treatment, the film was immersed in a dyeing solution (a dyeing solution containing iodine and potassium iodide in a molar ratio of 1:23, dyeing concentration 1.2 mmol / L) at 32°C for 2 minutes. After that, the film was washed with a 3% boric acid aqueous solution at 35°C for 30 seconds, and then stretched six times at 57°C in an aqueous solution containing 3% boric acid and 5% potassium iodide. Subsequently, the film was subjected to a complementary color treatment at 35°C in an aqueous solution containing 5% potassium iodide and 1.0% boric acid, and then dried at 60°C for 2 minutes. This procedure yielded a polarizer Pa1 with a thickness of 23 μm. The thickness of polarizer Pa1 was 7 μm. The moisture content of polarizer Pa1 was measured using an in-line moisture content analyzer manufactured by Kurabo Industries Ltd. and found to be 7.5%.

[0126] (1-6. Polarizing film) The resin layer (A) side of the transfer medium laminate obtained in (1-4) was subjected to inline corona treatment, and an ultraviolet-curing adhesive (product name "Arkulls KRX-7007", manufactured by ADEKA) was applied using a gravure coater to form an adhesive layer. The resin layer (A) and the polarizer Pa1 obtained in (1-5) were bonded together by pressing them with pinch rolls through the adhesive layer. Immediately afterward, the bonded material was exposed to ultraviolet light from the polarizer Pa1 side using an ultraviolet irradiation device at a rate of 750 mJ / cm². 2 The adhesive layer was cured by UV irradiation, forming an adhesive layer with a thickness of 2 μm. Through this procedure, a polarizing film Pb1 with a support was obtained, having a layer structure of (support) / (hard coat layer) / (resin layer (A)) / (adhesive layer) / (polarizer layer Pa1).

[0127] A portion of the obtained polarizing film Pb1 was used in the following steps (1-8) and beyond. The remaining portion was used to evaluate its curl and stretch properties. Specifically, the support was peeled off from the polarizing film Pb1 with the support attached to obtain a polarizing film Pc1 having a layer structure of (hard coat layer) / (resin layer (A)) / (adhesive layer) / (polarizer layer Pa1). The curl properties of this film were evaluated. In addition, the hard coat layer was peeled off from the polarizing film Pc1, and the hard coat layer was made into a rectangle with a length of 150 mm and a width of 20 mm. It was then freely uniaxially stretched in the length direction, and it was confirmed that it could be stretched up to 2.00 times without the occurrence of cracks.

[0128] Furthermore, at this point, the tackiness of the hard coat layer exposed on the surface of the polarizing film Pc1 was evaluated by touching it with a finger. As a result, when the hard coat layer was touched with a finger, the material constituting the hard coat layer did not adhere to the finger, and therefore it was evaluated as having no tackiness.

[0129] (1-7. Adhesive Compositions) 69 parts by weight of n-butyl acrylate (n-BA), 30 parts by weight of phenoxydiethylene glycol acrylate, 1 part by weight of 4-hydroxybutyl acrylate (4HBA), 120 parts by weight of ethyl acetate, and 0.1 parts by weight of azobisisobutyronitrile (AIBN) were placed in a reaction vessel. The air in the reaction vessel was replaced with nitrogen gas, and the reaction solution was heated to 66°C in a nitrogen atmosphere under stirring and reacted for 10 hours. After the reaction was complete, the solution was diluted with ethyl acetate to obtain an acrylic copolymer solution with a solid content of 20% by weight. The weight-average molecular weight (Mw) of the obtained acrylic copolymer, determined by GPC, was 1.1 million.

[0130] To 500 parts by weight (100 parts by weight of solids) of the obtained copolymer solution, 0.1 parts by weight of an isocyanate-based crosslinking agent (product name "Coronate L", manufactured by Nippon Polyurethane Co., Ltd.) and 0.1 parts by weight of a silane coupling agent (product name "KBM-402", manufactured by Shin-Etsu Polymer Co., Ltd.) were added and thoroughly mixed to obtain adhesive composition A1.

[0131] (1-8. Composite film with adhesive layer and release film) As a release film, a PET film (product name "MRV38", manufactured by Mitsubishi Chemical) treated with silicone for release was prepared. The adhesive composition A1 obtained in (1-7) was applied to the surface of the release film using a die coater and dried at 90°C for 3 minutes to evaporate the solvent and form a 20 μm adhesive layer, obtaining a laminate (iv) having a layer structure of (adhesive layer) / (release film).

