Light reduction film, method for manufacturing the same, and laminate

Abstract

The present invention relates to a light reduction film comprising a resin and an oil-soluble dye, the thickness of the light reduction film being 1 μm or more and less than 100 μm, the b* value in the CIE 1976 (L*, a*, b*) color space of the light reduction film being less than 0. The present invention relates to a method for producing a light reduction film, comprising: a step of preparing a coating liquid comprising the above-mentioned resin, the above-mentioned oil-soluble dye, and a solvent; a step of coating the above-mentioned coating liquid on a surface of a base material layer to form a coated film; and a step of removing the above-mentioned solvent from the above-mentioned coated film to obtain the above-mentioned light reduction film.

Description

Technical Field

[0001] This invention relates to neutral density films, methods for manufacturing the same, and laminates. Background Technology

[0002] The process involves combining resins with functional materials to impart desired functions to the resin composition (Patent Document 1).

[0003] In addition, there is a known technique for coloring a film formed from resin and using it for polarizing films (Patent Document 2).

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: International Publication No. 2016 / 163409 (corresponding foreign publication: U.S. Patent Application Publication No. 2018 / 086029);

[0007] Patent Document 2: Japanese Patent Application Publication No. 2004-151264. Summary of the Invention

[0008] The problem the invention aims to solve

[0009] To reduce the reflection of external light in image display devices, anti-reflective films containing linear polarizers and chromatic aberration filters are sometimes used. Linear polarizers are typically manufactured through multiple processes, resulting in high manufacturing costs.

[0010] Furthermore, the light transmittance of antireflective films containing linear polarizers is typically below 50%. Therefore, in image display devices using these antireflective films, the brightness is usually set high, resulting in increased power consumption. Thus, there is a need for optical films that do not contain linear polarizers and have antireflection capabilities.

[0011] Furthermore, in order to reduce the impact on the image clarity of the image display device, it is preferable that the anti-reflective film has low haze.

[0012] Therefore, there is a need for novel films with the function of reducing the reflection of external light in image display devices and low haze, as well as their manufacturing methods.

[0013] Solution for solving the problem

[0014] In order to solve the above problems, the inventors conducted in-depth research and found that the above problems could be solved by using a film containing resin and oil-soluble dye and having a specified thickness, thus completing the present invention.

[0015] That is, the present invention provides the following technical solutions.

[0016] [1] An anti-gloss film comprising a resin and an oil-soluble dye,

[0017] The thickness of the neutral density film is greater than 1 μm and less than 100 μm.

[0018] The b* value of this neutral density filter is less than 0 in the CIE 1976 (L*, a*, b*) color space.

[0019] [2] According to the anti-gloss film of [1], the proportion of the oil-soluble dye to the resin is 0.01% by weight or more and less than 2% by weight.

[0020] [3] The light-reducing film according to [1] or [2], wherein the resin comprises a polymer with an alicyclic structure.

[0021] [4] According to the light-reducing film described in [3], wherein the above-mentioned alicyclic polymer is a cyclic olefin polymer or its hydride.

[0022] [5] The light-reducing film according to any one of [1] to [4] has a linear transmittance of light with a wavelength of 550 nm of 25% or more and 85% or less.

[0023] [6] The light-reducing film according to any one of [1] to [5] has a linear transmittance of light with a wavelength of 480 nm that is greater than that of light with a wavelength of 610 nm.

[0024] [7] A laminate comprising any one of [1] to [6] an anti-light film and a light-transmitting thermoplastic resin layer, wherein the anti-light film is directly disposed on the surface of the thermoplastic resin layer.

[0025] [8] A method for manufacturing an anti-light coating, which is the method for manufacturing an anti-light coating as described in any one of [1] to [6], comprising:

[0026] The process of preparing a coating solution comprising the above-mentioned resin, the above-mentioned oil-soluble dye, and a solvent.

[0027] The process of applying the above-mentioned coating liquid to the surface of a substrate layer to form a coating film, and

[0028] The process of removing the solvent from the above-mentioned coated film to obtain the above-mentioned neutral density film.

[0029] Invention Effects

[0030] According to the present invention, a novel anti-light coating with the function of reducing the reflection of external light in an image display device and low haze, and a method for manufacturing the anti-light coating, are provided. Attached Figure Description

[0031] Figure 1 This is a schematic cross-sectional view of the laminated body according to Embodiment 1 of the present invention.

[0032] Figure 2 This is a schematic cross-sectional view of the laminated body according to Embodiment 2 of the present invention. Detailed Implementation

[0033] The present invention will now 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 may be implemented in any manner with modifications that do not depart from the scope of the claims of the present invention and their equivalents.

[0034] In the following description, unless otherwise specified, the in-plane retardation Re of the layer is represented by Re = (nx - ny) × d. Here, nx represents the refractive index in the direction perpendicular to the thickness direction of the layer (in-plane direction), which imparts the maximum refractive index. ny represents the refractive index in the direction orthogonal to nx in the aforementioned in-plane direction of the layer. d represents the thickness of the layer. Unless otherwise specified, the measurement wavelength is 590 nm.

[0035] [1. Neutralizing film]

[0036] An embodiment of the present invention provides an anti-gloss film comprising a resin and an oil-soluble dye, wherein the thickness of the anti-gloss film is greater than 1 μm and less than 100 μm, and the b* value of the anti-gloss film in the CIE 1976 (L*, a*, b*) color space is less than 0.

[0037] Neutral density films typically contain a resin composition comprising a resin and an oil-soluble dye, and are formed from this resin composition.

[0038] Neutral density (ND) films can have a single-layer structure or a multi-layer structure. In the case of a multi-layer structure, the multiple layers constituting the ND film typically each contain a resin composition comprising a resin and an oil-soluble dye, and are formed from the resin composition.

[0039] The light-reducing film preferably has a single-layer structure.

[0040] The light-reducing film can be combined with other components, such as being laminated with substrates like resin films and glass plates, or laminated with release films and protective films.

[0041] [1.1. Resin]

[0042] Neutral density coatings contain resins. Resins can typically contain polymers and any other components as needed.

[0043] Examples of resins that can be included in neutral density coatings include thermosetting resins and thermoplastic resins. From the viewpoint of easy adjustment of the b* value, thermoplastic resins are preferred.

[0044] Examples of polymers that can be included in thermoplastic resins include: polymers containing alicyclic structures such as norbornene polymers; polyolefins such as polyethylene and polypropylene; polyesters such as polyethylene terephthalate and polybutylene terephthalate; polyarylethers such as polyphenylene sulfide; polyvinyl alcohol; polycarbonate; polyarylethers; cellulose ester polymers; polyethersulfone; polysulfone; polyarylsulfone; polyvinyl chloride; rod-shaped liquid crystal polymers, etc.

[0045] Polymers can be used alone or in combination of two or more in any ratio. Furthermore, polymers can be homopolymers or copolymers. Among these, polymers containing alicyclic structures are preferred from the viewpoints of excellent mechanical properties, heat resistance, transparency, low moisture absorption, dimensional stability, and lightweight properties. Hereinafter, polymers containing alicyclic structures will sometimes be appropriately referred to as "alicyclic polymers".

[0046] Polymers containing alicyclic structures have alicyclic structural units. These polymers can have alicyclic main chains or alicyclic side chains.

[0047] Examples of alicyclic structures include saturated alicyclic hydrocarbons (cycloalkanes) and unsaturated alicyclic hydrocarbons (cycloalkenes, cycloalkynes). From the viewpoint of mechanical strength and heat resistance, cycloalkanes and cycloalkenes are preferred, with cycloalkanes being particularly preferred.

[0048] Regarding the number of carbon atoms constituting the alicyclic structure, each alicyclic structure preferably has 4 or more, more preferably 5 or more, more preferably 30 or less, more preferably 20 or less, and particularly preferably 15 or less. When the number of carbon atoms constituting the alicyclic structure is within the above range, mechanical strength, heat resistance, and formability of the anti-gloss film are highly balanced, and therefore preferred.

[0049] Examples of polymers containing alicyclic structures include: cyclic olefin polymers and their hydrides; cyclic conjugated diene polymers and their hydrides; and vinyl alicyclic hydrocarbon polymers and their hydrides.

[0050] When the resin contains an alicyclic polymer, the alicyclic polymer in the resin can be one type or a combination of two or more types in any ratio. For example, as an alicyclic polymer, the resin can contain only one type selected from cyclic olefin polymers and their hydrides, or it can contain two or more types selected from cyclic olefin polymers and their hydrides, or it can contain alicyclic polymers other than cyclic olefin polymers and their hydrides (e.g., copolymer A described later).

[0051] (Cyclic olefin polymers and their hydrides)

[0052] Cyclic olefin polymers are polymers comprising structural units having a structure obtained by polymerizing cyclic olefin monomers. Examples of cyclic olefin polymers include monocyclic and polycyclic cyclic olefin polymers.

