JP2012086475A - Thin-film transfer material, method for manufacturing the same, molding with thin film, and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thin-film transfer material for easily forming a thin film with excellent film strength on the surface of a molding.SOLUTION: The thin-film transfer material has a temporary support, and a fine-particle laminated film formed on at least one surface of the temporary support. (1) The laminated film is formed by laminating one or more fine-particle layers, each including fine particles, and having voids between fine particles at least in one part of each fine-particle layer. (2) The laminated film is formed by laminating two or more kinds of fine-particle layers having at least either different refractive indexes or different average primary particle diameters, or by laminating one or more fine-particle layers of one kind. (3) The average primary particle diameter of the fine particles constituting one or more fine-particle layers of one kind closest to the side of the temporary support of the laminated film is within a range of 70-500 nm.

Description

  The present invention relates to a thin film transfer material, a manufacturing method thereof, a molded body with a thin film using the thin film transfer material, and a manufacturing method thereof, and more specifically, a thin film can be formed on a molded body made of plastic or glass. The present invention relates to a thin film transfer material, a manufacturing method thereof, a molded body with a thin film, and a manufacturing method thereof.

  Organic materials typified by plastics have advantages such as moldability, mass productivity, flexibility and light weight compared to inorganic materials, so they are widely used in a wide range from daily goods to industrial fields. However, even with plastic, if the mechanical strength, optical characteristics, heat resistance, dimensional accuracy, substance permeability, etc. can be improved, its value will be further increased, and it can be used in place of inorganic materials. In recent years, plastic materials can be applied to applications that are impossible with plastic materials alone by combining them with inorganic materials, but as a composite technology, an inorganic thin film is formed on the surface of a plastic molded body. Technology to make progress.

  Conventional inorganic thin film forming techniques are mainly thin film forming methods utilizing a dry process. Examples include chemical vapor deposition (CVD), thermal CVD, plasma CVD (PCVD), photo CVD, CVD inorganic thin film applications, physical vapor deposition (PVD), vacuum deposition, sputtering, ions For example, plating.

  On the other hand, an inorganic thin film forming method using a wet process has been proposed. Examples of such methods include thin film formation methods using coating methods, spraying methods, spraying methods, thermal spraying methods, wet-on-wet methods, liquid phase deposition methods, plating methods, sol-gel methods, LB methods, fine particles. The usage method, the coating method, etc. are mentioned.

  Uses and application fields of such inorganic thin films are spreading not only for industrial use but also for medical use. Among these, antireflection films for flat panel displays are attracting attention.

  For example, a method of manufacturing an antireflection film that is generally used at present is a dry method such as vacuum deposition or sputtering, or a wet method such as a sol-gel method or a coating method. In recent years, the wet method of antireflection treatment, which replaces the dry method, has become the mainstream due to the demand of price.

  On the other hand, an alternate lamination method has been proposed as a method for forming a nanometer-scale thin film, although it is a wet method. The alternate lamination method is described in G.H. This is a method for forming an organic thin film published in 1992 by Decher et al., In which a substrate is alternately immersed in an aqueous solution of a polymer electrolyte having a positive charge (polycation) and a polymer electrolyte having a negative charge (polyanion). Thus, a combination of polycation and polyanion adsorbed by electrostatic attraction on the substrate is laminated to obtain a composite film (alternate laminated film).

  As a method for producing an inorganic thin film using this alternate lamination method, Y. Lvov et al. Have reported a method of laminating a polymer electrolyte having a charge opposite to the surface charge of fine particles by using a fine particle dispersion of silica, titania, and ceria (see Non-Patent Document 1). According to this report, silica particles having negative surface charges and polydiallyldimethylammonium chloride (PDDA) or polyethyleneimine (PEI), which are polycations having opposite charges, are alternately laminated to form silica particles. It is possible to form a fine-particle laminated thin film in which polymer electrolytes are alternately laminated.

  Although an antireflection film composed of an inorganic thin film formed using such an alternate lamination method has been proposed, the film is weak, and damage to the film due to physical friction, peeling easily occurs, It was not suitable for application to the outermost surface of a display or the like.

Therefore, a method of adhering a single-layer fine particle film (inorganic film) formed by an alternating lamination method to an adhesive transparent resin or by adhering it to a meltable transparent resin (see Patent Document 1), Alternatively, a method for producing an optical functional material by transferring a fine particle laminated film by attaching a transparent substrate to the upper surface of the fine particle laminated film formed by alternating lamination method on the base material and removing the base material has been proposed. ing. (See Patent Document 2)
On the other hand, as a method of obtaining an antireflection film having high film strength using fine particles, a functional fine particle layer is first formed on a release film, and finally a hard plastic before curing is formed on a transparent plastic substrate on which the antireflection film is formed. A coat resin layer is formed and pressed so that both the functional fine particle layer and the hard coat resin layer face each other, the functional fine particle layer is embedded in the hard coat resin layer, and the hard coat resin layer is cured (active light beam). Etc.) and peeling off the release film to obtain an antireflection film with high film strength (see Patent Document 3), or a functional ultrafine particle layer such as a low refractive index ultrafine particle layer or a high refractive index. A method of obtaining a transparent functional film by burying an ultrafine particle layer in a hard coat layer (see Patent Document 4 and Patent Document 5) has been proposed.

Japanese Patent Laid-Open No. 2002-6108 JP 2002-361767 A JP-A-7-156326 JP-A-7-225302 JP 2009-113476 A

Langmuir, Vol. 13, 1997, 6195-6203

  However, in the inventions of Patent Document 1 and Patent Document 2, one surface of the functional fine particle film is not completely buried in the transparent resin layer, and it is difficult to obtain sufficient film strength. In addition, when fat or the like enters the space between the fine particles on the surface, the refractive index changes and the optical function deteriorates.

  In addition, in the methods of Patent Document 3 and Patent Document 4, a method for forming a functional ultrafine particle layer (for example, a low refractive index ultrafine particle layer or a high refractive index ultrafine particle layer) is used as an ultrafine particle dispersion itself or an ultrafine particle layer. Since it was a method of forming an ultrafine particle film by applying a dispersion of ultrafine particles mixed with a binder resin to fine particles, it was difficult to obtain sufficient film strength. The ultrafine particle layer mixed with the binder resin does not have a gap between the fine particles, and the ultrafine particle layer is formed so that the resin of the hard coat resin layer enters the gap between the ultrafine particles of the ultrafine particle layer. There is a problem that it is difficult to be buried and it is difficult to obtain a sufficient film strength. In addition, even when the binder resin itself mixed with ultrafine particles is the same material as the hard coat resin, a process such as surface treatment may be required to obtain the adhesion strength because an interface is generated. .

  In the method of Patent Document 5, since the amount of voids formed between the fine particles is high, the film strength can be improved, but the mechanical strength is higher than that of the hard coat resin in which the fine particle film is not formed. May be significantly inferior.

  The present invention has been made in view of the above problems, and a thin film transfer material capable of forming a fine particle film capable of obtaining sufficient film strength by burying and transferring a fine particle layer on the surface of a molded body, and a method for producing the same The present invention also provides a molded body with a thin film and a method for producing the same.

  The present invention relates to the following.

(1) A thin film transfer material comprising a temporary support and a fine particle laminate film formed on at least one surface of the temporary support,
(1) The laminated film is a laminate of one or more fine particle layers containing fine particles, and has a void between at least one fine particle of each fine particle layer,
(2) The laminated film is a laminate of two or more kinds of fine particle layers different in at least one of the refractive index and the average primary particle diameter of the fine particles, or one or two or more of one kind of fine particle layer. ,
(3) The thin film transfer material, wherein an average primary particle diameter of fine particles constituting one or more fine particle layers of the first kind from the temporary support side of the laminated film is in a range of 70 to 500 nm.

(2) The thin film transfer material according to (1), wherein the fine particles are inorganic oxides.

(3) The above (2), wherein the inorganic oxide is composed of an oxide containing at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium, niobium, zinc, tin, cerium and magnesium. The thin film transfer material described.

(4) The thin film transfer material according to any one of (1) to (3), wherein the fine particles have a hollow or porous structure on the surface or inside thereof.

(5) The thin film transfer material according to any one of (1) to (4), wherein the fine particle layer is a laminate of fine particles and a polymer electrolyte, or is a layer in which a polymer electrolyte is mixed with the fine particles.

(6) The thin film transfer material according to any one of (1) to (5), wherein the fine particle multilayer film is an antireflection film.

(7) The thin film transfer material according to any one of (1) to (6), wherein a silicone oligomer having a polymerizable unsaturated double bond is attached to the fine particle laminated film.

(8) A step of immersing the temporary support alternately in one or more times in (1) a dispersion of fine particles having an ionic surface charge and a polymer electrolyte solution having a charge opposite to the surface charge of the fine particles, Or (2) a fine particle laminated film forming step for performing either one of a polymer electrolyte solution and a step of alternately immersing in a dispersion of fine particles having a surface charge opposite in sign to the charge of the polymer electrolyte. ,
In the fine particle laminated film forming step, at least the fine particles of the fine particle dispersion to be immersed first have an average primary particle diameter in the range of 70 to 500 nm,
A method for producing a thin film transfer material, wherein a fine particle laminated film having a gap between at least one fine particle is formed on a temporary support by the fine particle laminated film forming step.

(9) The method for producing a thin film transfer material according to (8), including a rinsing step after each dipping step and before the next step.

(10) A fine particle laminated film forming step in which a fine particle dispersion is applied to a temporary support at least once. The fine particles of the fine particle dispersion to be applied at least first have an average primary particle diameter in the range of 70 to 500 nm. A method for producing a thin film transfer material, comprising forming a fine particle laminated film having a void between at least one fine particle on the temporary support by the forming step.

(11) including a fine particle layered film forming step in which the temporary support is alternately applied to the fine particle dispersion and the polymer electrolyte solution at least once;
In the fine particle laminated film forming step, at least the fine particles of the fine particle dispersion to be applied first have an average primary particle diameter in the range of 70 to 500 nm,
A method for producing a thin film transfer material, wherein a fine particle laminated film having a gap between at least one fine particle is formed on a temporary support by the fine particle laminated film forming step.

(12) The method further includes a step of pulling out the sheet-like temporary support wound in a roll shape,
The method for producing a thin film transfer material according to any one of (8) to (11), wherein the fine particle multilayer film forming step is continuously performed.

(13) A step of attaching a silicone oligomer having one or more functional groups that react with a hydroxyl group and one or more polymerizable unsaturated double bonds in the molecule to the fine particles of the fine particle laminated film formed on the temporary support. The manufacturing method of the thin film transfer material in any one of said (8)-(12) containing.

(14) A molded body with a thin film in which the fine particle laminated film of the thin film transfer material according to any one of (1) to (7) is embedded and fixed on the surface of the molded body by transfer.

(15) The molded body with a thin film according to (14), wherein the molded body has a permanent support layer on the surface thereof.

(16) The molded article with a thin film according to (15), wherein the permanent support layer contains at least one of a thermoplastic resin, a thermosetting resin, or an active energy ray curable resin.

