JP2007188045A - Antireflection transfer film and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antireflection transfer film which is excellent in antireflection performance and has high thickness precision and uniformity of each layer. <P>SOLUTION: The method for manufacturing the antireflection transfer film comprises the steps of: forming a low refractive index layer and a high refractive index layer successively on a base material film directly or via a releasing layer to form a layered sheet; and of heating/stretching the layered sheet to control the thickness of the low refractive index layer at the least and that of the high refractive index layer. As a result, the thickness of each of the low refractive index layer and the high refractive index layer is controlled with high precision so as to become extremely thin, and the uniformity of each layer is improved. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an antireflection transfer film capable of transferring an antireflection optical function to a substrate, and in particular, various displays such as word processors, computers and televisions, polarizing plates used in liquid crystal display devices, and transparent plastics. To add anti-reflection function to the surface of various transparent substrates such as sunglasses lenses, lenses with prescription glasses, optical lenses such as camera finder lenses, covers for various instruments, window glass for cars and trains, etc. The present invention relates to a suitable antireflection transfer film and a manufacturing method thereof.

  Transparent substrates such as glass and plastic are used for curved mirrors, mirrors such as rearview mirrors, goggles, window glass, displays such as personal computers and word processors, and various other commercial displays. When observing visual information such as objects, characters, and figures through these transparent substrates, or when observing images from mirrors from the reflective layer through the transparent substrate, the necessary visual information is reflected on the surface of the transparent substrate. There was a problem that it was difficult to read.

  Therefore, conventionally, as a technique for preventing light reflection on the surface of the transparent substrate, for example, a method of applying an antireflection coating on the surface of the transparent substrate, an ultrathin film such as MgF2 having a thickness of about 0.1 μm, or a metal deposition film on the surface of the transparent substrate A method of applying an ionizing radiation curable resin on the surface of a plastic lens, etc., and forming a SiOx or MgF2 film thereon by vapor deposition, or a low refractive index on a cured film of an ionizing radiation curable resin A method of forming a coating film has been proposed.

Recently, a method has been proposed in which an optical thin film layer is provided in multiple layers on the surface of a base film, and the spectral minimum reflectance of the film is lowered by utilizing the light interference effect.
Furthermore, an antireflection film having a laminated structure in which a plurality of materials having different reflectivities are laminated to provide an antireflection effect over a wide wavelength region has been proposed. For example, in Patent Document 1, in an antireflection multilayer film in which a high refractive index material film and a low refractive index material film are laminated, a high refractive index material is interposed between the high refractive index material film and the low refractive index material film. An antireflection multilayer film has been proposed in which a mixed film of a low refractive index material is provided to improve adhesion.

JP 2003-279704 A

When an optical thin film is formed by laminating a plurality of layers, the management accuracy of the thickness of each layer is required. For example, in the case of a multi-layered optical thin film that utilizes the interference effect of light, if the spectral minimum reflectance is lowered locally in a specific wavelength region due to light interference, the value of the spectral reflectance in other wavelength regions inevitably becomes smaller. Therefore, in order to obtain a sufficient antireflection effect, it has been necessary to control the thickness of each layer with high accuracy to narrow the wavelength region where the effect of each layer is exhibited as much as possible.
In the case of an optical thin film layer having a multilayer structure, an antireflection effect is obtained, but the process is unstable, so that there is a problem that it is difficult to uniformize a color developed by light interference.
In addition, when laminating a plurality of materials having different refractive indices, the low refractive index layer is formed from a hardly adhesive resin such as a fluorine-based resin or a silicone-based resin. There was a problem that delamination of the film was likely to occur. This point was one of the important issues as an antireflection film used for liquid crystal displays and the like that are particularly required to be durable.

  Therefore, the present invention provides an antireflection transfer film having a laminated structure including at least a base film layer, a low refractive index layer, and a high refractive index layer, and is excellent in antireflection performance and has high thickness accuracy and uniformity of each layer, preferably Is intended to provide an antireflection transfer film having excellent adhesion to a low refractive index layer.

  The present invention provides an antireflection method comprising a step of forming a laminated sheet by sequentially laminating a low refractive index layer and a high refractive index layer on a base film, directly or via a release layer, and heating and stretching the laminated sheet. A method for producing an antireflection transfer film characterized by controlling at least the thickness of each of a low refractive index layer and a high refractive index layer by heating and stretching, and a method for producing the transfer film. An antireflection transfer film is proposed.

By manufacturing the antireflection transfer film in this way, the thickness of each of the low refractive index layer and the high refractive index layer can be controlled extremely thinly and with high accuracy, and the uniformity of each layer can be increased. It is particularly suitable for applications that require accurate and high-quality optical characteristics.
Moreover, since a series of processes are performed in a dry environment and no solvent is used, the environment is excellent.

In the above production method, the antireflective transfer film may be produced by forming the high refractive index layer from a thermosetting resin or an ultraviolet curable resin, and curing the high refractive index layer by heating or ultraviolet irradiation after heating and stretching. it can. If manufactured in this way, the resin of the high refractive index layer is soft with little uncrosslinked structure in the stage before stretching, and therefore, it is easy to be compatible with the resin of the low refractive index layer and promotes interface wetting at the time of stretching. The adhesion between the low refractive index layer and the high refractive index layer can be increased.
The timing for curing the high refractive index layer can be appropriately selected depending on the application. For example, the high refractive index layer may be cured immediately after heating and stretching, or may be cured simultaneously with heating during transfer, for example, without being cured by heating. You may make it make it. Further, it can be cured immediately after the heat stretching but not completely cured (semi-cured state), and can be completely cured simultaneously with the heating at the time of transfer.

  The present invention further provides a method for producing an antireflection transfer film, in which a low refractive index layer, a high refractive index layer and a primer layer are laminated on a first base film directly or via a release layer, In addition, a method for producing an antireflection transfer film, comprising a step of laminating a second base film directly or via a release layer to form a laminated sheet and heating and stretching the sheet, which is heated and stretched The present invention also proposes a method of manufacturing an antireflection transfer film, wherein the thicknesses of at least the low refractive index layer and the high refractive index layer are controlled.

  When forming a laminated sheet, the wettability is partially poor at the interface between the low-refractive index layer and the high-refractive index layer, pinholes occur at the repelled part, and there is no problem with the antireflection characteristics over the entire surface. There was a possibility that the characteristic was not. By providing a primer layer as described above, interfacial wettability and adhesion between the primer layer and the high refractive index layer are improved, and there is no repelling, so the high refractive index does not partially differ in thickness. A layer can be formed and it can prevent that a characteristic is not partially. Furthermore, by adhering to an adherend to be described later via a primer layer, it is possible to adhere the adherend to the adherend.

  Moreover, by providing the first and second substrate films on both sides of the laminated sheet, the stretchability is stabilized, and particularly when both films are made of the same material, the stretchability is further stabilized. When the high refractive index layer having relatively high volatility is cured, volatilization due to stretching heating can be suppressed.

  The laminated sheet is formed by sequentially laminating a low refractive index layer, a high refractive index layer and a primer layer on the first base film directly or via a release layer, and further directly or on the release layer. The laminated sheet can be formed by laminating the second base film.

  Moreover, the process of forming the 1st laminated body which laminated | stacked the low-refractive-index layer directly or through the mold release layer on the 1st base film, and a direct or mold release layer on the 2nd base film. A step of forming a second laminate in which the primer layer and the high refractive index layer are sequentially laminated, and the low refractive index layer of the first laminate and the high refractive index layer of the second laminate are opposed to each other. Thus, a laminated sheet can be formed.

  If the wettability is poor due to the difference in polarity between the high refractive index layer and the low refractive index layer, the low refractive index layer and the high refractive index layer are separately formed and laminated in this way. Can be good.

  In addition, the process of forming the 1st laminated body which laminated | stacked the low-refractive-index layer on the 1st base film directly or through the mold release layer, and the direct or mold release layer on the 2nd base film The step of forming the second laminated body in which the primer layer is laminated, and the low refractive index layer of the first laminated body and the primer layer of the second laminated body are inserted between the nip rolls so as to face each other, Forming the laminated sheet also in a method including a step of forming a laminated sheet by forming a high refractive index layer by forming a bank between the low refractive index layer of the laminated body and the primer layer of the second laminated body Can do.

