JP6042156B2 - Laminated body and manufacturing method thereof - Google Patents

Description

The present invention relates to a laminate in which a multilayer of silicon oxide is formed on the surface of a plastic material substrate, and a method for producing the same.
More specifically, it is a laminate in which a large number of silicon oxide films having excellent transparency, abrasion resistance and scratch resistance are laminated on the surface of a transparent plastic material, and it is used for vehicles such as automobiles, railways and aircrafts instead of glass. The present invention relates to a material having high usability as a window material and a manufacturing method thereof.

Window glass for automobiles, railways, aircraft, etc. (hereinafter referred to as “glazing material”) has been made into resin for weight reduction with the aim of improving fuel efficiency and safety. Development of glazing materials as raw materials is underway.
A major challenge in changing the raw material from glass to plastic was to impart the same scratch resistance and wear resistance as glass while maintaining high transparency.
Conventionally, it has been widely known that a silicone resin is coated on the surface of a plastic substrate such as polycarbonate as a transparent material instead of glass, and a partial condensation of trialkoxysilane and tetraalkoxysilane as a silicone resin to be coated on a plastic substrate. A product in which silica fine particles are blended with a product (Cited document 1; Japanese Patent Laid-Open No. 1-306476 / catalyst conversion) is known. Also, in order to improve the scratch resistance and wear resistance of the silica layer, paying attention to the influence of the wear resistance of the surface in contact with the underlying silica layer, at least a part of the primer layer is trifunctional or higher. Use a polyfunctional compound containing a polyfunctional compound as a coating material made of a curable composition containing polysilazane in the outermost layer (Cited document 2: Japanese Patent Laid-Open No. 11-240103 / Asahi Glass), and at least a primer layer A product having 50% by weight of an acrylic resin composition having, as an outer layer, an organosiloxane resin coating layer composed of colloidal silica, trialkoxysilane hydrolyzate and tetraalkoxysilane hydrolyzate (Cited document 3: Japanese Patent Application Laid Open No. 36870 / Teijin Kasei) is also known, but all should satisfy the abrasion resistance and scratch resistance as glazing materials. It wasn't.
In addition, a polycarbonate resin having a specific MW / Mn range and a specific viscosity average molecular weight range is used as a polycarbonate material (Patent Document 4: Japanese Patent Laid-Open No. 2001-354781 / Teijin Kasei). Also known is an acrylic resin intermediate layer having a film thickness limited to improve the scratch resistance in combination with a specific range of thickness of the outer layer silica resin (Patent Document 5: JP 2009-67049 A / Hitachi Chemical). ), However, a technology that has been devised for the arrangement of the inner and outer layers has been developed. Using plasma polymerization, a layer of silicon-containing compound that is optically transparent in the first stage is converted into a gas containing a silicon-containing reagent and an oxidizing agent. After glow discharge deposition of the gaseous mixture, the second step is to form a substantially uniform layer of polymer siloxane or silicon oxide compound, oxidizing agent and silicon-containing reagent. It is also known to improve the wear resistance by glow discharge deposition of a gaseous mixture containing benzene (cited document 6: Japanese translations of PCT publication No. 2008-518109 / Dow) (cited document 7: JP-A 64-43343). No./GE).
However, a glazing material having improved scratch resistance and abrasion resistance without impairing transparency has not been developed yet.

Japanese Patent Laid-Open No. 01-306476 JP-A-11-240103 JP 2002-36870 A JP 2001-354781 A JP 2009-67049 A Special table 2008-518109 gazette JP-A 64-004343

