WO2010095479A1

WO2010095479A1 - Dielectric laminate, laminated glass, process for producing dielectric laminate, and process for producing laminated glass

Info

Publication number: WO2010095479A1
Application number: PCT/JP2010/050444
Authority: WO
Inventors: 良孝後藤
Original assignee: コニカミノルタホールディングス株式会社
Priority date: 2009-02-20
Filing date: 2010-01-16
Publication date: 2010-08-26

Abstract

A dielectric laminate which has high adhesive force when bonded to a polyvinyl butyral sheet and which, when used in a laminated glass, attains improvements in quality evenness (crack resistance, freedom from air bubble inclusions, and blush resistance) and shows excellent heat-insulating properties; a laminated glass; and processes for producing the laminate and the glass. The dielectric laminate comprises a resin support and, superposed thereon, low-refractive-index dielectric films alternating with high-refractive-index dielectric films, and is characterized in that the resin support is polyethylene naphthalate, and the difference in hardness measured by a nanoindentation method between the low-refractive-index dielectric films and the high-refractive-index dielectric films is 1.4-3.0 GPa.

Description

Dielectric laminate, laminated glass, method for producing dielectric laminate, and method for producing laminated glass

The present invention relates to a dielectric laminate and laminated glass having a novel configuration, a dielectric laminate manufacturing method, and a laminated glass manufacturing method.

Laminated glass windows are used for transparent openings that require safety, for example, part of building windows. The basic structure of the laminated glass window is made of a transparent plate such as a glass plate and a thermoplastic resin, for example, a generally used polyvinyl butyral sheet, but for the purpose of imparting further functionality to the laminated glass window. Attempts have been made to interpose a functional film. For example, a method of interposing a film having excellent mechanical strength to enhance safety, a method of interposing a transparent film with a conductive film to prevent condensation, and the like have been proposed.

As another example, a functional film is not provided in the middle of the thermoplastic resin layer, and the functional film is directly attached to one of the transparent glass plates with an adhesive layer. A method of providing a thermoplastic resin layer on the surface has also been proposed.

In recent years, a heat ray blocking material effective for shielding sunlight entering through a window glass and suppressing an increase in room temperature has been disclosed and attracted attention (for example, see Patent Document 1). Electricity bill reduction by summer cooling, CO ₂ reduction and the like, it has been noted environmentally and effective.

In a conventional laminate of glass and resin support, generally, there is no separation between the functional film and the thermoplastic resin layer due to the hygroscopicity, thermal stretchability, or handling operation of the thermoplastic resin layer. It was necessary to pay attention to the storage method and handling method. In particular, when a functional film and a laminate are produced using a polyvinyl butyral sheet as a thermoplastic resin, delicate attention is required depending on the storage method and the handling method. That is, the polyvinyl butyral sheet used for a laminated glass window has a low heat softening temperature, expands and contracts according to the ambient temperature, and further has a very high hygroscopic property, and therefore swells according to humidity. As a result, if the laminate of the functional film and the polyvinyl butyral sheet is stored, a peeling phenomenon occurs at the interface between the film and the sheet, and when producing a laminated glass using such a laminate, In order to re-adhere the peeled part, it takes a lot of labor, and because of the partial peeling phenomenon between the film and the polyvinyl butyral sheet that is difficult to disappear, the laminated glass produced has optically uneven spots. Incurs the consequences.

JP 2003-267755 A

The present invention has been made in view of the above problems, and its purpose is to have strong adhesive strength with a polyvinyl butyral sheet and to improve the quality (crack resistance, bubble residual resistance, whitening resistance) when applied as a laminated glass. And it is providing the dielectric laminated body excellent in heat-shielding property, a laminated glass, and those manufacturing methods.

The above object of the present invention is achieved by the following configuration.

1. In a dielectric laminate in which a low refractive index dielectric film and a high refractive index dielectric film are alternately laminated on a resin support, the resin support is polyethylene naphthalate, and the low refractive index A dielectric laminate, wherein a difference in hardness measured by a nanoindentation method between a dielectric film having a high refractive index and the dielectric film having a high refractive index is 1.4 GPa or more and 3.0 GPa or less.

2. 2. The dielectric laminate according to 1 above, wherein the total thickness of the dielectric film is 500 nm or more.

3. It has a dielectric laminate in which a low refractive index dielectric film and a high refractive index dielectric film are alternately laminated on a resin support, and glass is pasted on the front and back surfaces of the dielectric laminate. In the laminated glass, the dielectric laminate is bonded to the glass with polyvinyl butyral, the resin support is polyethylene naphthalate, and the low refractive index dielectric film and the high refractive index A laminated glass, wherein a difference in hardness measured by a nanoindentation method with respect to a dielectric film is 1.4 GPa or more and 3.0 GPa or less.

4. In a dielectric laminate manufacturing method for manufacturing a dielectric laminate in which a low refractive index dielectric film and a high refractive index dielectric film having different hardnesses are alternately laminated on a resin support, the resin The support is polyethylene naphthalate, and the difference in hardness measured by the nanoindentation method between the low refractive index dielectric film and the high refractive index dielectric film is 1.4 GPa or more and 3.0 GPa or less And the dielectric film introduces a gas into the discharge space under atmospheric pressure or pressure near the atmosphere to form a high-frequency electric field in the discharge space, thereby bringing the gas into a plasma state, and A method for producing a dielectric laminate, wherein the dielectric laminate is formed by exposure to a gas in a plasma state.

5. 5. The method for manufacturing a dielectric laminate according to 4, wherein the total thickness of the dielectric film is 500 nm or more.

6. It has a dielectric laminate in which a low refractive index dielectric film and a high refractive index dielectric film are alternately laminated on a resin support, and glass is pasted on the front and back surfaces of the dielectric laminate. In the laminated glass manufacturing method, the dielectric laminate is bonded to glass with polyvinyl butyral, the resin support is polyethylene naphthalate, the low refractive index dielectric film and the high refractive index The difference in hardness measured by the nanoindentation method with respect to the dielectric film having a rate of 1.4 GPa or more and 3.0 GPa or less, and the dielectric film is a gas under atmospheric pressure or pressure near the atmosphere. Of the laminated glass formed by exposing the resin support to the plasma gas by introducing a gas into the discharge space and forming a high-frequency electric field in the discharge space to bring the gas into a plasma state. Production method.

According to the present invention, the dielectric laminate and the laminated glass have excellent adhesion to the polyvinyl butyral sheet, improved quality (crack resistance, bubble residual resistance, whitening resistance) when applied as a laminated glass, and excellent thermal insulation. And a manufacturing method thereof.

It is the schematic which showed an example of the jet-type atmospheric pressure plasma discharge processing apparatus. It is the schematic which shows an example of the atmospheric pressure plasma discharge processing apparatus of the system which processes a base material between counter electrodes. It is a perspective view which shows an example of the structure of the electroconductive metal base material of a roll rotating electrode, and the dielectric material coat | covered on it. It is a perspective view which shows an example of the structure of the electroconductive metal preform | base_material of a rectangular tube type electrode, and the dielectric material coat | covered on it.

Hereinafter, embodiments for carrying out the present invention will be described in detail.

As a result of intensive studies in view of the above problems, the present inventors have found that a dielectric laminate in which a low refractive index dielectric film and a high refractive index dielectric film are alternately laminated on a resin support. The resin support is polyethylene naphthalate, and the difference in hardness measured by the nanoindentation method between the low refractive index dielectric film and the high refractive index dielectric film is 1.4 GPa or more, A dielectric laminate characterized by being 3.0 GPa or less, or a dielectric laminate obtained by alternately laminating a low refractive index dielectric film and a high refractive index dielectric film on a resin support And the dielectric laminate is laminated to the glass with polyvinyl butyral, and the resin support is polyethylene naphthalate. And A laminated glass characterized in that the difference in hardness measured by the nanoindentation method between the low refractive index dielectric film and the high refractive index dielectric film is 1.4 GPa or more and 3.0 GPa or less. , With strong adhesion to polyvinyl butyral sheet, improved quality (crack resistance, bubble residual resistance, whitening resistance) when applied as laminated glass, and can realize a dielectric laminate and laminated glass with excellent heat insulation As a result, the present invention has been achieved.