  By forming the high refractive index layer in this way, the wettability between the high refractive index layer and the low refractive index layer or between the high refractive index layer and the primer layer can be improved.

  For example, as shown in FIG. 3, the bank formation means that the low refractive index layer of the first laminate and the primer layer of the second laminate are inserted between the nip rolls so as to face each other, and inserted between the nip rolls. First, a liquid resin that forms a high refractive index layer is stored at the joint of the low refractive index layer and the primer layer, and the liquid resin is poured between the low refractive index layer and the primer layer little by little. In this method, the laminate and the second laminate are pressed with a nip roll and a high refractive index layer is formed.

  The low refractive index layer of the antireflection transfer film produced by the above production method is preferably made of a thermoplastic fluororesin, and the primer layer is made of a thermoplastic resin or a thermosetting resin that is cured at a temperature higher than the heating stretching temperature. It is preferable.

  The antireflection transfer film obtained by the present invention includes, for example, a transparent resin film, various displays such as word processors, computers and televisions, polarizing plates used in liquid crystal display devices, sunglasses lenses made of transparent plastics, lenses for prescription glasses. , Optical lenses such as camera finder lenses, covers for various instruments, window glass for automobiles and trains, etc., on the surface of various transparent substrates, i.e., adherends, via an intermediate layer made of an adhesive or hard coat agent, The low refractive index layer and the high refractive index layer of the antireflection transfer film, or the low refractive index by superimposing the high refractive index layer or primer layer on the intermediate layer through an intermediate layer made of an adhesive or a hard coat agent. By transferring and laminating a layer, a high refractive index layer and a primer layer, that is, by transfer processing, for example, an antireflection film or It is possible to form the antireflection display.

  In general, "film" is a thin flat product whose thickness is extremely small compared to the length and width and whose maximum thickness is arbitrarily limited, and is usually supplied in the form of a roll. (Japanese Industrial Standard JISK6900), and “sheet” generally refers to a product that is thin according to the definition in JIS, and usually has a thickness that is small instead of length and width. However, since the boundary between the sheet and the film is not clear and it is not necessary to distinguish the two in terms of the present invention, in the present invention, even when the term “film” is used, the term “sheet” is included and the term “sheet” is used. In some cases, “film” is included.

  Embodiments of the present invention will be described in detail below, but the scope of the present invention is not limited to the embodiments described below.

In the present invention, the expression “main component” includes the intention to allow other components to be contained within a range that does not interfere with the function of the main component, unless otherwise specified. Is not specified, but the main component (when two or more components are main components, the total amount thereof) is 50% by mass or more, preferably 70% by mass or more, particularly preferably in the composition. Occupies 90% by mass or more (including 100%).
Further, when “X to Y” (X and Y are arbitrary numbers) is described, “X to Y” is intended unless otherwise specified, and “it is preferably larger than X and smaller than Y”. Includes intentions.

  In the first embodiment, a low refractive index layer and a high refractive index layer are sequentially formed on a base film directly or via a release layer to form a laminated sheet as shown in FIG. A method for manufacturing an antireflection transfer film by a manufacturing method including a step of controlling the thickness of each layer will be described.

(Base film)
Although there is no restriction | limiting in particular as a base film, As long as it has the molecular weight which can be self-supported as a film, a physical property, etc. and it has the coupling | bonding aspect which can be extended | stretched by heating, it can be used.
The base film is composed mainly of at least one resin selected from polyethylene resin, polypropylene resin, polyester resin, polyamide resin, polystyrene resin, and polyurethane resin. It is preferable in terms of stretchability, adhesion to a low refractive index layer, transfer processability, and the like. If these properties can be improved as long as they are not impaired, these resins may be homo- or copolymerized. Moreover, the blend with other resin may be sufficient. Furthermore, additives such as a plasticizer, a stabilizer and a lubricant may be included.

(Release layer)
The release layer is preferably a layer that maintains slight adhesion with the low refractive index layer until transfer processing and can be easily peeled off during transfer processing. From this point of view, the release layer may be a base film coated with a release agent composed of a silicone-based, fluorine-based, or long-chain alkyl-based composition having a release effect, or a silicone having a release effect. A release agent having a composition such as a system, fluorine, or long-chain alkyl, or a blend of a release resin obtained by graft-modifying the component on a polymer may be used so that the active ingredient is bleed on the surface. In some cases, it is not necessary to provide a release layer in particular because of adhesion with the low refractive index layer.

(Low refractive index layer)
The low refractive index layer is not particularly limited, but can be used as long as it has a molecular weight, physical properties, etc. that can be self-supported as a film, and has a bonding mode that can be stretched by heating. However, a fluororesin having a refractive index of 1.45 or less, particularly preferably 1.35 to 1.42 and a softening temperature of 200 ° C. or less, particularly preferably 80 to 180 ° C. is preferable. When the refractive index exceeds 1.45, the antireflection property is impaired, which is not preferable. On the other hand, if the softening temperature exceeds 200 ° C., the stretchability is impaired and the thickness accuracy is lowered, which is not preferable.
Among them, tetrafluoroethylene-hexafluoropropylene copolymer, ethylene-tetrafluoroethylene copolymer, vinylidene fluoride polymer, tetrafluoroethylene-vinylidene fluoride copolymer, hexafluoropropylene-vinylidene fluoride copolymer, And at least one fluororesin selected from the group consisting of tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer, stretchability, adhesion to substrate film / high refractive index layer, transfer processability In terms of stretchability of the high refractive index layer, it is more preferable.
Moreover, it is preferable that the viscosity in extending | stretching temperature is 0.2 or more by the ratio with respect to the viscosity of resin of a base film, Most preferably, it is 0.3-3. If it is less than 0.2, it diffuses into the resin of the adjacent base film at the time of stretching, and the antireflection property is impaired, which is not preferable.

(High refractive index layer)
Although there is no restriction | limiting in particular in a high refractive index layer, if it has the coupling | bonding state which can be extended | stretched by heating, it can be used. However, a thermosetting resin or an ultraviolet (UV) curable resin having a refractive index of 1.6 or more, particularly preferably 1.62-1.70 is preferable. If the refractive index is cut below 1.6, the antireflection characteristics are impaired, which is not preferable.
Thermosetting resins include curing agents based on epoxy resins, halogenated epoxy resins, bisphenol S epoxy resins, phenol resins, aromatic polyester resins, aliphatic polyamide resins, aromatic polyamide resins, urethane resins, melamine resins, Examples include a compound formulated with a catalyst or the like.
In addition, as UV curable resins, divinylbenzene, diallyl phthalate, acryloyl morpholine, polyfunctional thiol, mercapto or / and isothiocyanate or / and thiophene or / and sulfide or / and thioglycolic acid ester based polyfunctional Thiols, polyfunctional vinyls, polyfunctional allyls, polyfunctional acrylates, aliphatic urethane acrylates, aromatic urethane acrylates, bisphenol A epoxy acrylates, tetrabromobisphenol A epoxy acrylates and other aromatic rings, and halogens such as Br, I, and Cl Examples thereof include a compound in which an acrylate monomer, a polyfunctional acrylate crosslinking agent, an acrylate oligomer, a photoinitiator and the like are formulated based on a compound containing a chemical element, S, N, P, or the like.
Such a thermosetting resin or ultraviolet (UV) curable resin is more preferable in terms of stretchability, adhesion to a low refractive index layer, curability, and transfer processability.
Blends of resins such as oligomers or polymers such as non-curing acrylic, polyester, and polystyrene are also possible.

(Production method)
The base film may be formed by a generally known thermoplastic molding method. Of these, extrusion, calendering and the like are preferable in terms of the efficiency of continuous processing.

Low refractive index layer is known by air coating, blade coating, knife coating, reverse coating, transfer roll coating, gravure roll coating, kiss coating, cast coating, spray coating, slot orifice coating, calendar coating, which are conventionally known by solution coating processing It is also possible to form a low refractive index layer by drying the solvent after coating on the substrate film by electrodeposition coating, dip coating, die coating, etc., but by calendering, extrusion or extrusion coating, It is also possible to laminate a low refractive index layer on the base film by co-extrusion with the film, and this method is preferable from the viewpoint of dealing with harmful effects on the human body and the environment and the efficiency of continuous processing.

