JP2018039133A - Thin film with substrate - Google Patents

Abstract

[Problem] To provide a thin film on a substrate that can be formed without impairing the original properties and functions, and that can be peeled off easily and at low cost using simple equipment and that can be easily separated and recovered. [Solution] The thin film on a substrate includes a substrate, a release layer made of a water-soluble inorganic material provided on the substrate, and a raw thin film that is provided on the release layer and is to be separated, pulverized, and used as a powder, and is characterized in that the water-soluble inorganic material is an inorganic oxide that dissolves in water. [Selected Figure] Figure 1

Description

  The present invention relates to a thin film with a substrate.

  As the pulverization technology advances, it is possible to produce small-sized fine powder, and fine powder is used as a functional material in architecture, vehicles, electrical / electronic, optical, protection / reinforcement, surface modification, and other fields. Nanometer-sized fine powders are also used in biotechnology fields such as semiconductors and medicine.

  For example, in paints used for roofs, vehicles, home appliances, electronic devices, and the like, fine powders of aluminum, copper, nickel, titanium, and their compounds are dispersed for the purpose of decorating. In the construction field, a thin layer is formed using a paint in which fine metal powder is dispersed, and this is used for applications such as reflection / reduction of ultraviolet rays and heat rays, and adjustment of the daylighting of visible light.

Various production methods have been proposed as methods for producing fine powders, and physical methods include vapor deposition methods, sputtering methods, metal vapor synthesis methods, etc., and chemical methods include methods for reducing metal salts, sol-gel methods. Alkoxide method and reverse micelle method.
One of the methods for producing fine powder is a method for producing fine powder using vacuum. In this method, first, an organic release layer is formed on the surface of a substrate using an organic material such as a water-soluble resin. Next, a thin film is formed on the organic release layer formed on the base material under vacuum conditions by controlling parameters such as temperature, gas type, target evaporation rate, and the like. The thin film deposited and formed on the substrate surface in this way is recovered by dissolving the organic peeling layer in water and pulverized to a predetermined size with an ultrasonic pulverizer or the like (Patent Document 1). .

  As a method for producing an inorganic pigment, there is a method using an inorganic release layer. In this method, first, an inorganic release layer made of an inorganic material such as zinc oxide (ZnO) or sodium chloride (NaCl) is formed on a glass substrate. Next, an inorganic pigment film is formed on the inorganic release layer formed on the substrate using vacuum deposition or a sol-gel method. Then, an inorganic peeling layer is dissolved using an acidic aqueous solution such as nitric acid or hydrochloric acid or water as a solvent, and the inorganic pigment film peeled from the substrate is pulverized to an average particle size of about 10 to 40 μm by an ultrasonic pulverizer (Patent Literature). 2).

JP 2012-140692 A JP 2004-027085 A

  In Patent Document 1, an organic peeling layer is formed on the surface of the substrate, and the organic peeling layer is dissolved when the thin film is collected. At the same time, the process is complicated. In addition, since organic substances are used as the release layer, the target electrical properties are limited by the temperature at the time of film formation, the influence of the outgas released from the organic release layer, the composition change at the interface between the release layer and the thin film, etc. In some cases, a thin film having mechanical, optical, chemical, and mechanical properties cannot be obtained.

In Patent Document 2, ZnO (solubility in water: 1.6 mg / L (28 ° C.)) is used as the inorganic release layer, but it is insoluble in ordinary water, and an acidic aqueous solution such as nitric acid or hydrochloric acid is used as a solvent. Therefore, when a material that is weak against acid such as metal or alloy is laminated on the inorganic release layer, the metal or alloy may be affected by acid. Furthermore, when sodium chloride (NaCl) is used as the inorganic release layer, water can be used as a solvent, but the NaCl layer needs to be vacuum-deposited, and chloride ions (Cl ⁻ ) adversely affect the deposition apparatus. Or salt water generated when NaCl is dissolved may affect the thin film to be collected.

  This invention is made | formed in view of the said subject, The objective of this invention can form the thin film formed on a base material in the manufacturing process of a fine powder, without impairing an original characteristic and function. Another object is to provide a thin film with a substrate that can be easily separated and collected at low cost with simple equipment for peeling off the thin film.