[0053] In one embodiment, from the viewpoint of achieving good transparency and moldability of the resin, the alicyclic polymer that the resin can contain is preferably a cyclic olefin polymer or its hydrogenation, more preferably a polycyclic cyclic olefin polymer or its hydrogenation, and even more preferably a norbornene polymer or its hydrogenation.

[0054] In one embodiment, the proportion of the cyclic olefin polymer and its hydrides in the resin is preferably 50% by weight or more, more preferably 60% by weight or more, even more preferably 70% by weight or more, even more preferably 80% by weight or more, even more preferably 90% by weight or more, even more preferably 95% by weight or more, typically 100% by weight or less, or may be 100% by weight.

[0055] Examples of norbornene-based polymers and their hydrides include: ring-opening polymers of monomers having a norbornene structure, or ring-opening copolymers of monomers having a norbornene structure with other monomers; addition polymers of monomers having a norbornene structure, or addition copolymers of monomers having a norbornene structure with other monomers; and their hydrides. Among these, ring-opening (co)polymer hydrides of monomers having a norbornene structure are particularly preferred from the viewpoints of transparency, moldability, heat resistance, low moisture absorption, dimensional stability, and lightweight. Here, "(co)polymer" refers to polymers and copolymers.

[0056] Examples of monomers with the norbornene structure include: bicyclic [2.2.1]hept-2-ene (common name: norbornene), tricyclic [4.3.0.1]hept-2-ene (common name: norbornene), and tricyclic [4.3.0.1]hept-2-ene. 2,5 ] Dec-3,7-diene (common name: dicyclopentadiene), 7,8-benzotricyclo[4.3.0.1] 2,5 ] Dec-3-ene (common name: bridged methylenetetrahydrofluorene), tetracyclic [4.4.0.1] 2,5 .1 7,10 Dodecene-3-ene (common name: tetracyclic dodecene) and derivatives of these compounds (e.g., monomers with substituents on the ring). Examples of substituents include alkyl groups, alkylene groups, and polar groups. Furthermore, these substituents can be the same or different, and multiple substituents can be bonded to the ring. Additionally, monomers having the norbornene structure can be used alone or in combination of two or more in any ratio.

[0057] 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, carbonyl groups, epoxy groups, hydroxyl groups, oxygen groups, ester groups, silanol groups, silyl groups, amino groups, nitrile groups, sulfonic acid groups, etc.

[0058] Other monomers capable of ring-opening copolymerization with monomers having a norbornene structure include, for example, monocyclic olefins such as cyclohexene, cycloheptene, and cyclooctene, and their derivatives; cyclic conjugated dienes such as cyclohexadiene and cycloheptadiene, and their derivatives. Other monomers capable of ring-opening copolymerization with monomers having a norbornene structure can be used alone, or two or more can be used in any ratio.

[0059] Ring-opening polymers of monomers having a norbornene structure, as well as ring-opening copolymers of monomers having a norbornene structure and other monomers capable of copolymerizing with monomers having a norbornene structure, can be manufactured, for example, by polymerizing or copolymerizing the monomers in the presence of a known ring-opening polymerization catalyst.

[0060] Other monomers capable of addition copolymerization with monomers having a norbornene structure include, for example, α-olefins with 2 to 20 carbon atoms, such as ethylene, propylene, and 1-butene, and their derivatives; cycloolefins, such as cyclobutene, cyclopentene, and cyclohexene, and their derivatives; and non-conjugated dienes such as 1,4-hexadiene, 4-methyl-1,4-hexadiene, and 5-methyl-1,4-hexadiene. Among these, α-olefins are preferred, and ethylene is more preferred. Furthermore, other monomers capable of addition copolymerization with monomers having a norbornene structure can be used alone or in combination of two or more in any ratio.

[0061] Addition polymers of monomers having a norbornene structure, as well as addition copolymers of monomers having a norbornene structure and other monomers capable of copolymerizing with monomers having a norbornene structure, can be manufactured, for example, by polymerizing or copolymerizing the monomers in the presence of a known addition polymerization catalyst.

[0062] Specific examples of norbornene polymers and their hydrides include: "Zeonor" manufactured by Zeon Corporation of Japan; "ARTON" manufactured by JSR Corporation; and "TOPAS" manufactured by TOPASA DVANCED POLYMERS.

[0063] Examples of monocyclic cyclic olefin polymers and their hydrides include addition polymers of monocyclic cyclic olefin monomers such as cyclohexene, cycloheptene, and cyclooctene, as well as their hydrides.

[0064] (Cyclic conjugated diene polymers and their hydrides)

[0065] Examples of cyclic conjugated diene polymers and their hydrides include: polymers obtained by cyclizing addition polymers of conjugated diene monomers such as 1,3-butadiene, isoprene, and chloroprene; 1,2- or 1,4-addition polymers of cyclic conjugated diene monomers such as cyclopentadiene and cyclohexadiene; and their hydrides.

[0066] (Vinyl alicyclic hydrocarbon polymers and their hydrides)

[0067] Examples of vinyl alicyclic hydrocarbon polymers include: polymers of vinyl alicyclic hydrocarbon monomers such as vinylcyclohexene and vinylcyclohexane, and their hydrides; hydrides formed by hydrogenating the aromatic ring portion of polymers synthesized from vinyl aromatic hydrocarbon monomers such as styrene and α-methylstyrene; and aromatic ring hydrides of copolymers of vinyl alicyclic hydrocarbon monomers with other monomers, or random copolymers or block copolymers of vinyl aromatic hydrocarbon monomers with other monomers capable of copolymerizing with these vinyl aromatic hydrocarbon monomers. Examples of block copolymers include, for instance, diblock copolymers, triblock copolymers, or multiblock copolymers of more than one type, and gradient block copolymers.

[0068] In one embodiment, the alicyclic polymer that the resin may contain is selected from one or more of hydrogenated aromatic vinyl compounds-conjugated diene block copolymers (hereinafter also referred to as copolymer A) and modified versions of hydrogenated aromatic vinyl compounds-conjugated diene block copolymers based on silicon-containing polar groups.

[0069] Hydrogenated aromatic vinyl compound-conjugated diene block copolymers are hydrogenated forms of aromatic vinyl compound-conjugated diene block copolymers. Aromatic vinyl compound-conjugated diene block copolymers are copolymers comprising blocks containing aromatic vinyl compound units and blocks containing conjugated diene units.

[0070] The hydrogenated aromatic vinyl compound-conjugated diene block copolymer has a structure obtained by hydrogenating some or all of the carbon-carbon unsaturated bonds in the main chain and side chains, the carbon-carbon unsaturated bonds in the aromatic ring, or both of these. However, in this application, the hydride is not limited to its manufacturing method.

[0071] Aromatic vinyl compound units refer to structural units that have a structure obtained by polymerizing aromatic vinyl compounds, and conjugated diene units refer to structural units that have a structure obtained by polymerizing conjugated dienes.

[0072] As aromatic vinyl compounds, styrene and its derivatives are preferred; vinylnaphthalene and its derivatives are also preferred, with styrene being particularly preferred from the viewpoint of industrial availability. As conjugated dienes, chain-like conjugated dienes (straight-chain conjugated dienes, branched-chain conjugated dienes) are preferred; specifically, 1,3-butadiene, isoprene (2-methyl-1,3-butadiene), 2,3-dimethyl-1,3-butadiene, and 1,3-pentadiene are preferred. Among these, 1,3-butadiene and isoprene are particularly preferred from the viewpoint of industrial availability.

[0073] As aromatic vinyl compound-conjugated diene block copolymers, those selected are preferably styrene-butadiene block copolymers, styrene-butadiene-styrene block copolymers, styrene-isoprene block copolymers, styrene-isoprene-styrene block copolymers, and mixtures thereof. More specific examples include those described in prior art documents such as Japanese Patent Application Publication No. 2-133406, Japanese Patent Application Publication No. 2-305814, Japanese Patent Application Publication No. 3-72512, Japanese Patent Application Publication No. 3-74409, and International Publication No. 2015 / 099079.

[0074] The hydrogenation rate of the hydrogenated aromatic vinyl compound-conjugated diene block copolymer is preferably 90% or more, more preferably 97% or more, particularly preferably 99% or more, and typically 100% or less. A higher hydrogenation rate results in better heat resistance and light resistance of the neutral density film. Here, the hydrogenation rate of the hydride can be determined by… 1 It is determined by H-NMR measurement.

[0075] The hydrogenation rate of carbon-carbon unsaturated bonds in the main chain and side chains of the hydrogenated aromatic vinyl compound-conjugated diene block copolymer is preferably 95% or more, more preferably 99% or more, and typically 100% or less. By increasing the hydrogenation rate of carbon-carbon unsaturated bonds in the main chain and side chains of the hydrogenated aromatic vinyl compound-conjugated diene block copolymer, the lightfastness and oxidation resistance of the neutralizing film can be further improved.