  Although the high refractive index layer can also be formed on the low refractive index layer by the solution coating process as described above, extrusion coating, coextrusion coating with the low refractive index layer, base film and low refractive index layer Adopting a method of laminating a high refractive index layer on a low refractive index layer, such as by co-extrusion, is preferable from the standpoint of dealing with adverse effects on human bodies and the environment and the efficiency of continuous processing.

  As described above, a low refractive index layer and a high refractive index layer are sequentially laminated on the base film directly or via a release layer to form a laminated sheet, and then this is heated and stretched.

At this time, the heating temperature may be set to a temperature at which the base film, the low refractive index layer and the high refractive index layer melt and the base film does not fall off. What is necessary is just to perform by hot oil, hot air, a hot roll, infrared rays, etc.
The stretching subsequent to heating may be either uniaxial stretching or biaxial stretching, but biaxial stretching is preferred. The stretching means may be a known means such as a roll method, a tenter method, or a tubular method.
The draw ratio depends on the stretch characteristics of the base film and the thickness to be controlled. However, when the base film is mainly composed of polyester, polyamide, etc., about 10 times in each axial direction, and is composed mainly of polyethylene, polypropylene, etc. In some cases, it is preferable that the axial direction is 20 times or more in each axial direction.
After stretching, the film may be wound after being cooled with cold air or the like.

In the present invention, the low refractive index layer and the high refractive index layer are sequentially laminated on the base film in this way to form a laminated sheet, and then at least the low refractive index layer and the high refractive index layer are heated and stretched. The thickness of each layer is controlled. That is, by adjusting the thickness and the draw ratio of the low refractive index layer and the high refractive index layer before stretching, the thickness of each layer after stretching, particularly the low refractive index layer and the high refractive index layer, is controlled within a predetermined range.
Specifically, for example, the thickness before stretching of the low refractive index layer and the high refractive index layer is adjusted to an optimum thickness in the range of about 1 μm to 4 μm to form a laminated sheet, and the stretching ratio is adjusted for this. The thickness of the low refractive index layer and the high refractive index layer is adjusted to about 0.1 μm (that is, 0.05 μm to 0.2 μm) by heating and stretching.
For the base film, the processing thickness in calendering / extrusion may be controlled in accordance with the draw ratio from the optimum thickness in the antireflection transfer film configuration due to transfer processability and the like.

  Since the antireflective transfer film obtained as described above is in a state where the high refractive index layer is not cured, it is necessary to cure the high refractive index layer by heating or ultraviolet irradiation. However, the timing for curing the high refractive index layer may be appropriately selected depending on the application. For example, the high refractive index layer may be cured immediately after heating and stretching, or may be cured without heating and cured, for example, simultaneously with heating during transfer. It may be cured. Further, it can be cured immediately after the heat-stretching but not completely cured (semi-cured state), for example, it can be completely cured simultaneously with the heating at the time of transfer.

(Use)
The antireflective transfer film thus obtained is formed on the adherend by interposing an intermediate layer made of an adhesive or a hard coat agent with a high refractive index layer superimposed on the intermediate layer. A low refractive index layer and a high refractive index layer can be transferred and laminated.
More specifically, an adhesive or a hard coat agent is applied on an adherend such as a film or a display panel, and after application or simultaneously with application, a high refractive index layer is superimposed on the application surface and the base film is peeled off. An antireflection film or an antireflection display can be formed by transferring and laminating a high refractive index layer and a low high refractive index layer on an adherend.

  At this time, as the adhesive or the hard coat agent, general-purpose agents for the purpose of adhesion to an adherend, heat resistance, transparency, hardness, antistatic properties, and the like can be applied. Specifically, acrylic adhesives, urethane adhesives, epoxy adhesives, polyester adhesives and other main agents or adhesives composed of main agents and curing agents, acrylic adhesives, silicone adhesives, polyisobutylene adhesives Adhesives such as adhesives, thermosetting acrylic hard coating agents, UV curable acrylic hard coating agents, thermosetting silicone hard coating agents, UV curable silicone hard coating agents, etc., mainly polyfunctional monomers / oligomers and curing catalysts, Examples thereof include a hard coat agent comprising an antistatic agent.

The adhesive or hard coat agent may be applied to the adherend side, or may be applied to the high refractive index layer of the antireflection transfer film, and a known coating method is used as the method. can do.
Next, the high refractive index layer of the antireflection transfer film on the opposite side or the adherend is laminated with a roll, a press or the like while being pressed and heated, and wetted by heat melting, heat curing, UV curing, or heating UV curing. Accelerates curing and completes transfer processing.

  As the adherend, various plastic films / sheets / plates, glass, metal and the like can be applied without particular limitation, and the adhesiveness can be improved by electric discharge machining, etching processing, primer coating processing, or the like in advance. In particular, it can be processed into a cellulose triacetate film, PET film, polycarbonate film, polycyclic olefin film, etc. and applied as an antireflection film for display, or processed into glass etc., and applied to an antireflection display. .

  In the second embodiment, a low refractive index layer, a high refractive index layer and a primer layer are laminated on the first base film directly or via a release layer, and further, a direct or release layer is further formed thereon. Then, after the second base film is laminated to form a laminated sheet as shown in FIG. 2, a method for producing an antireflection transfer film by heating and stretching it will be described.

(First and second base film)
As the first and second substrate films, the same resin as the substrate film of the first embodiment can be used.
The first and second base films may be of the same type or different types, but the same type is preferred from the viewpoint of stretchability.

(Release layer)
The release layer can be formed in the same manner as the release layer of the first embodiment.

(Low refractive index layer)
The low refractive index layer is not particularly limited, but can be used as long as it has a molecular weight, physical properties, etc. that can be self-supported as a film, and has a bonding mode that can be stretched by heating, and particularly has a refractive index of 1.45. Hereinafter, a resin having a softening temperature of 1.35 to 1.42 and a softening temperature of 200 ° C. or less, particularly preferably 80 to 180 ° C., particularly a thermoplastic fluororesin is preferable. When the refractive index exceeds 1.45, the antireflection property is impaired, which is not preferable. On the other hand, if the softening temperature exceeds 200 ° C., the stretchability is impaired and the thickness accuracy is lowered, which is not preferable.
Among them, tetrafluoroethylene-hexafluoropropylene copolymer, ethylene-tetrafluoroethylene copolymer, vinylidene fluoride polymer, tetrafluoroethylene-vinylidene fluoride copolymer, hexafluoropropylene-vinylidene fluoride copolymer, And at least one fluororesin selected from the group consisting of tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer, stretchability, adhesion to substrate film / high refractive index layer, transfer processability In terms of stretchability of the high refractive index layer, it is more preferable.
Moreover, it is preferable that the viscosity in extending | stretching temperature is 0.2 or more by the ratio with respect to the viscosity of resin of a base film, Most preferably, it is 0.3-3. If it is less than 0.2, it diffuses into the resin of the adjacent base film at the time of stretching, and the antireflection property is impaired, which is not preferable.

(High refractive index layer)
The high refractive index layer is not particularly limited, but can be used as long as it has a bonding state that can be liquefied and stretched by heating not exceeding 200 ° C., and can be used as a thermosetting resin having a refractive index of 1.58 or more. Ultraviolet (UV) curable resins are preferred. If the refractive index is less than 1.58, the antireflection properties are impaired, which is not preferable.
Thermosetting resins include curing agents based on epoxy resins, halogenated epoxy resins, bisphenol S epoxy resins, phenol resins, aromatic polyester resins, aliphatic polyamide resins, aromatic polyamide resins, urethane resins, melamine resins, Examples include a compound formulated with a catalyst or the like.
In addition, as UV curable resins, divinylbenzene, diallyl phthalate, acryloyl morpholine, polyfunctional thiol, mercapto or / and isothiocyanate or / and thiophene or / and sulfide or / and thioglycolic acid ester based polyfunctional Thiols, polyfunctional vinyls, polyfunctional allyls, polyfunctional acrylates, aliphatic urethane acrylates, aromatic urethane acrylates, bisphenol A epoxy acrylates, tetrabromobisphenol A epoxy acrylates and other aromatic rings, and halogens such as Br, I, and Cl Examples thereof include a compound in which an acrylate monomer, a polyfunctional acrylate crosslinking agent, an acrylate oligomer, a photoinitiator and the like are formulated based on a compound containing a chemical element, S, N, P, or the like.
Such a thermosetting resin or ultraviolet (UV) curable resin is more preferable in terms of stretchability, adhesion to a low refractive index layer, curability, and transfer processability.
Blends of resins such as oligomers or polymers such as non-curing acrylic, polyester, and polystyrene are also possible.