According to the thin film with a base material of the present invention, the above-mentioned problem is provided with a base material, a release layer made of a water-soluble inorganic material provided on the base material, and provided on the release layer for separation and pulverization. In this case, the water-soluble inorganic material is an inorganic oxide that dissolves in water.
With the above structure, since the water-soluble inorganic material is used as the release layer, the release layer can be formed on the substrate without using a solvent as in the case of the organic release layer. As a result, there is no need for an extreme exhaust device, a wastewater treatment device, solvent management, and the like, so that costs can be reduced.
Further, since there is no outgas release from the organic layer and no temperature limitation during film formation, a raw material thin film can be formed on the release layer without impairing the original characteristics and functions.
Further, since the inorganic oxide does not contain halogen like NaCl, it does not adversely affect the film forming apparatus. In addition, when NaCl is used, salt water generated after dissolution affects the thin film to be recovered. However, when inorganic oxide is used, waste water generated after dissolution affects the raw material thin film to be recovered. There is no end to it.

At this time, the base material is preferably a polymer film.
Thus, the use of a polymer film has the advantages of low cost, easy handling, heat resistance, and chemical stability. In addition, some polymer films have water permeability such as polyethylene terephthalate (PET) film, and in the peeling process, water penetrates from the back side where the thin film laminate is not formed. There is an advantage that the body is easily peeled off.

At this time, the thickness of the release layer is 10 nm to 1.0 μm, and the release layer is preferably dissolved in water at 10 to 50 ° C. and pH 4.0 to 10.0.
Since inorganic oxides that dissolve in water that is not strong acidic or strong basic aqueous solutions are used at temperatures near room temperature, the peeling layer can be dissolved with water without using acidic aqueous solutions or basic aqueous solutions as solvents. Even if a raw material thin film that is weak against acid or base is laminated, it can be recovered without affecting the raw material thin film.
By using such a water-soluble inorganic release layer, it is possible to easily form and collect a raw material thin film having a desired property.

At this time, the water-soluble inorganic material constituting the water-soluble inorganic release layer is selected from the group including molybdenum oxide (MoO _x ), germanium oxide (GeO _x ), and tungsten oxide (WO ₃ ). One or more metal oxides are preferred.
Thus, the raw material thin film having the desired properties can be obtained by using a metal oxide that is water-soluble, does not affect the properties of the raw material thin film, has sufficient heat resistance, and is chemically stable. It is possible to easily achieve film formation and recovery.

At this time, the raw material thin film is preferably a single layer including at least one selected from the group including metals, alloys, metal oxides, metal nitrides, metal oxynitrides, and mixtures thereof.
As described above, since the water-soluble inorganic oxide is used for the release layer, the raw material thin film can be formed without any limitation such as metal or metal oxide.

At this time, the raw material thin film is composed of a laminate of a plurality of layers including at least one selected from the group including metals, alloys, metal oxides, metal nitrides, metal oxynitrides, and mixtures thereof. It is preferable.
Thus, since the water-soluble inorganic oxide is used for the peeling layer, the raw material thin film can be formed by laminating a plurality of layers without being limited to metals, metal oxides, and the like.

At this time, it is preferable that the release layer and the raw material thin film are alternately laminated on the base material, and the thicknesses of the layers of the raw material thin film are different from each other.
In this manner, by stacking a plurality of release layers and raw material thin films alternately, the amount of the raw material thin film that can be recovered at a time can be increased. Moreover, when the raw material thin film is produced with a different film thickness, it is possible to control the particle size distribution of the fine powder obtained in the subsequent pulverization step.

At this time, it is preferable that a plurality of layers of the release layer and the raw material thin film are alternately laminated on the base material, and the thickness of each layer of the raw material thin film is the same.
In this manner, by stacking a plurality of release layers and raw material thin films alternately, the amount of the raw material thin film that can be recovered at a time can be increased. Moreover, by producing the raw material thin film with the same film thickness, it is possible to obtain fine powder having a uniform particle size distribution in the subsequent pulverization step.

The raw material thin film is preferably a film for use as a fine powder after being separated from the substrate and the release layer by dissolving the release layer with water and pulverized.
Thus, since the raw material thin film can be obtained by dissolving the release layer with water, it is possible to easily collect the raw material thin film having the desired property and obtain a fine powder having the desired property. .

  In the thin film with a substrate of the present invention, since the release layer is formed of a water-soluble inorganic material, the raw material thin film formed on the release layer can be easily peeled by being immersed in water. Since an organic solvent is not used in the process, an extreme exhaust device, a waste water treatment device and the like are not required, so that the equipment cost can be reduced and the safety of work is ensured.

  Moreover, since the release layer is composed of a water-soluble inorganic material, the temperature, degree of vacuum, film formation rate, plasma conditions, and other conditions when forming the raw material thin film by vacuum deposition or sputtering are appropriately controlled. Therefore, a desired raw material thin film can be manufactured.