(17) The fine particle laminate film is transferred onto the surface of the compact by transferring the fine particle laminate film of the thin film transfer material according to any one of (1) to (7) to an uncured or softened surface of the compact. A method for producing a molded article with a thin film, characterized in that the film is buried.

(18) The method for producing a molded body with a thin film according to (17), wherein the molded body has a permanent support layer on the surface thereof.

(19) The method for producing a molded article with a thin film according to (18), wherein the permanent support layer contains at least one of a thermoplastic resin, a thermosetting resin, or an active energy ray curable resin.

(20) A step of sandwiching a thin film transfer material in an injection mold, and forming a molded body by injecting a molten material to the fine particle laminated film side of the thin film transfer material, and simultaneously, the thin film transfer material on the surface of the molded body The method for producing a molded article with a thin film according to (17), comprising a step of burying the fine particle laminated film, and a step of peeling the temporary support.

(21) A step of burying the fine particle laminated film of the thin film transfer material on the surface of the uncured or softened molded product by thermocompression bonding the fine particle laminated film side of the thin film transfer material on the molded product, The manufacturing method of the molded object with a thin film of the said (17) description including the process of peeling a support body.

(22) The permanent support layer is formed by using a molded body having a permanent support layer formed on the surface thereof, superposing the fine particle laminated film side of the thin film transfer material on the permanent support layer, and performing thermocompression bonding or actinic ray irradiation. The manufacturing method of the molded object with a thin film as described in said (19) which embeds the fine particle laminated film of the said thin film transfer material in the uncured or softened surface of this.

  In the thin film transfer material of the present invention, since the fine particle laminated film constituting the thin film has a large gap between the fine particles, the surface material of the molded body enters the fine particle laminated film by transfer to the surface of the molded object. It becomes easy and it becomes possible to increase the ratio with respect to the microparticles | fine-particles of the molded object surface material in the outermost surface layer of a molded object. As a result, it is possible to obtain a molded body with a thin film having a film strength as high as that of the surface material of the molded body. In addition, a thin film having excellent processing cost and productivity, and excellent optical characteristics, appearance, and durability can be formed on the surface of various molded articles.

Sectional drawing which shows an example of the thin film transfer material of this invention typically. Sectional drawing which shows an example of the molded object with a thin film of this invention. Sectional drawing which shows an example of the manufacturing method of a molded object with a thin film. The schematic diagram which shows an example of the continuous manufacturing method of the molded object with a thin film.

  The thin film of the present invention is a hard coat film, gas barrier film, transparent deposition, hybrid film, light reflection film, light reflection prevention film, conductive film, antistatic film, antistatic film, transparent conductive film, electromagnetic wave shielding film, and printing paper Thin film, ferrite film for magnetic tape, photocatalyst / hydrophilic / antifouling / antifogging / water repellent film, photocatalyst film, hydrophilic / lipophilic film, water repellent film, agricultural antifogging film, blocking film, near infrared blocking film, UV protection Membranes, transparent thermal insulation membranes, membranes with antibacterial / deodorant membranes, carbon-based thin films, diamond thin films, diamond-like carbon membranes, medical membranes, biological bone membranes, artificial blood vessel membranes, artificial organ membranes, etc. It is applied to medical use membranes and porous membranes.

  Applicable industrial products include sensors, recording / storage, optical discs, magneto-optical discs, magnetic tapes, optical tapes, recording paper, solar cells, displays, film LCDs, PDPs, touch panels, antireflection films, optics Examples include parts, transparent optical parts, optical waveguide members, mechanical members, and adhesive labels.

  Among them, in recent years, a cathode-ray tube (CRT), a liquid crystal display (LCD), a plasma display panel (PDP), an electroluminescent display panel, and an electroluminescent display panel (CRT). Advances in the display field, especially in the field of flat panel displays, such as displays (Electro-Chemical Display: ECD), are remarkable. These are not only indoors, but also outdoors, as mobile terminals such as mobile phones and portable information terminals spread. Has come to be used.

  In these displays, an anti-reflective coating is indispensable in order to improve the visibility of the display screen, especially when used outdoors. It is necessary to provide an optical thin film on the surface of various displays. The thin film in the present invention is particularly useful as such an antireflection film.

  The fine particle laminated film in the thin film transfer material of the present invention contains fine particles, and a void is formed between at least one fine particle. Further, it is preferable that large voids are formed between the fine particles in the fine particle laminated film near the surface of the temporary support. By transferring the thin film transfer material to the surface of the molded body, the molded body surface material enters the voids of the fine particle laminated film, and the molded body in the outermost surface layer of the molded body (the side closest to the temporary support side in the thin film transfer material) The ratio of the surface material to the fine particles can be increased. As a result, a molded body having a thin film having excellent mechanical properties and film strength can be obtained.

  The material of the temporary support constituting the thin film transfer material is not particularly limited, but a film made of plastic that can be deformed or bent is suitable. For example, polyester, cellulose acetate, polypropylene, polyethylene, polyamide, polyimide, polyether sulfone, polysulfone, polyvinyl acetal, polyether ketone, polyvinyl chloride, polyvinylidene chloride, polymethyl acrylate, polymethyl methacrylate, polycarbonate, polyurethane, etc. Stretched or unstretched transparent plastic film.

  The temporary support itself has releasability such that the fine particle laminated film does not remain on the temporary support when the fine particle laminated film is peeled off from the temporary support, or is provided with releasability. For example, it can be used as a temporary support. For example, a release agent such as a wax, a salt or ester of a higher fatty acid, a fluorinated alkylated compound, polyvinyl alcohol, or low molecular weight polyethylene is added. A surface modifier such as a coupling agent may be used.

  The thickness of the temporary support is not particularly limited, but it is usually in the range of 4 to 150 μm, preferably in the range of 12 to 100 μm, more preferably in the range of 20 to 50 μm. It is preferable from the viewpoint of easy production of a thin film transfer material free of the above.

  The film thickness of the fine particle laminated film formed on at least one surface of the temporary support is not particularly limited, but is preferably 50 to 150 nm when used as an optical thin film. The refractive index of the fine particle laminated film is preferably 1.12 to 2.00. For example, when a plurality of kinds of fine particle laminated films having different refractive indexes are laminated, they can be used as an antireflection film, a reflective film, an optical filter, or a semi-transmissive / semi-reflective film.

The fine particles contained in the fine particle laminated film are preferably inorganic fine particles, more preferably inorganic oxides and inorganic fluorides, and particularly metal-containing fine particles such as metal oxides and metal fluorides. Specifically, magnesium fluoride (MgF ₂ ), aluminum fluoride (AlF ₃ ), lithium fluoride (LiF), sodium fluoride (NaF), silica (SiO ₂ ), aluminum oxide (Al ₂ O ₃ ), Zirconia oxide (ZrO ₂ ), titanium oxide (TiO ₂ ), niobium oxide (Nb ₂ O ₅ ), indium tin oxide (ITO), zinc oxide (ZnO), tin oxide (SnO ₂ ), ceria (CeO ₂ ), Examples thereof include yttrium oxide (Y ₂ O ₃ ) and bismuth oxide (Bi ₂ O ₃ ). One kind selected from these fine particles or a mixture of two or more kinds of metal oxide fine particles can be used in combination.

  In order to obtain a transparent thin film, it is preferable to use an oxide containing at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium, niobium, zinc, tin, cerium and magnesium.

  In the fine particle laminated film in which the fine particles formed on the temporary support are stacked, there are voids between the fine particles. The void described here is a space in which a constituent material of an uncured or softened molded body or a permanent support layer described later can enter during the transfer process. Adjacent fine particles may or may not be in contact with each other. The thin film consisting of the above-mentioned fine particle laminated film is embedded on the surface of the molded body so that a part of the molded body or a part of the permanent support layer formed on the surface of the molded body enters the gap. And by integrating with a molded object, from a viewpoint of a thin film, mechanical characteristics, such as the adhesiveness and abrasion resistance, improve. The larger the size of the voids, the easier it is for the surface material of the molded body to enter, and the strength of the molded body with a thin film increases.

  It is preferable to use fine particles having a large particle size, rather than using particles having a shape in which primary particles are connected, because the voids can be easily enlarged.

  When the porosity is too small, the above penetration into the voids tends to be insufficient, and the binding between particles tends to be insufficient. Moreover, when the porosity is too large, it tends to be difficult to keep the shape of the fine particle laminated film.

  It is preferable that the fine particles have a hollow or porous structure on the surface or in the inside thereof, since the number of voids increases, and particularly when a thin film having a low refractive index is produced. While the permanent support layer formed on a part of the molded body or the surface of the molded body sufficiently enters the voids between the particles of the fine particle laminate film, while improving mechanical properties such as adhesion to fine particles and scratch resistance, A thin film with a reduced refractive index can be formed by voids inside the fine particles themselves.

  In the fine particle laminated film, the laminated film is a fine particle layer or a laminate of two or more fine particle layers, and has a void between at least one fine particle in each fine particle layer.

  Further, the laminated film is a laminate of two or more kinds of fine particle layers different in at least one of the refractive index and the average primary particle diameter of fine particles, or one or two layers of one kind (same kind) of fine particle layers. That's it. In the case of two or more types, each type of fine particle layer in the fine particle laminated film may be a single layer or a laminate of two or more layers. That is, it may be a laminated film having only the same kind of fine particle layer, or a laminated film made of another fine particle layer having a different type from the fine particle layer may be formed thereon.

  Note that “one type” of the layered film of the fine particle layer is localized not only in the layered film of the fine particle layer consisting of only one type of fine particles but also in the whole of the multilayered film consisting of the fine particle layer of a mixture of different fine particles. It includes the case where the particles are evenly dispersed and the case where a fine particle layer composed of fine particles and a polymer described later is laminated.

  When there are two or more types of laminated films, in the present invention, the first type, the second type,. Since the first type of fine particle layer is located on the surface of the molded body after the transfer, for example, the first type of fine particle layer has a predetermined refractive index, and the second type of fine particle laminated film is a surface material of the molded body. By using fine particles having a predetermined average primary particle size so as to be easily buried in the film, a multifunctional fine particle laminated film can be obtained. These two or more types of fine particle layers differ in at least one of the refractive index and the average primary particle diameter of the fine particles. Differences in the physical properties of the plural types of fine particle layers can be further adjusted by the elemental component of the fine particles, the mixing ratio of the fine particles, and the like. The same applies to the third and subsequent fine particle layers.

  In the present invention, the average primary particle diameter of the fine particles constituting one or more fine particle layers (hereinafter also referred to as the first type layer) from the temporary support side is within a range of 70 to 500 nm. There must be. The reason for this is that if the average primary particle diameter of the fine particles is too small, the size of the voids between the fine particles and the fine particles becomes small, making it difficult for the fine particles to be embedded in the surface of the molded product when transferred to the surface of the molded product. Because it becomes. Since this layer becomes the surface when it is integrated with the molded body, it is preferable that the porosity is large.

  A preferred lower limit is 70 nm because of the size of the voids between the fine particles, and a more preferred lower limit is 80 nm. Moreover, a preferable upper limit is 150 nm for the reason of reducing the unevenness | corrugation of the fine particle laminated film surface, and a more preferable upper limit is 120 nm. In the present invention, the average primary particle diameter of the fine particles is a value measured by the BET method unless otherwise specified.