Further, in a dielectric laminate manufacturing method for manufacturing a dielectric laminate in which a low refractive index dielectric film and a high refractive index dielectric film having different hardnesses are alternately laminated on a resin support The resin support is polyethylene naphthalate, and the difference in hardness measured by the nanoindentation method between the low refractive index dielectric film and the high refractive index dielectric film is 1.4 GPa or more, 3 0.0 GPa or less, and the dielectric film introduces a gas into the discharge space under an atmospheric pressure or a pressure in the vicinity of the atmosphere to form a high-frequency electric field in the discharge space, thereby bringing the gas into a plasma state. A method for manufacturing a dielectric laminate, wherein the support is formed by exposing the plasma to a gas in a plasma state, or a low refractive index dielectric film and a high refractive index dielectric film on a resin support And dielectric In a method for producing a laminated glass having a laminate and bonding glass to the front and back surfaces of the dielectric laminate, the dielectric laminate is bonded to glass with polyvinyl butyral, and the resin support Is a polyethylene naphthalate, and the difference in hardness measured by the nanoindentation method between the low refractive index dielectric film and the high refractive index dielectric film is 1.4 GPa or more and 3.0 GPa or less. And the dielectric film introduces a gas into the discharge space under atmospheric pressure or a pressure in the vicinity of the atmosphere to form a high-frequency electric field in the discharge space, thereby bringing the resin support into the plasma state. Adhesive strength with polyvinyl butyral sheet is applied by the laminated glass manufacturing method, which is characterized by being formed by exposing to a state gas. Quality uniformity when the (crack resistance, the remaining resistance of the bubble, whitening resistance) is improved, excellent dielectric stack in thermal barrier is up the finding that it is possible to produce a laminated glass.

That is, in the present invention, a dielectric laminated film in which a low refractive index dielectric film and a high refractive index dielectric film are alternately laminated, and polyethylene naphthalate is used as a resin support. When the difference in hardness measured by the nanoindentation method between the dielectric film and the high refractive index dielectric film is 1.4 GPa or more and 3.0 GPa or less, wrinkles and bubbles are generated without uneven spots. It was possible to obtain a laminated glass with extremely high homogeneity.

In general, the low refractive index dielectric film and the high refractive index dielectric film according to the present invention have different hardnesses between the dielectric films. Therefore, after stacking a plurality of dielectric films, polyvinyl butyral It was found that there was a failure that caused cracks in the interface of the dielectric film and in the film when it was bonded to the glass using a glass, and there was a failure that deteriorated the performance. The difference in hardness measured by the nanoindentation method between the low refractive index dielectric film formed on the resin support and the high refractive index dielectric film on the resin support is 1.4 GPa or more. It has been found that the above-mentioned problem can be achieved by setting the pressure to 0.0 GPa or less.

In the present invention, the difference in hardness measured by the nanoindentation method between the low refractive index dielectric film and the high refractive index dielectric film is set to 1.4 GPa or more and 3.0 GPa or less. The reason why the intended effect is exhibited is presumed as follows.

That is, when the difference in hardness between the low refractive index and the high refractive index dielectric is less than 1.4 GPa, low refractive index is applied when polyethylene naphthalate is applied as a resin support and bonded to glass using polyvinyl butyral. Since there is little difference in hardness between the dielectric film having a high refractive index and a high refractive index, stress is concentrated at the interface between the dielectric film having a low refractive index and the dielectric film having a high refractive index, resulting in cracks. appear. It was found that the appearance of micro cracks in the film due to the occurrence of cracks of various shapes deteriorates the visual appearance and the heat shielding performance.

Also, when the difference in hardness between the low refractive index and high refractive index dielectric is 3.0 GPa or more, low refractive index is applied when polyethylene naphthalate is applied as a resin support and bonded to glass using polyvinyl butyral. The difference in hardness between the dielectric film of high refractive index and high refractive index is large, so the hardness of the entire low-refractive index and high-refractive index dielectric laminated film using polyethylene naphthalate as the resin support It was found that a difference was generated and the glass could not be followed and adhered uniformly, and stress was locally generated in the entire dielectric laminated film, resulting in cracks.

Therefore, in the present invention, it is important that the difference in hardness measured by the nanoindentation method is 1.4 GPa or more and 3.0 GPa or less.

Hereinafter, the dielectric laminate of the present invention, the laminated glass using the dielectric laminate, and the details of each manufacturing method will be described.

<Resin support>
In the dielectric laminate of the present invention, the resin support is a support for laminating dielectric films. In the present invention, polyethylene naphthalate (hereinafter abbreviated as PEN) is used as the resin support. Is one of the features.

The surface of the resin support on which the dielectric film is laminated may be subjected to easy contact treatment, or may be subjected to easy contact treatment on the opposite surface side where the dielectric film is not laminated. There is no particular limitation. Moreover, it is preferable that PEN which is a resin support body is transparent, high light resistance, and high weather resistance. The PEN that is the resin support may be an unstretched film or a stretched film.

PEN that is a resin support according to the present invention can be manufactured by a conventionally known general method. For example, an unstretched resin base material that is substantially amorphous and not oriented can be produced by melting a resin as a material with an extruder, extruding with an annular die or a T die, and quenching. In addition, the unstretched resin base material is uniaxially stretched, tenter-type sequential biaxial stretching, tenter-type simultaneous biaxial stretching, tubular simultaneous biaxial stretching, and other known methods, such as the base material flow (vertical axis) direction, Alternatively, a stretched substrate can be produced by stretching in a direction perpendicular to the flow direction of the substrate (horizontal axis). The draw ratio in this case can be appropriately selected according to the resin as the raw material of the base material, but is preferably 2 to 10 times in each of the vertical axis direction and the horizontal axis direction.

As a specific method for producing PEN, for example, calcium acetate hydrate is added as a transesterification catalyst to dimethyl 2,6-naphthalenedicarboxylate and ethylene glycol, and transesterification is performed according to a conventional method. Subsequently, antimony trioxide and phosphoric acid trimethyl ester are added to the obtained product as a polycondensation catalyst, and the temperature is gradually raised and reduced, and polycondensation is performed at 285 ° C. and 66 Pa to obtain polyethylene naphthalate (PEN). Can do.

The obtained polyethylene naphthalate master chip is melted and kneaded, melt-extruded into a film form at 300 ° C from a T-die, electrostatically applied, and rapidly cooled on a cooling drum at about 30 ° C to obtain an unstretched film. It is done. A biaxially stretched polyethylene naphthalate film can be obtained by preheating this unstretched film to 135 ° C. and stretching it in the longitudinal direction, followed by heat treatment at 250 ° C.

The PEN that is the resin support according to the present invention can contain an appropriate filler, if necessary.

Examples of fillers applicable to the PEN according to the present invention include calcium carbonate, calcium oxide, aluminum oxide, kaolin, silicon oxide, zinc oxide, carbon black, silicon carbide, tin oxide, crosslinked acrylic resin particles, and crosslinked polystyrene resin particles. , Melamine resin particles, crosslinked silicon resin particles, and the like. The average particle size of the filler is 0.01 to 10 μm, and the content is within the range in which the PEN film maintains transparency, and is preferably 0.0001 to 5% by mass.

In the PEN according to the present invention, surface treatment such as corona treatment, flame treatment, plasma treatment, glow discharge treatment, roughening treatment, chemical treatment, etc. may be performed before forming the dielectric film. In addition, the PEN that is a resin support is conveniently a long product wound up in a roll shape. The thickness of PEN that is a resin support is not particularly limited. In the present invention, a PEN that is a resin support may contain an ultraviolet absorber as necessary.