As described above, conventional glazing materials used for automobiles and vehicles having a silicon-based resin hard film as an outer layer have not had sufficient scratch resistance and wear resistance.
The product thus obtained was not satisfactory in terms of scratch resistance and abrasion resistance. Furthermore, in order to produce a conventional plastic glazing material, the temperature at which the plastic substrate could withstand during surface treatment was used. Even within the range, there is a problem in the production method that long-time heat curing is required, and moreover, the hydrocarbon solvent used as a solvent is frequently released during the surface treatment.
In addition, an intermediate layer mainly made of acrylic resin is provided on the base material as a primer material for improving the adhesion between the base material and the silicon-based resin hard film. It was not linked to improved wear. In addition, there was a product in which a silica thin film was formed on the surface of the acrylic resin intermediate layer by a plasma CVD method to form a laminated film, but the resulting product was not sufficient in abrasion resistance and scratch resistance. When applying the plasma CVD method, since a high degree of pressure reduction is required at the time of film formation, a great amount of equipment and time are required for film formation. It was difficult to perform uniform film formation in a vacuum chamber.
The object of the present invention is excellent in transparency and abrasion resistance, little solvent release during film formation, a short manufacturing process, high economic efficiency, and plastic glazing materials for automobiles, other transportation vehicles and aircraft. It is an object of the present invention to provide a suitable laminate and a method for producing the same.

In order to solve the above problems, the present inventors have intensively studied, and as a result, a laminated structure in which a resin cured film is provided as an intermediate layer on the surface of a plastic substrate, and then a multilayer of unit silicon oxide films is provided as an outermost layer. It was found that a glazing material having the intended scratch resistance and friction resistance can be obtained.
In the laminate of the present invention, a photocurable resin layer as a primer layer or an intermediate layer (hereinafter referred to as “intermediate layer”) is coated with a photocurable resin that forms an intermediate layer on a plastic substrate, and ultraviolet rays are applied. It is obtained by curing using an energy beam such as a resin cured film.

  In the present invention, in order to obtain a film having high scratch resistance and abrasion resistance, after curing the acrylic resin of the intermediate layer, sufficient oxygen is applied to the organosilicon compound by plasma CVD at normal pressure. The scratch resistance and wear resistance required by forming a multi-layered silicon oxide film by repeating the formation process of the unit silicon oxide film a number of times by converting to plasma are realized.

  Since each of the unit silicon oxide films formed as the outer layer is composed of a high-density core layer and a low-density layer having a gradient characteristic in each silicon oxide film, such high-density / 2 to 20 layers of silicon oxide films having a low density structure are laminated, and the wear progress rate is suppressed by this many laminated structures, so that the wear resistance and scratch resistance are compared with conventional products. This is considered to be further improved.

Further, when the silicon / silicon oxide microcrystals are present in a state of being uniformly dispersed in each of the obtained unit silicon oxide films, the laminated body of the present invention is particularly resistant to scratch resistance due to the presence of the microcrystals. It was also found that the anti-wear effect was fully demonstrated.
This is because the cured resin layer of the intermediate layer functions as a cushion to disperse the local load during the wear test, and the microcrystalline silicon oxide in the outermost silicon oxide film collectively collects the scratch resistance and resistance. This is thought to be due to the display of wear.
Furthermore, it was also found that when microcrystalline silica (colloidal silica) having a diameter of, for example, 100 nm or less is dispersed in the thermosetting resin of the intermediate layer, the transparency is not impaired and the wear resistance is further improved.

In the laminate of the present invention, in order to provide a laminated structure of the unit silicon oxide film on the intermediate layer, a diluent gas composed of an inert gas or nitrogen and a vaporized organosilicon compound are mixed in advance. The raw material gas is mixed with oxygen gas to form a discharge plasma under normal pressure by applying a high frequency voltage to the raw material gas, and the raw material gas that has been converted to a discharge plasma is brought into contact with the resin cured film to form a surface of the resin cured film. Although the silicon oxide film is formed, it is necessary to repeat the operation of contacting the raw material gas with the cured resin film a plurality of times. Then, after exiting the discharge plasma region, the multilayered laminate of silicon oxide films obtained by cooling under an inert gas or nitrogen atmosphere gas containing water vapor is much more remarkable than conventional products. It was found to have excellent scratch resistance and wear resistance.
The laminated body of the present invention includes an embodiment in which the primer layer and the organosilicon compound layer are not provided only on one side of the plastic substrate, but are provided on both sides of the plastic substrate.

  The laminate of the present invention is represented in FIG. 1, and an intermediate layer 102 of a curable resin such as acrylic and a unit silicon oxide film 103 are treated on the surface of a plastic substrate 101 such as polycarbonate (PC). It is comprised from the silicon oxide film multilayered by repeating.