[0076] Furthermore, the hydrogenation rate of the carbon-carbon unsaturated bonds in the aromatic ring of the hydrogenated aromatic vinyl compound-conjugated diene block copolymer is preferably 90% or more, more preferably 93% or more, particularly preferably 95% or more, and typically 100% or less. By increasing the hydrogenation rate of the carbon-carbon unsaturated bonds in the aromatic ring, the glass transition temperature of the hydride increases, thus effectively improving the heat resistance of the neutral density film. Furthermore, it is possible to reduce the photoelasticity of the neutral density film and decrease the appearance of retardation.

[0077] As a hydrogenated aromatic vinyl compound-conjugated diene block copolymer, it is preferable to have a structure formed by hydrogenating both the unsaturated bond and the aromatic ring from the conjugated diene.

[0078] A particularly preferred configuration of the hydrogenated aromatic vinyl compound-conjugated diene block copolymer is a triblock copolymer in which blocks [B] of the aromatic vinyl polymer hydride are bonded to both ends of blocks [B] of the conjugated diene polymer hydride; and a pentablock copolymer in which polymer blocks [B] are bonded to both ends of polymer blocks [A], and further polymer blocks [A] are bonded to the other ends of the two polymer blocks [B]. In particular, from the viewpoint of ease of manufacture, triblock copolymers of [A]-[B]-[A] are particularly preferred.

[0079] When the mass fraction of all aromatic vinyl monomer units in the total block copolymer is wA, and the mass fraction of all conjugated diene monomer units in the total block copolymer is wB, the ratio of wA to wB (wA / wB) is preferably 20 / 80 or more, more preferably 30 / 70 or more, more preferably 60 / 40 or less, and more preferably 55 / 45 or less. By setting the ratio wA / wB to the lower limit of the above range, the heat resistance of the neutral density film can be improved. Furthermore, by setting the ratio wA / wB to the upper limit of the above range, the flexibility of the neutral density film can be improved.

[0080] The modified version of the hydrogenated aromatic vinyl compound-conjugated diene block copolymer (polymer A) based on silicon-containing polar groups has a structure obtained by graft polymerization of the above-mentioned hydrogenated aromatic vinyl compound-conjugated diene block copolymer with a compound having silicon-containing polar groups as a monomer. However, the modified version is not limited by its manufacturing method.

[0081] As a silicon-containing polar group, alkoxysilyl is preferred.

[0082] Examples of compounds with silicon-containing polar groups that can be used as monomers for graft polymerization include: vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, dimethoxymethylvinylsilane, diethoxymethylvinylsilane, p-styryltrimethoxysilane, p-styryltriethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltriethoxysilane, and 2-norbornene-5-yltrimethoxysilane, etc., which are alkoxysilane compounds with alkoxymethylsilane groups.

[0083] By reacting copolymer A with a compound having a silicon-containing polar group, a silicon-containing polar group can be introduced into copolymer A, resulting in a modified product having a silicon-containing polar group. When alkoxysilane is introduced as the silicon-containing polar group, the amount of alkoxysilane introduced relative to 100 parts by weight of copolymer A is preferably 0.1 parts by weight or more, more preferably 0.2 parts by weight or more, even more preferably 0.3 parts by weight or more, preferably 10 parts by weight or less, more preferably 5 parts by weight or less, and even more preferably 3 parts by weight or less. When the amount of alkoxysilane introduced is controlled within the above range, excessive crosslinking of the alkoxysilanes that are decomposed by moisture, etc., can be prevented, thus maintaining high adhesion. Examples of substances containing alkoxysilane and modification methods used in the introduction of alkoxysilanes include those described in prior art documents such as International Publication No. 2015 / 099079.

[0084] The amount of polar groups introduced can be controlled by... 1 Measurements were performed using H-NMR spectroscopy. Furthermore, when measuring the amount of polar groups introduced, the number of cumulative measurements could be increased even with low amounts of introduced groups.

[0085] Introducing alkoxysilyl groups as polar groups into copolymer A is called silane modification. During silane modification, the alkoxysilyl group can be directly bonded to copolymer A, or it can be bonded to copolymer A via divalent organic groups such as alkylene groups. Hereinafter, the polymer obtained by silane modification of copolymer A will also be referred to as a "silane-modified product".

[0086] As a modifier of copolymer A based on silicon-containing polar groups, a silane-modified hydrogenated aromatic vinyl compound-conjugated diene block copolymer is preferred, and more than one silane-modified styrene-butadiene block copolymer, a silane-modified hydrogenated styrene-butadiene-styrene block copolymer, a silane-modified hydrogenated styrene-isoprene block copolymer, and a silane-modified hydrogenated styrene-isoprene-styrene block copolymer are preferred.

[0087] In one embodiment, the resin may contain a modified version of the alicyclic polymer, preferably a copolymer A based on a silicon-containing polar group; more preferably a modified version of copolymer A based on an alkoxysilane; and even more preferably one or more silane modifiers selected from hydrogenated styrene-butadiene-styrene block copolymers, hydrogenated styrene-isoprene block copolymers, and hydrogenated styrene-isoprene-styrene block copolymers.

[0088] In one embodiment, the proportion of the modified copolymer A in the resin based on silicon-containing polar groups is preferably 50% by weight or more, more preferably 60% by weight or more, even more preferably 70% by weight or more, even more preferably 80% by weight or more, even more preferably 90% by weight or more, even more preferably 95% by weight or more, typically 100% by weight or less, or 100% by weight.

[0089] The weight-average molecular weight (Mw) of the alicyclic polymer is preferably 10,000 or more, more preferably 15,000 or more, even more preferably 20,000 or more, preferably 200,000 or less, more preferably 100,000 or less, and even more preferably 80,000 or less. Polymers with such a weight-average molecular weight exhibit an excellent balance of mechanical strength, processability, and heat resistance.

[0090] The molecular weight distribution (Mw / Mn) of the alicyclic polymer is preferably 1 or more, preferably 4 or less, and more preferably 3.5 or less. When the molecular weight distribution is at or above the lower limit of the above range, the productivity of the alicyclic polymer can be improved and manufacturing costs can be reduced. Furthermore, when the molecular weight distribution is at or below the upper limit of the above range, the amount of low molecular weight components is reduced, thereby improving the stability of the layer containing the alicyclic polymer.

[0091] Gel permeation chromatography (GPC) using cyclohexane as a solvent allows for the determination of the weight-average molecular weight (Mw) and number-average molecular weight (Mn) of alicyclic polymers, expressed as polyisoprene. In cases where the resin is insoluble in cyclohexane, GPC using toluene or tetrahydrofuran as solvents allows for the determination of these values, expressed as polystyrene.

[0092] The glass transition temperature of the polymer containing alicyclic structure is preferably above 50°C, more preferably above 70°C, more preferably below 200°C, and even more preferably below 180°C.

[0093] When the resin contains a polymer with an alicyclic structure, the proportion of the polymer with an alicyclic structure in the resin is preferably 50% by weight or more, more preferably 60% by weight or more, even more preferably 70% by weight or more, even more preferably 80% by weight or more, even more preferably 90% by weight or more, even more preferably 95% by weight or more, usually 100% by weight or less, or may be 100% by weight.

[0094] Examples of any components other than polymers that a resin can contain include: antioxidants; plasticizers; UV absorbers; and lubricants. Any component can be used alone or in combination of two or more in any ratio.

[0095] The total proportion of any components other than polymers in the resin is preferably 5% by weight or less, more preferably 3% by weight or less, even more preferably 1% by weight or less, usually 0% by weight or more, or may be 0% by weight.

[0096] [1.2. Oil-soluble dyes]

[0097] Neutral density coatings contain oil-soluble dyes. Oil-soluble dyes are those classified as "solvent dyes" in the color index (a database of the British Institute of Dyes and Colorants and the American Society for Fiber Chemistry and Dyeing Technology).