[0132] The adhesive layer side surface of the laminate (iv) was bonded to the polarizer layer Pa1 side surface of the polarizing film Pb1 with support obtained in (1-6), thereby obtaining a polarizing film composite Pd1 with an adhesive layer and a release film, having a layer structure of (support) / (hard coat layer) / (resin layer (A)) / (adhesive layer) / (polarizer layer Pa1) / (adhesive layer) / (release film).

[0133] (1-9. Bending Test) The obtained polarizing film composite Pd1 was matured by storing it for 5 days under conditions of 23°C and 55% humidity. After that, the release film was peeled off from the polarizing film composite Pd1 to expose the adhesive layer. The adhesive layer was bonded to a 0.5 mm thick aluminum plate, and the support was peeled off. This yielded a bending test laminate having a layer structure of (hard coat layer) / (resin layer (A)) / (adhesive layer) / (polarizer layer Pa1) / (adhesive layer) / (aluminum plate). A bending test was performed on this bending test laminate.

[0134] [Example 2] In the production of the transfer medium laminates of (1-4), the thickness of the solution (iii) was changed, and the thickness of the formed resin layer (A) was changed to 1 μm. Except for these changes, the same procedure as in Example 1 was used to obtain and evaluate the transfer medium laminates, polarizing films, and bending test laminates.

[0135] [Example 3] (3-1.Resin A2) Resin A2 was obtained by mixing 100 parts by weight of norbornene-based polymer resin (product name "ZEONOR1430", manufactured by Nippon Zeon Co., Ltd.) and 50 parts by weight of polyisobutene as a plasticizer (product name "Nisseki Polybutene HV-300", manufactured by JX Nippon Oil & Energy Corporation, number average molecular weight 1,400). When the water vapor permeability of resin A2 was measured, it was found to be 1 g / (m³). 2 It was (day).

[0136] (3-2. Transfer medium laminates, etc.) In the production of the transfer medium laminate of (1-4), resin A2 obtained in (3-1) was used instead of resin A1, except that the same procedure as in (1-1) to (1-2) and (1-4) to (1-9) of Example 1 was used to obtain and evaluate the transfer medium laminate, polarizing film, and bending test laminate.

[0137] [Example 4] Except for the changes described below, the transfer medium laminate, polarizing film, and bending test laminate were obtained and evaluated by the same procedure as in (1-1) to (1-2) and (1-4) to (1-9) of Example 1. • In the production of the transfer medium laminate of (1-4), resin A2 obtained in (3-1) of Example 3 was used instead of resin A1. • In the production of the transfer medium laminate of (1-4), the coating thickness of solution (iii) was changed to change the thickness of the formed resin layer (A) to 1 μm.

[0138] [Example 5] Except for the changes described below, the transfer medium laminate, polarizing film, and bending test laminate were obtained and evaluated using the same procedure as in Example 1. • When forming the hard coat layer in (1-2), the same peel-treated PET film used in (1-8) was used as the support instead of the biaxially oriented polypropylene film. • In the production of the transfer medium laminate of (1-4), the coating thickness of solution (iii) was changed to change the thickness of the formed resin layer (A) to 1 μm.

[0139] [Example 6] (6-1. Polarizer) Polarizer Pa2 was prepared using the same procedure as in Example 1 (1-5), except that a thicker film than the one used in (1-5) was used as the base film. The thickness of polarizer Pa2 was 5 μm.

[0140] (6-2. Transfer medium laminates, etc.) In the production of the polarizing film (1-6), the polarizer Pa2 obtained in (6-1) was used instead of the polarizer Pa1, except that the same procedure as in (1-1) to (1-4) and (1-6) to (1-9) of Example 1 was used to obtain and evaluate the transfer medium laminate, polarizing film, and bending test laminate.

[0141] [Comparative Example 1] (C1-1. Resin layer (CA)) A triacetylcellulose (TAC) film (Fujifilm's "Fujitac T25," 25 μm thick) was prepared as the film constituting the resin layer (CA). The storage modulus and water vapor permeability of the triacetylcellulose constituting this film were measured.