  The laminated body shown in FIG. 2 is another example in which silicon / silicon oxide microcrystals 105 are uniformly dispersed in a unit silicon oxide film 103 having an amorphous structure forming the silicon oxide film 104. It is preferable.

In the production of the laminate of the present invention, it is essential to repeatedly form the unit silicon oxide film by repeating the work in the discharge plasma region, but this silicon oxide film has the same 2 to 20 layers. And a unit silicon oxide film having a composition and a structure laminated to each other, the unit silicon oxide film has a thickness of 20 to 100 nm and a depth of 10 from the outermost surface in the outer direction with respect to the plastic substrate. The density of the remaining core layer excluding the outer surface layer of ˜50 nm is in the range of 2.4 to 2.8 g / cm ³ , and particularly in the outer surface layer (hereinafter referred to as the low density layer), the core layer (hereinafter referred to as the high density layer) It is characterized by a gradient characteristic in which the density decreases in a gradient range from 0.2 to 0.8 g / cm ³ from the boundary to the outermost surface to the outermost surface.
FIG. 3 is an enlarged view of a state in which the low density layer 106 and the high density layer 107 in the unit silicon oxide film 103 and the silicon oxide 105 of the silicon / silicon oxide microcrystal are uniformly dispersed. is there.
The thickness of the resin cured film is 2 to 10 μm, and the total thickness of the silicon oxide film is preferably 0.2 to 1 μm.

In the method for producing a laminate according to the present invention, a laminate is first formed on a transparent PC sheet substrate having a thickness of 12 to 100 μm by the above method, and then the laminate sheet is attached to a transparent PC plate having a thickness of several mm. Also included is a glazing material.
Further, the silicon film has a scratch resistance and an anti-scratch property that silicon / silicon oxide microcrystals having an average particle diameter of 2 to 10 nm are dispersed in an amorphous network structure composed of silicon and oxygen. It was also found that this was a major factor that dramatically improved the wear resistance. The outer surface layer contains hydrogen atoms in the range of 1 to 2 atom%, contains nitrogen atoms less than 0.01 atom%, contains carbon atoms less than 0.05 atom%, and the high-density layer contains hydrogen atoms. It is preferable to contain less than 1 atom%, nitrogen atoms in the range of 0.01 to 0.5 atom%, and carbon atoms in the range of 0.05 to 0.5 atom%.
The laminate of the present invention has a weight of 500 g in a Taber abrasion test according to JIS K7204, a CS-10F wheel, a haze value change rate before and after the test at 1000 revolutions of 4% or less, and a pencil according to JIS K5600-5-4. The pencil hardness in the hardness test is 5H or more.

The plastic substrate used in the present invention includes any form of organic polymer plastic. Examples of substrates include thermoplastics, for example polyolefins such as polyethylene, polypropylene, ethylene, propylene copolymer mixtures, and / or C4-8α-olefins, polystyrene, polycarbonate, polyethylene terephthalate, polylactic acid, and polybutylene. There are films, sheets, and the like of polyesters such as terephthalate, polyacrylates, polymethacrylates, and interpolymers of monomers used in the above polymers. Moreover, the three-dimensional structure which has the curved surface etc. which consist of these materials is also contained.
The plastic substrate can have one layer or two or more layers, and can coat the first and / or second surface of the plastic substrate.
The plastic substrate is preferably a polycarbonate resin (PC) as a material satisfying transparency and economy, but is not particularly limited to this resin.

  The organosilicon compound used in the present invention is not particularly limited, but is at least one selected from the group consisting of tetraethoxysilane (TEOS), tetramethoxysilane (TMOS), and hexamethyldisiloxane (HMDSO). Preferably there is.

The silicon oxide film forming step includes forming a silicon oxide film having a thickness of 20 to 100 nm, and then performing a cooling step to form a unit silicon oxide film 2 to 20 times. The ratio of oxygen atoms of the oxygen gas to silicon atoms contained in the organosilicon compound is in the range of oxygen / silicon = 360 to 800/1 in atomic ratio. The surface temperature of the plastic substrate is preferably in the range of 80 to 120 ° C.
Although it is economically preferable that the dilution gas and the atmospheric gas are nitrogen gas, the gas is not particularly limited as long as it corresponds to this.