[0098] Specific examples of oil-soluble yellow dyes include Oil Yellow 105 (trade name, manufactured by Oriental Chemical Industry Co., Ltd.), Oil Yellow 107 (trade name, manufactured by Oriental Chemical Industry Co., Ltd.), Oil Yellow 129 (trade name, manufactured by Oriental Chemical Industry Co., Ltd., CISolvent Yellow 29), Oil Yellow 3G (trade name, manufactured by Oriental Chemical Industry Co., Ltd., CISolvent Yellow 16), Oil Yellow GGS (trade name, manufactured by Oriental Chemical Industry Co., Ltd., CISolvent Yellow 56), Valifafast Yellow 1101 (trade name, manufactured by Oriental Chemical Industry Co., Ltd.), Valifafast Yellow 1105 (trade name, manufactured by Oriental Chemical Industry Co., Ltd.), Valifafast Yellow 4120 (trade name, manufactured by Oriental Chemical Industry Co., Ltd., CISolvent Yellow 82), and Oleosol Brilliant Yellow 5G (trade name, manufactured by Taoka Chemical Industry Co., Ltd., CISolvent Yellow). 150), Oleosol Fast Yellow 2G (trade name, manufactured by Taoka Chemical Industry Co., Ltd., CISolvent Yellow 21), Oleosol Fast Yellow GCN (trade name, manufactured by Taoka Chemical Industry Co., Ltd., CISolvent Yellow 151), Aizensot Yellow 1 (trade name, manufactured by Hodogaya Chemical Industry Co., Ltd., CISolvent Yellow 56), Aizensot Yellow 3 (trade name, manufactured by Hodogaya Chemical Industry Co., Ltd., CISolvent Yellow 16), Aizensot Yellow 6 (trade name, manufactured by Hodogaya Chemical Industry Co., Ltd., CISolvent Yellow 33), Aizen Spilon Yellow GRLH (trade name, manufactured by Hodogaya Chemical Industry Co., Ltd.), Aizen Spilon Yellow 3RH (trade name, manufactured by Hodogaya Chemical Industry Co., Ltd.), Orasol Yellow 2GLN (trade name, manufactured by Siba-Gage Co., Ltd., CISolvent Yellow 88), Orasol Yellow 2RLN (trade name, manufactured by Siba-Gage, CISolvent Yellow 89), Orasol Yellow 3R (trade name, manufactured by Siba-Gage, CISolvent Yellow 89)Solvent Yellow 25), Oracle Yellow GHS (trade name, manufactured by CISolvent Yellow 163), Filamid Yellow R (trade name, manufactured by CISolvent Yellow 21), Oil Yellow 185 (trade name, manufactured by Central Synthetic Chemicals Co., Ltd., similar to CISolvent Red 18), Alcohol Yellow Y-10 (trade name, manufactured by Central Synthetic Chemicals Co., Ltd.), and Diaresin Yellow L3G (trade name, manufactured by Mitsubishi Chemicals Co., Ltd., CISolvent Yellow 93).

[0099] Specific examples of oil-soluble red dyes include Oil Red 5B (trade name, manufactured by Oriental Chemical Industry Co., Ltd., CISolvent Red 27), Oil Red RR (trade name, manufactured by Oriental Chemical Industry Co., Ltd., CISolvent Red 24), Valifast Red 1306 (trade name, manufactured by Oriental Chemical Industry Co., Ltd., CISolvent Red 109), Valifast Red 1355 (trade name, manufactured by Oriental Chemical Industry Co., Ltd.), Valifast Red 2303 (trade name, manufactured by Oriental Chemical Industry Co., Ltd.), Valifast Red 3304 (trade name, manufactured by Oriental Chemical Industry Co., Ltd., CISolvent Red 8), Valifast Red 3306 (trade name, manufactured by Oriental Chemical Industry Co., Ltd.), Valifast Red 3320 (trade name, manufactured by Oriental Chemical Industry Co., Ltd., CISolvent Red 132), and Oil Pink. 312 (trade name, manufactured by Oriental Chemical Industry Co., Ltd.), Valifafast Pink 2310N (trade name, manufactured by Oriental Chemical Industry Co., Ltd., CISolvent Red 218), Oleosol Fast Red BL (trade name, manufactured by Taoka Chemical Industry Co., Ltd., CISolvent Red 132), Oleosol Fast Red RL (trade name, manufactured by Taoka Chemical Industry Co., Ltd., CISolvent Red 122), Oleosol Fast Red GL (trade name, manufactured by Taoka Chemical Industry Co., Ltd., CISolvent Red 132), Oleosol Red 2G (trade name, manufactured by Taoka Chemical Industry Co., Ltd.), Oleosol Fast Pink FB (trade name, manufactured by Taoka Chemical Industry Co., Ltd., CISolvent Red 218), Aizensot Red 1 (trade name, manufactured by Hodogaya Chemical Industry Co., Ltd., CISolvent Red 24), Aizensot Red 2 (trade name, manufactured by Hodogaya Chemical Industry Co., Ltd., CISolvent Red 27), Aizensot Red 3 (trade name, manufactured by Hodogaya Chemical Industry Co., Ltd., CISolvent Red 18), Aizen Spilon Red BEH (trade name, manufactured by Hodogaya Chemical Industry Co., Ltd.), Aizen Spilon Fiery Red BH (trade name, manufactured by Hodogaya Chemical Industry Co., Ltd., CISolvent Red 18),Solvent Red 81), Aizen Spilon Red GEH (trade name, manufactured by Hodogaya Chemical Industry Co., Ltd.), Aizen Spilon Red C-GH (trade name, manufactured by Hodogaya Chemical Industry Co., Ltd.), Aizensot Pink 1 (trade name, manufactured by Hodogaya Chemical Industry Co., Ltd., CISolvent Red 49), Orasol Red 3GL (trade name, manufactured by Siba-Gage Co., Ltd., CISolvent Red 130), Orasol Red 2BL (trade name, manufactured by Siba-Gage Co., Ltd., CISolvent Red 132), Orasol Red G (trade name, manufactured by Siba-Gage Co., Ltd., CISolvent Red 125), Orasol Red B (trade name, manufactured by Siba-Gage Co., Ltd., CISolvent Red 7), Filamid Red GR (trade name, manufactured by Siba-Gage Co., Ltd., CISolvent Red 225), Filester Red GA (trade name, manufactured by Siba-Gage Co., Ltd., CISolvent Red 81), 135), Filester Red RBA (trade name, manufactured by Siba-Gage, CISolventRed230), Orasol Pink 5BLG (trade name, manufactured by Siba-Gage, CISolvent Red 127), Oil Pink 330 (trade name, manufactured by Central Synthetic Chemicals, CISolvent Red 49), Alcohol Pink P-30 (trade name, manufactured by Central Synthetic Chemicals, CISolvent Red 155), Diaresin Red K (trade name, manufactured by Mitsubishi Chemicals, CISolvent Red 155), and Diaresin Red H5B (trade name, manufactured by Mitsubishi Chemicals, CISolventRed 52).

[0100] Specific examples of oil-soluble blue dyes include Oil Blue 613 (trade name, manufactured by Oriental Chemical Industry Co., Ltd.), Oil Blue 2N (trade name, manufactured by Oriental Chemical Industry Co., Ltd., CISolvent Blue 35), Oil Blue BOS (trade name, manufactured by Oriental Chemical Industry Co., Ltd.), Valifast Blue 1603 (trade name, manufactured by Oriental Chemical Industry Co., Ltd.), Valifast Blue 1605 (trade name, manufactured by Oriental Chemical Industry Co., Ltd., CISolvent Blue 38), Valifast Blue 1607 (trade name, manufactured by Oriental Chemical Industry Co., Ltd.), Valifast Blue 2606 (trade name, manufactured by Oriental Chemical Industry Co., Ltd., CISolvent Blue 70), Valifast Blue 2610 (trade name, manufactured by Oriental Chemical Industry Co., Ltd.), Oleosol Fast Blue ELN (trade name, manufactured by Taoka Chemical Industry Co., Ltd., CISolvent Blue 70), and Oleosol Fast Blue. GL (trade name, manufactured by Taoka Chemical Industry Co., Ltd., CISolvent Blue 70), Oleosol Blue G (trade name, manufactured by Taoka Chemical Industry Co., Ltd.), Aizensot Blue 1 (trade name, manufactured by Hodogaya Chemical Industry Co., Ltd., CISolvent Blue 25), Aizensot Blue 2 (trade name, manufactured by Hodogaya Chemical Industry Co., Ltd., CISolvent Blue 14), Aizen Spilon Blue GNH (trade name, manufactured by Hodogaya Chemical Industry Co., Ltd.), Aizen Spilon Blue 2BNH (trade name, manufactured by Hodogaya Chemical Industry Co., Ltd.), Aizen Spilon Blue BPNH (trade name, manufactured by Hodogaya Chemical Industry Co., Ltd.), Aizen Spilon Blue E2BH (trade name, manufactured by Hodogaya Chemical Industry Co., Ltd., CISolvent Blue 73), Orasol Blue GN (trade name, manufactured by Siba-Gage Co., Ltd., CISolvent Blue 67), Orasol Blue 2GLN (trade name, manufactured by Siba-Gage Co., Ltd., CISolvent Blue 48), Oceant Blue2R (trade name, manufactured by Siba-Gage Co., Ltd., CISolvent Blue 68), Oil Blue BO (trade name, manufactured by Central Synthetic Chemical Co., Ltd., CISolvent Blue 48)Solvent Blue 25), Filamid Blue R (trade name, manufactured by Siba-Gage, CISolvent Blue 132), Filester Blue GN (trade name, manufactured by Siba-Gage, CISolvent Blue 67), Kayaset Blue K-FL (trade name, manufactured by Nippon Kayaku Co., Ltd.), Alcohol Blue B-10 (trade name, manufactured by Chuo Synthetic Chemical Co., Ltd.), and Diaresin Blue H3G (trade name, manufactured by Mitsubishi Chemical Co., Ltd.).