(Primer layer)
The primer layer is not particularly limited, but can be used as long as it is solid at normal temperature and has a binding state that can be liquefied and stretched by heating not exceeding 200 ° C., and can be cured sufficiently with a thermoplastic resin or stretched. A thermosetting resin that does not progress in the process and cures by heating during transfer processing is preferable.
As the thermoplastic resin, a polyester resin, an acrylic resin, a polyamide resin, a polyurethane resin, a polycarbonate resin, a polyolefin resin, an EVA resin, or the like can be used, and a copolymer blend or a functional group modification thereof can also be used. A silane coupling agent, a phenol resin, an adhesion promoting additive such as polyethyleneimine, and the like can be added to these.
The thermosetting resin is a compound in which the curing temperature is adjusted to 200 ° C. or more by mixing a curing agent, a catalyst, an adhesion promoting additive, etc. into an epoxy resin, phenol resin, polyester resin, polyamide resin, urethane resin, melamine resin, etc. Things can be used.

(Production method)
A laminated sheet can be formed by sequentially laminating the above layers and films.
The first substrate film may be formed by a generally known thermoplastic molding method. Of these, extrusion, calendering and the like are preferable in terms of the efficiency of continuous processing.
The side of the first base film on which the low refractive index layer is laminated is preferably made to have a small surface roughness so that the thickness of these layers does not fluctuate due to the surface roughness and the antireflection properties are not impaired. The point average roughness Rz is preferably 10 μm or less.

  Low refractive index layer is known by air coating, blade coating, knife coating, reverse coating, transfer roll coating, gravure roll coating, kiss coating, cast coating, spray coating, slot orifice coating, calendar coating, which are conventionally known by solution coating processing It is also possible to form a low refractive index layer by drying the solvent after coating on the substrate film by electrodeposition coating, dip coating, die coating, etc., but by calendering, extrusion or extrusion coating, It is also possible to laminate a low refractive index layer on the first substrate film by coextrusion with the film, and this method is preferable in terms of dealing with harmful effects on the human body and the environment and the efficiency of continuous processing.

  The high refractive index layer can be formed on the low refractive index layer by the solution coating process as described above, but the low refractive index layer can be formed by extrusion coating, co-extrusion with the base film and the low refractive index layer, or the like. It is also possible to laminate a high refractive index layer on the layer, which is preferable in terms of dealing with harmful effects on the human body and the environment and the efficiency of continuous processing.

  The primer layer can be formed on the high refractive index layer by the solution coating process as described above. However, the primer layer may be formed by extrusion coating, coextrusion coating with a base film, and coexistence with the base film and the high refractive index layer. It is also possible to laminate a primer layer on the high refractive index layer by extrusion or the like, which is preferable in terms of dealing with harmful effects on the human body and the environment and the efficiency of continuous processing.

The molding of the second base film may be performed by a generally known thermoplastic molding method. Of these, extrusion, calendering and the like are preferable in terms of the efficiency of continuous processing.
The side on which the primer layer of the second substrate film is laminated preferably has a surface roughness that is small so that the thickness of these layers does not fluctuate due to the surface roughness and the antireflection properties are not impaired. The roughness Rz is preferably 10 μm or less.

  As described above, a low refractive index layer, a high refractive index layer and a primer layer are sequentially laminated on the first base film directly or via a release layer, and further, directly or on the release layer. Then, the second base film is laminated to form a laminated sheet, which is then stretched by heating.

At this time, the heating temperature may be set to a temperature at which the first and second base film, the low refractive index layer, the high refractive index layer, and the primer layer are melted and the base film is not dropped. The heating means may be performed by hot water, hot oil, hot air, hot roll, infrared rays, or the like.
The stretching subsequent to heating may be either uniaxial stretching or biaxial stretching, but biaxial stretching is preferred. The stretching means may be a known means such as a roll method, a tenter method, or a tubular method.
The draw ratio depends on the stretch characteristics of the base film and the thickness to be controlled. However, when the base film is mainly composed of polyester, polyamide, etc., about 10 times in each axial direction, and is composed mainly of polyethylene, polypropylene, etc. In some cases, it is preferable that the axial direction is 20 times or more in each axial direction.
After stretching, the film may be wound after being cooled with cold air or the like.

In the present invention, after laminating the low refractive index layer, the high refractive index layer, the primer layer on the first base film in this way, and further laminating the second base film thereon to form a laminated sheet, By heating and stretching this, at least the thicknesses of the low refractive index layer and the high refractive index layer are controlled. That is, by adjusting the thickness and the draw ratio of the low refractive index layer and the high refractive index layer before stretching, the thickness of each layer after stretching, particularly the low refractive index layer and the high refractive index layer, is controlled within a predetermined range.
Specifically, for example, the thickness before stretching of the low refractive index layer and the high refractive index layer is adjusted to an optimum thickness in the range of about 1 μm to 4 μm to form a laminated sheet, and the stretching ratio is adjusted for this. The thickness of the low refractive index layer and the high refractive index layer is adjusted to about 0.1 μm (that is, 0.05 μm to 0.2 μm) by heating and stretching.
For the first and second base films, the processing thickness in calendering and extrusion may be controlled in accordance with the draw ratio from the optimum thickness in the antireflection transfer film configuration due to transfer processability and the like.

  Since the antireflective transfer film obtained as described above is in a state where the high refractive index layer is not cured, it is necessary to cure the high refractive index layer by heating or ultraviolet irradiation. However, the timing for curing the high refractive index layer may be appropriately selected depending on the application. For example, the high refractive index layer may be cured immediately after heating and stretching, or may be cured without heating and cured, for example, simultaneously with heating during transfer. It may be cured. Further, it can be cured immediately after the heat-stretching but not completely cured (semi-cured state), for example, it can be completely cured simultaneously with the heating at the time of transfer.

  In the above, the low refractive index layer, the high refractive index layer, and the primer layer are sequentially laminated on the first base film directly or via the release layer, and further, directly or release on the laminated sheet. Although the second base film is laminated through the layers, it can be formed as follows.

  A first laminate is formed by laminating a low refractive index layer directly or via a release layer on the first substrate film, and a primer directly or via a release layer on the second substrate film. A second laminated body in which a layer and a high refractive index layer are sequentially laminated, and a low refractive index layer of the first laminated body and a high refractive index layer of the second laminated body are laminated so as to face each other. it can.

  The first laminate and the second laminate are laminated on the low refractive index layer immediately after the material of the high refractive index layer is applied with a bar coater, and pressed by a pressing means such as a press or a nip roll. Can be done.

  Moreover, the 1st laminated body which laminated | stacked the low-refractive-index layer on the 1st base film directly or through the mold release layer is formed, and on the 2nd base film directly or through the mold release layer The second laminate is formed by laminating the primer layer, and is inserted between the nip rolls so that the low refractive index layer of the first laminate and the primer layer of the second laminate face each other. A high refractive index layer can be formed by bank formation between the index layer and the primer layer of the second laminate.

  At this time, the thickness of the high refractive index layer can be controlled by appropriately determining nip pressure, speed, resin viscosity nip roll temperature, and the like.

(Use)
The antireflection transfer film thus obtained has a low refractive index of the antireflection transfer film by overlaying a primer layer on the adherend via an intermediate layer made of an adhesive or a hard coat agent. The refractive index layer and the high refractive index layer can be transferred and laminated.
More specifically, an adhesive or a hard coat agent is applied on an adherend such as a film or a display panel, and after or simultaneously with the application, a primer layer is overlaid on the coated surface and the base film is peeled off. An antireflection film or an antireflection display can be formed by transferring and laminating a primer layer, a high refractive index layer and a low high refractive index layer on the adherend.

  At this time, as the adhesive or the hard coat agent, general-purpose agents for the purpose of adhesion to an adherend, heat resistance, transparency, hardness, antistatic properties, and the like can be applied. Specifically, acrylic adhesives, urethane adhesives, epoxy adhesives, polyester adhesives and other main agents or adhesives composed of main agents and curing agents, acrylic adhesives, silicone adhesives, polyisobutylene adhesives Adhesives such as adhesives, thermosetting acrylic hard coating agents, UV curable acrylic hard coating agents, thermosetting silicone hard coating agents, UV curable silicone hard coating agents, etc., mainly polyfunctional monomers / oligomers and curing catalysts, Examples thereof include a hard coat agent comprising an antistatic agent.