It is a schematic cross section which shows the thin film with a base material which concerns on one Embodiment of this invention. It is a flowchart of the manufacturing method of the thin film with a base material and fine powder which concern on one Embodiment of this invention. It is a schematic cross section which shows the thin film with a base material which laminated | stacked multiple layers of the raw material thin film and peeling layer which concern on the modification of embodiment of this invention alternately. It is a schematic cross section which shows the thin film laminated body which multilayered the some raw material thin film which concerns on the modification of embodiment of this invention. It is a schematic diagram which shows the roll body which rounded the thin film with a base material which concerns on one Embodiment of this invention. It is a graph which shows the result of the base-material transmittance | permeability measurement before and behind a peeling process.

Hereinafter, the thin film with a substrate according to an embodiment of the present invention will be described.
As shown in FIG. 1, the thin film 100 with a base material of the present embodiment includes a base material 1, a release layer 2 formed on the base material 1, and a raw material thin film 3 formed on the release layer 2. It is laminated.
In the present embodiment, in the thin film with substrate 100, the release layer 2 formed on the substrate 1 and the raw material thin film 3 formed on the release layer 2 are referred to as a thin film laminate 10.

The substrate 1 in the present embodiment functions as a support when the thin film laminate 10 is manufactured, transported after manufacture, handling during storage, etc., and heating in the step of laminating the film on the substrate 1, Any material that can withstand vacuum, stress, and the like may be used.
Examples of materials that can be used as the substrate 1 in the present embodiment include polymers such as resins, semiconductors such as silicone, metals, ceramics, glass, paper, and nonwoven fabric. The shape of the substrate 1 can be an arbitrary shape such as a film, a sheet, a plate, or a shape having a curved surface. Among them, a polymer film such as a resin film having flexibility is preferable in consideration of mass productivity and handleability.

  The polymer film resin may be either a thermoplastic resin or a thermosetting resin, such as polyethylene (high density, medium density or low density), polypropylene (isotactic or syndiotactic), polybutene, Polyolefins such as ethylene-propylene copolymer, ethylene-vinyl acetate copolymer (EVA), ethylene-propylene-butene copolymer, cyclic polyolefin, modified polyolefin, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, polyimide, Polyamideimide, polycarbonate, poly- (4-methylbenten-1), ionomer, acrylic resin, polymethyl methacrylate, polybutyl (meth) acrylate, methyl (meth) acrylate-butyl (meth) acrylate copolymer, (Meth) acrylate-styrene copolymer, acrylic-styrene copolymer (AS resin), butadiene-styrene copolymer, polio copolymer (EVOH), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), Polyethylene such as ethylene-terephthalate-isophthalate copolymer, polyethylene naphthalate, precyclohexane terephthalate (PCT), polyether, polyetherketone (PEK), polyetheretherketone (PEEK), polyetherimide, polyacetal (POM) , Polyphenylene oxide, modified polyphenylene oxide, polyarylate, aromatic polyester (liquid crystal polymer), polytetrafluoroethylene (PTFE), polyvinylidene fluoride, other fluorine-based trees Various thermoplastic elastomers such as styrene, polyolefin, polyvinyl chloride, polyurethane, fluoro rubber, and chlorinated polyethylene, epoxy resin, phenol resin, urea resin, melamine resin, unsaturated polyester, silicone resin, polyurethane , Cellulose resins such as nylon, nitrocellulose, cellulose acetate, cellulose acetate propionate, etc., or copolymers, blends, polymer alloys, etc. mainly containing these, and one or two of them The above can be combined (for example, as a laminate of two or more layers).

  Among these polymer films, a PET film is preferable from the viewpoints of cost, ease of handling, heat resistance, chemical stability, and adhesiveness of the release layer. In addition, when the thin film laminate 10 is formed only on one surface of a PET film or the like having water permeability, water penetrates from the back side where the thin film laminate 10 is not formed in the peeling step. There exists an advantage that the thin film laminated body 10 becomes easy to peel.

  The thickness of the polymer film as the substrate 1 is from several μm to several hundred μm, preferably from 5 μm to 500 μm, preferably from 10 μm to 400 μm, preferably from 15 μm to 300 μm, more preferably from 20 μm to 250 μm. Hereinafter, it is more preferable that the thickness is 25 μm or more and 200 μm or less. When the thickness is less than 20 μm, it becomes difficult to handle in the film forming process or the like, and when it exceeds 200 μm, the flexibility becomes poor, and the thin film laminate 10 becomes difficult to peel from the substrate 1.

  Examples of the paper include thin paper, kraft paper, high quality paper, linter paper, baryta paper, sulfuric acid paper, and Japanese paper.