[0101] Specific examples of black oil-soluble dyes include Oil Black HBB (trade name, manufactured by Oriental Chemical Industry Co., Ltd., CISolvent Black 3), Oil Black 860 (trade name, manufactured by Oriental Chemical Industry Co., Ltd., CISolvent Black 3), Oil Black BS (trade name, manufactured by Oriental Chemical Industry Co., Ltd., CISolvent Black 7), Oil Black BY (trade name, manufactured by Oriental Chemical Industry Co., Ltd.), ValifastBlack 1802 (trade name, manufactured by Oriental Chemical Industry Co., Ltd.), Valifast Black 1807 (trade name, manufactured by Oriental Chemical Industry Co., Ltd.), Valifast Black 3804 (trade name, manufactured by Oriental Chemical Industry Co., Ltd., CISolvent Black 34), Valifast Black 3810 (trade name, manufactured by Oriental Chemical Industry Co., Ltd., CISolvent Black 29), and Valifast Black 3820 (trade name, manufactured by Oriental Chemical Industry Co., Ltd., CISolvent Black 34). 27), Valifafast Black 3830 (trade name, manufactured by Oriental Chemical Industry Co., Ltd.), Spirit Black SB (trade name, manufactured by Oriental Chemical Industry Co., Ltd., CISolvent Black 5), Spirit Black SSBB (trade name, manufactured by Oriental Chemical Industry Co., Ltd., CISolvent Black 5), Spirit Black AB (trade name, manufactured by Oriental Chemical Industry Co., Ltd., CISolvent Black 5), Nigrosine Base (trade name, manufactured by Oriental Chemical Industry Co., Ltd., CISolvent Black 7), Oleosol Fast Black RL (trade name, manufactured by Taoka Chemical Industry Co., Ltd., CISolvent Black 27), Oleosol Black AR (trade name, manufactured by Taoka Chemical Industry Co., Ltd.), Aizensot Black 6 (trade name, manufactured by Hodogaya Chemical Industry Co., Ltd., CISolvent Black 3), Aizensot Black 8 (trade name, manufactured by Hodogaya Chemical Industry Co., Ltd., CISolvent Black 8), CIThe following are product lines: Solvent Black 7, AizenSpilon Black MH (trade name, manufactured by Hodogaya Chemical Industry Co., Ltd.), Aizen Spilon Black GMHSpecial (trade name, manufactured by Hodogaya Chemical Industry Co., Ltd.), Aizen Spilon Black RLH Special (trade name, manufactured by Hodogaya Chemical Industry Co., Ltd.), Orasol Black CN (trade name, manufactured by Siba-Gage Co., Ltd., CISolvent Black 28), Orasol Black RLI (trade name, manufactured by Siba-Gage Co., Ltd., CISolvent Black 29), and Oil Black FS Special A (trade name, manufactured by Chuo Synthetic Chemical Co., Ltd., CISolvent Black 7).

[0102] Oil-soluble dyes can be used alone or in combination of two or more in any ratio. Furthermore, oil-soluble dyes that dissolve at room temperature (preferably 20 ± 5 °C) in cyclohexane at a concentration of 0.02% by weight or more are preferred. By using such oil-soluble dyes, they can be easily combined with various thermoplastic resins (e.g., resins containing alicyclic polymers).

[0103] From the viewpoint of effectively imparting anti-gloss properties to the anti-gloss film, the proportion of oil-soluble dye to resin is preferably 0.01% by weight or more, more preferably 0.05% by weight or more, and from the viewpoint of effectively reducing the haze of the anti-gloss film, it is preferably less than 2% by weight, more preferably 1.5% by weight or less.

[0104] Here, the proportion of the oil-soluble dye mentioned above is the value when the weight of the resin contained in the neutral density film is taken as 100% by weight.

[0105] [1.3. Thickness of the neutral density coating]

[0106] From the viewpoint of imparting light reduction properties to the light-reducing film, the thickness of the light-reducing film is usually 1 μm or more, preferably 1.5 μm or more, and more preferably 2 μm or more. From the viewpoint of reducing the haze of the light-reducing film, the thickness of the light-reducing film is usually less than 100 μm, preferably 50 μm or less, and more preferably 20 μm or less.

[0107] The thickness of the neutral density film can be adjusted using conventionally known methods depending on the manufacturing method of the neutral density film. For example, in the case of manufacturing the neutral density film by coating using a coating device, the thickness of the neutral density film can be adjusted by adjusting the viscosity of the coating liquid by adjusting the amount of solvent, and by adjusting the gap of the coating device for coating the coating liquid.

[0108] The thickness of the neutral density film can be measured using a fine shape measuring device, a spectrophotometric film thickness measuring device, or similar methods. For example, when the neutral density film is formed on a substrate layer such as a release film, a portion of the neutral density film is peeled off from the substrate layer, and the height difference between the surface of the substrate layer and the surface of the neutral density film is measured using a fine shape measuring device.

[0109] [1.4. b* value of neutral density coating]

[0110] The b* value of the neutral density (ND) film in the CIE 1976 (L*, a*, b*) color space is typically less than 0, preferably -1 or less, and more preferably -2 or less. This balances the linear transmittance of light in the blue region of the ND film with its light-reducing properties. Therefore, the ND film can be preferably used as an anti-reflective film in image display devices (e.g., organic electroluminescent image display devices) that have reflective elements and where the luminous intensity in the blue region is lower than that in other regions.

[0111] The b* value of the neutral density film is preferably -40 or higher, and more preferably -25 or higher.

[0112] The b* value of the neutral density film can be measured using a colorimeter.

[0113] The b* value of the neutral density film can be adjusted by regulating the color and concentration of the oil-soluble dye contained in the film.

[0114] [1.5. Linear transmittance of light from neutral density coating]

[0115] The preferred linear transmittance T of the light-reducing film for a wavelength of 550 nm is... 550 Typically, it is 25% or more, preferably 27.5% or more, more preferably 30% or more, typically 85% or less, preferably 80% or less, more preferably 75% or less.

[0116] By ensuring that the linear transmittance of light with a wavelength of 550 nm is within the aforementioned range, the light reduction characteristics of the neutral density film can be made more moderate. As a result, when the neutral density film is used as an anti-reflective film for an image display device, it is possible to further achieve a balance between image clarity and reflection reduction performance of the image display device.

[0117] The preferred linear transmittance T of the light-reducing film for a wavelength of 480 nm is... 480 Linear transmittance T of light with a wavelength of 610 nm 610 Large. Therefore, the light-reducing film can be preferably used as an anti-reflective film for image display devices (e.g., organic electroluminescent image display devices) that have reflective elements and where the luminous intensity of the blue region is lower than that of other regions.

[0118] Linear transmittance T of light at a wavelength of 480 nm 480 Linear transmittance T of light with wavelength of 610 nm610 The difference (T) 480 -T 610 The content is preferably 2% or more, more preferably 3% or more, even more preferably 5% or more, preferably 30% or less, more preferably 25% or less, even more preferably 21% or less or 20% or less.

[0119] The linear transmittance of light can be measured using a spectrophotometer.

[0120] [1.6. Characteristics of Neutral Density Films]

[0121] The neutral density film has a low haze value. The haze value of the neutral density film is preferably less than 1%, more preferably less than 0.5%, even more preferably less than 0.3%, and usually more than 0%.

[0122] The haze value of the neutral density film can be measured using a haze meter.

[0123] [1.7. Applications of Neutral Density Films]

[0124] As described above, the neutral density film has a low haze value and a light reduction function. Therefore, the neutral density film can be preferably used as an anti-reflective film that reduces reflected light in an image display device without significantly impairing image clarity.

[0125] [2. Layered structure]

[0126] One embodiment of the laminate includes the aforementioned anti-light film and a light-transmitting thermoplastic resin layer. The anti-light film is directly disposed on the surface of the thermoplastic resin layer. By having the above-described configuration, curling of the laminate can be reduced.

[0127] The examples and preferred examples of the neutral density coating contained in the laminate are the same as those of the examples and preferred examples of neutral density coatings described above.

[0128] The thermoplastic resin layer is a layer containing and formed from thermoplastic resin. Thermoplastic resin typically contains a thermoplastic polymer and any other components as needed. Examples of polymers that can be contained in thermoplastic resins include those similar to those that can be contained in neutral density films. In these examples, polymers containing alicyclic structures are preferred from the viewpoints of mechanical properties, heat resistance, transparency, low moisture absorption, dimensional stability, and lightweight.

[0129] Among polymers containing alicyclic structures, cyclic olefin polymers and their hydrides are preferred, and norbornene polymers and their hydrides are more preferred.

[0130] The proportion of polymer in the thermoplastic resin is preferably 50% by weight or more, more preferably 60% by weight or more, even more preferably 70% by weight or more, even more preferably 80% by weight or more, even more preferably 90% by weight or more, even more preferably 95% by weight or more, usually 100% by weight or less, or may be 100% by weight.

[0131] Any components that can be included in thermoplastic resins include: antioxidants; plasticizers; ultraviolet absorbers; and lubricants. Any component can be used alone or in combination of two or more in any ratio.