<Dielectric film>
The dielectric film laminate of the present invention is formed by alternately laminating a low refractive index dielectric film and a high refractive index dielectric film on at least one surface of the resin support PEN. Features. A typical dielectric film according to the present invention is a laminated body optically designed so that dielectric films having different refractive indexes are alternately laminated to reflect infrared rays.

As the material for forming the dielectric film according to the present invention, a material mainly composed of metal oxide, nitride oxide, or nitride can be preferably used. The high refractive index dielectric film having a refractive index of 1.60 or more is composed mainly of an oxide, nitride oxide or nitride containing at least Zn, Ti, Sn, In, Nb, Si, Ta or Al. It is preferable. Further, the low refractive index dielectric film having a refractive index of less than 1.60 is preferably composed mainly of an oxide, nitride oxide or nitride containing at least Si or Al, and particularly composed of silicon oxide. . As a method for forming the dielectric film, a vapor phase growth method is preferable, and a vacuum vapor deposition method, a sputtering method, an ion plating method, a catalytic chemical vapor deposition (Cat-CVD) method, or a plasma CVD method may be mentioned. In the present invention, in particular, a gas is introduced into the discharge space under atmospheric pressure or a pressure in the vicinity thereof, and the gas is excited by forming a high-frequency electric field in the discharge space, and the resin support is excited into a plasma state. It is formed by an atmospheric pressure plasma treatment method in which a dielectric film is formed on the resin support by exposure to gas. A dielectric film formed by the atmospheric pressure plasma processing method is preferable because of its low residual stress.

For the low refractive index film, a material mainly composed of calcium, barium, lithium and magnesium fluorides can be used. In the present invention, among the layers having different refractive indexes, at least one layer can have a graded configuration.

Further, details of the dielectric film according to the present invention will be described.

The dielectric laminate of the present invention is characterized by being formed by alternately laminating low refractive index dielectric films and high refractive index dielectric films. The dielectric film is defined as a film having a refractive index of 1.60 or more with respect to light having a wavelength of 633 nm, preferably a dielectric film having a refractive index of 1.70 or more. As for the refractive index of the dielectric film, the reflectance is measured under the condition of regular reflection at 5 degrees using, for example, a spectrophotometer 1U-4000 type (manufactured by Hitachi, Ltd.). In the measurement, the back surface on the observation side is roughened and then light absorption processing is performed using a black spray to prevent reflection of light on the back surface of the film and reflectivity (for wavelengths of 400 nm to 700 nm). Measurements were made. The optical film thickness is calculated from the λ / 4 value of the spectrum, and based on this, a method of calculating the refractive index at 633 nm or an automatic birefringence meter (manufactured by Oji Scientific Instruments, KOBRA-21ADH) is used. Thus, under the environment of 23 ° C. and 55% RH, it is possible to use a method of measuring 10 points at a wavelength of 590 nm and performing a three-dimensional refractive index measurement to measure the refractive index. The measured refractive index value was used.

Specific examples of the main component of the high refractive index dielectric film according to the present invention include titanium oxide, zinc oxide, indium oxide, tin oxide, and indium and tin oxide. Metal oxides such as oxides, magnesium oxide, aluminum oxide, zirconium oxide, niobium oxide, and cerium oxide. These may be contained alone or in combination of two or more. Further, these metal oxides may be double oxides in which two or more metal oxides are combined.

As the metal oxide, titanium oxide (IV) (TiO ₂ ), titanate, ITO, zinc oxide (ZnO), tin oxide (SnO ₂ ), etc., in particular, from the viewpoint of easily obtaining a high refractive index. Can be illustrated as suitable. These may be contained alone or in combination of two or more.

The low refractive index dielectric film as used in the present invention is defined as a film having a refractive index of less than 1.60 with respect to light having a wavelength of 633 nm, preferably a dielectric film having a refractive index of 1.45 or less. is there.

Examples of the main component for forming the low refractive index dielectric film according to the present invention include fluorine-containing (meth) acrylate, silicone resin, and silicon oxide such as SiO ₂ . These may be contained alone or in combination of two or more.

The dielectric film laminate of the present invention is formed by forming one or more sets of units composed of a low refractive index dielectric film and a high refractive index dielectric film on a PEN which is a resin support. However, two units or more units may be formed.

In the dielectric film laminate of the present invention, the total thickness of the low refractive index dielectric film and the high refractive index dielectric film is preferably 500 nm or more, more preferably 500 nm or more and 2000 nm or less. The film thickness of the low refractive index dielectric film constituting the dielectric film stack is approximately 100 to 500 nm, and the film thickness of the high refractive index dielectric film is approximately 50 to 300 nm.

In the present invention, for measuring the thickness of the dielectric film, examples of the optical film thickness measuring apparatus include a USB simplified film thickness measuring apparatus, Solid Lambda Thickness (manufactured by Spectra Corp.). Or the cross-sectional part of the formed dielectric film laminated body is cut out using a microtome etc., The cross-sectional part is observed using an electron microscope etc., and the total film thickness of a dielectric film can be calculated | required. In this invention, it measured using the latter method.

In the present invention, the difference in hardness measured by the nanoindentation method between the low refractive index dielectric film and the high refractive index dielectric film is 1.4 GPa or more and 3.0 GPa or less. One.

In the present invention, the hardness of each dielectric film is a value measured by the nanoindentation method, but the hardness measurement method by the nanoindentation method uses a minute diamond indenter with an extremely small load on the sample. In this method, the relationship between the load and the indentation depth (displacement amount) is measured while the material is pressed into the dielectric film, and the hardness and the elastic modulus (Reduced Modulus) are measured from the obtained load-displacement curve.

<Measurement principle of nanoindentation method>
The nanoindentation method can be used to measure indentation hardness at the nano level by adding an indentation hardness measurement module (configured with a transducer and an indentation tip) to an atomic force microscope (AFM). This is the latest measurement method. While applying a load of μN or less, a diamond indenter is pushed into the sample, and the indentation depth is measured with nanometer accuracy. From this measurement, a load-displacement curve diagram can be obtained, and the hardness characteristics of the material can be quantitatively measured.

<Atmospheric pressure plasma method>
In the method of forming the dielectric film according to the present invention on the PEN which is the resin support, the dielectric film is manufactured by the atmospheric pressure plasma method. The dielectric used in the atmospheric pressure plasma method according to the present invention The raw material compound for the film will be further described.

A dielectric film is an oxide or nitride oxide containing Si or Al by selecting conditions such as an organometallic compound, a decomposition gas, a decomposition temperature, and an input power as a raw material (also referred to as a raw material) in an atmospheric pressure plasma method. A dielectric film having a refractive index different from that of a ceramic layer containing nitride as a main component can be formed.

For example, if a silicon compound is used as a raw material compound and oxygen is used as a decomposition gas, silicon oxide is generated. Further, if silazane or the like is used as a raw material compound, silicon oxynitride is generated. This is because highly active charged particles and active radicals exist in the plasma space at a high density, so that multistage chemical reactions are accelerated at high speed in the plasma space, and the elements present in the plasma space are thermodynamic. This is because it is converted into an extremely stable compound in a very short time.

As a raw material for forming such a dielectric film, as long as it is a silicon compound, it may be in a gas, liquid, or solid state at normal temperature and pressure. In the case of gas, it can be introduced into the discharge space as it is, but in the case of liquid or solid, it is used after being vaporized by means such as heating, bubbling, decompression or ultrasonic irradiation. Further, it may be used after being diluted with a solvent. As the solvent, an organic solvent such as methanol, ethanol, n-hexane or a mixed solvent thereof can be used. Since these diluted solvents are decomposed into molecular and atomic forms during the plasma discharge treatment, the influence can be almost ignored.