[0142] (C1-2. Hard coat layer) The hard coat material solution (ii) obtained in (1-1) of Example 1 was applied to one surface of the resin layer (CA) using gravure coating and dried (90°C for 2 minutes). This operation formed a hard coat layer with a thickness of 7 μm, and a laminate (Ci) having a layer structure of (hard coat layer) / (resin layer (CA)) was obtained.

[0143] (C1-3. Polarizing film) The resin layer (CA) side surface of the laminate (Ci) obtained in (C1-2) was subjected to inline corona treatment, and an ultraviolet-curing adhesive (the same as that used in Example 1) was applied by a gravure coater to form an adhesive layer. The resin layer (CA) and the polarizer Pa1 obtained in (1-5) of Example 1 were bonded together by pressing them with pinch rolls through the adhesive layer. Immediately afterward, the bonded material was exposed to ultraviolet light from the polarizer Pa1 side using an ultraviolet irradiation device at a rate of 750 mJ / cm². 2 The adhesive layer was cured by UV irradiation, forming an adhesive layer with a thickness of 2 μm. Through this procedure, a polarizing film PC was obtained having a layer structure of (hard coat layer) / (resin layer (CA)) / (adhesive layer) / (polarizer layer Pa1).

[0144] A portion of the obtained polarizing film PC was used in the following steps (C1-4) and beyond. The remaining portion was used to evaluate its curlability and stretchability. For the evaluation of stretchability, the hard coat layer was peeled off from the polarizing film PC, and the hard coat layer was made into a rectangle with a length of 150 mm and a width of 20 mm. When it was freely uniaxially stretched in the length direction, cracks occurred before the stretching ratio reached 1.50 times, and further stretching could not be performed.

[0145] (C1-4. Bending Test) In the production of the adhesive layer and polarizing film composite with release film of (1-8), the polarizing film PC obtained in (C1-3) was used instead of the polarizing film Pb1, except that the bending test laminate was obtained and evaluated by the same procedure as in (1-7) to (1-9) of Example 1. However, since the polarizing film PC does not have a support, the support was not peeled off in (1-9).

[0146] [Comparative Example 2] (C2-1. Resin layer (CA)) Acrylic resin (Sumitomo Chemical's "Sumipex HT55X") was supplied to a hot melt extrusion film molding machine equipped with a T-die. The acrylic resin was extruded from the T-die and wound onto a roll at a take-up speed of 4 m / min to form a film. This yielded a long film (40 μm thick) made of acrylic resin. This film was used as the film constituting the resin layer (CA). The storage modulus and water vapor permeability of the acrylic resin constituting this film were measured.

[0147] (C2-2.Polarizer) Polarizer Pa3 was prepared using the same procedure as in Example 1 (1-5), except that a thicker film than the one used in (1-5) was used as the base film. The thickness of polarizer Pa3 was 23 μm.

[0148] (C2-3. Laminates, etc.) Except for the changes described below, the laminate (Ci), polarizing film, and bending test laminate were obtained and evaluated using the same procedure as in Comparative Example 1 (C1-2) to (C1-4). • For the resin layer (CA), (C2-1) was used instead of (C1-1). • Instead of using polarizer Pa1 obtained in Example 1, polarizer Pa3 obtained in (C2-2) was used as the polarizer.

[0149] In the evaluation of the stretchability of the hard court layer, cracks appeared before the stretch ratio reached 1.50 times, making further stretching impossible.

[0150] [Comparative Example 3] (C3-1. Resin layer (CA)) Norbornene-based polymer resin (the same as used in Example 3) was supplied to a hot melt extrusion film molding machine equipped with a T-die. The resin was extruded from the T-die and wound onto a roll at a take-up speed of 4 m / min to form a film. This yielded a long film (23 μm thick) made of norbornene-based resin. This film was used as the film constituting the resin layer (CA). The storage modulus and water vapor permeability of the resin constituting this film were measured.

[0151] (C3-2. Laminates, etc.) Except for using (C3-1) instead of (C1-1) as the resin layer (CA), the laminate (Ci), polarizing film, and bending test laminate were obtained and evaluated by the same procedure as in (C1-2) to (C1-4) of Comparative Example 1.

[0152] In the evaluation of the stretchability of the hard court layer, cracks appeared before the stretch ratio reached 1.50 times, making further stretching impossible.