  In order to adjust the refractive index and enhance the optical function, the first kind of fine particles includes fine particles having different particle diameters and elemental components within an average primary particle diameter of 70 to 500 nm. You may mix. In the case of mixing fine particles having different primary particle diameters, particle diameters and mixing amounts that significantly reduce the voids between the fine particles are not preferable. Specifically, the primary particle size is preferably 10 to 500 nm, more preferably 20 to 50 nm. The mixing amount is preferably 10 to 50% by weight, more preferably 20 to 30% by weight. This is because if the mixing amount is too large, the large voids are filled, and if the mixing amount is too small, the optical function cannot be improved.

  The fine particles constituting the second and subsequent layers formed on the temporary support are not particularly limited in the shape of the particles, but the average primary particle size is preferably 10 to 500 nm, more preferably 15 to 50 nm. The reason for this is that if the average primary particle diameter of the fine particles is too small, the size of the voids between the fine particles and the fine particles becomes small, making it difficult for the fine particles to be embedded in the surface of the molded product when transferred to the surface of the molded product. This is because particles having a diameter of 500 nm or more tend to precipitate during coating because water dispersion is difficult. Further, if the average primary particle diameter of the fine particles is larger than 50 nm, the film tends to be whitened due to Mie scattering, so that it is not suitable for transparent optical thin film applications.

  In addition, as disclosed in Patent Document 3, the method of transferring the thin film of the fine particle layer formed by mixing the fine particle dispersion and the binder resin and applying the mixture to the temporary support is sufficient to allow the curable resin to enter. Since the gap cannot be formed in the fine particle layer, it is difficult to bind the fine particles.

  The fine particle laminated film in the present invention can be produced by a method of directly applying a fine particle dispersion to a temporary support, an alternating lamination method, or the like. According to the alternating lamination method, the surface potential of fine particles is adjusted, such as pH adjustment (the porosity is controlled to be relatively large when the pH is adjusted to 3 to 9, and the porosity is controlled to be relatively small in other ranges). Therefore, it is easy to control the porosity of the formed fine particle laminated film.

  According to the alternating lamination method, the temporary support is immersed alternately in a polymer electrolyte solution (polycation or polyanion) and a fine particle dispersion to produce a fine particle laminated film on the temporary support. As described above, in the case of the alternating lamination method, the formed fine particle layer is formed by laminating the polymer electrolyte and the fine particles, but the ratio of the polymer electrolyte contained in the fine particle laminated film is 1% by weight or less. Not all the voids between the fine particles are filled.

  First, the temporary support is used as it is or after being subjected to a release treatment. Moreover, in order to adsorb the polymer electrolyte and fine particles onto the temporary support surface, as a method for efficiently introducing surface charges onto the temporary support surface, polydiallyldimethylammonium chloride (PDDA) or polyethylene, which is a strong electrolyte polymer, is used. There is a method in which an alternate laminated film of imine (PEI) and polystyrene sulfonic acid (PSS) is previously formed on a temporary support.

  If the surface charge of the temporary support is negative, it is first immersed in a cationic solution or dispersion. Conversely, if the surface charge of the temporary support is positive, it is first immersed in an anionic solution or dispersion. That is, (1) a step of alternately immersing a temporary support in a dispersion of fine particles having an ionic surface charge and a polymer electrolyte solution having a charge opposite in sign to the surface charge of the fine particles, or (2) A fine particle laminated film forming step for performing either one of a polymer electrolyte solution and a step of alternately immersing in a dispersion of fine particles having a surface charge opposite to the charge of the polymer electrolyte at least once.

  Since the dispersion liquid of the fine particles applied or immersed at least first on the temporary support becomes the first type layer in the fine particle laminated film, the average primary particle diameter is in the range of 70 to 500 nm. When the second and subsequent layers of the fine particle laminated film are laminated, the second type fine particle dispersion and / or the polymer electrolyte solution are subsequently used.

  The immersion time is appropriately adjusted according to the polymer electrolyte, fine particles, and the film thickness to be laminated. For example, in the case of an optical thin film, 50 to 150 nm is preferable. The immersion in the polymer electrolyte solution and the fine particle dispersion is alternately repeated until the fine particle laminated film has an appropriate film thickness.

  After each immersion step, it is preferable to pass through a step (rinsing step) of rinsing excess by washing with only the solvent or dispersion medium before the step of immersing in the next solution or dispersion having the opposite charge. Further, although the laminated polymer electrolyte and fine particles form a film, they are not separated in this rinsing step because they are electrostatically adsorbed to each other. In addition, a polyelectrolyte or fine particle that is not electrostatically adsorbed in an oppositely charged solution, in other words, a substance that is adsorbed by a weak bond such as intermolecular force and easily desorbed is brought into the next operation or process. In order to prevent this, the rinsing step is preferably performed. When a substance having an opposite charge is brought into the next operation or process, cations and anions may be mixed in the solution to cause precipitation. By rinsing after immersion in the polymer electrolyte solution, there is an effect of removing excess polymer electrolyte that has entered between the fine particles.

  The concentration of the polyelectrolyte is appropriately determined depending on the solubility of the polyelectrolyte in the solvent and the concentration, but if it is higher than the appropriate concentration, it is difficult to wash away excess solution in the rinsing step. End up. On the other hand, if the concentration is too low, the amount of polymer electrolyte as a solute is not sufficient with respect to the area of the temporary support to be adsorbed, so that film formation by alternating lamination cannot be performed.

  The concentration of the polymer electrolyte and the concentration of the fine particles are each suitably selected from the range of 0.00001 wt% to 30 wt%, more preferably 0.001 wt% to 20 wt%, The weight percentage is particularly preferably 10% by weight or more. The immersion time with the polymer electrolyte solution and the fine particle dispersion is preferably appropriately selected from 1 second to 120 minutes, and more preferably from 10 seconds to 300 seconds.

  In the above alternate lamination method, the formation of the polymer electrolyte or fine particle layer has been described by immersing the solution or dispersion containing them in a temporary support. However, the present invention is not limited to such a case. Any method may be used as long as the solution or the dispersion liquid can form a film in contact with the temporary support. Specifically, a dispersion of fine particles and a polymer electrolyte solution are applied directly and alternately on a temporary support using spraying, casting, bar coating, die coating, gravure coating, roll coating, etc. Then, a fine particle laminated film can be formed by drying. In this case, the order of application according to the surface charge of the temporary support is not particularly limited.

  The fine particle dispersion is preferably a sol fine particle dispersion dispersed in water or alcohol. The dispersion medium of the fine particle dispersion includes alcohol solvents such as methanol and ethanol, ether solvents such as ethylene glycol monomethyl ether, ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, and amides such as N, N-dimethylformamide. Examples thereof include an aromatic hydrocarbon solvent such as toluene and xylene, an ester solvent such as ethyl acetate, a nitrile solvent such as butyronitrile, water, and the like, and a dispersion medium in which two or more kinds are mixed may be used.

  Furthermore, in order to improve the wettability with the temporary support, a surfactant may be added to such an extent that the fine particle dispersibility is not deteriorated. Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, and zwitterionic surfactants. Nonionic surfactants and anionic surfactants are preferable. is there. The concentration of the surfactant is preferably appropriately selected from the range of 0.001% by weight to 5% by weight, and more preferably 0.01% by weight to 0.5% by weight.

  In addition, the method of directly applying the fine particle dispersion is to apply the fine particle dispersion directly to the temporary support by a spray method, a cast method, a bar coat method, a die coat method, a gravure coat method, a roll coat method, etc., and then dry. Can be repeated as necessary to obtain a fine particle laminated film having a desired thickness. Examples of the dispersion solvent for the sol-shaped fine particle dispersion include the same solvent as described above, water, and the like, and a mixed solvent of two or more kinds of solvents may be used. In addition, a surfactant may be added to the fine particle dispersion.

  Also, the sheet-like temporary support is drawn out in a roll shape, and one of the fine particle laminated film forming steps is preferably performed continuously, including the step of rinsing after each dipping. A thin film transfer material can also be manufactured by a lamination method. This method can be suitably used when a long film substrate is used as a temporary support.

  As the polymer electrolyte (polyanion or polycation), a polymer having a functional group having a charge in the main chain or side chain can be used. In this case, the polyanion generally has a negatively charged functional group such as sulfonic acid, sulfuric acid, and carboxylic acid. For example, polystyrene sulfonic acid (PSS), polyvinyl sulfate (PVS), dextran, and the like. Sulfuric acid, chondroitin sulfate, polyacrylic acid (PAA), polymethacrylic acid (PMA), polymaleic acid, polyfumaric acid and the like are used. The polycation generally has a positively charged functional group such as a quaternary ammonium group or an amino group, such as polyethyleneimine (PEI), polyallylamine hydrochloride (PAH), polydiallyldimethyl. Ammonium chloride (PDDA), polyvinyl pyridine (PVP), polylysine and the like can be used. Any of these organic polymer ions is water-soluble or soluble in a mixed solution of water and an organic solvent.

  The fine particle laminated film is formed by adsorbing or binding fine particles, fine particles, and temporary support by intermolecular force acting between fine particles or between fine particles and polycation or polyanion, hydrogen bond, covalent bond, ionic bond, etc. ing. The adhesive force between the temporary support and the temporary support is such that it does not hinder peeling during transfer. It is desirable that the peel strength with respect to the temporary support can be easily peeled off with an adhesive tape having an adhesive strength in the range of 0.1 N / 10 mm to 10 N / 10 mm. This is because it can be easily peeled off from the temporary support in the transferring step and is easily buried in the curable resin.

  An ionic or reactive functional group may be added to the fine particle laminated film. By adding a reactive group, it is possible to chemically bond the fine particle laminate film constituting the thin film transfer material and the resin constituting the thin film molded article, and the molded article with a thin film having excellent mechanical properties and film strength. Can be obtained.

  Examples of a method of imparting an ionic or reactive functional group to the fine particle laminated film include a method of attaching a silicone oligomer to the fine particles. The silicone oligomer is not particularly limited in molecular weight or structure as long as it has at least one functional group that reacts with a hydroxyl group and at least one polymerizable unsaturated double bond in the molecule.

  When the silicone oligomer is attached, it is preferable to have a hydroxyl group on the surface of the fine particles. If it contains a metal oxide, surface hydroxyl groups exist due to adsorption of water molecules from the atmosphere (see “Wet Technology Handbook”, Techno System, Inc., December 20, 2005, p. 81). Similarly, metal fluorides have surface hydroxyl groups. Further, the fine particles may be subjected to a surface treatment for introducing more hydroxyl groups on the surface. As the surface treatment method, a method of generating a large amount of hydroxyl groups on the surface of the oxide by surface modification treatment by a dry process such as oxygen plasma treatment, corona treatment, plasma ashing treatment, or sodium hydroxide or potassium hydroxide. There is a method in which a hydroxide ion reacts with a surface oxide to generate a large amount of hydroxyl groups by contacting with a strongly alkaline aqueous solution, an alcohol solution, or a mixed solution of water and alcohol.