Examples of such silicon compounds include silane, tetramethoxysilane, tetraethoxysilane, tetra n-propoxysilane, tetraisopropoxysilane, tetra n-butoxysilane, tetrat-butoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, Diethyldimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, phenyltriethoxysilane, (3,3,3-trifluoropropyl) trimethoxysilane, hexamethyldisiloxane, bis (dimethylamino) dimethylsilane Bis (dimethylamino) methylvinylsilane, bis (ethylamino) dimethylsilane, N, O-bis (trimethylsilyl) acetamide, bis (trimethylsilyl) carbodiimide, die Ruaminotrimethylsilane, dimethylaminodimethylsilane, hexamethyldisilazane, hexamethylcyclotrisilazane, heptamethyldisilazane, nonamethyltrisilazane, octamethylcyclotetrasilazane, tetrakisdimethylaminosilane, tetraisocyanatosilane, tetramethyldisilazane , Tris (dimethylamino) silane, triethoxyfluorosilane, allyldimethylsilane, allyltrimethylsilane, benzyltrimethylsilane, bis (trimethylsilyl) acetylene, 1,4-bistrimethylsilyl-1,3-butadiyne, di-t-butylsilane, 1,3-disilabutane, bis (trimethylsilyl) methane, cyclopentadienyltrimethylsilane, phenyldimethylsilane, phenyltrimethylsilane, pro Rugyltrimethylsilane, tetramethylsilane, trimethylsilylacetylene, 1- (trimethylsilyl) -1-propyne, tris (trimethylsilyl) methane, tris (trimethylsilyl) silane, vinyltrimethylsilane, hexamethyldisilane, octamethylcyclotetrasiloxane, tetramethyl Examples thereof include cyclotetrasiloxane, hexamethylcyclotetrasiloxane, M silicate 51, and the like.

Examples of the aluminum compound include aluminum ethoxide, aluminum triisopropoxide, aluminum isopropoxide, aluminum n-butoxide, aluminum-butoxide, aluminum t-butoxide, aluminum acetylacetonate, triethyldialuminum tri-s-butoxide, and the like. It is done.

In addition, as a decomposition gas for decomposing the source gas containing silicon or aluminum to obtain silicon oxide or an aluminum oxide film, hydrogen gas, methane gas, acetylene gas, carbon monoxide gas, carbon dioxide gas, nitrogen gas, Ammonia gas, nitrous oxide gas, nitrogen oxide gas, nitrogen dioxide gas, oxygen gas, water vapor, fluorine gas, hydrogen fluoride, trifluoroalcohol, trifluorotoluene, hydrogen sulfide, sulfur dioxide, carbon disulfide, chlorine gas, etc. Can be mentioned.

For example, a dielectric film containing silicon oxide, nitride, carbide, or the like can be obtained by appropriately selecting a source gas containing silicon and a decomposition gas.

In the atmospheric pressure plasma method according to the present invention, these reactive gases are mixed mainly with a discharge gas that tends to be in a plasma state, and the gas is sent to a plasma discharge generator. As such a discharge gas, nitrogen gas or 18th group atom of the periodic table, specifically, helium, neon, argon, krypton, xenon, radon or the like is used. Among these, nitrogen, helium, and argon are preferably used.

The dielectric film is formed by mixing the discharge gas and the reactive gas and supplying the mixed gas as a dielectric film forming (mixed) gas to a plasma discharge generator (plasma generator). Although the ratio of the discharge gas and the reactive gas varies depending on the properties of the film to be obtained, the reactive gas is supplied with the ratio of the discharge gas being 50% or more with respect to the entire mixed gas.

In the dielectric film according to the present invention, for example, the organic silicon compound is further combined with oxygen gas and nitrogen gas at a predetermined ratio, and silicon oxide containing at least one of O atom and N atom and Si atom is mainly used. A dielectric film can be obtained.

Next, the atmospheric pressure plasma method will be described in detail.

In the method for producing a dielectric film laminate according to the present invention, an atmospheric pressure plasma method is used for forming the dielectric film according to the present invention.

The atmospheric pressure plasma method is described in, for example, Japanese Patent Laid-Open Nos. 10-154598, 2003-49272, and WO 02/048428. A dielectric film is formed by supplying a gas containing a body film forming gas and a discharge gas, exciting the gas by forming a high-frequency electric field in the discharge space, and exposing the gas to the excited gas.

In particular, the thin film forming method described in JP-A-2004-68143 is preferable for forming a dense dielectric film. In addition, PEN, which is a web-like resin support, is drawn out from a roll-shaped original winding, so that dielectric films having different refractive indexes can be continuously formed.

The high frequency referred to in the present invention means one having a frequency of at least 0.5 kHz.

The above atmospheric pressure plasma method used for forming the dielectric film according to the present invention is a plasma CVD method performed under atmospheric pressure or a pressure in the vicinity thereof, and the atmospheric pressure or the pressure in the vicinity thereof is about 20 to 110 kPa. In order to obtain the good effects described in the present invention, 93 to 104 kPa is preferable.

As discharge conditions in the present invention, the frequency of the high-frequency electric field is preferably 1 kHz to 2500 MHz and the supplied power is preferably 1 to 50 W / cm ^{2. The} frequency is 50 kHz or more and the supplied power is 5 W / cm ² or more. More preferably. Furthermore, it is more preferable that two or more electric fields having different frequencies are applied to the discharge space and superimposed.

Although the superposition of continuous waves such as sine waves has been described above, the present invention is not limited to this, and both pulse waves may be used, one may be continuous waves and the other may be pulse waves. Further, it may have a third electric field having a different frequency.

As a specific method for applying the high-frequency electric field of the present invention to the same discharge space, for example, a first power source that applies a high-frequency electric field having a frequency ω1 is connected to the first electrode constituting the counter electrode, An atmospheric pressure plasma discharge processing apparatus in which a second power source that forms a high-frequency electric field having a frequency ω2 is connected to the second electrode is used.

Here, the frequency of the first power source is 1 kHz to 1 MHz, and 200 kHz or less can be preferably used. The electric field waveform may be a continuous wave or a pulse wave.

On the other hand, the frequency of the second power source is preferably 1 MHz to 2500 MHz, and more preferably 800 kHz or more. The higher the frequency of the second power source, the higher the plasma density, and a dense and high-quality dielectric film can be obtained.

In addition, a first filter that makes it difficult to pass a high-frequency electric field current from the second power source between the first electrode and the first power source or between them, and the second electrode, the second power source, or between them It is preferable to connect a 2nd filter to either.

In the present invention, the strength of the electric field at which discharge starts is the lowest electric field intensity that can cause discharge in the discharge space (electrode configuration, etc.) and reaction conditions (gas conditions, etc.) used in the actual thin film formation method. Point to. The discharge start electric field strength varies somewhat depending on the gas type supplied to the discharge space, the dielectric type of the electrode, the distance between the electrodes, and the like, but is controlled by the discharge start electric field strength of the discharge gas in the same discharge space.

Here, the applied electric field strength and the discharge starting electric field strength referred to in the present invention are those measured by the following method.

Measuring method of applied electric field strengths V1 and V2 (unit: kV / mm):
A high-frequency voltage probe (P6015A) is installed in each electrode portion, and an output signal of the high-frequency voltage probe is connected to an oscilloscope (Tektronix, TDS3012B), and the electric field strength at a predetermined time is measured.

Measuring method of electric discharge starting electric field intensity IV (unit: kV / mm):
A discharge gas is supplied between the electrodes, the electric field strength between the electrodes is increased, and the electric field strength at which discharge starts is defined as a discharge starting electric field strength IV. The measuring instrument is the same as the applied electric field strength measurement.

The above atmospheric pressure plasma discharge treatment apparatus includes gas supply means for supplying a discharge gas and a dielectric film forming gas between the counter electrodes. Furthermore, it is preferable to have an electrode temperature control means for controlling the temperature of the electrode.

As described above, the atmospheric pressure plasma discharge treatment apparatus used in the present invention discharges between the counter electrodes, puts the gas introduced between the counter electrodes into a plasma state, and places the gas between the counter electrodes or between the electrodes. By exposing the transferred resin support to the plasma state gas, a dielectric film is formed on the resin support. As another method, the atmospheric pressure plasma discharge treatment apparatus discharges between the counter electrodes similar to the above, excites the gas introduced between the counter electrodes or puts it in a plasma state, and excites or jets the gas outside the counter electrode. A jet system in which a dielectric film is formed on a resin support by blowing out gas in a plasma state and exposing a resin support (which may be stationary or transferred) in the vicinity of the counter electrode There is a device.