The adhesive or hard coat agent may be applied to the adherend side or may be applied to the primer layer of the antireflection transfer film, and a known coating processing method is adopted as the method. Can do.
Next, the primer layer or adherend on the opposite side of the antireflection transfer film is laminated with a roll or press while being pressed and heated, and wetted and cured by heat melting, heat curing, UV curing, or heating UV curing. To complete the transfer process.

  As the adherend, various plastic films / sheets / plates, glass, metal and the like can be applied without particular limitation, and the adhesiveness can be improved by electric discharge machining, etching processing, primer coating processing, or the like in advance. In particular, it can be processed into a cellulose triacetate film, PET film, polycarbonate film, polycyclic olefin film, etc. and applied as an antireflection film for display, or processed into glass etc., and applied to an antireflection display. .

The antireflection transfer film obtained by the present invention has a high thickness accuracy of the low refractive index layer and the high refractive index layer, and the stretchability is uniformly controlled by lamination stretching, so that a high-quality low reflectance can be imparted. it can.
In addition, compared to existing methods, one of the features is that the adhesion between the low refractive index layer and the high refractive index layer is high and the durability is excellent due to the promotion of wetting of the interface during stretching. .
In addition, since the manufacturing method of the present invention is a dry process, it is of great significance even if it can be provided with reduced environmental load.

Examples of the present invention will be described below, but the scope of the present invention is not limited to the following examples.
First, the following evaluation test was performed.

<Reflectance>
According to JIS K7105, the spectral reflectance of 550 nm was measured from the low refractive index layer side, and the following determination was performed.
○: Less than 1% △: 1% or more and less than 2% ×: 2% or more

<Adhesion>
In accordance with JIS K5400, 100 notches were made at 1 mm intervals from the low refractive index layer side, evaluated by a cross-cut tape method, and the following determinations were made.
○: 10 points (no peeling)
×: 0 point (with peeling)

Example 1
A 1 mm thick extruded sheet made of 1,4 cyclohexanedimethanol-terephthalic acid polyester resin is prepared as a base film, and tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride co-polymerized on one side of the base film. A solution obtained by dissolving 5% by weight of the combined material (refractive index 1.39, melting point 85 ° C.) in 2-butanone was applied with a bar coater and dried at 80 ° C. for 2 minutes to form a low refractive index layer having a thickness of 1 μm. Further, a UV curable resin (refractive index 1.62 after curing) composed of 90 parts by weight of tetrabromobisphenol A epoxy acrylate, 10 parts by weight of acryloylmorpholine, and 2 parts by weight of a benzoin ether-based initiator in toluene. A high-refractive-index layer having a thickness of 1 μm is applied by applying a solution dissolved in wt% with a bar coater and drying at 80 ° C. for 5 minutes. Formed, to obtain a laminated sheet consisting of three layers.

This laminated sheet was preheated for 2 minutes at 90 ° C. with a clip-type stretching machine (manufactured by TM Long), then stretched 3.2 × 3.2 times by simultaneous biaxial stretching, and immediately after that, 20 ° C. The film was quickly cooled with the air and removed from the clip to obtain a laminated film (low refractive index layer 0.10 μm, high refractive index layer 0.10 μm) having a thickness of 100 μm.
The viscosity of the tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer of the low refractive index layer at the stretching temperature, ie, 90 ° C., is a ratio to the viscosity of the polyester resin of the base film (the viscosity of the polyester resin is 0.7).

The laminated film thus formed was irradiated with 200 mJ / cm ² (in terms of illuminance of 365 nm) with a high-pressure mercury lamp from the side of the high refractive index layer to cure the high refractive index layer, thereby obtaining an antireflection transfer film.

Then, 100 μm urethane-based easy-adhesion layer-coated PET film was coated with 3 μm of UV curable hard coat agent consisting of 100 parts by weight of pentaerythritol tetraacrylate and 2 parts by weight of benzoin ether-based initiator with a bar coater, Immediately thereafter, the antireflective transfer film is laminated with a high refractive index layer, and is irradiated with 400 mJ / cm ² (in terms of illuminance of 365 nm) with a high-pressure mercury lamp from the PET surface to cure the adhesion of the antireflective transfer film and the hard coat layer. An antireflection film was obtained.

  This antireflection film was subjected to an evaluation test on the reflectance and adhesion, particularly the adhesion between the low refractive index layer and the high refractive index layer, and the results are shown in Table 2.

(Example 2)
As the base film, an extruded sheet having a thickness of 1 mm made of a linear low density polyethylene resin was prepared, and a tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer (refractive index 1.) was prepared on one side of the base film. 36, melting point 120 ° C.) in a solution of 5% by weight in 2-butanone was applied with a bar coater and dried at 80 ° C. for 2 minutes to form a low refractive index layer having a thickness of 2 μm. A solution prepared by dissolving 20% by weight of a UV curable resin (refractive index 1.62 after curing) composed of 90 parts by weight of bisphenol A epoxy acrylate, 10 parts by weight of acryloyl morpholine and 2 parts by weight of a benzoin ether initiator in a bar It was applied with a coater and dried at 80 ° C. for 5 minutes to form a high refractive index layer having a thickness of 2 μm to obtain a laminated sheet consisting of three layers.

This laminated sheet was preheated at 130 ° C. for 2 minutes with a clip-type stretching machine (manufactured by TM Long), then stretched 4.5 × 4.5 times by simultaneous biaxial stretching, and immediately after that, winded at 20 ° C. The film was quenched and removed from the clip to obtain a laminated film (low refractive index layer 0.10 μm, high refractive index layer 0.10 μm) having a thickness of 100 μm.
The viscosity of the tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer of the low refractive index layer at 130 ° C. was 0.8 as a ratio to the viscosity of the linear low density polyethylene resin of the base film.

  Hereinafter, an antireflection transfer film and an antireflection film were obtained in the same manner as in Example 1, and an evaluation test was conducted on the reflectance and adhesion of the antireflection film. The results are shown in Table 2.

(Example 3)
As a base film, an extruded sheet made of polypropylene resin and having a thickness of 1.2 mm was prepared, and a tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer (refractive index 1.36, A 4 μm film obtained by coextrusion with polyethylene at 120 ° C. was preheated at 120 ° C. for 2 minutes and laminated with a roll to form a low refractive index layer having a thickness of 4 μm. Tetrabromobisphenol A -A UV curable resin (refractive index 1.62 after curing) composed of 90 parts by weight of epoxy acrylate, 10 parts by weight of acryloyl morpholine, and 2 parts by weight of a benzoin ether-based initiator was applied with a roll coater, and 80 ° C x 5 minutes. A high refractive index layer having a thickness of 4 μm was formed by drying to obtain a laminated sheet composed of three layers.

This laminated sheet was preheated at 165 ° C. for 2 minutes with a clip-type stretching machine (manufactured by TM Long), then stretched 6.3 × 6.3 times by simultaneous biaxial stretching, and immediately followed by wind at 20 ° C. The film was quenched and removed from the clip to obtain a laminated film (low refractive index layer 0.10 μm, high refractive index layer 0.10 μm) having a thickness of 30 μm.
The viscosity of the tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer of the low refractive index layer at 165 ° C. was 0.5 as a ratio of the base film to the viscosity of the polypropylene resin.

  Hereinafter, an antireflection transfer film and an antireflection film were obtained in the same manner as in Example 1, and the antireflection film was subjected to an evaluation test for reflectance and adhesion. The results are shown in Table 2.

Example 4
As a base film, an extruded sheet made of polypropylene resin and having a thickness of 1.2 mm was prepared, and a tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer (refractive index 1.36, A 4 μm film obtained by coextrusion with polyethylene at a melting point of 120 ° C. is preheated at 120 ° C. for 2 minutes and laminated with a roll to form a low refractive index layer having a thickness of 4 μm. A UV curable resin (refractive index of 1.68 after curing) consisting of 90 parts by weight of a polyfunctional thiol acrylate, 10 parts by weight of acryloyl morpholine, and 2 parts by weight of a benzoin ether initiator was applied by a bar coater, A high refractive index layer having a thickness of 4 μm was formed by drying for 5 minutes to obtain a laminated sheet consisting of three layers.