  Also in the metal fluoride, oxygen plasma treatment causes high energy oxygen radicals to react with metal elements to form oxides on the surface, and then surface hydroxyl groups are generated by moisture adsorption from the atmosphere.

  Furthermore, as a method of increasing the density of surface hydroxyl groups in the fine particles, metal alkoxides, typically tetramethoxysilane, tetraethoxysilane, polysilazane, and hydrolyzed silanol groups (Si—OH) are used. There is also a method in which a plurality of polymers in the molecule and fine particles are brought into contact with each other so that some of the hydroxyl groups contained in the polymer are chemically bonded to the fine particles, and some of the hydroxyl groups remain as surface hydroxyl groups. In addition, after processing with a silicone oligomer, the hydroxyl group of the surface of microparticles | fine-particles and a group reactive with a hydroxyl group may remain partially.

  As the functional group that reacts with the hydroxyl group of the silicone oligomer, a halogen, an alkoxyl group, an acyl group, a silanol group, or the like is preferable. A halogen, an alkoxyl group, an acyl group, or the like is a group bonded to Si and is a group that generates a silanol group by hydrolysis.

The silicone oligomer in the present invention is selected from monofunctional siloxane units (R ₃ SiO _1/2 ), bifunctional siloxane units (R ₂ SiO _2/2 ), and trifunctional siloxane units (RSiO _3/2 ). And at least one siloxane unit selected from a bifunctional siloxane unit (R ₂ SiO _2/2 ) and a trifunctional siloxane unit (RSiO _3/2 ). (In any of the above formulas, R is an organic group, a hydroxyl group, a halogen, etc., and a plurality of R groups or a plurality of R groups in a silicone oligomer are the same as each other) Or it may be different). The silicone oligomer in the present invention may contain a tetrafunctional siloxane unit (SiO _4/2 ).

  The degree of polymerization of the silicone oligomer is preferably 2 to 30, more preferably 3 to 10. If the degree of polymerization of the silicone oligomer is too large, it will be difficult for the silicone oligomer to enter the voids between the fine particles of the fine particle laminated film, and the reaction between the fine particles near the surface of the temporary support and the silicone oligomer will be insufficient, improving the film strength. There is a tendency to decrease. Here, the degree of polymerization is calculated from the molecular weight of the polymer (in the case of a low degree of polymerization) or the number average molecular weight measured by gel permeation chromatography using a standard polystyrene or polyethylene glycol calibration curve.

  R in the above siloxane unit is an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group or a butoxy group, an acyl group such as an acetyloxy group, a hydroxyl group-reactive group, a vinyl group, a methacryloyloxy group, an acryloyl group. A group having a polymerizable unsaturated double bond such as an oxy group, an alkyl group such as a methyl group, an ethyl group, a propyl group and a butyl group, an aryl group such as a phenyl group, a halogen such as chlorine and bromine, and other groups. The silicone oligomer in the present invention has one or more groups each having a hydroxyl group-reactive group and a polymerizable unsaturated double bond in the molecule.

  The silicone oligomer of the present invention reacts with at least a part of the hydroxyl group and reactive group contained in the molecule and a part of the hydroxyl group on the surface of the fine particle, so that the silicone oligomer is firmly bonded to the fine particle. By reacting the polymerizable unsaturated double bond with the curable resin, the fine particle laminated film and the curable resin are firmly bonded.

The progress of the reaction can be confirmed by measuring the infrared absorption spectrum of the film. Specifically, the peak wavelength of the infrared absorption spectrum of Si-OH having a silanol group, for example, the decrease or disappearance of absorption in the band of 3500-3800 cm ⁻¹ and the peak of the infrared absorption spectrum of the polymerizable unsaturated bond, respectively. It can be confirmed by the decrease or disappearance of absorption at wavelengths such as 955 to 985 cm ⁻¹ band, 915 to 905 cm ⁻¹ band.

  The silicone oligomer in the present invention can be obtained by hydrolyzing and polycondensing a silane compound.

This silane compound is, for example, the general formula (I)
[Chemical 1]
R ′ _n SiX _4-n (I)
(In the formula, X is a group that hydrolyzes to generate an OH group, and represents, for example, halogen such as chlorine and bromine, or —OR ″, where R ″ is an alkyl group having 1 to 4 carbon atoms or carbon. R 1 represents an acyl group having 1 to 4 carbon atoms, R ′ represents a group containing a polymerizable unsaturated double bond, an organic group such as an alkyl group having 1 to 4 carbon atoms or an aryl group, and n represents 0 or Represents an integer of 1 to 3).

  Among the silane compounds represented by the general formula (I), at least one of the compounds in which n is 1, 2 or 3 (referred to as a trifunctional silane compound, a bifunctional silane compound and a monofunctional silane compound sequentially). The type is preferably used as an essential component, and in particular, a trifunctional silane compound or a bifunctional silane compound is preferably used as an essential component. A tetrafunctional silane compound (a compound in which n is 0 in the general formula (I)) may be partially used.

  When the silane compound (raw material monomer) is hydrolyzed, an OH group (silanol group) is introduced and condensed to be oligomerized. At this time, when the remaining OH group or the alkoxy group or acyl group (—OR ″) in the raw material monomer remains, these remaining groups are reactive with a hydroxyl group (present in the silicone oligomer molecule). These remaining amounts can be adjusted by adjusting the amount of water and the degree of condensation during hydrolysis.

  The silicone oligomer in the present invention has a polymerizable double bond in the molecule. For this reason, as the silane compound, a 1-3 functional silane compound in which R ′ (at least one R ′ when there are a plurality of R ′) is a group containing a polymerizable unsaturated double bond ( Preferably, a bi- or trifunctional silane compound) is used as an essential component.

  In addition, when the silicone oligomer in the present invention contains a non-reactive organic group such as an alkyl group or an aryl group as the R ′ in the molecule, the fine particle laminated film to which it is attached becomes oleophilic. Thus, the affinity with the curable resin in which the fine particle laminated film is to be embedded can be improved.

  Specifically, the trifunctional silane compound is, as a silane compound containing a polymerizable unsaturated double bond, vinyltrichlorosilane, vinyltrimethoxysilane, vinylethoxysilane, vinyltriacetoxysilane, vinyltriisopropoxysilane. , 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-methacryloyloxypropyldimethoxysilane, 3-methacryloyloxypropyldiethoxysilane, 3-acryloyloxypropyltrimethoxysilane, and the like. Silane compounds that do not contain unsaturated double bonds include methyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, phenyltriethoxysilane, hexyltrimethoxy. Silane, hexyl triethoxysilane, decyl trimethoxysilane, methyl triacetyl silane and the like.

  Specifically, the bifunctional silane compound includes, as a silane compound containing a polymerizable unsaturated double bond, 3-methacryloyloxypropylmethyldimethoxysilane, 3-acryloyloxypropylmethyldimethoxysilane, vinylmethyldimethoxysilane, Examples of silane compounds that include vinylmethyldiethoxysilane and that do not contain polymerizable unsaturated double bonds include dimethyldimethoxysilane, dimethyldiethoxysilane, diphenidimethoxysilane, diphenidiethoxysilane, and dimethyldiacetyloxysilane. .

  Examples of the monofunctional silane compound include 3-methacryloyloxypropyldimethylmethoxysilane, trimethylmonomethoxysilane, trimethylmonoethoxysilane, and trimethylmonoacetyloxysilane.

  Examples of the tetrafunctional silane compound include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, and tetraacetyloxysilane.

  A preferred amount of the silane compound is as follows. The silane compound having a group containing a polymerizable unsaturated double bond is 50 to 100 mol%, particularly 70 to 100 mol%, and the other silane compound is 0 to 50 mol%, particularly 0, relative to the entire silane compound. Used in a proportion of ˜30 mol%, and the bifunctional silane compound or the trifunctional silane compound is 50 to 100 mol%, the tetrafunctional silane compound and the monofunctional silane compound are each 0 to 50 mol%, particularly It is used in such a proportion that it is 0 to 30 mol% and the whole is 100 mol%.

  The silicone oligomer in the present invention is produced by hydrolysis and polycondensation of the aforementioned silane compound. At this time, the catalyst includes inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid and hydrofluoric acid, acetic acid, It is preferable to use an organic acid such as acid, maleic acid, sulfonic acid or formic acid, and a basic catalyst such as ammonia or trimethylammonium can also be used. These catalysts are used in an appropriate amount depending on the amount of the silane compound represented by the general formula (I), but preferably 0.001 to 0.003 per mole of the silane compound represented by the general formula (I). It is used in the range of 5 moles.

  In addition, the hydrolysis and polycondensation include alcohol solvents such as methanol and ethanol, ether solvents such as ethylene glycol monomethyl ether, ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, N, N-dimethylformamide, and the like. It is preferably carried out in a solvent such as an amide solvent, an aromatic hydrocarbon solvent such as toluene or xylene, an ester solvent such as ethyl acetate, or a nitrile solvent such as butyronitrile.

  Also, water is present during this reaction. The amount of water can also be determined as appropriate, but if the amount is too large, the storage stability of the coating solution is reduced, so the amount of water is 1 mol of the silane compound represented by the general formula (I). 0 to 5 mol% is preferable, and a range of 0.5 to 4 mol is more preferable.

  The production of the silicone oligomer is carried out so as not to gel by adjusting the above conditions and blending.

  It is preferable from the viewpoint of workability that the silicone oligomer is used by dissolving in the same solvent as the reaction solvent. For this purpose, the reaction product solution may be used as it is, or the silicone oligomer may be separated from the reaction product solution and dissolved in the solvent again.

  For the silanol group present in the molecule of the silicone oligomer that reacts with the hydroxyl group on the surface of the fine particles, a silanol residue generated in the process of synthesizing the oligomer and not contributing to the condensation reaction is used. Further, in order to enhance the reactivity, the above-mentioned acid or alkali catalyst and water are added to a silicone oligomer solution dissolved in a solvent, and the remaining hydroxyl group is hydrolyzed in the oligomer molecule. It can also be increased by promoting a decomposition reaction (for example, a dealcoholization reaction of an alkoxy group). It is preferable that the silanol is introduced immediately before contact with the fine particles. This is because the reactivity is so high that self-polymerization of oligomers proceeds and the solution may gel.

  The method for treating the fine particle laminated film with the silicone oligomer is not particularly limited, but dip coating, spray coating, and the like are preferably used. The adhesion amount of the silicone oligomer to the fine particle laminated film is preferably in the range of 0.01 to 5% by weight, and more preferably 0.05 to 2% by weight. If the adhesion amount is less than 0.01% by weight, the effect of improving the mechanical strength is difficult to obtain, and if it exceeds 5% by weight, the curable resin may not easily enter the voids of the fine particle multilayer film during the transfer process.