FIG. 1 is a schematic view showing an example of a jet-type atmospheric pressure plasma discharge treatment apparatus useful for the present invention.

In addition to the plasma discharge processing apparatus and the electric field application means having two power sources, the jet type atmospheric pressure plasma discharge processing apparatus is not shown in FIG. And an electrode temperature adjusting means.

The plasma discharge processing apparatus 10 has a counter electrode composed of a first electrode 11 and a second electrode 12, and the first electrode 11 has a frequency ω1 from the first power source 21 between the counter electrodes. A high frequency electric field is applied, and a high frequency electric field having a frequency ω2 from the second power source 22 is applied from the second electrode 12.

The dielectric film forming gas G described above is introduced into the gap (discharge space) 13 between the first electrode 11 and the second electrode 12 from the gas supply means as shown in FIG. A power source 21 and a second power source 22 form the above-described high-frequency electric field between the first electrode 11 and the second electrode 12 to generate a discharge. The substrate is blown out in the form of a jet on the lower side (the lower side of the paper), and the processing space created by the lower surface of the counter electrode and the base material F is filled with a gas G ° in a plasma state. A dielectric film is formed in the vicinity of the processing position 14 on the base material F that is unwound and transported or transported from the previous process. During the formation of the dielectric film, the medium heats or cools the electrode through the pipe from the electrode temperature adjusting means as shown in FIG. Depending on the temperature of the base material during the plasma discharge treatment, the physical properties, composition, etc. of the obtained dielectric film may change, and it is desirable to appropriately control this. As the temperature control medium, an insulating material such as distilled water or oil is preferably used. During the plasma discharge treatment, it is desirable to uniformly adjust the temperature inside the electrode so that temperature unevenness in the width direction or longitudinal direction of the substrate does not occur as much as possible.

By arranging a plurality of jet-type atmospheric pressure plasma discharge treatment devices in parallel with the transport direction of the resin support F and simultaneously discharging the gas in the same plasma state, a plurality of dielectric films can be formed at the same position. Thus, a desired film thickness can be formed in a short time. Also, a plurality of dielectric films having different refractive indexes can be stacked by arranging a plurality of units parallel to the transport direction of the resin support F, supplying different dielectric film forming gases to each device, and jetting different plasma states of the gas. A dielectric film can also be formed.

FIG. 2 is a schematic view showing an example of an atmospheric pressure plasma discharge processing apparatus for processing a substrate between counter electrodes useful for the present invention.

The atmospheric pressure plasma discharge treatment apparatus is an apparatus having at least a plasma discharge treatment apparatus 30, an electric field application means 40 having two power supplies, a gas supply means 50, and an electrode temperature adjustment means 60.

Between the opposing electrodes 32 of the roll rotating electrode (first electrode) 35 and the fixed electrode group (second electrode) 36 (hereinafter, the interval between the opposing electrodes is also referred to as the discharge space 32), the resin support F is subjected to plasma discharge treatment to generate a dielectric. A body membrane is formed.

In the discharge space 32 formed between the roll rotating electrode 35 and the fixed electrode group 36, the roll rotating electrode 35 receives a high-frequency electric field having a frequency ω1 from the first power source 41, and the fixed electrode group 36 has a second power source 42. A second high-frequency electric field having a frequency ω2 is applied.

In the present invention, the roll rotation electrode 35 may be the second electrode, and the fixed electrode group 36 may be the first electrode. In any case, the first power source is connected to the first electrode, and the second power source is connected to the second electrode.

The dielectric film forming gas G generated by the gas generator 51 of the gas supply means 50 is introduced into the plasma discharge treatment vessel 31 from the air supply port 52 while controlling the flow rate by a gas flow rate adjusting means (not shown).

The resin support F is unwound from the original winding (not shown) and conveyed, or is conveyed in the direction of the arrow from the previous process, and accompanied by the nip roll 65 via the guide roll 64 and the substrate. The air or the like is shut off and transferred to the fixed electrode group 36 while being wound while being in contact with the roll rotating electrode 35.

During transfer, an electric field is applied from both the roll rotating electrode 35 and the fixed electrode group 36 to generate discharge plasma between the counter electrodes (discharge space) 32. The resin support F forms a dielectric film with gas in a plasma state while being wound while being in contact with the roll rotating electrode 35.

A plurality of fixed electrodes are installed along a circumference larger than the circumference of the roll electrode, and the discharge area of the electrodes is a roll of all the fixed electrodes facing the roll rotating electrode 35. It is represented by the sum of the areas of the surfaces facing the rotating electrode 35.

The resin support F passes through the nip roll 66 and the guide roll 67 and is taken up by a winder (not shown) or transferred to the next process.

Discharged treated exhaust gas G ′ is discharged from the exhaust port 53.

During the formation of the dielectric film, in order to heat or cool the roll rotating electrode 35 and the fixed electrode group 36, the medium whose temperature is adjusted by the electrode temperature adjusting means 60 is sent to both electrodes via the pipe 61 by the liquid feed pump P, Adjust the temperature from the inside of the electrode.

Reference numerals

68 and 69 denote partition plates that partition the plasma discharge processing vessel 31 from the outside.

FIG. 3 is a perspective view showing an example of the structure of the conductive metallic base material of the roll rotating electrode shown in FIG. 2 and the dielectric material coated thereon.

In FIG. 3, a roll electrode 35a has a conductive metallic base material 35A and a dielectric 35B coated thereon. In order to control the electrode surface temperature during the plasma discharge treatment and to keep the surface temperature of the resin support F at a predetermined value, a temperature adjusting medium (water or silicon oil or the like) can be circulated.

FIG. 4 is a perspective view showing an example of the structure of the conductive metallic base material of the electrode and the dielectric material coated thereon. Although the structure of the electrode is not shown, it has a jacket structure so that the temperature during discharge can be adjusted.

In FIG. 4, the fixed electrode 36a has a coating of a dielectric 36B similar to that shown in FIG. 3 on the conductive metallic base material 36A.

The shape of the fixed electrode 36a shown in FIG. 4 is not particularly limited, and may be a cylindrical electrode or a rectangular tube electrode.

3 and 4, a roll electrode 35a and an electrode 36a are formed by spraying ceramics as

dielectrics

35B and 36B on conductive

metallic base materials

35A and 36A, respectively, and then using a sealing material of an inorganic compound. Sealed. The ceramic dielectric may be covered by about 1 mm with a single wall. As the ceramic material used for thermal spraying, alumina, silicon nitride, or the like is preferably used. Among these, alumina is particularly preferable because it is easily processed. The dielectric layer may be a lining-processed dielectric provided with an inorganic material by lining.

Examples of the conductive

metal base materials

35A and 36A include titanium metal or titanium alloy, metal such as silver, platinum, stainless steel, aluminum, and iron, a composite material of iron and ceramics, or a composite material of aluminum and ceramics. Can be mentioned.

The distance between the opposing first electrode and second electrode is the shortest distance between the surface of the dielectric and the surface of the conductive metallic base material of the other electrode when a dielectric is provided on one of the electrodes. That means. When a dielectric is provided on both electrodes, it means the shortest distance between the dielectric surfaces. The distance between the electrodes is determined in consideration of the thickness of the dielectric provided on the conductive metallic base material, the magnitude of the applied electric field strength, the purpose of using the plasma, etc. From the viewpoint of carrying out, 0.1 to 20 mm is preferable, and 0.5 to 5 mm is particularly preferable.

The plasma discharge treatment vessel 31 is preferably a treatment vessel made of Pyrex (registered trademark) glass or the like, but may be made of metal as long as it can be insulated from the electrodes. For example, polyimide resin or the like may be attached to the inner surface of an aluminum or stainless steel frame, and ceramic spraying may be performed on the metal frame to achieve insulation. In FIG. 2, it is preferable to cover both side surfaces (up to the vicinity of the base material surface) of both parallel electrodes with a material as described above.