  As a nonwoven fabric, the nonwoven fabric which consists of fibers, such as a polyester resin, an acrylic resin, nylon, vinylon, glass, is mentioned, for example. The paper or non-woven fabric may have a strengthened interlayer strength between the fibers or other layers. Also, in order to prevent injuring or to suppress permeability, it may be added with resin such as acrylic resin, styrene butadiene rubber, melamine resin, urethane resin (impregnated with resin after paper making or embedded during paper making) Good.

  Examples of the glass include silicate glass (quartz glass), alkali silicate glass, soda lime glass, potassium lime glass, lead (alkali) glass, barium glass, and borosilicate glass.

  Examples of the metal include gold, chromium, silver, copper, iron, titanium, nickel, tungsten, tantalum, aluminum, and platinum. Further, these alloys are stainless steel such as SUS316L, shape memory alloy such as Ti—Ni alloy or Cu—Al—Mn alloy, Cu—Zn alloy, Ni—Al alloy, titanium alloy, tantalum alloy, platinum alloy or An alloy such as a tungsten alloy can also be used.

  Examples of ceramics include oxides (eg, aluminum oxide, zinc oxide, titanium oxide, silicon oxide, zirconia, barium titanate), nitrides (eg, silicon nitride, boron nitride), carbides (eg, silicon carbide), etc. Is mentioned. A mixture of these can also be used.

The inorganic oxide that dissolves in the water constituting the release layer 2 dissolves in the water used in the release step, and does not affect the characteristics of the raw material thin film 3 in the lamination step of the raw material thin film 3, and has sufficient heat resistance. Any water-soluble metal oxide that is chemically stable may be used. Examples of the metal oxide dissolved in water include molybdenum oxide (MoO _x , x = stoichiometric ratio, 2 ≦ x ≦ 3), germanium oxide (GeO _x , x = stoichiometric ratio, 1 ≦ x ≦ 2), tungsten oxide (WO ₃ ) and the like, but are not limited thereto.

  The water-soluble inorganic material constituting the release layer 2 may be any inorganic oxide that dissolves in water at 10 to 50 ° C. and pH 4.0 to 10.0 in the bulk state, but is insoluble in the bulk state. Even if it is an inorganic oxide which dissolves in water at 10 to 50 ° C. and pH 4.0 to 10.0 when the film is formed to a film thickness of several tens nm to several μm.

In addition, when the metal oxide is represented by the general formula MO _x (M = metal, x = stoichiometric ratio), the value of x is usually a value at which the charge balance between the metal ion and the oxide ion becomes zero. However, the value of x may be slightly different from zero in the electrification balance between metal ions and oxide ions.

The solubility of these metal oxides in water is 0.14 g / 100 mL (20 ° C.) for molybdenum oxide MoO ₃ , and 0.447 g / 100 mL for hexagonal GeO ₂ germanium oxide. In WO ₃ which is a tungsten oxide, it is less than 0.46 g / 100 mL.

  The thickness of the release layer 2 is preferably several nm or more and several μm or less, more preferably several nm or more and 30 μm or less, more preferably several nm or more and 10 μm or less, still more preferably 10 nm or more and 5.0 μm or less, and still more preferably Is preferably 10 nm or more and 1.0 μm or less. If the thickness of the release layer 2 becomes too thin, the gap between the substrate 1 and the raw material thin film 3 becomes small, and it becomes difficult for water to penetrate into the release layer 2 in the release process, so that the release layer 2 is dissolved. As a result, peeling of the raw material thin film 3 becomes insufficient. On the other hand, if the release layer 2 is too thick, it takes a long time to dissolve in water in the release step.

  The method for forming the release layer 2 on the substrate 1 can use a physical vapor deposition method such as a vacuum vapor deposition method, a sputtering method, or an ion plating method, but is not limited thereto. Chemical methods such as gel method can also be used.

  The raw material thin film 3 is formed on the release layer 2, but the material constituting the raw material thin film 3 is not particularly limited as long as it does not dissolve in the solvent water, and is not limited to metals, alloys, metal oxides, The raw material thin film 3 may be a single layer or multiple layers as long as it is a metal nitride, a metal oxynitride, and a mixture thereof.

Examples of the metal include, but are not necessarily limited to, aluminum, copper, gold, silver, platinum, indium, palladium, iron, nickel, titanium, chromium, manganese, zinc, tin, and tungsten.
An alloy is obtained by adding one or more metal elements or non-metal elements to the metal element. The alloy structure includes eutectic alloys in which the component elements become separate crystals, solid solutions in which the component elements are completely dissolved, and those in which the component elements form an intermetallic compound or a compound of a metal and a nonmetal. Although there is, it is not necessarily limited to this.