  The treatment liquid and treatment conditions of the silicone oligomer when the fine particle laminated film is treated with the silicone oligomer are not particularly limited, but after being immersed in a solution in which the silicone oligomer is dissolved in a solvent or after spraying the solution In order to condense and bond the hydroxyl group on the surface of the fine particles and the functional group of the silicone oligomer (hydrolyzed if necessary) for drying, heating to 50 to 200 ° C., preferably 80 to 150 ° C. The heating time at this time is preferably 5 to 60 minutes, more preferably 10 to 30 minutes. When the solvent is used, the amount used is not particularly limited, but the amount that the solid content concentration of the silicone oligomer is 0.01 to 10% by weight, more preferably 0.05 to 5% by weight is suitable. The solvent is not particularly limited, and for example, alcohol solvents such as methanol and ethanol, and ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone are preferably used.

  By treating the fine particle laminate film with a silicone oligomer, a polymerizable unsaturated double bond can be imparted to the fine particle laminate film, and after transferring this to a molded body, a thermal radical reaction, electron beam irradiation, etc. Since it can be chemically bonded to the curable resin, the surface strength of the molded body can be improved.

  Examples of the molded body in which a thin film is formed on the surface using the thin film transfer material of the present invention include a curable resin film or sheet, other molded bodies, and a molded body obtained by coating an underlying molded body with a curable resin. is there. Examples of the curable resin include a coating resin such as a hard coat film resin, an acrylic film or a sheet resin.

  Examples of the base molded body include all solid products made of semiconductors such as resin, glass, and silicon, metals, inorganic oxides, and the like. The shape includes a film, a sheet, a plate, a curved shape, a cylindrical shape, a thread shape, and the like. Examples of the film-like or sheet-like material include polyesters such as polyethylene terephthalate, triacetyl cellulose, diacetyl cellulose, acetate butyrate cellulose, polyether sulfone, polyamide, polyimide, polypropylene, polymethylpentene, polyvinyl chloride, polyvinyl acetal, There are thermoplastic resins such as polymethyl methacrylate, polycarbonate, and polyurethane, and glass substrates. Those having a resin film or an inorganic film coated on the surface are also included. For example, a polyester film subjected to an easy adhesion treatment on one side, particularly an easily adhesive polyethylene terephthalate (adhesive PET) film can be preferably used.

  As the base molded body, an injection molded body can be used. As the resin for this, the material is not particularly limited as long as it can constitute the surface of the light guide plate, the optical lens, the display unit of various instruments, the window glass of automobiles, trains, etc. , Acrylic resins, styrene resins (ABS resins, AS resins, polyphenylene oxide styrene copolymers, etc.), polyolefin resins (polyethylene, polypropylene, etc.), polycarbonate resins, and the like.

  When the thin film is an antireflection film, a transparent material is used as the molded body, and the thin film formed on the surface itself has a wide range of applications as an antireflection material. Further, a thin film having an antireflection function may be formed on a polarizing plate used for an LCD display. For example, the front plate of various displays such as word processors, computers, TVs, display panels, mobile phones, the surface of the light guide plate used for liquid crystal display devices, sunglasses lenses made of transparent plastics, prescription glasses lenses, camera finder lenses Such as optical lenses, display portions of various instruments, window glass of automobiles, trains, and the like. In addition, even if these molded objects are the cases where they are formed with materials other than resin, for example, glass etc., the effect similar to resin can be exhibited.

  The thin film transfer material is laminated on the surface of the thin film transfer material by thermocompression bonding, so that the thin film transfer material fine particle film is embedded in the surface of the formed material, and then the temporary support is peeled off. The (fine particle laminated film) is transferred to the surface of the molded body. For this purpose, when the thin film (fine particle laminate film) of the thin film transfer material is in contact with the surface of the molded body (curable resin), the curable resin is not so large that the curable resin can enter the voids between the fine particles of the thin film. It must be hardened or softened and have fluidity. Further, the curable resin can be cured after the thin film is embedded in the curable resin. Further, the molded body may have a permanent support layer for imparting mechanical strength and environmental resistance on its surface, and using such a molded body having a permanent support layer formed on its surface, thin film transfer The thin film transfer material fine particle laminated film is buried in the uncured or softened surface of the permanent support layer by superimposing the fine particle laminated film side of the material on the permanent support layer and performing thermocompression bonding or actinic ray irradiation. Can be made. In this case, the resin of the permanent support layer enters the voids between the fine particles.

  Since the fine particle laminated film formed by the alternating lamination method has a higher ratio of voids to fine particles, it is easy to embed fine particles even on a surface having a certain degree of viscosity.

  Even if the surface to which the thin film (fine particle laminated film) on the surface of the curable resin is transferred is solid, it is only necessary that the fine particle laminated film can be buried by flowing or deforming by heating or pressing. . The surface to which the thin film (fine particle laminated film) on the surface of the curable resin is transferred preferably has a viscosity at a transfer temperature in the range of 1 mP · s to 500,000 mP · s.

  When a thin film transfer material for forming the antireflection film is transferred to the surface of the molded body, an excellent functional film such as an antireflection film can be formed on the surface of the molded body. Furthermore, if the thin film transfer material of the present invention is used, the functional film can be formed by a simple method by transfer, not by a vapor phase method such as vapor deposition or sputtering.

  Among the curable resins, for example, the permanent support layer preferably includes at least one of a thermoplastic resin, a thermosetting resin, or an active energy ray curable resin. Further, for example, useful as a resin for a hard coat layer includes a thermosetting monomer or a photocurable monomer, or an oligomer or polymer thereof and a mixture of a thermosetting monomer or a photocurable monomer, or a thermal polymerization initiator or Examples thereof include liquid substances obtained by blending a photopolymerization initiator and the like.

  As the resin for the hard coat layer, in particular, a liquid material obtained by blending a photopolymerization initiator or the like with an ultraviolet curable monomer, an oligomer thereof, a mixture of a polymer and the monomer, or the like can be suitably exemplified. Furthermore, a crosslinking agent component may be included.

  As said thermosetting monomer or photocurable monomer, a (meth) acrylate-type monomer is preferable, and it is more preferable that an acrylate-type monomer is included from the point which can be photocured in a short time. Examples of such acrylate monomers include n-butyl acrylate, n-pentyl acrylate, n-hexyl acrylate, n-octyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, stearyl acrylate, and the like. , N-butyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate and n-octyl acrylate are preferable, and 2-ethylhexyl acrylate is particularly preferable. Examples of methacrylate monomers include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, n-pentyl methacrylate, n-hexyl methacrylate, n-octyl methacrylate, isooctyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, stearyl methacrylate, and the like. These (meth) acrylate monomers may be used in combination of two or more.

  In addition to these (meth) acrylate monomers, white turbidity at the time of moisture absorption can be suppressed by appropriately using a (meth) acrylate monomer having a polar group. As the (meth) acrylate monomer having a polar group for this purpose, 2-hydroxyethyl acrylate, 1-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 1-hydroxypropyl acrylate, 4-hydroxybutyl Hydroxyl group-containing acrylates such as acrylate, 3-hydroxybutyl acrylate, 2-hydroxybutyl acrylate, 1-hydroxybutyl acrylate, polyethylene glycol monoacrylates such as diethylene glycol and triethylene glycol, polypropylene glycol monoacrylates such as dipropylene glycol and tripropylene glycol , Polybutylene glycol monoacrylates such as dibutylene glycol and butylene glycol Acrylate monomers bets such as the acryloyl groups of these monomers, such as methacrylate-based monomer was changed to methacryloyl group. Of these, acrylate monomers are preferred, and 2-hydroxyethyl acrylate, 1-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 1-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 3- Hydroxybutyl acrylate, 2-hydroxybutyl acrylate, and 1-hydroxybutyl acrylate are more preferable, and 2-hydroxyethyl acrylate is particularly preferable. Further, these (meth) acrylates may be used in combination of two or more kinds of system monomers.

  As the crosslinking agent component, a compound having two or more polymerizable unsaturated bonds in the molecule can be used. Such compounds include bisphenol A dimethacrylate, 1,4-butanediol dimethacrylate, 1,3-butylene glycol dimethacrylate, diethylene glycol dimethacrylate, glycerol dimethacrylate, neopentyl glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene. Glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, tris (methacryloxyethyl) isocyanurate, pentaerythritol tetramethacrylate, dipentaerythritol tetramethacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol Pentame Acrylate, bisphenol A diacrylate, 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, diethylene glycol diacrylate, glycerol diacrylate, neopentyl glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, Tetraethylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, tris (acryloxyethyl) isocyanurate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, etc. Can be mentioned.

  As the compound having two or more polymerizable unsaturated bonds in the molecule, the following can be used. These monomers can be used alone or in combination of two or more.

Formula (a)

  (In the formula, R represents an ethylene group or a propylene group, and m and n each independently represents an integer of 1 to 20.) Diacrylate compounds of an alkylene oxide adduct of bisphenol A, A compound in which the acryloyl group is replaced with a methacryloyl group.

General formula (b)

  (In the formula, m and n each independently represents an integer of 1 to 10.) An epichlorohydrin modified product of bisphenol A and an addition esterified product of acrylic acid, and these acryloyl groups were changed to methacryloyl groups. Compound.

Formula (c)

  (In the formula, R represents an ethylene group or a propylene group, and m and n each independently represents an integer of 1 to 20.) Diacrylate compounds of an alkylene oxide adduct of phosphoric acid represented by these, A compound in which an acryloyl group is replaced with a methacryloyl group.

General formula (d)

  (In the formula, m and n each independently represent an integer of 1 to 10.) An epichlorine modified product of phthalic acid and an addition esterified product of acrylic acid, and these acryloyl groups were replaced with methacryloyl groups. Compound.

General formula (e)

  (In the formula, m and n each independently represents an integer of 1 to 20.) 1,6-hexanediol epichlorine-modified product and acrylic acid addition esterified product (acryloyl group in one molecule) 2), a compound obtained by replacing these acryloyl groups with methacryloyl groups.

Formula (f)

  (Wherein, R represents an ethylene group or a propylene group, and three m's each independently represents an integer of 1 to 20). Triacrylate compounds of alkylene oxide adducts of phosphoric acid represented by these, A compound in which the acryloyl group is replaced with a methacryloyl group.

General formula (g)

(In the formula, R represents an ethylene group or a propylene group, and m, m ′ and m ″ each independently represents an integer of 1 to 20.) Trimethylolpropane alkylene oxide adduct tri Acrylate compounds, compounds obtained by replacing these acryloyl groups with methacryloyl groups.

  As the polymerization initiator used together with the heat or photocurable monomer, any of those that can be used for normal radical polymerization, such as a thermal polymerization initiator, a redox catalyst, and a photopolymerization initiator, can be used. The polymerization initiator is preferably used in the range of 0.01 to 10% by weight based on the total amount of monomers.

  As the thermal polymerization initiator, benzoyl peroxide, lauroyl peroxide, di-t-butylperoxyhexahydroterephthalate, t-butylperoxy-2-ethylhexanoate, 1,1-t-butylperoxy-3 Organic peroxides such as 1,3,5-trimethylcyclohexane, azo such as azobisisobutyronitrile, azobis-4-methoxy-2,4-dimethylvaleronitrile, azobiscyclohexanone-1-carbonitrile, azodibenzoyl Examples of redox catalysts include water-soluble catalysts such as potassium persulfate and ammonium persulfate, and peroxides or combinations of persulfates and reducing agents.