As the first power source (high frequency power source) installed in the atmospheric pressure plasma discharge treatment apparatus of the present invention, SPG5-4500 (5 kHz) manufactured by Shinko Electric Co., Ltd., AGI-023 (15 kHz) manufactured by Kasuga Electric Co., Ltd. and PHF-6k manufactured by HEIDEN Laboratory (100 kHz *), commercially available products such as CF-2000-200k (200 kHz) manufactured by Pearl Industry, and any of them can be used.

As the second power source (high frequency power source), commercially available products such as CF-2000-800k (800 kHz), CF-5000-13M (13.56 MHz), CF-2000-150M (150 MHz) manufactured by Pearl Industries, Ltd. Any of these can be preferably used.

Of the above power sources, * indicates a HEIDEN Laboratory impulse high-frequency power source (100 kHz in continuous mode). Other than that, it is a high-frequency power source that can apply only a continuous sine wave.

In the present invention, it is preferable to employ an electrode capable of maintaining a uniform and stable discharge state by applying such an electric field in an atmospheric pressure plasma discharge treatment apparatus.

In the present invention, the power applied between the electrodes facing each other is such that power (power density) of 1 W / cm ² or more is supplied to the second electrode (second high-frequency electric field) to excite the discharge gas to generate plasma. The energy is applied to the dielectric film forming gas to form the dielectric film. The upper limit value of the power supplied to the second electrode is preferably 50 W / cm ² , more preferably 20 W / cm ² . The lower limit is preferably 1.0 W / cm ² . The discharge area (cm ² ) refers to an area in a range where discharge occurs between the electrodes.

Further, the film quality can be further improved by supplying power (power density) of 1 W / cm ² or more to the first electrode (first high-frequency electric field). Preferably it is 5 W / cm ² or more. The upper limit value of the power supplied to the first electrode is preferably 50 W / cm ² .

Here, the waveform of the high-frequency electric field is not particularly limited. There are a continuous sine wave continuous oscillation mode called a continuous mode, an intermittent oscillation mode called ON / OFF intermittently called a pulse mode, and either of them may be adopted, but at least the second electrode side (second The high-frequency electric field is preferably a continuous sine wave because a denser and better quality film can be obtained.

In the present invention, dielectric films having different refractive indexes supply a dielectric film forming gas and a gas containing a discharge gas to the discharge space under atmospheric pressure or a pressure in the vicinity thereof, thereby forming a high-frequency electric field in the discharge space. Preferably, the dielectric film is formed by a dielectric film forming method in which the gas is excited and exposed to the excited gas.

The discharge gas is nitrogen gas, and the high-frequency electric field applied to the discharge space is a superposition of the first high-frequency electric field and the second high-frequency electric field, and the frequency ω1 of the first high-frequency electric field The frequency ω2 of the second high-frequency electric field is high, and the relationship among the first high-frequency electric field strength V1, the second high-frequency electric field strength V2, and the discharge start electric field strength IV is V1 ≧ IV> V2. Alternatively, it is preferable that the relationship of V1> IV ≧ V2 is satisfied and the output density of the second high-frequency electric field is 1 W / cm ² or more.

<Laminated glass>
The laminated glass of the present invention has a dielectric laminate in which a low refractive index dielectric film and a high refractive index dielectric film are alternately laminated on a resin support. In the laminated glass in which glass is bonded to the front and back surfaces, the dielectric laminate is bonded to glass with polyvinyl butyral, and the resin support is polyethylene naphthalate.

The glass material used for the laminated glass of the present invention is a transparent glass substrate, and there is no particular limitation other than that as long as it has high light transmissivity, its raw material, manufacturing method, shape, structure, thickness, hardness, etc. Can be appropriately selected from known ones. For example, quartz glass, soda lime glass, silicate glass, aluminosilicate glass, borosilicate glass, phosphate glass, and fluorophosphate glass can be used.

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, although the display of "part" or "%" is used in an Example, unless otherwise indicated, "part by mass" or "mass%" is represented.

<Production of laminated glass>
[Preparation of Sample 1]
[Preparation of dielectric laminate 1]
(Preparation of resin support 1)
Using a PEN (polyethylene naphthalate) film (thickness: 100 μm) as a resin support, a coating liquid 1 containing an ultraviolet absorber as a light stabilizer having the following composition was prepared on this PEN, and the film thickness after curing was Coating was performed using a micro gravure coater so as to have a thickness of 5 μm, and then, in a drying process, hot air drying was performed stepwise at 80 ° C./110° C./125° C. (each zone was 30 sec) to provide a polymer layer 1.

<Preparation of coating solution 1>
65% by mass of methyl methacrylate and 35% by mass of 2-hydroxyethyl methacrylate were copolymerized to obtain a hydroxyl group-introduced methacrylate resin having an average molecular weight of 50000. For this resin, 2- (2H-benzotriazol-2-yl) -4,6-di-t-pentylphenol (TINUVIN328; Ciba Japan Co., Ltd.), which is a benzotriazole-based ultraviolet absorber as an ultraviolet absorber. 5% by weight of decanedioic acid bis [2,2,6,6-tetramethyl-1 (octyloxy) -4-piperidinyl] ester (TINUVIN123; Ciba (Made by Japan Co., Ltd.) was blended in an amount of 5% by mass, diluted with methyl ethyl ketone to adjust the viscosity, and the main component (a) adjusted to a solid content of 20% by mass was obtained. On the other hand, as a polyisocyanate compound serving as a cross-linking agent (curing agent), a curing agent (b) obtained by adjusting adduct-type hexamethylene diisocyanate with methyl ethyl ketone so that the solid content was 75% by mass was obtained. The coating agent 1 was prepared by adding 15% by mass of the curing agent (b) to the main agent (a).

On the polymer layer 1 of the resin support 1, a high refractive index layer (thickness: 120 nm, refractive index: 2.1) and a low refractive index layer (thickness: 190 nm, refractive index 1.46) are as follows: Seven layers were alternately provided in the layer structure shown, and a dielectric film laminate composed of seven layers was formed to obtain Sample 1.

Layer structure: resin support / polymer layer 1 / high refractive index layer / low refractive index layer / high refractive index layer / low refractive index layer / high refractive index layer / low refractive index layer / high refractive index layer (dielectric film Formation)
<Preparation of high refractive index layer>
[High refractive index layer forming mixed gas composition]
Discharge gas: Nitrogen 97.9% by volume
Thin film forming gas: tetraisopropoxy titanium 0.1% by volume
Additive gas: 2.0% by volume of hydrogen
[High refractive index layer deposition conditions]
1st electrode side Power supply type HEIDEN Laboratory 100 kHz (continuous mode)
PHF-6k
Frequency 100kHz
Output density 10 W / cm ² (the voltage Vp at this time was 7 kV)
Electrode temperature 120 ° C
Second electrode side Power supply type Pearl Industry 13.56MHz
CF-5000-13M
Frequency 13.56MHz
Output density 5 W / cm ² (the voltage Vp at this time was 1 kV)
Electrode temperature 90 ° C
(Preparation of low refractive index layer)
<Low refractive index layer mixed gas composition>
Discharge gas: Nitrogen 98.9% by volume
Thin film forming gas: Hexamethyldisiloxane 0.1% by volume
Addition gas: Oxygen 1.0% by volume
<Low refractive index layer deposition conditions>
1st electrode side Power supply type HEIDEN Laboratory 100 kHz (continuous mode)
PHF-6k
Frequency 100kHz
Output density 10 W / cm ² (the voltage Vp at this time was 7 kV)
Electrode temperature 120 ° C
Second electrode side Power supply type Pearl Industry 13.56MHz
CF-5000-13M
Frequency 13.56MHz
Output density 10 W / cm ² (the voltage Vp at this time was ² kV)
Electrode temperature 90 ° C
<Measurement of hardness of each dielectric film>
The hardness of the low refractive index dielectric film and the high refractive index dielectric film formed by the above method was measured by the nanoindentation method.