This laminated sheet was preheated for 2 minutes at 165 ° C. with a clip-type stretching machine (manufactured by TM Long), then stretched 6.3 × 6.3 times by simultaneous biaxial stretching, and immediately at 20 ° C. The film was rapidly cooled and removed from the clip to obtain a laminated film (low refractive index layer 0.10 μm, high refractive index layer 0.10 μm) having a thickness of 30 μm.
The viscosity of the tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer of the low refractive index layer at 165 ° C. was 0.5 as a ratio of the base film to the viscosity of the polypropylene resin.

  Hereinafter, an antireflection transfer film and an antireflection film were obtained in the same manner as in Example 1, and an evaluation test was conducted on the reflectance and adhesion of the antireflection film. The results are shown in Table 2.

(Example 5)
As a base film, an extruded sheet made of polypropylene resin and having a thickness of 1.2 mm was prepared, and a tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer (refractive index 1.36, A 4 μm film obtained by coextrusion with polyethylene at 120 ° C. was preheated at 120 ° C. for 2 minutes and laminated with a roll to form a low refractive index layer having a thickness of 4 μm. Tetrabromobisphenol A A solution obtained by dissolving 20% by weight of a thermosetting resin (refractive index of 1.60 after curing) consisting of 60 parts by weight of an epoxy resin and 40 parts by weight of a 2,6-dimethyl-1,4-phenylenediamine curing agent with a bar coater It was applied and dried at 80 ° C. for 5 minutes to form a high refractive index layer having a thickness of 4 μm, thereby obtaining a laminated sheet consisting of three layers.

This laminated sheet was preheated at 165 ° C. for 2 minutes with a clip-type stretching machine (manufactured by TM Long) and then stretched 6.3 × 6.3 times by simultaneous biaxial stretching, and at the same time, the high refractive index layer was heated. Cured (semi-cured state), immediately cooled rapidly at 20 ° C., and removed from the clip to obtain an antireflection transfer film having a thickness of 30 μm (low refractive index layer 0.10 μm, high refractive index layer 0.10 μm).
As for the viscosity of the tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer of the low refractive index layer at 165 ° C., the viscosity ratio of the base film to the polypropylene resin was 0.5.

  Hereinafter, an antireflection transfer film and an antireflection film were obtained in the same manner as in Example 1, and an evaluation test was conducted on the reflectance and adhesion of the antireflection film. The results are shown in Table 2.

(Example 6)
An extruded sheet made of polypropylene resin and having a thickness of 1.2 mm is prepared as a base film, and vinylidene fluoride / PMMA blend butyl acetate (refractive index 1.45, softening point 50 ° C.) is provided on one side of the base film. A coating agent of 30% by weight solution was applied with a bar coater and dried at 100 ° C. for 2 minutes to form a low refractive index layer having a thickness of 4 μm, on which 90 parts by weight of tetrabromobisphenol A epoxy acrylate, acryloyl morphol. A UV curable resin (refractive index after curing of 1.62) consisting of 10 parts by weight of phosphorus and 2 parts by weight of a benzoin ether-based initiator is applied with a roll coater and dried at 80 ° C. for 5 minutes to give a high refractive index of 4 μm. A rate layer was formed to obtain a laminated sheet consisting of three layers.

This laminated sheet was preheated at 165 ° C. for 2 minutes with a clip-type stretching machine (manufactured by TM Long), then stretched 6.3 times × 6.3 times by simultaneous biaxial stretching, and immediately after that, winded at 20 ° C. The film was quenched and removed from the clip to obtain a 30 μm thick laminated film (low refractive index layer 0.03 μm to 0.31 μm, high refractive index layer 0.02 μm to 0.23 μm).
The viscosity of the vinylidene fluoride / PMMA blend of the low refractive index layer at 165 ° C. was 0.09 as a ratio of the base film to the viscosity of the polypropylene resin.

Hereinafter, an antireflection transfer film and an antireflection film were obtained in the same manner as in Example 1. The antireflection film was subjected to an evaluation test for reflectance and adhesion. The results are shown in Table 2.
It was thought that the refractive index layer, particularly the intermediate low refractive index layer became low in viscosity, and the components of the high refractive index layer and the low refractive index layer diffused between the layers during heat stretching, resulting in loss of thickness accuracy. Moreover, the thickness of the obtained high refractive index layer and low refractive index layer varied.

(Comparative Example 1)
A film having a thickness of 50 μm made of a linear low density polyethylene resin was prepared as a base film, and a tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer (refractive index 1.36) was formed on one side of the base film. , Melting point 120 ° C.) was dissolved in 2-butanone 0.5 wt% solution with a bar coater and dried at 80 ° C. for 2 minutes to form a low refractive index layer having a thickness of 0.1 μm. 1 wt% of a UV curable resin (refractive index 1.62 after curing) composed of 90 parts by weight of tetrabromobisphenol A epoxy acrylate, 10 parts by weight of acryloylmorpholine, and 2 parts by weight of a benzoin ether initiator was dissolved in toluene. The solution is applied with a bar coater and dried at 80 ° C. for 5 minutes to form a high refractive index layer having a thickness of 0.1 μm. Got.

Hereafter, without extending | stretching, the antireflection film was obtained similarly to Example 1, the evaluation test was done about the reflectance and adhesiveness about the antireflection film, and the result was shown in Table 2.
This was thought to be due to the conventional lamination / curing process that was not heat-stretched.

(Comparative Example 2)
100 μm urethane-based easy-adhesion layer-coated PET film is coated with 3 μm of UV curable hard coat agent consisting of 100 parts by weight of pentaerythritol tetraacrylate and 2 parts by weight of benzoin ether-based initiator using a bar coater. To 400 mJ / cm ² (converted to an illuminance of 365 nm) with a high-pressure mercury lamp to obtain a film in which the hard coat layer was cured.
Furthermore, a UV curable resin (refractive index 1.62 after curing) composed of 90 parts by weight of tetrabromobisphenol A epoxy acrylate, 10 parts by weight of acryloyl morpholine, and 2 parts by weight of a benzoin ether initiator is added to toluene by 1 weight. % Dissolved solution was applied with a bar coater and dried at 80 ° C. for 5 minutes to form a high refractive index layer having a thickness of 0.1 μm. From the surface of the high refractive index layer, 200 mJ / cm ² (illuminance of 365 nm) was obtained using a high pressure mercury lamp. (Conversion) Irradiated to cure the high refractive index layer.
From above the high refractive index layer, a solution of 5% by weight of tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer (refractive index 1.36, melting point 120 ° C.) dissolved in 2-butanone was applied with a bar coater. Then, it was dried at 80 ° C. for 2 minutes to form a low refractive index layer having a thickness of 0.1 μm to obtain an antireflection film.

  Hereinafter, the antireflection film was evaluated in the same manner as in Example 1 without stretching, and the results are shown in Table 2.

  The configurations of the above examples and comparative examples are shown in Table 1 below.

  Next, the following evaluation test was performed about the manufacturing method of the antireflection transfer film provided with the primer layer.

<Reflectance>
According to JIS K7105, the spectral reflectance of 550 nm was measured from the low refractive index layer side, and the following determination was performed.
○: Less than 1% △: 1% or more and less than 1.5% ×: 1.5% or more

<Reflectance variation>
According to JISK7105, a sample of 100 mm × 100 mm is partitioned into 20 mm × 20 mm, the spectral reflectance of 550 nm is measured from the low refractive index layer side of each partition, the number of partitions with a reflectance of 1.5% or more is measured, The following judgment was made.
: 0
○: Less than 3 ×: 3 or more

<Adhesion>
In accordance with JIS K5400, 100 notches were made at 1 mm intervals from the low refractive index layer side, evaluated by a cross-cut tape method, and the following determinations were made.
○: 10 points (no peeling)
×: 0 point (with peeling)

(Example 7)
As the first base film, an extruded sheet made of linear low density polyethylene resin having a thickness of 1 mm is used, and an acrylic-modified polydimethylsiloxane compound (refractive index: 1.41, viscosity: 100,000 mPa · s) is applied to this one surface. A solution in which 5% by weight of toluene was dissolved was applied by a bar coater, and dried at 80 ° C. for 2 minutes to form a low refractive index layer having a thickness of 2 μm to obtain a first laminate.
Also, as the second base film, an extruded sheet made of linear low density polyethylene resin having a thickness of 1 mm is used, and on one side, a thermoplastic amorphous polyester resin (glass transition temperature 60 ° C., molecular weight 15,000). A solution of 10% by weight in 2-butanone / toluene (weight ratio 1/1) was applied with a bar coater and dried at 80 ° C. for 5 minutes to form a primer layer having a thickness of 10 μm. Further, on the primer layer, a UV curable resin (refractive index 1.62 after curing) composed of 90 parts by weight of tetrabromobisphenol A epoxy acrylate, 10 parts by weight of acryloylmorpholine, and 2 parts by weight of a benzoin ether-based initiator. A solution in which 20% by weight of toluene was dissolved was applied by a bar coater and dried at 80 ° C. for 5 minutes to form a high refractive index layer having a thickness of 2 μm to obtain a second laminate.