[0132] The total proportion of any components other than polymers in the resin is preferably 5% by weight or less, more preferably 3% by weight or less, even more preferably 1% by weight or less, usually 0% by weight or more, or may be 0% by weight.

[0133] The thermoplastic resin layer is transparent. Here, "transparent" means that the linear transmittance of light in the wavelength range of 480 nm to 610 nm is 85% or more. The linear transmittance of light in this wavelength range is typically less than 100%. By making the thermoplastic resin layer transparent, optical properties such as light-reducing characteristics of the anti-light film in the laminate can be imparted.

[0134] From the viewpoint of further reducing curling of the laminate, the thickness of the thermoplastic resin layer is preferably 20 μm or more, more preferably 30 μm or more, and even more preferably 50 μm or more. From the viewpoint of achieving thinness of the laminate, the thickness of the thermoplastic resin layer is preferably 250 μm or less, more preferably 200 μm or less, and even more preferably 150 μm or less.

[0135] (Implementation Method 1)

[0136] Figure 1 This is a schematic cross-sectional view of a laminate according to Embodiment 1 of the present invention. The laminate 100 has an anti-gloss film 110 and a thermoplastic resin layer 120. The anti-gloss film is disposed directly on one side 120U of the thermoplastic resin layer 120.

[0137] (Implementation Method 2)

[0138] In another embodiment, the laminate may include a first anti-gloss film, a second anti-gloss film, and a thermoplastic resin layer.

[0139] Figure 2This is a schematic cross-sectional view of the laminate according to Embodiment 2 of the present invention. The laminate 200 sequentially includes a first neutral density film 210, a thermoplastic resin layer 220, and a second neutral density film 230. The first neutral density film 210 is directly disposed on one side surface 220U of the thermoplastic resin layer 220. The second neutral density film 230 is directly disposed on the other side surface 220D of the thermoplastic resin layer 220.

[0140] In this embodiment, the laminate has anti-gloss films directly disposed on both sides of the thermoplastic resin layer. This effectively reduces curling of the laminate.

[0141] The proportion of oil-soluble dyes, thickness, and b* value of the first and second neutral density films can differ. From the viewpoint of simplifying the manufacturing process and effectively reducing the curling of the laminate, it is preferable that the first and second neutral density films are of the same type.

[0142] (Optical properties of laminates)

[0143] The lag Re in the in-plane direction of a laminate can have any value.

[0144] In one embodiment, the in-plane retardation Re of the laminate can be 20 nm to 200 nm, or 200 nm to 350 nm. Therefore, the neutral density film can also function as a retardation film such as a λ / 4 or λ / 2 film.

[0145] In one embodiment, the in-plane retardation Re of the laminate can also be 0 nm to 20 nm.

[0146] [3. Manufacturing method of neutral density film]

[0147] Neutral density (ND) films can be manufactured by any method. From the viewpoint of being able to manufacture thin films relatively stably, the coating method is preferred.

[0148] The light-reducing film can be manufactured by, for example, a method including the following steps (1) to (3).

[0149] Step (1): The step of preparing a coating solution containing the above-mentioned resin, the above-mentioned oil-soluble dye and solvent.

[0150] Step (2): The step of applying the above coating liquid onto the surface of the substrate layer to form a coating film, and

[0151] Step (3): The process of removing the solvent from the above-mentioned coated film to obtain the above-mentioned anti-gloss film.

[0152] Processes (1), (2), and (3) are usually performed in this order.

[0153] [3.1. Process (1)]

[0154] In step (1), a coating solution is prepared. The coating solution contains resin, oil-soluble dye, and solvent.

[0155] From the viewpoint of reducing the haze of the neutral density film and ensuring that oil-soluble dyes are evenly distributed in the neutral density film, a solvent that can dissolve the components contained in the neutral density film, such as resins and oil-soluble dyes, is preferred as a solvent.

[0156] Examples of solvents include aliphatic or alicyclic hydrocarbon solvents (e.g., pentane, hexane, cyclopentane, cyclohexane, decahydronaphthalene), aromatic hydrocarbon solvents (e.g., toluene, xylene, trimethylbenzene, ethylbenzene, tetrahydronaphthalene), halogenated hydrocarbon solvents (e.g., dichloromethane, chloroform, dichloroethane, chlorobenzene), and ether solvents (e.g., 1,4-dichloroethane). Alkane, tetrahydrofuran), and ketone solvents (e.g., dimethyl ketone, cyclopentanone).

[0157] The amount of solvent in the coating solution can be arbitrary, depending on the desired viscosity of the coating solution and the thickness of the formed coating film. The amount of solvent in the coating solution is not particularly limited, but is preferably 1 part by weight or more, more preferably 1.5 parts by weight or more, even more preferably 3 parts by weight or more, preferably 20 parts by weight or less, and more preferably 10 parts by weight or less, relative to 1 part by weight of resin.

[0158] The ratio of oil-soluble dye to resin in the coating solution can be the same as the ratio of oil-soluble dye to resin in the neutral density film.

[0159] The coating solution can be prepared by any method. For example, it can be prepared by dissolving an oil-soluble dye in a solvent to form a dye solution, or by adding a resin to the dye solution. In the preparation of the coating solution, the dye solution can be filtered using a filter.

[0160] In the coating solution, oil-soluble dyes can exist in a state of being dissolved in the solvent. Here, the state of dissolution of oil-soluble dyes does not refer to either the state of oil-soluble dyes after emulsification or the state of oil-soluble dyes as solid particles dispersed in the dispersion medium, but rather to the state of oil-soluble dyes and solvents forming a homogeneous system.

[0161] [3.2. Process (2)]

[0162] In step (2), the coating liquid is applied to the surface of the substrate layer to form a coating film.

[0163] As the substrate layer, any layer can be used. For example, as the substrate layer, a glass plate, a release film after demolding treatment (e.g., a release polyethylene terephthalate (PET) film), or the thermoplastic resin layer contained in the above-described laminate can be used.

[0164] The substrate layer is preferably the above-mentioned thermoplastic resin layer, more preferably a layer formed of a resin containing alicyclic polymers, even more preferably a layer formed of a resin containing cyclic olefin polymers or their hydrogenates, and particularly preferably a layer formed of a resin containing norbornene polymers or their hydrogenates.

[0165] Examples and preferred examples of the polymers that can be included in the resin forming the substrate layer, such as alicyclic polymers, cyclic olefin polymers and their hydrides, norbornene polymers and their hydrides, are the same as those that can be included in the above-described anti-gloss film.

[0166] Coating can be performed by any method. Examples of coating methods include curtain coating, extrusion coating, roller coating, spin coating, dip coating, bar coating, spray coating, sliding coating, printing coating, gravure coating, die coating, slot coating, and impregnation.

[0167] The thickness of the coating film can be appropriately set according to the resin concentration in the coating solution, the desired thickness of the neutral density film, etc.

[0168] [3.3. Process (3)]

[0169] In step (3), the solvent is removed from the above-mentioned coated film to obtain the above-mentioned anti-gloss film.

[0170] Solvent removal can be carried out by any method. Examples of solvent removal methods include natural drying, heating drying, vacuum drying, and vacuum heating drying.

[0171] Solvent need not be completely removed from the coated film as long as it does not impede the effect of the present invention. Therefore, the neutral density film obtained by this manufacturing method may also contain solvent, as long as it does not impede the effect of the present invention. Preferably, the amount of solvent in the neutral density film is 1% by weight or less, usually 0% by weight or more, and may also be 0% by weight.

[0172] [3.4. Arbitrary Process]

[0173] In addition to the above-mentioned steps (1) to (3), the manufacturing method of the light-reducing film may also include any other steps.

[0174] Examples of any process include: peeling the neutral density film obtained in process (3) from the substrate layer; transferring the neutral density film obtained in process (3) to the transfer object; and winding the neutral density film.

[0175] [4. Manufacturing method of laminated bodies]

[0176] The above-described laminate can be manufactured by any method. For example, in the manufacturing method of the anti-gloss film including the above-described steps (1) to (3), the laminate can be manufactured by using a thermoplastic resin layer as a substrate layer. Furthermore, by performing steps (2) and (3) multiple times, coating films can be formed on both sides of the substrate layer (thermoplastic resin layer) to obtain a laminate having a first anti-gloss film and a second anti-gloss film.

[0177] Furthermore, the manufacturing method of the laminate can also include any step other than steps (1) to (3). As such an arbitrary step, the step of stretching the laminate obtained by steps (1) to (3) can be cited.

[0178] Example

[0179] The present invention will now be specifically described with reference to the embodiments shown below. However, the present invention is not limited to the embodiments shown below, and can be implemented in any way without departing from the scope of the claims and their equivalents.

[0180] In the following descriptions, unless otherwise specified, "%" and "parts" refer to quantities based on weight. Furthermore, unless otherwise specified, the operations described below are performed under normal temperature and pressure conditions.