  As said photoinitiator, what has a sensitivity to light rays, such as an ultraviolet-ray, is used, for example. For example, benzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone (Michler's ketone), 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-hydroxy-2-methyl-1- Phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, oligo (2-hydroxy-2-methyl-1- (4- (1-methyl Vinyl) phenyl) propanone) and the like, but those that do not color the resin composition are 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [4 -(2-Hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propyl Α-hydroxyalkylphenone compounds such as pan-1-one, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl- Acylphosphine oxide compounds such as pentylphosphine oxide and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) Propanone) and combinations thereof are preferred. In order to produce a particularly thick sheet, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, A photopolymerization initiator containing an acylphosphine oxide compound such as 2,4,6-trimethylbenzoyl-diphenylphosphine oxide is preferred. In order to reduce the odor of the sheet, oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone) is preferable. A preferable blending amount of these photopolymerization initiators is 0.5 to 2% by weight with respect to the total amount of monomers, and a plurality thereof may be used in combination. Furthermore, when using a photopolymerization initiator, a photosensitizer such as benzophenone or naphthalene can be added as necessary. Furthermore, mercaptan compounds, thioglycol, carbon tetrachloride, α-methylstyrene dimer, etc. can be added as necessary as molecular weight modifiers.

  Such a curable resin is particularly preferably applied as a hard coat agent on the base molded body, for example, about 0.5 to 5.0 μm. As a coating method, a known method such as roll coating, spin coating, dip coating or the like can be employed.

  As the curable resin for the acrylic film or sheet, those having the same composition as described above can be used.

  As described above, the film (or layer) of the curable resin can be formed by a method of coating on the base molded body. Further, instead of the base molded body, a curable resin film may be formed by coating or the like on a peelable substrate made of a resin film, glass, metal or the like. At this time, after the thin film is transferred to the surface, the peelable substrate is peeled off, and a molded body without a base molded body is obtained.

  Moreover, the film | membrane (or layer) of curable resin can also be obtained by the continuous cast board manufacturing method. For example, the thin film transfer material of the present invention is formed in a space formed by the opposed surfaces of a pair of endless belts that run facing each other at a predetermined interval, and two gaskets that run following the running of the endless belt. In addition, the curable resin is injected and the fine particle laminated film of the thin film transfer material is buried to cure the curable resin. Thereafter, the molded body with the temporary support 2 is taken out from the endless belt, and the temporary support is peeled off to obtain a molded body with a thin film.

  In addition, in the injection molding method, a thin film transfer material is sandwiched in an injection mold, and then a molded material is formed by injecting a molten material onto the fine particle laminated film side of the thin film transfer material. Then, the fine particle laminated film of the thin film transfer material is buried. Then, a molded object with a thin film is obtained by peeling a temporary support body.

  Next, the present invention will be described with reference to the drawings.

  FIG. 1 is a cross-sectional view schematically showing an example of the thin film transfer material of the present invention. The thin film transfer material 1 has a structure in which a fine particle laminated film 3 is formed on the surface of a temporary support 2. The fine particle laminated film 3 includes fine particles and a polymer electrolyte, and the fine particles form a layer. A plurality of such fine particle layers are laminated (shown as three layers in the drawing), and a polymer electrolyte exists between each layer. To do.

  There are voids between the fine particles of the fine particle laminated film 3, and a silicone oligomer is attached so as to enter the voids (not shown).

  FIG. 2 is a cross-sectional view showing an example of a molded body with a thin film according to the present invention. Are embedded to form the fine particle transfer layer 6. The space between the fine particles of the fine particle transfer layer 6 is filled with plastic, which is the constituent material 5 of the molded body, and the surface is said that the fine particle laminated film 3 and the constituent material 5 are integrated into a composite. Good. A silicone oligomer is interposed between the fine particles in the fine particle laminated film 3 and the constituent material 5 (not shown).

  FIG. 3 is a cross-sectional view showing an example of a method for producing a molded body with a thin film. A thin film transfer material 1 and a molded body 7 are prepared (FIG. 3A). The thin film transfer material 1 is obtained by laminating a fine particle laminated film 3 to which a silicone oligomer is attached on a temporary support 2. In the molded body 7, a curable resin layer (however, an uncured precursor) 9 is laminated on the surface of a resin molded body (underlying molded body) 8. The curable resin layer 9 is made of a resin that can be cured by heating or irradiation with actinic rays. Next, the thin film transfer material 1 and the molded body 7 are overlaid so that the fine particle laminated film 3 and the curable resin layer 9 are in contact with each other. In this overlapped state, pressure is applied from the temporary support 3 side, and further heating and / or irradiation with actinic rays is performed. At this time, curing may be performed completely or partially. At this point, the fine particle transfer layer 6 is formed in a state where the fine particle multilayer film 3 is buried in the curable resin layer 9 which is partially or completely cured (FIG. 3B). Thereafter, the temporary support 3 is peeled off. The partially cured curable resin layer 9 is then further cured as necessary. In this way, a molded body with a thin film is obtained (FIG. 3C).

  The degree of curing in the above is preferably such that the temporary support 3 can be easily peeled off and the thin film or the curable resin layer 9 does not remain on the temporary support 3 when peeled off.

  In the above, a peelable substrate may be used instead of the resin molded body (base molded body) 8.

  The degree of cure (curing rate) of the curable resin layer can be measured by observing, with an infrared absorption spectrum, a functional group that causes a curing reaction upon heating and / or irradiation with actinic rays and disappears due to the reaction. .

For example, in the case of a monomer containing a polymerizable unsaturated bond, it can be calculated by observing the absorption of ethylenic double bonds observed in the vicinity of a wave number of 1630 cm ⁻¹ in the infrared absorption spectrum. By normalizing the initial value of the strength and the value after disappearance to 100 and 0, it is possible to calculate the curing rate during curing (the degree of curing of partial curing) (“Measurement of the degree of curing / curing behavior of the resin”) And Evaluation Method ”Science and Technology, published July 13, 2007).

  Moreover, in the case of a thermosetting type, it can measure using DSC (differential scanning thermal analysis). DSC (Differential Scanning Calorimetry) is based on the zero level method in which the amount of heat is supplied or removed so as to constantly cancel out the temperature difference from a standard sample that does not generate heat or endotherm within the measurement temperature range. A measuring device is commercially available and can be measured using it. The reaction of the thermosetting adhesive is an exothermic reaction, and when the temperature of the sample is increased at a constant temperature increase rate, the sample reacts to generate heat. The calorific value is output to a chart, the area surrounded by the calorific curve and the base line is obtained with the baseline as a reference, and this is defined as the calorific value. Measurement is performed at a temperature increase rate of 5 to 10 ° C./min from room temperature to 200 ° C., and the above calorific value is obtained. Some of these are performed automatically, and can be easily performed by using them. Next, the calorific value obtained by applying a permanent support layer to the support and drying it is determined as follows. First, the total calorific value of the uncrosslinked / uncured permanent support layer obtained by drying the solvent using a vacuum dryer at 25 ° C. is measured, and this is defined as A (J / g). Next, the calorific value of the coated and dried permanent support layer is measured. The curing rate C (%) of the permanent support layer (the state in which heat generation is completed by heating and drying) is given by the following mathematical formula (I).

Formula (I)
[Equation 1]
C (%) = {(A−B / A)} × 100 (I)
In this way, a thin film can be applied to the surface of the resin molded body. The pressurization and heating from the temporary support can be performed using a silicon rubber roll, for example. In this case, the surface of the silicon rubber roll is suitably at a temperature of about 15 ° C. or more and 250 ° C. or less and a pressure of about 1 kg / cm ² or more and 20 kg / cm ² or less.

  A thin film with a thin film on both sides, using a thin film transfer material in which a fine film laminated film with a silicone oligomer attached is formed on the temporary support as a temporary support, and is wound into a roll. An example of the continuous manufacturing method of the attached molded body will be described with reference to FIG.

  In FIG. 4, a resin sheet 401 is a continuously formed molded body, and a curable resin layer 402 (uncured) is coated on both surfaces of the resin sheet 401 by coating heads 411 and 412. Further, the coated resin sheet 401 is bonded to the thin film transfer materials 421 and 422 from both sides, and the curable resin layer 402 and the thin film transfer are controlled while controlling the film thickness by adjusting the press pressure by the press rolls 431 and 432. The materials 421 and 422 are stacked so that they are in contact with each other. The curable resin layer 402 is made of a resin that can be cured by irradiation with actinic rays, and the thin film transfer materials 421 and 422 are fine particles in which silicone oligomers adhere to the surfaces of the temporary supports 451 and 452 that are in contact with the curable resin layer 402. A laminated film is formed. Actinic rays are irradiated to the resin sheet 401 on which the thin film transfer materials 421 and 422 are superimposed by actinic ray irradiation devices 441 and 442. The irradiation amount of the actinic ray is set such that the temporary supports 451 and 452 can be easily peeled off and the thin film and the curable resin layer 402 are not left on the temporary supports 451 and 452 when peeled off.

  Next, the temporary supports 451 and 452 are peeled from the resin sheet 401 irradiated with actinic rays through the press rolls 461 and 462. The thin film-formed body 403 obtained by this peeling is irradiated with actinic rays using actinic ray irradiation devices 471 and 472, and the degree of cure of the curable resin layer 402 is promoted. It is preferable that the curing rate of the curable resin layer 402 is 74% or more at the end of irradiation.

  In this manner, a molded body with a thin film having excellent processing cost and productivity can be obtained. The curable resin layer 402 may be a resin that can be cured by heating. At this time, the curable resin layer 402 is cured by heating. Further, when the surface on which the thin film is formed may be one side, the thin film may be formed by coating the curable resin layer only on one side.

  Hereinafter, the present invention will be described by way of examples. The present invention is not limited to these examples.

1. Temporary support A PET film (A4100, manufactured by Toyobo Co., Ltd., 150 mm × 150 mm × 125 μm thickness) having a resin layer provided with a polar group called an easy adhesion layer on one side was used.

2. Preparation of inorganic thin film transfer material (formation of fine particle laminated film on temporary support)
As a fine particle aqueous dispersion, 1% by weight of silica water dispersion (Snowtex (ST) ZL, manufactured by Nissan Chemical Industries, silica sol) in which spherical silica fine particles having an average primary particle diameter of 85 nm measured by BET method are dispersed, and 1 wt% of zinc antimonate aqueous dispersion in which conductive zinc antimonate fine particles having an average primary particle diameter of 15 nm measured by the BET method are dispersed (CELNAX CXZ330H-F2, manufactured by Nissan Chemical Industries, Ltd., zinc oxide sol) Prepared. The pH of these fine particle dispersions was not adjusted. As the polymer electrolyte, a PDDA aqueous solution of 0.3% by weight was prepared, and the pH was adjusted to 9.