  Immediately after forming the second laminate, that is, without cooling, place the low refractive index layer side of the first laminate on the high refractive index layer, and from the first substrate film with a rubber nip roll Lamination was performed at 25 ° C. to form a laminated sheet.

  This laminated sheet was preheated at 130 ° C. for 2 minutes with a clip type stretching machine (manufactured by TM Long), then stretched 4.5 × 4.5 times by simultaneous biaxial stretching, and immediately after that, 20 ° C. The film was quickly cooled with the air and removed from the clip to obtain a laminated film (low refractive index layer 0.10 μm, high refractive index layer 0.10 μm) having a thickness of 100 μm.

The laminated film thus formed was irradiated with 200 mJ / cm ² (in terms of illuminance of 365 nm) with a high-pressure mercury lamp from the first base film side to cure the high refractive index layer, thereby obtaining an antireflection transfer film.

Then, 100 μm urethane-based easy-adhesion layer-coated PET film was coated with 3 μm of UV curable hard coat agent consisting of 100 parts by weight of pentaerythritol tetraacrylate and 2 parts by weight of benzoin ether-based initiator with a bar coater, Immediately after that, the second substrate film of the above-mentioned antireflection transfer film was peeled on this, the exposed primer layer was laminated, and 400 mJ / cm ² (converted to 365 nm illuminance) with a high-pressure mercury lamp from the first substrate film side. Irradiation was performed to cure the adhesion of the antireflection transfer film and the hard coat layer, and the first substrate film was peeled off to obtain an antireflection film.

  This antireflection film was subjected to an evaluation test on reflectance, dispersion of reflectance, and adhesion, particularly adhesion between the low refractive index layer and the high refractive index layer, and the results are shown in Table 4 below.

(Example 8)
A 1 mm thick extruded sheet made of 1,4 cyclohexanedimethanol-terephthalic acid-based polyester resin is prepared as the first base film, and tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer thermoplastic is provided on one side thereof. A solution obtained by dissolving 5% by weight of fluororesin (refractive index 1.39, melting point 85 ° C.) in 2-butanone was applied with a bar coater and dried at 80 ° C. for 2 minutes to form a low refractive index layer having a thickness of 1 μm. It formed and it was set as the 1st laminated body.
In addition, an extruded sheet having a thickness of 1 mm made of 1,4 cyclohexanedimethanol-terephthalic acid-based polyester resin is prepared as the second base film, and a thermoplastic acrylic resin (glass transition temperature 45 ° C.) 2 on one side. -A solution prepared by dissolving 10% by weight in butanone was applied with a bar coater and dried at 80 ° C for 2 minutes to form a primer layer having a thickness of 10 µm to obtain a second laminate.

The low refractive index layer side of the first laminate and the primer layer side of the second laminate face each other and are inserted between rubber nip rolls, and 100 parts by weight of biphenyloxyglycidyl ether acrylate, the benzoin ether system starts, at these joints A UV curable liquid resin (refractive index after curing of 1.58) composed of 2 parts by weight of an agent was stored, and a high refractive index layer having a thickness of 1 μm was bank-formed to obtain a laminated sheet.
The nip roll was rotated under the conditions of 25 ° C., linear pressure 0.4 N / m, and speed 0.5 m / min.

  This laminated sheet was preheated for 2 minutes at 90 ° C. with a clip-type stretching machine (manufactured by TM Long), then stretched 3.2 × 3.2 times by simultaneous biaxial stretching, and immediately after that, 20 ° C. Then, the film was quickly cooled and removed from the clip to form a laminated film (low refractive index layer 0.10 μm, high refractive index layer 0.10 μm) having a thickness of 200 μm.

The laminated film thus formed was irradiated with 200 mJ / cm ² (in terms of illuminance of 365 nm) with a high-pressure mercury lamp from the side of the high refractive index layer to cure the high refractive index layer, thereby obtaining an antireflection transfer film.

Then, 100 μm urethane-based easy-adhesion layer-coated PET film was coated with 3 μm of UV curable hard coat agent consisting of 100 parts by weight of pentaerythritol tetraacrylate and 2 parts by weight of benzoin ether-based initiator with a bar coater, Immediately after that, the second substrate film of the above-mentioned antireflection transfer film was peeled on this, the exposed primer layer was laminated, and 400 mJ / cm ² (converted to 365 nm illuminance) with a high-pressure mercury lamp from the first substrate film side. Irradiation was performed to cure the adhesion of the antireflection transfer film and the hard coat layer, and the first substrate film was peeled off to obtain an antireflection film.

  This antireflection film was subjected to an evaluation test on reflectance, dispersion of reflectance, and adhesion, particularly adhesion between the low refractive index layer and the high refractive index layer, and the results are shown in Table 4.

Example 9
An extruded sheet made of polypropylene resin and having a thickness of 1.2 mm is prepared as the first base film, and vinylidene fluoride / PMMA blend butyl acetate (refractive index: 1.45, softening point: 50 ° C.) 30 wt. A coating solution of% solution was applied with a bar coater and dried at 100 ° C. for 2 minutes to form a low refractive index layer having a thickness of 4 μm to form a first laminate.
Also, an extruded sheet made of polypropylene resin and having a thickness of 1.2 mm is prepared as the second base film, and 20% by weight of thermoplastic acrylic resin (glass transition temperature 45 ° C.) is dissolved in 2-butanone on one side. The solution was applied with a bar coater and dried at 80 ° C. for 2 minutes to form a primer layer having a thickness of 10 μm. Further, 100 parts by weight of biphenyloxyglycidyl ether acrylate and 2 parts by weight of a benzoin ether initiator were used. A UV curable liquid resin (refractive index after curing of 1.58) was formed into a second laminate by forming a high refractive index layer having a thickness of 4 μm at 60 ° C. with a roll coater.

  Immediately after forming the second laminate, that is, without cooling, the low refractive index layer side of the first laminate is placed on the high refractive index layer, and the first base film is placed on a rubber nip roll with 25 Lamination was performed at 0 ° C. to form a laminated sheet.

  This laminated sheet was preheated for 2 minutes at 165 ° C. with a clip-type stretching machine (manufactured by TM Long), then stretched 6.3 × 6.3 times by simultaneous biaxial stretching, and immediately after that, 20 The film was rapidly cooled at 0 ° C. and removed from the clip to obtain a laminated film (low refractive index layer 0.10 μm, high refractive index layer 0.10 μm) having a thickness of 65 μm.

The laminated film thus formed was irradiated with 200 mJ / cm ² (in terms of illuminance of 365 nm) with a high-pressure mercury lamp from the side of the high refractive index layer to cure the high refractive index layer, thereby obtaining an antireflection transfer film.

Then, 100 μm urethane-based easy-adhesion layer-coated PET film was coated with 3 μm of UV curable hard coat agent consisting of 100 parts by weight of pentaerythritol tetraacrylate and 2 parts by weight of benzoin ether-based initiator with a bar coater, Immediately after that, the second substrate film of the above-mentioned antireflection transfer film was peeled on this, the exposed primer layer was laminated, and 400 mJ / cm ² (converted to 365 nm illuminance) with a high-pressure mercury lamp from the first substrate film side. Irradiation was performed to cure the adhesion of the antireflection transfer film and the hard coat layer, and the first substrate film was peeled off to obtain an antireflection film.