[0181] [Evaluation Method]

[0182] (Linear transmittance of the neutral density coating)

[0183] The linear transmittance of light through the neutral density coating was measured using a spectrophotometer (V-570, manufactured by Japan Spectrophotometer Co., Ltd.) in the range of wavelengths above 400 nm and below 700 nm.

[0184] (Haze value)

[0185] The haze value of the neutral density film was measured using a haze meter (NDH4000 manufactured by Nippon Denshoku Kogyo Co., Ltd.) in accordance with JIS K7136.

[0186] (Thickness of the neutral density coating)

[0187] A portion (approximately 5mm square) of the neutral density film on the release PET film is peeled off. The height difference between the surface of the release PET film and the surface of the neutral density film is measured using a fine shape measuring device (Surfcorder ET-4000A, Kosaka Research Institute, Ltd.), and the thickness of the neutral density film is measured. When the neutral density film is formed on a substrate layer, the total thickness of the neutral density film and the substrate layer is measured using a micrometer (MDC-25MJ, Mitutoyo Corporation, Japan). The thickness of the neutral density film is then calculated by subtracting the thickness of the substrate layer.

[0188] (b* value in the CIE 1976 (L*, a*, b*) color space)

[0189] The measurements were taken using a colorimeter (SUGA Testing Machine Co., Ltd., "SC-T").

[0190] [Manufacturing Example 1]

[0191] (P1-1. Preparation of hydrogenated block copolymers (hydrogenated aromatic vinyl compounds-conjugated diene block copolymers))

[0192] Using styrene as an aromatic vinyl compound and isoprene as a chain-like conjugated diene compound, a hydride of a block copolymer (hydrogenated block copolymer) is prepared by the following steps. The prepared hydride of the block copolymer has a triblock structure in which polymer block [A] is bonded to both ends of polymer block [B].

[0193] In a stirred reactor that had undergone thorough nitrogen replacement, 256 parts of dehydrated cyclohexane, 25.0 parts of dehydrated styrene, and 0.615 parts of dibutyl ether were added. While stirring at 60°C, 1.35 parts of n-butyllithium (15% cyclohexane solution) were added to initiate polymerization. The reaction was then carried out at 60°C for 60 minutes with stirring. The polymerization conversion rate was 99.5% at this point (polymerization conversion rate was determined by gas chromatography; the same applies below).

[0194] Next, 50.0 parts of dehydrated isoprene were added, and the mixture was stirred for another 30 minutes at the same temperature. At this point, the polymerization conversion rate was 99%.

[0195] Next, 25.0 parts of dehydrated styrene were added, and the mixture was stirred at the same temperature for 60 minutes. At this point, the polymerization conversion rate was approximately 100%.

[0196] Next, 0.5 parts of isopropanol were added to the reaction solution to stop the reaction and obtain a solution (i) containing the block copolymer.

[0197] The block copolymer in the obtained solution (i) had a weight-average molecular weight (Mw) of 44,900 and a molecular weight distribution (Mw / Mn) of 1.03 (determined by gel permeation chromatography with tetrahydrofuran as solvent, converted to polystyrene values. The same applies below).

[0198] Next, solution (i) was transferred to a pressure reactor equipped with a stirrer. 4.0 parts of a silica-alumina supported nickel catalyst (E22U, 60% nickel loading; manufactured by Nichih Chemical Industry Co., Ltd.) and 350 parts of dehydrated cyclohexane were added to solution (i) and mixed. The reactor was purged with hydrogen, and hydrogen was supplied while the solution was stirred. The block copolymer was hydrogenated by performing a hydrogenation reaction at 170°C and 4.5 MPa for 6 hours, yielding a solution (iii) containing hydride (ii) of the block copolymer. The weight-average molecular weight (Mw) of hydride (ii) in solution (iii) was 45,100, and the molecular weight distribution (Mw / Mn) was 1.04.

[0199] After the hydrogenation reaction is complete, solution (iii) is filtered to remove the hydrogenation catalyst. Then, 1.0 part of a xylene solution containing 0.1 part of 6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetratert-butyldibenzo[d,f][1.3.2]dioxaphosphazene (Sumitomo Chemical Co., Ltd., "Sumilizer (registered trademark) GP", hereinafter referred to as "antioxidant A") as a phosphorus-based antioxidant is added to the filtered solution (iii) to dissolve it, yielding solution (iv).

[0200] Next, the solution (iv) was filtered through a ZetaPlus (registered trademark) 30H filter (manufactured by CUNO Inc., pore size 0.5μm~1μm), and then sequentially filtered through another metal fiber filter (pore size 0.4μm, manufactured by NICHIDAI Co., Ltd.) to remove minute solid components. Using a cylindrical concentrator (product name "CONTRO", manufactured by Hitachi, Ltd.), cyclohexane, xylene, and other volatile components used as solvents were removed from the filtered solution (iv) at a temperature of 260°C and a pressure of 0.001MPa or lower. Then, the solid components were extruded in a molten state into strands through a die directly connected to the aforementioned concentrator, cooled, and cut using a granulator to obtain 85 parts of granules (v) containing the hydride of the block copolymer and antioxidant A. The hydrogenated block copolymer in the obtained particles (v) has a weight-average molecular weight (Mw) of 45,000 and a molecular weight distribution (Mw / Mn) of 1.08. Furthermore, through... 1 The hydrogenation rate, as determined by H-NMR, was 99.9%.

[0201] A film-like test piece was made from this particle (v), and the glass transition temperature Tg was evaluated using the tanδ peak of a dynamic viscoelasticity measuring device, which yielded a result of 130℃.

[0202] (P2-1. Preparation of silane-modified hydrogenated block copolymers)

[0203] To obtain a mixture, 2.0 parts of vinyltrimethoxysilane and 0.2 parts of di-tert-butyl peroxide were added to 100 parts of the granules (v) obtained in (P1-1). This mixture was compounded using a biaxial extruder at a barrel temperature of 210°C and a residence time of 80–90 seconds. The compounded mixture was extruded and cut using a granulator to obtain granules (vi) of the silane-modified hydrogenated block copolymer. Film-like test pieces were prepared from these granules (vi), and the glass transition temperature (Tg) was evaluated using a dynamic viscoelasticity assay with the tanδ peak, yielding a result of 124°C.

[0204] [Example 1]

[0205] Mix 0.2 parts of an oil-soluble dye (Oil Black 860, Oriental Chemical Industry Co., Ltd.) with 100 parts of cyclohexane, and sonicate for 10 minutes to dissolve the dye in the cyclohexane. Then filter the solution through a 5 μm filter to obtain a dye solution. Add 20 parts of a resin containing a cyclic olefin ring-opening polymer hydride (Zeonor 1430, manufactured by Zeon Corporation, Japan) to 80 parts of the obtained dye solution and dissolve it to obtain a black coating solution containing the resin and the oil-soluble dye.

[0206] The coating liquid is applied to one side of the release PET film (manufactured by Higashiyama Film Co., Ltd., "HY-S10") using a coating applicator to form a coated film.

[0207] The coated film was dried in an oven at 100°C for 10 minutes to remove the solvent, resulting in an anti-gloss film. The thickness of the obtained anti-gloss film was measured using the above method, and the result was 6 μm.

[0208] The neutral density film was peeled off from the release PET film, and its optical properties were measured. The results showed a b* value of -7.2, linear transmittance of 75% at 480nm, 61% at 550nm, and 63% at 610nm, and a haze of 0.1%. The neutral density film demonstrated the ability to maintain image sharpness when assembled into a display.

[0209] [Example 2]

[0210] The thickness of the coating film was varied by adjusting the gap of the coater to achieve a neutral density film thickness of 10 μm. Except as described above, the process was the same as in Example 1 to obtain the neutral density film, and its thickness and optical properties were measured in the same manner as in Example 1. For the neutral density film, the b* value was -10, and the linear transmittance was 70% at 480 nm, 51% at 550 nm, and 53% at 610 nm. The haze was 0.1%. The neutral density film exhibits the property of not compromising image sharpness when assembled into a display.

[0211] In addition, a coating liquid is applied to one side of a resin film (ZF14 film manufactured by Zeon Corporation of Japan, with a thickness of 100 μm, which is a transparent film formed from a resin containing cyclic olefin polymer hydrogenates) that serves as a substrate layer and a thermoplastic resin layer, using a coating applicator to obtain a coated film.

[0212] The coated film was dried in an oven at 100°C for 10 minutes to remove the solvent, resulting in a laminate containing an anti-gloss film and a ZF14 film. The laminate has a configuration in which an anti-gloss film is directly disposed on one side of the ZF14 film, which is a light-transmitting thermoplastic resin layer.

[0213] The thickness of the neutral density film in the laminate was determined using the method described above, and the result was 10 μm. The haze of the obtained laminate was 0.1%, and almost no curling was observed in the laminate.