[0153] Tables 1 and 2 show an overview of the examples and comparative examples, as well as their evaluation results.

[0154] [Table 1]

[0155] [Table 2]

[0156] The meanings of the abbreviations in the table are as follows: Resin material: The resin material used as resin layer (A) or resin layer (CA). A1: Resin A1 prepared in Example 1. A2: Resin A2 prepared in Example 3. TAC: Triacetylcellulose. PMMA: Acrylic resin. 1430: Norbornene polymer resin. Elastic modulus: The storage modulus of a resin material. Unit: MPa. Water vapor permeability: Water vapor permeability of resin materials. Unit: g / (m³) 2 (day). Measurement value on a 100 μm thick measuring film. Resin layer thickness: The thickness of resin layer (A) or resin layer (CA). Unit: μm. Resin layer Re: In-plane retardation Re of resin layer (A) or resin layer (CA). Unit: nm. Polarizer thickness: Unit: μm. Support type: The type of support used. OPP: Biaxially oriented polypropylene film. Si-PET: PET film with silicone release treatment. Total thickness: The sum of the (hard coat layer) / (resin layer (A)) / (adhesive layer) / (polarizer layer) / (adhesive layer), or the sum of the (hard coat layer) / (resin layer (CA)) / (adhesive layer) / (polarizer layer) / (adhesive layer). Unit: μm. Stretchability: Evaluation results of the stretchability of the hard coat layer at the time of polarizing film formation. Yes: The hard coat layer could be freely uniaxially stretched up to 1.50 times its original strength without the occurrence of cracks. No: The hard coat layer could not be freely uniaxially stretched up to 1.50 times its original strength without the occurrence of cracks. Tackiness: Evaluation results of the tackiness of the hard coat layer at the time of polarizing film formation. None: When the hard coat layer is touched with a finger, the materials constituting the hard coat layer do not adhere to the finger. Present: When the hard coat layer is touched with a finger, the materials constituting the hard coat layer adhere to the finger. Curl: The value of h1 in the curl evaluation. Unit: mm. Unmeasurable: The curl was too strong to measure h1. Curl: Evaluation results for curliness. Bending: Evaluation results of the bending test.

[0157] As is clear from the results in Tables 1 and 2, the polarizing film of the present invention obtained using the transfer medium laminate of the present invention has little tendency to curl and conforms well to the curved shape when laminated to an aluminum plate having a curved surface. Therefore, the polarizing film of the present invention can be suitably used in the manufacture of a molded article with a polarizer layer having a curved surface.

Claims

1. A method for manufacturing a molded body with a polarizer layer, Step (A) for manufacturing a polarizing film, wherein the polarizing film is a transfer medium laminate comprising a hard coat layer and a resin layer (A) provided on one surface of the hard coat layer, wherein the hard coat layer is stretchable, and the resin layer (A) contains an ultraviolet absorber and has a storage modulus of 1000 MPa or less; a polarizer layer provided on the resin layer (A) side of the transfer medium laminate; and an adhesive layer interposed between the transfer medium laminate and the polarizer layer, wherein Step (A) includes the steps of bonding the transfer medium laminate and the polarizer layer together via an ultraviolet-curable adhesive to form a laminate; and irradiating the laminate with ultraviolet light from the polarizer layer side of the laminate; Step (B) of laminating the polarizing film to the base material, (C) A step of fully curing the hard coat layer in the polarizing film. Includes, A method for manufacturing a molded article with a polarizer layer, wherein the base member subjected to step (B) is a member having a curved surface, or further comprising a step (Bx) of bending the base member after step (B) and before step (C).

2. The method for manufacturing a molded article with a polarizer layer according to claim 1, wherein the thickness of the resin layer (A) is 0.1 μm or more and 10 μm or less.

3. A method for manufacturing a molded article with a polarizer layer according to claim 1 or 2, wherein the in-plane retardation Re of the resin layer (A) is 0 nm or more and 5 nm or less.

4. The transfer medium laminate is A process of spreading a hard coat material onto the surface of a support, A step of partially curing the hard coat material to form a stretchable hard coat layer, and A step of spreading resin on the hard coat layer to form a resin layer (A) with a storage modulus of 1000 MPa or less. A method for manufacturing a polarizer layered molded article according to any one of claims 1 to 3, comprising manufacturing by a manufacturing method including the above.

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