  First, the above PET film (temporary support) is immersed in an aqueous PDDA solution for 1 minute, immersed in ultrapure water for rinsing for 3 minutes (a), immersed in an aqueous silica dispersion for 1 minute, and then rinsed. Step (a) of immersing in ultrapure water for 3 minutes was performed in this order. This step (a) once and step (b) once are sequentially performed as one cycle, and this cycle is repeated four times (the number of fine particles alternately laminated), and the silica fine particle laminated film (first type) is formed on the temporary support surface. Was made. Subsequently, the zinc antimonate aqueous dispersion and the PDDA aqueous solution were used, and the antimony zinc oxide fine particle laminated film (second type) was formed on the silica fine particle laminated film in accordance with the method for producing the silica fine particle laminated film with the number of alternate laminations being five. ) To obtain a temporary support (inorganic thin film transfer material) having two kinds of fine particle laminated films.

3. Undermolded body with an uncured coating film (curable resin layer)
Polymethyl methacrylate (PMMA, manufactured by Mitsubishi Rayon Co., Ltd., Acrylite L, refractive index 1.49, 150 mm × 150 mm × 1 mm thickness) was used as the base molded body. PMMA was subjected to a primer treatment in order to enhance the adhesion with the permanent support layer. As a primer agent, a urethane coating agent diluted with 1.0% by weight of methyl ethyl ketone (Cortron MW-060, manufactured by Sanyo Chemical Industries, Ltd.) was used. The primer agent was applied to a molded body with a thickness of 30 μm using an applicator, and heat-treated at 80 ° C. for 30 minutes after drying.

  In addition, as a curable resin, 97 parts by weight of a photocurable hard coat resin (Hitaroid 7902, manufactured by Hitachi Chemical Co., Ltd.) and 3 parts by weight of a photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone) A mixed photocurable resin was used. This photocurable resin was applied to a thickness of 30 μm using an applicator on the primer-treated surface of the base molded body. The photocurable resin was in an uncured state.

4). 2. Fabrication of molded body to which fine particle laminated film is transferred 1. An undermolded body having a coating film of an uncured photocurable resin prepared in 1. The thin film transfer material was placed so that the coating surface of the photocurable resin and the fine particle laminated film formed on the surface without the easy adhesion layer face each other. Bonding was performed using a roll laminator (HLM-1500, manufactured by Hitachi Chemical Co., Ltd.) under conditions of a roll load of 3 kg / cm ² , a feed rate of 2 m / min, and a temperature of 25 ° C. The viscosity of the above-mentioned photocurable resin at this temperature was 9,000 mP · s (the viscosity was measured with an E-type viscometer (for example, TV-33 manufactured by Tokyo Keiki Co., Ltd. can be used) Viscosity at a temperature of 25 ° C. The same applies hereinafter. The above steps were performed in an atmosphere where ultraviolet rays were blocked.

This bonded product was irradiated with 2000 mJ / cm ² of ultraviolet light from the thin film transfer material side using an ultraviolet exposure device (Dainippon Screen Mfg. Co., Ltd., MAP-1200) to partially cure the photocurable resin layer.

Subsequently, the PET film which is a temporary support was peeled from the molded body. It was confirmed that the fine particle laminated film was peeled off from the PET film. That is, the fine particle laminated film was transferred to a partially cured photocurable resin layer (hard coat layer) on the molded body. In order to increase the curing rate of the photocurable resin layer (hard coat layer), 3000 mJ / cm ² of ultraviolet rays were additionally irradiated from the fine particle laminated film side.

  In this manner, a molded body to which the fine particle laminated film was transferred was produced.

  In this molded body, a layer formed by transferring the fine particle laminate film (hereinafter referred to as “fine particle transfer layer”) is located on the outermost surface of the hard coat layer, and the fine particle laminate film is buried in the hard coat layer. . The total thickness of the hard coat layer including the fine particle transfer layer was 20 μm.

5. Measurement of hardness, transmittance, and surface reflectance The pencil hardness of the fine particle transfer layer of the molded body onto which the fine particle laminated film was transferred is 4H, and the steel wool resistance is not damaged at a load of 500 g, and is scratched at 600 g. It was.

  When the transmission spectrum of the molded product (PMMA) onto which the fine particle laminated film was transferred was measured with a visible ultraviolet spectrophotometer (manufactured by JASCO Corporation, V-570), the maximum transmittance at a wavelength of 400 to 800 nm was It was 92.5%.

  Also, black adhesive tape (VT-196, manufactured by Nichiban Co., Ltd.) is bubbled on the surface of the molded body (PET film) to which the fine particle laminated film is transferred, on which the hard coat layer is not formed, so that reflection on the back surface can be ignored. The surface reflectance spectrum of the hard coat layer surface was measured with an instantaneous photometric spectrophotometer (F20, manufactured by Filmetrics Co., Ltd.). The minimum surface reflectance at a wavelength of 400 to 800 nm was 2.7%.

  Since the transmittance of the molded body in which only the hard coat layer to which the fine particle laminated film is not transferred is formed is 92.0% and the surface reflectance is 4.3%, the fine particle transfer layer functions as an antireflection film. I understood it.

  A PET film (A4100, manufactured by Toyobo Co., Ltd., 150 mm × 150 mm × 125 μm thickness) having a resin layer provided with a polar group called an easy adhesion layer on one side was used.

  As fine particles, a silica dispersion (IPA-ST-ZL, manufactured by Nissan Chemical Industries, Ltd., silica sol) in which spherical silica fine particles having an average primary particle diameter of 85 nm measured by the BET method were dispersed in isopropanol (IPA) was prepared. . As the fine particle dispersion, a 1.0% by weight fine particle dispersion was prepared. The fine particle dispersion was coated on a surface of the PET film without an easy-adhesion layer using an applicator so as to have a dry film thickness of 0.1 μm, thereby preparing a silica fine particle laminated film. A drying machine (manufactured by Yamato Kagaku, 80 ° C., 10 minutes) was used for drying the coating film. Next, a zirconia dispersion (ELCOM HK-1002ZRV, JGC Catalysts and Chemicals, zirconia sol) in which spherical zirconia fine particles having an average primary particle diameter of 20 nm measured by the BET method were dispersed in IPA was prepared. As the fine particle dispersion, a 1.0% by weight fine particle dispersion was prepared. A thin film transfer material was prepared by coating the silica fine particle laminated film with an applicator so as to have a dry film thickness of 0.1 μm. A drying machine (manufactured by Yamato Kagaku, 80 ° C., 10 minutes) was used for drying the coating film.

  Except for using this thin film transfer material, a molded body to which the fine particle laminated film was transferred was prepared according to Example 1.

  The pencil hardness of the fine particle transfer layer of the molded product to which the fine particle laminated film was transferred was 4H, and the steel wool resistance was not damaged at a load of 500 g, and was damaged at 600 g.

  When the transmission spectrum of the molded body to which the fine particle laminated film was transferred was measured in the same manner as in Example 1, the maximum transmittance at a wavelength of 400 to 800 nm was 92.7%. When the surface reflection spectrum on the surface of the hard coat layer was measured in the same manner as in Example 1, the minimum surface reflectance was 2.4%, and it was found that the fine particle transfer layer functions as an antireflection film.

1.2 Production of Temporary Support Having Fine Particle Laminate Film PET Film (A4100, manufactured by Toyobo Co., Ltd., 150 mm × 150 mm × 125 μm) having a resin layer provided with a polar group called an easy adhesion layer on one side Thickness) was used.

  In accordance with the method for producing the thin film transfer material of Example 1, two types of fine particle laminated films, that is, a laminated film of silica fine particles and a laminated film of antimony zinc oxide fine particles are provided on the surface of the PET film without the easy adhesion layer. A temporary support was obtained.

2. Preparation of silicone oligomer A glass flask equipped with a stirrer and a thermometer was charged with a solution containing 30 g of 3-methacryloxypropyltrimethoxysilane (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.) and 30 g of methanol, Acetic acid 0.23g and pure water 6.5g were added, and it stirred at room temperature (25 degreeC) for 1 hour. The obtained silicone oligomer has a degree of polymerization of siloxane units of 3 (converted from a weight average molecular weight by GPC, the same shall apply hereinafter), and has a silanol group as a terminal functional group that reacts with a hydroxyl group. Methyl isobutyl ketone was added to the obtained silicone oligomer solution and diluted to a solid content of 1% by weight to prepare a silicone oligomer treatment liquid.

3. Production of Thin Film Transfer Material The temporary support having the fine particle laminated film obtained above was immersed in the silicone oligomer treatment liquid for 30 seconds, pulled up at 2 mm / second, and dried at 100 ° C. for 30 minutes to obtain a thin film transfer material.

4). Preparation of molded body to which fine particle laminated film was transferred [transfer of fine particle laminated film to molded body (curable resin layer)] and measurement of physical properties According to Example 1, except that the thin film transfer material was used. A molded body to which the laminated film was transferred was produced.

  The pencil hardness of the fine particle transfer layer of the molded body to which the fine particle laminated film was transferred was 4H, and the steel wool resistance was not damaged at a load of 700 g, and was damaged at 800 g.

  When the transmission spectrum of the molded body to which the fine particle laminated film was transferred was measured in the same manner as in Example 1, the maximum transmittance at a wavelength of 400 to 800 nm was 93.9%. When the surface reflection spectrum on the surface of the hard coat layer was measured in the same manner as in Example 1, the minimum surface reflectance was 1.2%, and it was found that the fine particle transfer layer functions as an antireflection film.

  Using the same apparatus as in Example 3, 0.23 g of acetic acid and pure water 6. were added to a solution prepared by mixing 30 g of 3-acryloxypropyltrimethoxysilane (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.) and 30 g of methanol. 9g was added and it stirred at room temperature (25 degreeC) for 1 hour. The obtained silicone oligomer has a siloxane unit polymerization degree of 4 and has a silanol group as a terminal functional group that reacts with a hydroxyl group. Methyl isobutyl ketone was added to the obtained silicone oligomer solution and diluted to 1% by weight of solid content to prepare a silicone oligomer treatment liquid.

  A thin film transfer material was prepared according to Example 3 except that this silicone oligomer treatment liquid was used. Further, except that this thin film transfer material was used, a fine particle laminated film was prepared according to Example 1. A transferred molded body was produced.

  The pencil hardness of the fine particle transfer layer of the molded body to which the fine particle laminated film was transferred was 4H, and the steel wool resistance was not damaged at a load of 700 g, and was damaged at 800 g.

  When the transmission spectrum of the molded body to which the fine particle laminated film was transferred was measured in the same manner as in Example 1, the maximum transmittance at a wavelength of 400 to 800 nm was 94.2%. When the surface reflection spectrum on the surface of the hard coat layer was measured in the same manner as in Example 1, the minimum surface reflectance was 1.2%, and it was found that the fine particle transfer layer functions as an antireflection film.

(Comparative Example 1)
(Preparation of molded product with zinc antimonate fine particles transferred)
As a fine particle aqueous dispersion, 1% by weight of a zinc antimonate aqueous dispersion in which conductive zinc antimonate fine particles having an average primary particle diameter of 15 nm measured by the BET method are dispersed (CELNAX CXZ330H-F2, manufactured by Nissan Chemical Industries, Ltd.) Zinc oxide sol) was prepared. The pH of the fine particle dispersion was not adjusted. As the polymer electrolyte, a PDDA aqueous solution of 0.3% by weight was prepared, and the pH was adjusted to 9.