[0214] [Example 3]

[0215] 0.1 parts of an oil-soluble dye (Oil Black 860, Oriental Chemical Industry Co., Ltd.) were mixed with 33 parts of toluene and sonicated for 10 minutes to dissolve the oil-soluble dye in the toluene, thus obtaining a dye solution. 10 parts of silane-modified particles (vi) of the hydrogenated block copolymer used as a resin, manufactured in Manufacturing Example 1, were added to the obtained dye solution and dissolved to obtain a black coating liquid containing the resin and the oil-soluble dye.

[0216] The coating liquid is applied to one side of the release PET film (manufactured by Higashiyama Film Co., Ltd., "HY-S10") using a coating applicator to form a coated film.

[0217] The coated film was dried in an oven at 100°C for 10 minutes to remove the solvent, resulting in an anti-gloss film. The thickness of the obtained anti-gloss film was measured using the above method, and the result was 10 μm.

[0218] The neutral density film was peeled off from the release PET film, and its optical properties were measured. The results showed a b* value of -10, linear transmittance of 66% at 480nm, 50% at 550nm, and 50% at 610nm, and a haze of 0.1%. The neutral density film demonstrated the ability to maintain image sharpness when assembled into a display.

[0219] In addition, a coating liquid is applied to one side of a resin film (ZF14 film manufactured by Zeon Corporation of Japan, with a thickness of 50 μm, which is a transparent film formed from a resin containing cyclic olefin polymer hydrogenates) that serves as a substrate layer and a thermoplastic resin layer, using a coating applicator to obtain a coated film.

[0220] The coated film was dried in an oven at 100°C for 10 minutes to remove the solvent, resulting in a laminate containing an anti-gloss film and a ZF14 film. The laminate has a configuration in which an anti-gloss film is directly disposed on one side of the ZF14 film, which is a light-transmitting thermoplastic resin layer.

[0221] The thickness of the neutral density film in the laminate was determined using the method described above, and the result was 10 μm. The haze of the obtained laminate was 0.1%, and almost no curling was observed in the laminate.

[0222] [Example 4]

[0223] The thickness of the coating film was varied by adjusting the gap of the coater to achieve a neutral density film thickness of 15 μm. Except as described above, the process was the same as in Example 1 to obtain the neutral density film, and its thickness and optical properties were measured in the same manner as in Example 1. For the neutral density film, the b* value was -20, and the linear transmittance was 57% at 480 nm, 32% at 550 nm, and 36% at 610 nm. The haze was 0.1%. The neutral density film exhibits the property of not compromising image sharpness when assembled into a display.

[0224] In addition, a coating liquid is applied to one side of a resin film (ZF14 film manufactured by Zeon Corporation of Japan, with a thickness of 150 μm, which is a transparent film formed from a resin containing cyclic olefin polymer hydrogenates) which serves as a substrate layer and a thermoplastic resin layer, using a coating applicator to obtain a coated film.

[0225] The coated film was dried in an oven at 100°C for 10 minutes to remove the solvent, resulting in a laminate containing an anti-gloss film and a ZF14 film. The laminate has a configuration in which an anti-gloss film is directly disposed on one side of the ZF14 film, which is a light-transmitting thermoplastic resin layer.

[0226] The thickness of the neutral density film in the laminate was determined using the method described above, and the result was 10 μm. The haze of the obtained laminate was 0.1%, and almost no curling was observed in the laminate.

[0227] [Example 5]

[0228] Oil Black 803 (Oriental Chemical Industry Co., Ltd.) was used instead of Oil Black 860 as the oil-soluble dye. Furthermore, the coating thickness was varied by adjusting the gap of the coater to achieve a neutral density film thickness of 10 μm.

[0229] Except as described above, the same procedures were followed as in Example 1 to obtain the neutral density film, and the thickness and optical properties were measured in the same manner as in Example 1. For the neutral density film, the b* value was -2.8, and the linear transmittance was 69% at 480 nm, 64% at 550 nm, and 63% at 610 nm. The haze was 0.1%. The neutral density film exhibits the property of not compromising image sharpness when assembled into a display.

[0230] [Example 6]

[0231] Oil Black HBB (Oriental Chemical Industry Co., Ltd.) was used instead of Oil Black 860 as the oil-soluble dye. Furthermore, the coating thickness was varied by adjusting the gap of the coater to achieve a neutral density film thickness of 10 μm.

[0232] Except as described above, the same procedures were followed as in Example 1 to obtain the neutral density film, and the thickness and optical properties were measured in the same manner as in Example 1. For the neutral density film, the b* value was -9.8, and the linear transmittance was 75% at 480 nm, 61% at 550 nm, and 63% at 610 nm. The haze was 0.1%. The neutral density film exhibits the property of not compromising image sharpness when assembled into a display.

[0233] [Comparative Example 1]

[0234] A titanium oxide dispersion was prepared by adding 0.5 parts of dispersant "SOLSEPERSE21000" (Lubrizol Corporation, Japan) and 95 parts of cyclohexane to 4.5 parts of titanium oxide "13M-T" (particle diameter 67nm, manufactured by Mitsubishi Materials Corporation), and dispersing the mixture using a paintshaker.

[0235] Next, 70 parts of cyclohexane were added to 30 parts of the silane-modified particles (vi) of the hydrogenated block copolymer used as a resin in Manufacturing Example 1 to prepare a resin solution. 8.4 parts of a titanium oxide dispersion were then added to the solution to obtain a coating liquid containing 1.3% titanium oxide particles relative to the resin.

[0236] The coating liquid containing titanium oxide particles is applied to one side of a release PET film (manufactured by Higashiyama Film Co., Ltd., "HY-S10") using a coating applicator to form a coated film.

[0237] The coated film was dried in an oven at 100°C for 10 minutes to remove the solvent, resulting in an anti-gloss film. The thickness of the obtained anti-gloss film was measured using the above method, and the result was 11 μm.

[0238] The neutral density film was peeled off from the release PET film, and its optical properties were measured. The results showed a b* value of -4, linear transmittance of 73% at 480nm, 71% at 550nm, and 69% at 610nm, and a haze of 8%. The neutral density film exhibits the characteristic of impairing image sharpness when assembled into a display.

[0239] The results are shown in the table below.

[0240] In the table below, the abbreviations have the following meanings.

[0241] "1430": "Zeonor 1430" made by Zeon Co., Ltd. of Japan

[0242] "Si-modified product": silane-modified product of the hydrogenated block copolymer manufactured in Example 1.

[0243] The colorant concentration item in the table shows the percentage (%) of colorant (oil-soluble dye or titanium oxide particles) in the coating solution relative to the resin.

[0244] [Table 1]

[0245]

[0246] Based on the above results, the following points can be determined.

[0247] The haze of the neutral density film of Comparative Example 1, which does not contain oil-soluble dyes, is significantly higher than that of the neutral density films of Examples 1-6.

[0248] On the other hand, the light-reducing film of the embodiment has low haze and the ability to maintain image sharpness when assembled into a display.

[0249] Explanation of reference numerals in the attached figures

[0250] 100: Layered body;

[0251] 110: Neutral density coating;

[0252] 120: Thermoplastic resin layer;

[0253] 120U: Surface;

[0254] 200: Layered body;

[0255] 210: First neutral density film;

[0256] 220: Thermoplastic resin layer;

[0257] 220U: Surface;

[0258] 220D: Surface;

[0259] 230: Second neutral density film.

Claims

1. A neutral density coating comprising a resin and an oil-soluble dye, The thickness of the neutral density film is greater than 1 μm and less than 100 μm. The neutral density film has a b* value less than 0 in the CIE 1976 (L*, a*, b*) color space. The linear transmittance of the light-reducing film at a wavelength of 550 nm is above 25% and below 75%. The light-reducing film has a single-layer structure.

2. The neutral density film according to claim 1, wherein, The oil-soluble dye is present in a proportion of 0.01% by weight or more and less than 2% by weight relative to the resin.

3. The neutral density film according to claim 1 or 2, wherein, The resin comprises a polymer with an alicyclic structure.

4. The neutral density film according to claim 3, wherein, The alicyclic polymer is a cyclic olefin polymer or its hydride.

5. The light-reducing film according to claim 1 or 2, wherein the linear transmittance of light with a wavelength of 550 nm is 25% or more and 64% or less.

6. The light-reducing film according to claim 1 or 2 has a higher linear transmittance of light with a wavelength of 480 nm than that with a wavelength of 610 nm.

7. A laminate comprising a light-transmitting thermoplastic resin layer and a light-reducing film according to any one of claims 1 to 6, wherein the light-reducing film is disposed directly on the surface of the thermoplastic resin layer.

8. A method for manufacturing an anti-light coating, comprising the method for manufacturing an anti-light coating according to any one of claims 1 to 6, including: The process of preparing a coating solution comprising the resin, the oil-soluble dye, and the solvent. The process of applying the coating liquid onto the surface of a substrate layer to form a coating film, and The process of removing the solvent from the coated film to obtain the neutral density film.

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