  This antireflection film was subjected to an evaluation test on reflectance, dispersion of reflectance, and adhesion, particularly adhesion between the low refractive index layer and the high refractive index layer, and the results are shown in Table 4.

(Example 10)
As the first substrate film, an extruded sheet having a thickness of 1 mm made of linear low-density polyethylene resin was prepared, and tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer (refractive index 1.36, melting point) was prepared on one side. 120 ° C.) and polyethylene coextruded film were preheated at 120 ° C. for 2 minutes and laminated with a roll to form a low refractive index layer having a thickness of 4 μm to form a first laminate.
Also, an extruded sheet made of polypropylene resin and having a thickness of 1.2 mm is prepared as the second base film, and thermoplastic polyethyleneimine-modified acrylic resin (glass transition temperature 40 ° C.) is 20% by weight in ethyl acetate on one side. The dissolved solution was applied with a bar coater and dried at 80 ° C. for 2 minutes to form a primer layer having a thickness of 12 μm to obtain a second laminate.

The low refractive index layer side of the first laminate and the primer layer side of the second laminate are opposed to each other and inserted between nip rolls made of rubber, and 100 parts by weight of biphenyloxyglycidyl ether acrylate, benzoin ether type at the joint between these An organic sulfur compound-based polyfunctional thiol acrylate 90 parts by weight consisting of 2 parts by weight of an initiator, 10 parts by weight of acryloylmorpholine, and 2 parts by weight of a benzoin ether-based initiator (refractive index after curing 1. 68) was stored and a high refractive index layer having a thickness of 4 μm was bank-formed to obtain a laminated sheet.
The nip roll was rolled under the conditions of 15 ° C., linear pressure 0.1 N / m, and speed 5 m / min.

  This laminated sheet was preheated at 165 ° C. for 2 minutes with a clip-type stretching machine (manufactured by TM Long), then stretched 6.3 × 6.3 times by simultaneous biaxial stretching, and immediately after that, 20 ° C. Then, the film was rapidly cooled and removed from the clip to form a laminated film (low refractive index layer 0.10 μm, high refractive index layer 0.10 μm) having a thickness of 60 μm.

The laminated film thus formed was irradiated with 200 mJ / cm ² (in terms of illuminance of 365 nm) with a high-pressure mercury lamp from the side of the high refractive index layer to cure the high refractive index layer, thereby obtaining an antireflection transfer film.

Then, 100 μm urethane-based easy-adhesion layer-coated PET film was coated with 3 μm of UV curable hard coat agent consisting of 100 parts by weight of pentaerythritol tetraacrylate and 2 parts by weight of benzoin ether-based initiator with a bar coater, Immediately after that, the second substrate film of the above-mentioned antireflection transfer film was peeled on this, the exposed primer layer was laminated, and 400 mJ / cm ² (converted to 365 nm illuminance) with a high-pressure mercury lamp from the first substrate film side. Irradiation was performed to cure the adhesion of the antireflection transfer film and the hard coat layer, and the first substrate film was peeled off to obtain an antireflection film.

  With respect to this antireflection film, an evaluation test was conducted on the reflectance, the dispersion of the reflectance, and the adhesion, particularly the adhesion between the low refractive index layer and the high refractive index layer, and the results are shown in Table 4.

(Comparative Example 3)
An antireflection film is formed in the same manner as in Example 3 except that the primer layer is not provided on the second base film. The antireflection film has a low reflectance, a variation in reflectance, and adhesion, particularly low. An evaluation test was performed on the adhesion between the refractive index layer and the high refractive index layer, and the results are shown in Table 4.

(Comparative Example 4)
An antireflection film is formed in the same manner as in Example 4 except that the primer layer is not provided on the second base film. The antireflection film has a low reflectance, a variation in reflectance, and an adhesive property that is particularly low. An evaluation test was performed on the adhesion between the refractive index layer and the high refractive index layer, and the results are shown in Table 4.

  The configurations of the above examples and comparative examples are shown in Table 3 below.

(result)
In Comparative Example 3, the reflectance varies, which is considered to be because the thickness of the high refractive index layer is partially different.
In Comparative Example 4, the reflectance varies, and it is considered that the thickness of the high refractive index layer is partially different as in Comparative Example 3.
In Examples 7 to 10, satisfactory results were obtained in all items.

It is the side view which showed typically the lamination sheet used with one Embodiment of the manufacturing method of the reflection preventing transfer film of this invention. It is the side view which showed typically the lamination sheet used with other embodiment of the manufacturing method of the reflection preventing transfer film of this invention. It is the side view which showed an example of bank formation roughly.

Claims (12)

  Production of an antireflection transfer film comprising a step of laminating a low refractive index layer and a high refractive index layer sequentially on a base film, directly or via a release layer, to form a laminated sheet, and heating and stretching it. A method for producing an antireflection transfer film, which comprises controlling at least the thickness of each of a low refractive index layer and a high refractive index layer by heating and stretching.   2. The method for producing an antireflection transfer film according to claim 1, wherein the high refractive index layer is formed from a thermosetting resin or an ultraviolet curable resin, and the high refractive index layer is cured by heating or ultraviolet irradiation after heat stretching. .   An antireflection transfer film obtained by the production method according to claim 1. The base film is made of at least one resin selected from polyethylene resin, polypropylene resin, polyester resin, polyamide resin, polystyrene resin and polyurethane resin,
The low refractive index layer is made of a fluororesin having a refractive index of 1.45 or less, a softening temperature of 200 ° C. or less, and a viscosity at the stretching temperature of 0.2 or more in terms of the ratio of the resin constituting the base film. Become
The antireflective transfer film according to claim 3, wherein the high refractive index layer is made of a thermosetting resin or an ultraviolet curable resin having a refractive index of 1.6 or more.   5. The antireflection transfer film according to claim 3 or 4, wherein the high refractive index layer is laminated on the intermediate layer via an intermediate layer made of an adhesive or a hard coat agent on a film or display panel as an adherend. An antireflection film or an antireflection display having a structure obtained by transferring and laminating a low refractive index layer and a high refractive index layer.   On the first substrate film, a low refractive index layer, a high refractive index layer and a primer layer are sequentially laminated directly or via a release layer, and further on the second base material directly or via a release layer. A method for producing an antireflection transfer film comprising a step of laminating a base film to form a laminated sheet, and heating and stretching the sheet, and by heating and stretching, at least the low refractive index layer and the high refractive index layer A method for producing an antireflection transfer film, wherein the thickness of each layer is controlled.   A step of forming a first laminate in which a low refractive index layer is laminated directly or via a release layer on the first substrate film; and directly or via a release layer on the second substrate film. A step of forming a second laminate in which the primer layer and the high refractive index layer are sequentially laminated, and the low refractive index layer of the first laminate and the high refractive index layer of the second laminate are laminated so as to face each other. A method for producing an antireflection transfer film comprising a step of forming a laminated sheet and heating and stretching the laminated sheet, wherein the thickness of at least each of the low refractive index layer and the high refractive index layer is controlled by heating and stretching. A method for producing an antireflection transfer film.   A step of forming a first laminate in which a low refractive index layer is laminated directly or via a release layer on the first substrate film; and directly or via a release layer on the second substrate film. The step of forming the second laminated body in which the primer layer is laminated, and the low refractive index layer of the first laminated body and the primer layer of the second laminated body are inserted between the nip rolls so as to face each other. A method for producing an antireflection transfer film comprising a step of forming a high refractive index layer by bank formation between a low refractive index layer and a primer layer of a second laminate to form a laminated sheet, and heating and stretching the laminated sheet. A method for producing an antireflection transfer film, wherein at least the thicknesses of the low refractive index layer and the high refractive index layer are controlled by heating and stretching.   An antireflection transfer film obtained by the production method according to claim 6.   The antireflection transfer film according to claim 9, wherein the low refractive index layer is made of a thermoplastic fluororesin.   The antireflective transfer film according to claim 9 or 10, wherein the primer layer is made of a thermoplastic resin or a thermosetting resin that is hardened at a temperature higher than the heating stretching temperature.   The antireflection transfer according to any one of claims 9 to 11, wherein the primer layer is superimposed on the intermediate layer via an intermediate layer made of an adhesive or a hard coat agent on a film or a display panel as an adherend. An antireflection film or an antireflection display having a structure obtained by transferring and laminating a low refractive index layer, a high refractive index layer and a primer layer of a film.

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