Examples of metal oxides include oxides and indium oxides containing the above metals, aluminum, copper, gold, silver, platinum, indium, palladium, iron, nickel, titanium, chromium, manganese, zinc, tin, tungsten, and the like as metals. Tin (ITO), aluminum oxide (Al ₂ O ₃ ), titanium oxide (TiO ₂ ), silicon oxide (SiO ₂ ), tin oxide (SnO ₂ , SnO), iron oxide (Fe ₂ O ₃ , Fe ₃ O ₄ ) And composite oxides having a perovskite structure, a spinel structure, and an ilmenite structure, but are not necessarily limited thereto.

Examples of the metal nitride include titanium nitride (TiN), zirconium nitride (ZrN), vanadium nitride (VN), niobium nitride (NbN), tantalum nitride (TaN), chromium nitride (CrN, Cr ₂ N), and hafnium nitride (HfN). ), But is not necessarily limited to this.

  The thickness of the raw material thin film 3 is preferably from several tens of nm to several tens of μm, more preferably from 20 nm to 90 μm, more preferably 50 nm in consideration of the desired particle size when making fine powder in the pulverization step. The thickness is more preferably 10 μm or less and particularly preferably 75 nm or more and 1 μm or less.

The method of forming the raw material thin film 3 can use a physical vapor deposition method such as a vacuum vapor deposition method, a sputtering method, or an ion plating method, but is not limited to this, and a chemical method such as a sol-gel method. A method is also available.
If the method for forming the release layer 2 and the method for forming the raw material thin film 3 are the same as, for example, a vacuum deposition method or a sputtering method, the thin film stack 10 is formed on the substrate 1 consistently by a dry process. be able to.

As shown in FIG. 2, the thin film laminate 10 and the thin film with substrate 100 of the present embodiment are manufactured by the following manufacturing method.
A substrate 1 such as a PET film is prepared (step S1), and a release layer 2 is formed on the substrate 1 by a vacuum deposition method, a sputtering method, or the like (step S2). Subsequently, a raw material thin film 3 is formed on the formed release layer 2 by a vacuum deposition method, a sputtering method, or the like (step S3). The thin film with substrate 100 is completed through the above steps S1 to S3.

The thin film with substrate 100 manufactured as described above has the release layer 2 dissolved in the release step (step S4).
In the peeling step (FIG. 2, step S4), water can be used as a solvent capable of dissolving only the peeling layer 2 without dissolving the raw material thin film 3. The water used here only needs to be able to dissolve the release layer 2 without affecting the properties of the raw material thin film 3, and the temperature is 0 to 80 ° C., preferably 5 to 60 ° C., more preferably 10 to 50 ° C. Water, more preferably 20-50 ° C. water, particularly preferably 30-50 ° C. water. Water having a temperature of 20 ° C. or higher and 50 ° C. or lower is preferable because a long-time heat treatment is unnecessary even when a large amount of water is required, and water for peeling can be easily prepared.
The pH of water should just be in the range which can melt | dissolve a peeling layer, without affecting the characteristic of the raw material thin film 3, pH4-10 are good, Preferably it is pH5-9, More preferably, it is good that it is pH6-8. . If pH is 6 or more and 8 or less, it is possible to process the water after peeling as waste water without adjusting the pH.
It is more preferable to use neutral water at a temperature around 20 to 40 ° C. and pH 6 to 8 near room temperature.

In addition, it is desirable to use water from which various metal ions and impurities have been removed, such as distilled water, pure water, and ultrapure water, but is not limited to this, and water such as tap water, industrial water, well water, etc. It is also possible to use.
Distilled water is water having an electrical conductivity of about 1 to 10 μS / cm, which is heated to water vapor and then returned to a liquid by cooling.
Pure water is high-purity water having an electrical conductivity of 1 μS / cm or less from which impurities such as ions, fine particles, microorganisms, and organic substances are removed.
Ultrapure water is extremely high-purity water having a higher purity than that of pure water removed from suspended substances, dissolved substances, and high efficiency in an ultrapure water production apparatus, and has an electric conductivity of less than 0.055 μScm.

  In the present embodiment, an inorganic oxide that dissolves in water at 10 to 50 ° C. and pH 4.0 to 10.0 is selected as the water-soluble inorganic material that constitutes the release layer 2. The peeling layer 2 can be dissolved without using an acidic aqueous solution such as sodium hydroxide or a basic aqueous solution such as sodium hydroxide aqueous solution.