The laminated film of the present invention is particularly effective when a PC substrate is used, and is suitable as an automotive glazing material. As for the abrasion resistance of PC base materials, the rate of change in haze value is about 50% in the Taber abrasion test, and it tends to become cloudy compared to glass (haze value change rate 1%). .
The standard of wear resistance that can be practically used as a glazing material is that the rate of change in haze value after 1000 revolutions in a Taber abrasion test is 2% or less (ECE Regulation R43 and ANSI / SAE Z26.1 (2007)) It is supposed that it is a wear resistance regulation). When an acrylic resin is formed on a PC by ultraviolet curing, the wear resistance is a haze change rate of 25 to 30%, and the improvement effect is insufficient.

  When a silicon oxide film is directly formed on a PC by atmospheric pressure plasma CVD, the wear resistance is about 30 to 48% in haze value change rate in the Taber abrasion test. The wear resistance was hardly improved. This is mainly due to inadequate adhesion between the silicon oxide film and the PC substrate, and since the silicon oxide film is thin, the load during the wear test is locally applied and deformed and subjected to shear stress. This is because the difference in thermal expansion coefficient between the PC substrate and the silicon oxide film is large, and cracks and peeling are likely to occur. In addition, it was found that when the silicon oxide film is formed thick, cracks and delamination easily occur due to the compressive stress of the film itself, and because the film is highly brittle, it is easily damaged by physical impact.

1st invention of this application is a laminated body which has a plastic base material, the resin cured film which consists of photocuring resin as an intermediate | middle layer, and a silicon oxide film as an outermost layer, Comprising: This silicon oxide film is two or more layers. The unit silicon oxide film is laminated and has a thickness of 0.2 to 1 μm, and the unit silicon oxide film is formed by laminating two or more unit silicon oxide films, and the unit silicon oxide for each layer of the film, it becomes a low-density layer of depth 1 0 to 50 nm from the outer surface of the outer direction of the unit a silicon oxide film, from the rest of the high density layer excluding said low density layer to the substrate, The density of the high-density layer is in the range of 2.4 to 2.8 g / cm ³ , and the low-density layer has a density from the boundary with the high-density layer toward the outer surface of the unit silicon oxide film. Lamination characterized by decreasing in a range of 0.2 to 0.8 g / cm ^{3 in} an inclined manner In the body.

  According to a second invention of the present application, the unit silicon oxide film has a thickness of 10 to 50 nm in the depth direction from the outermost surface except for at least one unit silicon oxide film located in the outermost layer. The layered product of the first invention is characterized in that the layer and the remaining thickness are composed of a high-density layer.

In a fifth invention of the present application, the high density layer contains 0.3 to 0.8 atomic% of hydrogen atoms, and the low density layer has a hydrogen atom concentration from the boundary with the high density layer toward the outer surface. It is a laminate selected from any one of the above-mentioned items 1 to 4, which continuously increases and contains 1 to 1.5 atomic% of hydrogen atoms on the outermost surface.

6th invention of this application exists in the laminated body selected from any one of the said 1st- 5th invention characterized by the thickness of the said resin cured film being 2-10 micrometers.

According to a seventh invention of the present application, the silicon oxide film is formed by uniformly dispersing silicon / silicon oxide microcrystals having an average particle diameter of 2 to 10 nm in an amorphous network structure composed of silicon and oxygen. The laminate is selected from any one of the first to sixth inventions.

The eighth invention of the present application is a load of 500 g in a Taber abrasion test according to JIS K7204, CS-1 OF oil, a haze value change rate before and after the test at 1000 revolutions is 2% or less, and according to JIS K5600-5-4 The laminated body selected from any one of the first to seventh inventions, wherein the pencil hardness in the pencil hardness test is 5H or more.

The ninth invention of the present application is selected from any one of the first to eighth inventions, wherein the cured resin film and the silicon oxide film are disposed on at least one surface of the plastic substrate. It is in a laminate.

A tenth invention of the present application resides in a laminate selected from any one of the first to ninth inventions, wherein the plastic substrate is a polycarbonate resin (PC) or polymethyl methacrylate (PMMA). .