  First, using the zinc antimonate aqueous dispersion and the PDDA aqueous solution, zinc antimonate fine particles on a PET film (temporary support) with the number of alternate laminations set to 5 according to the method for producing the thin film transfer material of Example 1 A laminated film was produced.

  Except for using the temporary support on which the zinc antimonate fine particle laminated film was formed, a molded body to which the fine particle laminated film was transferred was produced in the same manner as in Example 1.

  The pencil hardness of the fine particle transfer layer of the molded body to which the fine particle laminated film was transferred was 4H, and the steel wool resistance was not damaged at a load of 200 g, and was damaged at 300 g.

(Comparative Example 2)
As a fine particle aqueous dispersion, 0.5% by weight of silica water dispersion in which spherical silica fine particles having an average primary particle diameter of 50 nm measured by the BET method are dispersed (Snowtex (ST) XL, manufactured by Nissan Chemical Industries, Ltd., silica sol ) And 1% by weight of zinc antimonate aqueous dispersion in which conductive zinc antimonate fine particles having an average primary particle diameter of 15 nm measured by BET method are dispersed (CELNAX CXZ330H-F2, manufactured by Nissan Chemical Industries, Ltd., zinc oxide) Sol) was prepared. The pH of these fine particle dispersions was not adjusted. As the polymer electrolyte, a PDDA aqueous solution of 0.3% by weight was prepared, and the pH was adjusted to 9.

  First, using the silica aqueous dispersion and the PDDA aqueous solution, a silica fine particle laminated film is produced on a PET film (temporary support) with the number of alternate laminations three times according to the method for producing the thin film transfer material of Example 1. did. Subsequently, using the zinc antimonate aqueous dispersion and the PDDA aqueous solution, an antimony zinc oxide fine particle laminated film is formed on the silica fine particle laminated film with an alternate lamination number of 5 according to the method for producing the silica fine particle laminated film, A temporary support (thin film transfer material) having two kinds of fine particle laminated films was obtained.

  Except for using this thin film transfer material, a molded body to which the fine particle laminated film was transferred was prepared according to Example 1.

  The pencil hardness of the fine particle transfer layer of the molded body onto which the fine particle laminated film was transferred was 4H, and the steel wool resistance was not damaged at a load of 100 g, and was damaged at 200 g.

(Comparative Example 3)
As a fine particle aqueous dispersion, 0.5% by weight of silica water dispersion in which spherical silica fine particles having an average primary particle diameter of 15 nm measured by the BET method are dispersed (Snowtex (ST) 20, manufactured by Nissan Chemical Industries, Ltd., silica sol ) And 1% by weight of zinc antimonate aqueous dispersion in which conductive zinc antimonate fine particles having an average primary particle diameter of 15 nm measured by BET method are dispersed (CELNAX CXZ330H-F2, manufactured by Nissan Chemical Industries, Ltd., zinc oxide) Sol) was prepared. The pH of these fine particle dispersions was not adjusted. As the polymer electrolyte, a PDDA aqueous solution of 0.3% by weight was prepared, and the pH was adjusted to 9.

  First, using the silica aqueous dispersion and the PDDA aqueous solution, a silica fine particle laminated film is produced on a PET film (temporary support) with the number of alternate laminations three times according to the method for producing the thin film transfer material of Example 1. did. Subsequently, using the zinc antimonate aqueous dispersion and the PDDA aqueous solution, an antimony zinc oxide fine particle laminated film is formed on the silica fine particle laminated film with an alternate lamination number of 5 according to the method for producing the silica fine particle laminated film, A temporary support (thin film transfer material) having two kinds of fine particle laminated films was obtained.

  Except for using this thin film transfer material, a molded body to which the fine particle laminated film was transferred was prepared according to Example 1. The pencil hardness of the fine particle transfer layer of the molded body to which the fine particle laminated film was transferred was 4H, and the steel wool resistance was 100 g and was damaged.

Table 1 summarizes the compositions and evaluations of Examples and Comparative Examples.

  Measurement methods and evaluation methods other than the transmittance and surface reflectance described in Example 1 will be described below.

(Measurement of pencil hardness)
The pencil hardness was measured as follows according to JIS standards (JIS-K-5400-1990).

  First, the sample was pressed against a pencil fixed at an angle of 45 ° with respect to the sample. The load applied by the pencil to the sample was 1.00 ± 0.05 kg. The pencil powder adhering to the sample was blown with air, and the remaining pencil powder was removed by pressing a plastic eraser (PE01, manufactured by dragonfly pencil). When scratches that slightly bite on the surface of the film were seen, it was determined that “scratched”. The pencil hardness symbol of the sample was the pencil density symbol when the film was scratched twice or more in five tests. For example, the pencil hardness of a sample in which a 2H pencil scratches twice and an H pencil scratches once is H.

(Evaluation of steel wool resistance)
The hard coat layer surface of the molded product (PET film) onto which the fine particle laminated film has been transferred is loaded with steel wool (manufactured by Nippon Steel Wool Co., Ltd., # 0000), and 10 times reciprocating friction at a stroke width of 25 mm and a speed of 25 mm / sec The surface after the treatment was visually evaluated for scratches. Steel wool is gathered to about 10mmφ, and the surface is made uniform by cutting and rubbing so that the surface is uniform. The load is in the range of 100 to 800g, and the load is changed in units of 100g. went. In the table, it is indicated by the load that was not damaged.

1: Thin film transfer material 2: Temporary support 3: Fine particle laminated film 4: Molded body 5 with thin film: Plastic 6: Fine particle transfer layer 7: Molded body precursor 8: Resin molded body 9: Curable resin layer 401: Continuous Resin sheet 402 formed into: curable resin layer 403: molded body with thin film 411, 412: coating head 421, 422: thin film transfer material 431, 432, 461, 462: press rolls 441, 442, 471, 472: Actinic ray irradiation devices 451 and 452: peeled temporary support

Claims (22)

A thin film transfer material comprising a temporary support and a fine particle laminated film formed on at least one surface of the temporary support,
(1) The laminate film is a laminate of one or two or more fine particle layers containing fine particles, and has a void between at least one fine particle of each fine particle layer,
(2) The laminated film is a laminate of two or more kinds of fine particle layers different in at least one of the refractive index and the average primary particle diameter of the fine particles, or one or two or more of one kind of fine particle layer. ,
(3) The thin film transfer material, wherein an average primary particle diameter of fine particles constituting one or more fine particle layers of the first kind from the temporary support side of the laminated film is in a range of 70 to 500 nm.   The thin film transfer material according to claim 1, wherein the fine particles are inorganic oxides.   3. The thin film transfer according to claim 2, wherein the inorganic oxide is made of an oxide containing at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium, niobium, zinc, tin, cerium and magnesium. Wood.   The thin film transfer material according to any one of claims 1 to 3, wherein the fine particles have a hollow or porous structure on the surface or inside thereof.   The thin film transfer material according to claim 1, wherein the fine particle layer is a laminate of fine particles and a polymer electrolyte, or a layer obtained by mixing a polymer electrolyte with fine particles.   The thin film transfer material according to claim 1, wherein the fine particle laminated film is an antireflection film.   The thin film transfer material according to claim 1, wherein a silicone oligomer having a polymerizable unsaturated double bond is attached to the fine particle laminated film. (1) a step of alternately immersing the temporary support in a dispersion of fine particles having an ionic surface charge and a polymer electrolyte solution having a charge opposite in sign to the surface charge of the fine particles, or (2 ) Including a fine particle laminate film forming step of performing either one of a polymer electrolyte solution and a step of alternately immersing at least once in a dispersion of fine particles having a surface charge opposite in sign to the charge of the polymer electrolyte;
In the fine particle laminated film forming step, at least the fine particles of the fine particle dispersion to be immersed first have an average primary particle diameter in the range of 70 to 500 nm,
A method for producing a thin film transfer material, wherein a fine particle laminated film having a gap between at least one fine particle is formed on a temporary support by the fine particle laminated film forming step.   9. The method for manufacturing a thin film transfer material according to claim 8, further comprising a rinsing step after each dipping step and before the next step.   Including a fine particle layered film forming step of applying the fine particle dispersion once or more to the temporary support, and the fine particles of the fine particle dispersion to be applied at least first have an average primary particle diameter in the range of 70 to 500 nm, A method for producing a thin film transfer material, comprising forming a fine particle laminated film having a void between at least one fine particle on the temporary support by the forming step. Including a fine particle multilayer film forming step in which the temporary support is alternately applied to the fine particle dispersion and the polymer electrolyte solution at least once;
In the fine particle laminated film forming step, at least the fine particles of the fine particle dispersion to be applied first have an average primary particle diameter in the range of 70 to 500 nm,
A method for producing a thin film transfer material, wherein a fine particle laminated film having a gap between at least one fine particle is formed on a temporary support by the fine particle laminated film forming step. Furthermore, it includes a step of pulling out the sheet-like temporary support wound up in a roll shape,
The manufacturing method of the thin film transfer material in any one of Claims 8-11 which perform the said microparticle laminated film formation process continuously.   A process comprising a step of attaching a silicone oligomer having one or more functional groups that react with hydroxyl groups and one or more polymerizable unsaturated double bonds in the molecule to the fine particles of the fine particle laminated film formed on the temporary support. The manufacturing method of the thin film transfer material in any one of 8-12.   A molded body with a thin film in which the fine particle laminated film of the thin film transfer material according to any one of claims 1 to 7 is buried and fixed by transfer on a surface of the molded body.   The molded body with a thin film according to claim 14, wherein the molded body has a permanent support layer on the surface thereof.   The molded article with a thin film according to claim 15, wherein the permanent support layer contains at least one of a thermoplastic resin, a thermosetting resin, and an active energy ray curable resin.   The fine particle laminated film of the thin film transfer material according to any one of claims 1 to 7 is transferred to an uncured or softened surface of the molded body to bury the fine particle laminated film on the surface of the molded body. The manufacturing method of the molded object with a thin film.   The method for producing a molded body with a thin film according to claim 17, wherein the molded body has a permanent support layer on the surface thereof.   The method for producing a molded body with a thin film according to claim 18, wherein the permanent support layer contains at least one of a thermoplastic resin, a thermosetting resin, or an active energy ray curable resin.   A step of sandwiching a thin film transfer material in an injection mold, and forming a molded body by injecting a molten material to the fine particle laminated film side of the thin film transfer material, and at the same time, fine particle lamination of the thin film transfer material on the surface of the molded body The manufacturing method of the molded object with a thin film of Claim 17 including the process of embedding a film | membrane and the process of peeling a temporary support body after that.   A step of burying the fine particle laminated film of the thin film transfer material on the surface of the uncured or softened molded article by thermocompression bonding the fine particle laminated film side of the thin film transfer material on the molded article, and then a temporary support The manufacturing method of the molded object with a thin film of Claim 17 including the process to peel.   By using a molded body having a permanent support layer formed on the surface, the fine particle laminated film side of the thin film transfer material is overlaid on the permanent support layer, and then subjected to thermocompression bonding or actinic ray irradiation, whereby the permanent support layer is uncured. The manufacturing method of the molded object with a thin film of Claim 19 which embed | buries the fine particle laminated film of the said thin film transfer material in the surface of which it was softened.

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