  In the peeling step, the raw material thin film 3 is preferably peeled off, for example, within 60 minutes, and more preferably peeled off within 10 minutes, by immersing the thin film with substrate 100 in water. It is particularly preferable that the raw material thin film 3 is peeled off immediately after the thin film with substrate 100 is immersed in water. In addition, in order to promote dissolution of the peeling layer 2 in water and peeling of the raw material thin film 3, the thin film with a substrate 100 immersed in water may be subjected to ultrasonic irradiation or stirring with a high-speed stirrer. Is possible.

  In the pulverization step (FIG. 2, step S5), the peeled raw material thin film 3 is pulverized to a predetermined particle size by performing ultrasonic irradiation or stirring with a high-speed stirrer, following the peeling step. By classifying the pulverized fine powder as necessary, it can be finally used for applications such as pigments.

  Through the above process, the raw material thin film 3 becomes fine powder pulverized to a predetermined size (step S6). Steps S4 to S6 may be performed by a person who manufactures the thin film with substrate 100, or may be performed by the user who purchased the thin film with substrate 100 from this person.

In addition, as shown in FIG. 3, a release layer 2 is formed on the raw material thin film 3 formed in Step 3, a raw material thin film 3 is provided, and a thin film in which a plurality of raw material thin films 3 and release layers 2 are alternately stacked It is also possible to create the laminate 12. At this time, the film thickness of each layer of the plurality of raw material thin films 3 may be the same or different from each other.
In such a thin film laminated body 12, the quantity of the raw material thin film 3 which can be collect | recovered at once can be increased by laminating | stacking multiple layers of the peeling layer 2 and the raw material thin film 3 alternately. Moreover, when the raw material thin film 3 is produced with a different film thickness, it is possible to control the particle size distribution of the fine powder obtained in the subsequent pulverization step.

Furthermore, as shown in FIG. 4, a thin film laminate 11 in which a plurality of raw material thin films 3 are formed by laminating raw material thin films having the same or different components on the raw material thin film 3 formed in step 3 may be prepared. Is possible.
In such a thin film laminated body 12, the quantity of the raw material thin film which can be collect | recovered at once can be increased by laminating | stacking multiple layers of the peeling layer 2 and the raw material thin film 3 by turns. Moreover, by producing the raw material thin film with the same film thickness, it is possible to obtain fine powder having a uniform particle size distribution in the subsequent pulverization step.

When a flexible material such as a PET film is used as the substrate 1, the release layer 2 and the raw material thin film 3 can be formed on the substrate 1 using a flexible film deposition apparatus. When a roll-to-roll (roll-to-roll) film forming apparatus is used as the flexible film forming apparatus, as shown in FIG. 5, a roll body 101 in which the thin film with substrate 100 is rolled is obtained. Is possible. If the thin film with substrate 100 is sold in the state of the roll body 101, the person who purchased the roll body 101 performs the peeling step using the roll body 101 as it is, or the necessary amount of the thin film with substrate 100 is obtained. A fine powder having a desired size can be obtained by performing a pulverization step of pulverizing the peeled raw material thin film 3 by cutting it out from the roll body 101.
In addition, when the plate-shaped board | substrate with few softness | flexibility is used as the base material 1, it can provide to a user side in the state which accumulated the some thin film 100 with a base material.

  Moreover, although the raw material thin film 3 of this embodiment is provided to a user side in the state of the thin film 100 with a base material with easy handling, it is in the state of the raw material thin film 3 which isolate | separated the base material 1 from the thin film 100 with a base material. It may be provided to the user. If the raw material thin film 3 peeled from the base material 1 is put into a container and sold after the thin film 100 with the base material is manufactured, the person who purchased the raw material thin film 3 puts the necessary amount of the raw material thin film 3 into the container. It is possible to obtain a fine powder of a desired size simply by taking it out from the process and performing a pulverization step.

In the present embodiment, the thin film laminate, the thin film with a base material, and the manufacturing method thereof according to the present invention have been mainly described.
However, said embodiment is only an example for making an understanding of this invention easy, and does not limit this invention. The present invention can be changed and improved without departing from the gist thereof, and the present invention includes the equivalents thereof.