Eleventh invention of the present application, a photocurable resin is applied to the surface of the plastic substrate, the process you to cure the resin and cured resin film, it was diluted gas and vaporized consisting inert gas or nitrogen gas Mixing an organosilicon compound and further mixing oxygen gas to form a raw material gas, applying a high frequency voltage under normal pressure to form discharge plasma, and contacting the material plasma gasified by discharge plasma to the resin cured film The unit silicon oxide film is formed on the surface of the cured resin film, and then the unit silicon oxide film formed is taken out from the plasma, and the combination of the following step A and step B is repeated at least once. The method includes a step of forming two or more silicon oxide films.
Step A: a step of adsorbing moisture on the surface of the unit silicon oxide film under an atmospheric pressure of nitrogen gas or inert gas having a moisture concentration of 10 to 10 ppm,
Step B: Next to Step A, the unit silicon oxide film on which moisture has been adsorbed is put into the plasma again, and the plasma source gas is brought into contact with the unit silicon oxide film so as to have a depth of 10 to 50 nm from the surface of the unit silicon oxide film. The process of increasing the hydrogen content within the range and further forming a unit silicon oxide film on the surface of the unit silicon oxide film

A twelfth invention of the present application, the above step A and a combination of process B performed 1-19 times, method for producing a laminate of the eleventh aspect of the unit of silicon oxide film and forming 2-20 layers It is in.

The thirteenth invention of the present application is characterized in that a laminate is first formed on a transparent PC sheet substrate having a thickness of 12 to 100 μm by the above method, and then the laminate sheet is pasted on a transparent PC plate of several mm. It exists in the manufacturing method of the laminated body of said 11th or 12th invention.

A fourteenth invention of the present application is the invention according to any one of the eleventh to thirteenth inventions, wherein the organosilicon compound is selected from tetraethoxysilane, tetramethoxysilane, and hexamethyldisiloxane. It is in the manufacturing method of the selected laminated body.

  The laminate of the present invention is highly transparent, and has both scratch resistance and abrasion resistance that can replace glass as a glazing material for automobiles. Especially when a transparent polycarbonate resin substrate is used, automobiles It is suitable as a plastic glazing material for aircraft, railway vehicles and the like. Further, the outermost silicon oxide film is an oxide film having excellent weather resistance and can be made thinner than the conventional film, so that the material cost and the film formation time can be reduced. Furthermore, since the silicon oxide film as the outermost layer of the laminate can be formed at normal pressure, it can be easily formed on the three-dimensionally curved plastic substrate and the like, and a vacuum chamber, a vacuum pump, etc. Equipment is not required, and plastic glazing material can be manufactured at low cost.

Conceptual diagram of the laminate of the present invention Conceptual diagram of a laminate (another example) of the present invention Enlarged view of FIG. Manufacturing apparatus for laminate of the present invention Schematic diagram of the first stage of unit silicon oxide film formation Schematic diagram of exposure to atmospheric gas containing moisture outside the plasma region Schematic of the state exposed to plasma again Schematic of the state exposed to atmospheric gas containing moisture again outside the plasma region X-ray reflectivity angle spectrum of the 10-layer laminate of the present invention (A) Hydrogen density of the 10-layer laminate of the present invention, and (B) Density profile of the 10-layer laminate of the present invention. TEM photograph of silicon oxide film of laminate of the present invention Partial enlarged view of a TEM photograph of the silicon oxide film of the laminate of the present invention

  The laminate of the present invention is a laminate comprising a cured resin film as an intermediate layer on at least one surface of a plastic substrate and a multilayer silicon oxide film as an outermost layer. After the resin cured film is provided as a layer, a glazing material having significantly superior scratch resistance and wear resistance compared to conventional products is obtained by forming a laminated structure in which a silicon oxide film is provided as the outermost layer. Although the photo-curing resin layer as an intermediate layer is coated with a photo-curing resin that forms a resin-cured film on a plastic substrate, it is cured using energy rays such as ultraviolet rays to form a resin-cured film. It is formed by doing.