Using ENT1100a manufactured by Elionix, the hardness when measured with a load of 20 μN was measured. The nanoindentation probe is a Berkovich indenter in which a diamond triangular pyramid with a tip radius of curvature of 25 nm or less, a ridge angle of 60 degrees, and a height of 100 μm is fixed to a base having a length of 350 μm, a width of 100 μm, a thickness of 13 μm, and a spring constant of 263 N / m. Was used.

The hardness difference between the low refractive index dielectric film and the high refractive index dielectric film of the dielectric laminate 1 measured by the above method was 1.5 GPa.

[Preparation of laminated glass 1]
A polyvinyl butyral film (ST type, manufactured by Sekisui Chemical Co., Ltd.) having a thickness of 0.38 mm is bonded to both surfaces of the obtained dielectric film laminate 1, and the pressure is 9.8 N / cm ² at room temperature. A laminate was obtained by laminating with a roller. It was 300 g / cm when the adhesive force between the dielectric film laminated body 1 of the obtained laminated body and polyvinyl butyral was measured. The laminate was stored for 2 weeks in an environment of 25 ° C. and 10% RH, and then left for 5 hours in an environment of 25 ° C. and 80% RH. Then, bending was performed and a peel test was performed. Further, even if it was attempted to peel by hand, it could not be easily peeled. In order to make a laminated glass, the laminated body is squeezed with a glass plate having a thickness of 3 mm, laminated with a roller, put in a vacuum bag, reduced in pressure with a vacuum pump so that the laminated glass is subjected to atmospheric pressure, After heat-processing at 90 degreeC for 40 minutes, it put into the autoclave, the pressure of 1.3 MPa was applied under 130 degreeC, and it processed for 40 minutes, and the laminated glass 1 was produced.

[Preparation of Sample 2]
In the preparation of the above sample 1, a low refractive index dielectric was similarly formed except that the formation conditions of the high refractive index layer and the low refractive index layer when forming the dielectric film were changed to the conditions described below. A sample 2 having a hardness difference of 1.2 GPa measured by the nanoindentation method between the body film and the high refractive index dielectric film was prepared.

<Preparation of high refractive index layer>
[High refractive index layer forming mixed gas composition]
Discharge gas: Nitrogen 97.9% by volume
Thin film forming gas: tetraisopropoxy titanium 0.1% by volume
Additive gas: 2.0% by volume of hydrogen
[High refractive index layer deposition conditions]
1st electrode side Power supply type HEIDEN Laboratory 100 kHz (continuous mode)
PHF-6k
Frequency 100kHz
Output density 10 W / cm ² (the voltage Vp at this time was 7 kV)
Electrode temperature 120 ° C
Second electrode side Power supply type Pearl Industry 13.56MHz
CF-5000-13M
Frequency 13.56MHz
Output density 5 W / cm ² (the voltage Vp at this time was 1 kV)
Electrode temperature 90 ° C
(Preparation of low refractive index layer)
<Low refractive index layer mixed gas composition>
Discharge gas: Nitrogen 83.9 vol%
Thin film forming gas: Hexamethyldisiloxane 0.1% by volume
Addition gas: oxygen 16.0% by volume
<Low refractive index layer deposition conditions>
1st electrode side Power supply type HEIDEN Laboratory 100 kHz (continuous mode)
PHF-6k
Frequency 100kHz
Output density 10 W / cm ² (the voltage Vp at this time was 7 kV)
Electrode temperature 120 ° C
Second electrode side Power supply type Pearl Industry 13.56MHz
CF-5000-13M
Frequency 13.56MHz
Output density 10 W / cm ² (the voltage Vp at this time was ² kV)
Electrode temperature 90 ° C
[Preparation of Sample 3]
In the preparation of the above sample 1, a low refractive index dielectric was similarly formed except that the formation conditions of the high refractive index layer and the low refractive index layer when forming the dielectric film were changed to the conditions described below. A sample 3 having a difference in hardness measured by the nanoindentation method between the body film and the dielectric film having a high refractive index of 2.9 GPa was produced.

<Preparation of high refractive index layer>
[High refractive index layer forming mixed gas composition]
Discharge gas: Nitrogen 97.9% by volume
Thin film forming gas: tetraisopropoxy titanium 0.1% by volume
Additive gas: 2.0% by volume of hydrogen
[High refractive index layer deposition conditions]
1st electrode side Power supply type HEIDEN Laboratory 100 kHz (continuous mode)
PHF-6k
Frequency 100kHz
Output density 10 W / cm ² (the voltage Vp at this time was 7 kV)
Electrode temperature 120 ° C
Second electrode side Power supply type Pearl Industry 13.56MHz
CF-5000-13M
Frequency 13.56MHz
Output density 5 W / cm ² (the voltage Vp at this time was 1 kV)
Electrode temperature 90 ° C
(Preparation of low refractive index layer)
<Low refractive index layer mixed gas composition>
Discharge gas: Nitrogen 99.6% by volume
Thin film forming gas: Hexamethyldisiloxane 0.1% by volume
Addition gas: Oxygen 0.3% by volume
<Low refractive index layer deposition conditions>
1st electrode side Power supply type HEIDEN Laboratory 100 kHz (continuous mode)
PHF-6k
Frequency 100kHz
Output density 10 W / cm ² (the voltage Vp at this time was 7 kV)
Electrode temperature 120 ° C
Second electrode side Power supply type Pearl Industry 13.56MHz
CF-5000-13M
Frequency 13.56MHz
Output density 10 W / cm ² (the voltage Vp at this time was ² kV)
Electrode temperature 90 ° C
[Preparation of Sample 4]
In the preparation of the above sample 1, a low refractive index dielectric was similarly formed except that the formation conditions of the high refractive index layer and the low refractive index layer when forming the dielectric film were changed to the conditions described below. A sample 4 having a difference in hardness measured by the nanoindentation method between the body film and the dielectric film having a high refractive index of 3.3 GPa was produced.

<Preparation of high refractive index layer>
[High refractive index layer forming mixed gas composition]
Discharge gas: Nitrogen 97.9% by volume
Thin film forming gas: tetraisopropoxy titanium 0.1% by volume
Additive gas: 2.0% by volume of hydrogen
[High refractive index layer deposition conditions]
1st electrode side Power supply type HEIDEN Laboratory 100 kHz (continuous mode)
PHF-6k
Frequency 100kHz
Output density 10 W / cm ² (the voltage Vp at this time was 7 kV)
Electrode temperature 120 ° C
Second electrode side Power supply type Pearl Industry 13.56MHz
CF-5000-13M
Frequency 13.56MHz
Output density 5 W / cm ² (the voltage Vp at this time was 1 kV)
Electrode temperature 90 ° C
(Preparation of low refractive index layer)
<Low refractive index layer mixed gas composition>
Discharge gas: Nitrogen 99.8% by volume
Thin film forming gas: Hexamethyldisiloxane 0.1% by volume
Addition gas: Oxygen 0.1% by volume
<Low refractive index layer deposition conditions>
1st electrode side Power supply type HEIDEN Laboratory 100 kHz (continuous mode)
PHF-6k
Frequency 100kHz
Output density 10 W / cm ² (the voltage Vp at this time was 7 kV)
Electrode temperature 120 ° C
Second electrode side Power supply type Pearl Industry 13.56MHz
CF-5000-13M
Frequency 13.56MHz
Output density 10 W / cm ² (the voltage Vp at this time was ² kV)
Electrode temperature 90 ° C
[Preparation of Sample 5]
In the preparation of the sample 1, a high refractive index layer (thickness: 120 nm, refractive index: 2.1), low refractive index is formed on the polymer layer 1 of the resin support 1 in the same manner as in the preparation of the sample 1. Sample 5 was obtained in the same manner except that three layers (thickness: 190 nm, refractive index 1.46) were alternately provided in the layer configuration shown below, and a dielectric film laminate having a total film thickness of 430 nm was formed. .