Hereinafter, although the specific Example of the thin film laminated body of this invention and the thin film with a base material is demonstrated, this invention is not limited to this.
(Formation of thin film laminates and thin films with base materials according to Examples and Comparative Examples)
(Peeling layer forming process)
Under the following conditions, release layers according to Examples 1 to 4 and Comparative Examples 1 to 4 were formed on a PET substrate.
Sputtering device: Carousel type batch type sputtering device Target: φ150, thickness 6mm
Example 1, Example 2: Molybdenum (Mo) 100%
Example 3: Germanium oxide (GeO ₂ ) 100%
Example 4: 100% tungsten (W)
Comparative Example 1: 100% zinc oxide (ZnO)
Comparative Example 2: Iron oxide (Fe ₃ O ₄ ) 100%
Comparative Example 3: Indium tin oxide (ITO), 90% indium, 10% tin
Comparative Example 4: Silicon oxide (SiO ₂ ) 100%
Sputtering method:
Examples 1, 2, 4 and Comparative Example 3: DC magnetron sputtering Example 3, Comparative Examples 1, 2, and 4: RF sputtering Exhaust device: Turbo molecular pump Ultimate vacuum: 5 × 10 ⁻⁴ Pa
Substrate temperature: 25 ° C. (room temperature)
Sputtering power: 0.5 kW / cm ²
Substrate used: PET film substrate (25 μm thick)
Release layer thickness:
Example 1: 500 ± 10 cm
Examples 2-4, Comparative Examples 1-4: 1000 ± 10cm
Ar flow rate: 120 sccm
Oxygen flow rate:
Example 1, Example 2: 40 sccm
Example 3: 0 sccm
Example 4: 20 sccm
Comparative Example 1 and Comparative Example 2: 10 sccm
Comparative Example 3: 5 sccm
Comparative Example 4: 0 sccm

(Raw material thin film forming process)
On the following conditions, the aluminum film (Al film) as a raw material thin film was formed on the peeling layer which concerns on Examples 1-4 and Comparative Examples 1-4, and the thin film laminated body and the thin film with a base material were obtained.
Sputtering device: Carousel type batch type sputtering device Target: φ150, thickness 6mm, aluminum (Al) 100%
Sputtering method: DC magnetron sputtering Exhaust device: Turbo molecular pump Ultimate vacuum: 5 × 10 ⁻⁴ Pa
Substrate temperature: 25 ° C. (room temperature)
Sputtering power: 5.52 W / cm ²
Al film thickness: 1000 ± 10 mm
Ar flow rate: 120 sccm

以上より、剥離層として、水溶性の無機酸化物であるＭｏＯ_ｘやＧｅＯ_２を用いた場合（実施例１〜３）、浸漬直後に剥離層が全て溶解することがわかった。また、剥離層としてＷＯ_３を用いた場合（実施例４）、溶解速度がやや遅いものの、ＺｎＯやＦｅ_３Ｏ_４、ＩＴＯ、ＳｉＯ_２等の水不溶性無機酸化物（比較例１〜４）と比較すると溶解性は高いことがわかった。 (Peeling test of peeling layer)
The water solubility of the release layers formed on the PET substrates of Examples 1 to 4 and Comparative Examples 1 to 4 was tested.
A PET base material with a release layer (50 x 100 x 0.025 mm) is immersed in pure water (manufactured by Mac Ace KN type, Kurita Kogyo Co., Ltd., pH 7.0) at room temperature (25 ° C), and the release layer is dissolved. The dissolution rate of the release layer in water was calculated by measuring the time until the release.
The results are shown in Table 1 below.

From the above, as the release layer, when using the MoO _x and GeO ₂ is a water-soluble inorganic oxide (Example 1-3), a peeling layer immediately after immersion was found to dissolve all. Further, when WO ₃ is used as the release layer (Example 4), although the dissolution rate is slightly low, water-insoluble inorganic oxides (Comparative Examples 1 to 4) such as ZnO, Fe ₃ O ₄ , ITO, and SiO ₂ are used. In comparison, it was found that the solubility was high.

以上のように、剥離層として、水溶性の無機酸化物であるＭｏＯ_ｘ、ＧｅＯ_２、ＷＯ_３を用いた場合（実施例１〜４）、２５℃の水に浸漬することで６０分以内にＡｌ膜を全て又は部分的に剥離することができた。また、４０℃の水に浸漬することで６０分以内にＡｌ膜を全て剥離することができた。特に、剥離層にＭｏＯ_ｘ、ＧｅＯ_２を用いた場合、４０℃の水に浸漬することで、浸漬直後、又は１０分以内の短時間でＡｌ膜を全て剥離することができた。一方、ＺｎＯやＦｅ_３Ｏ_４、ＩＴＯ、ＳｉＯ_２等の水不溶性の無機酸化物を用いた際（比較例１〜４）には、水に浸漬して６０分以上してもＡｌ膜が全く剥離しなかった。 (Al film peeling test)
The peelability of the Al films formed on the release layers on the PET substrates of Examples 1 to 4 and Comparative Examples 1 to 4 was measured.
A PET base material (50 mm × 100 mm × 0.025 mm) on which a release layer and an Al film are formed is immersed in pure water (pH 7.0) at 25 ° C. or 40 ° C. to facilitate the peeling of the Al film. investigated.
The peelability was evaluated according to the following criteria.
5: All Al film is peeled off immediately after immersion in water 4: All Al film is peeled off within 10 minutes after being immersed in water 3: All Al film is peeled off within 10 minutes to 60 minutes after being immersed in water 2: Water The Al film was partially peeled within 10 minutes to 60 minutes after being immersed in 1: The Al film was not peeled at all even after being immersed in water for 60 minutes or more. The results are shown in Table 2 below.

As described above, when MoO _x , GeO ₂ , and WO ₃ that are water-soluble inorganic oxides are used as the release layer (Examples 1 to 4), it is within 60 minutes by being immersed in water at 25 ° C. The Al film could be completely or partially peeled off. Moreover, all the Al films could be peeled off within 60 minutes by being immersed in water at 40 ° C. In particular, when MoO _x or GeO ₂ was used for the release layer, all the Al film could be peeled off immediately after the immersion or within a short time of 10 minutes by being immersed in water at 40 ° C. On the other hand, when a water-insoluble inorganic oxide such as ZnO, Fe ₃ O ₄ , ITO, or SiO ₂ is used (Comparative Examples 1 to 4), the Al film is completely removed even after being immersed in water for 60 minutes or more. It did not peel.

In FIG. 6, the result of the base-material transmittance | permeability measurement before and behind a peeling process is shown. The transmittance was measured in a wavelength region of 400 nm to 700 nm using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation).
In the case of only the PET base material on which the release layer and the Al film were not laminated, a high transmittance of 87% or more was shown (FIG. 6, solid line). The thin film with a PET substrate (25 μm) / GeO ₂ (100 nm) / Al (100 nm) substrate in Example 3 showed a low transmittance of 0.5% or less (FIG. 6, broken line). Moreover, the transmittance | permeability after immersing the thin film with a base material of Example 3 in 40 degreeC pure water (pH 7.0) for 60 minutes showed the high transmittance | permeability of 87% or more (FIG. 6, dotted line).

  The transmittance after immersing the thin film with a base material of Example 3 in pure water was almost the same as that of the PET base material alone, and it was found that the release layer and the Al film were completely peeled off.

DESCRIPTION OF SYMBOLS 1 Base material 2 Release layer 3 Raw material thin film 10, 11, 12 Thin film laminated body 100 Thin film 101 with a base material Roll body

Claims (9)

A substrate;
A release layer made of a water-soluble inorganic material provided on the substrate;
A raw material thin film provided on the release layer and separated and ground for use as a powder,
The thin film with a base material, wherein the water-soluble inorganic material is an inorganic oxide dissolved in water.   The said base material is a polymer film, The thin film with a base material of Claim 1 characterized by the above-mentioned. The thickness of the release layer is 10 nm or more and 1.0 μm or less,
The thin film with a substrate according to claim 1 or 2, wherein the release layer is dissolved in water at 10 to 50 ° C and pH 4.0 to 10.0. The water-soluble inorganic material constituting the release layer is one or more metal oxides selected from the group including molybdenum oxide (MoO _x ), germanium oxide (GeO _x ), and tungsten oxide (WO ₃ ). The thin film with a substrate according to claim 1, wherein the thin film has a base material.   2. The raw material thin film is a single layer including at least one selected from the group including metals, alloys, metal oxides, metal nitrides, metal oxynitrides, and mixtures thereof. 4. The thin film with a substrate according to any one of 4 above.   The raw material thin film comprises a laminate of a plurality of layers including at least one selected from the group including metals, alloys, metal oxides, metal nitrides, metal oxynitrides, and mixtures thereof. The thin film with a substrate according to any one of claims 1 to 4.   5. The release layer and the raw material thin film are alternately laminated on the base material, and the thicknesses of the layers of the raw material thin film are different from each other. The thin film with a base material according to item 1.   5. The method according to claim 1, wherein a plurality of layers of the release layer and the raw material thin film are alternately laminated on the base material, and the thickness of each layer of the raw material thin film is the same. The thin film with a base material according to claim 1.   The said raw material thin film is a film | membrane for isolate | separating from the said base material and the said peeling layer by melt | dissolving the said peeling layer with water, and grind | pulverizing and using it as a fine powder. The thin film with a base material according to item 1.

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