Layer structure: resin support / polymer layer 1 / high refractive index layer / low refractive index layer / high refractive index layer [Preparation of Sample 6]
In the preparation of Sample 1, after the polymer layer 1 was formed on both surfaces of the resin support 1, the same high refractive index layer (thickness: 120 nm, refractive index: same as that used for the preparation of Sample 1 on one surface). 2.1), three low-refractive index layers (thickness: 190 nm, refractive index 1.46) are alternately provided in the layer configuration shown below, and a high refractive index layer (thickness: 120 nm, refractive index) is also provided on the other surface. : Sample 2.1 was prepared in the same manner except that three low-refractive index layers (thickness: 190 nm, refractive index 1.46) were alternately provided in the layer configuration shown below.

Layer structure: high refractive index layer / low refractive index layer / high refractive index layer / polymer layer 1 / resin support / polymer layer 1 / high refractive index layer / low refractive index layer / high refractive index layer [Preparation of Sample 7]
Sample 2 was prepared in the same manner as in the preparation of Sample 1, except that the dielectric film laminate 1 was omitted.

[Preparation of Sample 8]
In the production of the dielectric film laminate 1 of Sample 1, the resin support was changed to a triacetylcellulose film (thickness: 100 μm, abbreviated as TAC) instead of a PEN (polyethylene naphthalate) film (thickness: 100 μm). Sample 8 was produced in the same manner as Sample 1 except that.

[Preparation of Sample 9]
In the production of the dielectric film laminate 1 of the sample 1, the resin support was changed to a polypropylene film (thickness: 100 μm, abbreviated as PP) instead of a PEN (polyethylene naphthalate) film (thickness: 100 μm). A sample 9 was prepared in the same manner as sample 1.

[Preparation of Sample 10]
In the production of the dielectric film laminate 1 of the sample 1, the resin support was changed to a polysulfone film (thickness 100 μm, abbreviated as PSF) instead of a PEN (polyethylene naphthalate) film (thickness 100 μm). A sample 10 was prepared in the same manner as sample 1.

<Evaluation of laminated glass>
[Evaluation of crack resistance]
The dielectric film surface of each laminated glass was visually observed using a 100-fold magnifier, and crack resistance was evaluated according to the following evaluation rank.

5: No occurrence of cracks is observed at all. 4: Generation of cracks is slightly recognized, but the quality is acceptable for use. 3: The generation of cracks is recognized and the quality is of concern for practical use. It is a quality that causes a lot of occurrence and is a problem in practical use. 1: Many cracks are observed, and the quality cannot withstand practical use. [Evaluation of appearance]
The appearance of the laminated glass after bonding was visually observed, and the appearance was evaluated according to the following criteria.

5: Very good bonded state 4: Although the appearance of the bonded part is slightly bad, it is acceptable quality 3: Some unevenness is observed in the bonded part, and there are practical concerns There is a certain quality 2: There are uneven spots in the bonded part, and it is a quality that is a problem in practical use 1: Strong uneven spots are observed in the bonded part, and it is a quality that cannot withstand practical use [Resistance of remaining bubbles] Evaluation of〕
The bubble remaining state of each of the produced laminated glass samples was visually observed, and the bubble remaining resistance was evaluated according to the following criteria.

5: Residual air bubbles are not observed at all 4: Residual air bubbles are slightly observed, but the quality is acceptable for use 3: Residual air bubbles are observed, and there is a practical concern 2 : Obvious residual bubbles are observed, and this is a quality that is a problem in practical use. 1: A large amount of residual bubbles is observed, and the quality is not practical. [Evaluation of whitening resistance]
The produced laminated glass samples were visually observed for occurrence of whitening failure, and the whitening resistance was evaluated according to the following criteria.

5: Generation of whitening is not observed at all. 4: Generation of whitening is slightly observed, but the quality is acceptable for use. 3: The occurrence of slight whitening is observed, and there is a practical concern 2 : Appearance of obvious whitening is observed and is a quality that is a problem in practical use. 1: Appearance of many whitenings is observed, and the quality is unacceptable for practical use [Evaluation of heat shielding properties]
Place each laminated glass under sunlight, hold your hand under it, evaluate the degree of heat transfer to the hand with a monitor of 20 people, rank according to the following criteria, and evaluate the heat shielding performance from the total score did. The perfect score is 100 points, and the minimum score is 20 points.

5: Feels very cool 4: Feels cool 3: Feels a little cool 2: Doesn't feel much difference from the state that received direct sunlight 1: Cannot feel the difference from the state that received direct sunlight Table 1 shows the evaluation results obtained by the above.

As is clear from the results shown in Table 1, the laminated glass provided with the dielectric laminate having the structure of the present invention has a crack resistance, the appearance of the laminated glass, the residual resistance of bubbles, the whitening resistance and the comparative example. It turns out that it is excellent in thermal insulation.

DESCRIPTION OF SYMBOLS 10 Plasma discharge processing apparatus 11 1st electrode 12 2nd electrode 21 1st power supply 22 2nd power supply 24 2nd filter 30 Plasma discharge processing apparatus 32 Discharge space 35 Roll rotation electrode 35a Roll electrode 35A Metal base material 35B Dielectric 36 Angle Cylindrical fixed electrode group 40 Electric field applying means 41 1st power supply 42 2nd power supply 43 1st filter 44 2nd filter 50 Gas supply means 51 Gas generator 52 Air supply port 53 Exhaust port 60 Electrode temperature adjusting means G Thin film forming gas G ° Gas in plasma G 'treated exhaust gas F Resin support

Claims

In a dielectric laminate in which a low refractive index dielectric film and a high refractive index dielectric film are alternately laminated on a resin support, the resin support is polyethylene naphthalate, and the low refractive index A dielectric laminate, wherein a difference in hardness measured by a nanoindentation method between a dielectric film having a high refractive index and the dielectric film having a high refractive index is 1.4 GPa or more and 3.0 GPa or less.
The dielectric laminate according to claim 1, wherein a total thickness of the dielectric film is 500 nm or more.
It has a dielectric laminate in which a low refractive index dielectric film and a high refractive index dielectric film are alternately laminated on a resin support, and glass is pasted on the front and back surfaces of the dielectric laminate. In the laminated glass, the dielectric laminate is bonded to the glass with polyvinyl butyral, the resin support is polyethylene naphthalate, and the low refractive index dielectric film and the high refractive index A laminated glass, wherein a difference in hardness measured by a nanoindentation method with respect to a dielectric film is 1.4 GPa or more and 3.0 GPa or less.
In a dielectric laminate manufacturing method for manufacturing a dielectric laminate in which a low refractive index dielectric film and a high refractive index dielectric film having different hardnesses are alternately laminated on a resin support, the resin The support is polyethylene naphthalate, and the difference in hardness measured by the nanoindentation method between the low refractive index dielectric film and the high refractive index dielectric film is 1.4 GPa or more and 3.0 GPa or less And the dielectric film introduces a gas into the discharge space under atmospheric pressure or pressure near the atmosphere to form a high-frequency electric field in the discharge space, thereby bringing the gas into a plasma state, and A method for producing a dielectric laminate, wherein the dielectric laminate is formed by exposure to a gas in a plasma state.
The method for manufacturing a dielectric laminate according to claim 4, wherein the total thickness of the dielectric film is 500 nm or more.
It has a dielectric laminate in which a low refractive index dielectric film and a high refractive index dielectric film are alternately laminated on a resin support, and glass is pasted on the front and back surfaces of the dielectric laminate. In the laminated glass manufacturing method, the dielectric laminate is bonded to glass with polyvinyl butyral, the resin support is polyethylene naphthalate, the low refractive index dielectric film and the high refractive index The difference in hardness measured by the nanoindentation method with respect to the dielectric film having a rate of 1.4 GPa or more and 3.0 GPa or less, and the dielectric film is a gas under atmospheric pressure or pressure near the atmosphere. Laminated glass formed by introducing gas into a discharge space, forming a high-frequency electric field in the discharge space, bringing the gas into a plasma state, and exposing the resin support to the plasma state gas Manufacturing method.