  In order to obtain the laminate of the present invention, it is necessary to provide a multilayer structure of an amorphous silicon oxide multilayer film on a photocured resin cured film, but a multilayer amorphous silicon oxide film is formed. In order to do this, a dilute gas composed of an inert gas or nitrogen and a vaporized organosilicon compound are mixed in advance, and oxygen gas is mixed with this to form a raw material gas, and a high frequency voltage is applied to the raw material gas under normal pressure. The plasma gas is made into discharge plasma, and the raw material gas made into discharge plasma is brought into contact with the cured resin film to form a silicon oxide film on the surface of the cured resin film. It is essential to repeat the operation of contact of the raw material gas with the resin cured film a plurality of times, and after exiting the discharge plasma region after the formation of the multilayer silicon oxide film, the inert gas or nitrogen containing water vapor Atmosphere gas Laminate a silicon oxide film of interest is multilayered can be obtained by cooling.

  The laminate of the present invention is a laminate in which a multilayer silicon oxide film provided as an outer layer on a photo-curing resin film as an intermediate layer is provided on at least one surface of a plastic substrate, and a more preferable laminate is a multilayer. The silicon / silicon oxide microcrystals having an average particle diameter of 1 to 10 nm are uniformly dispersed in the amorphous network structure of the unit silicon oxide film constituting the structure.

  Examples of the plastic substrate used in the present invention include polyethylene, polypropylene, and polyolefins such as a copolymer mixture of ethylene and propylene, polyesters such as C4-8α-olefin, polystyrene, polycarbonate, polyethylene terephthalate, polylactic acid, and polybutylene terephthalate. In the present invention, durability, strength, transparency, economy, and the like can be exemplified by films, sheets or three-dimensional structures having a thickness of 0.001 to 0.1 cm, such as polyacrylate and polymethacrylate. In view of properties and the like, the most preferable plastic substrate is polycarbonate.

The cured resin film as an intermediate layer in the laminate of the present invention functions as a primer, and can use a photocurable acrylic resin, organosiloxane resin, or the like. It is formed between the film and its function is to improve the adhesion between the plastic substrate and the outermost silicon oxide film and to absorb the difference in linear expansion coefficient between the plastic substrate and the silicon oxide film. Thus, the silicon oxide film can be prevented from cracking and peeling.
Furthermore, when the silicon oxide film receives physical stress from the outside during use, the intermediate layer acts as a cushion to disperse the stress and prevent the silicon oxide film from receiving excessive stress locally. In particular, wear and damage caused by external stress can be reduced.
In the present invention, it was also found that, for example, when microcrystalline silica (colloidal silica) having a diameter of 100 nm or less is dispersed in the intermediate layer, the transparency is not impaired and the wear resistance is further improved.

  Examples of the photocurable acrylic resin used in the present invention include a homopolymer of one ester of (meth) acrylic acid, a copolymer of an ester of (meth) acrylic acid, and one or more copolymerizable ones. Although there are copolymerized derivatives of comonomers, highly preferred esters of (meth) acrylic acid are hydrocarbyl esters, especially alkyl esters, in which each ester group has 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms. Some contain carbon atoms, and preferred esters include butyl acrylate and methyl methacrylate. Further, these polymers can include copolymerizable comonomers, and can also include cross-linked poly (meth) acrylate polymers and the like. For example, di (meth) acrylate esters of dialcohols, especially alkylene glycols and poly (alkylene) glycols.

  In particular, the acrylic resin raw material used in the present invention contains an acrylic resin monomer or oligomer containing a UV absorber, a light stabilizer, an active energy ray polymerization initiator such as a UV polymerization initiator, colloidal silica, and a surfactant. Any suitable acrylic resin raw material is used, but as appropriate, “UVHC3000” manufactured by Momentive Performance Materials, “Fujihard” manufactured by Fujikura Kasei Co., Ltd., “UVHC3000” manufactured by Momentive Performance Materials, etc. Can be mentioned.

  As the polymerization initiator used in the present invention, acetophenone-based 1-hydroxy-cyclohexyl-phenylketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-hydroxy, which are known as photopolymerization initiators, are used. 2-methyl-1-phenyl-propan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1 -(4-morpholinophenyl) -butanone-1-one, phosphine oxide-based 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, and also benzophenone and polymerization accelerator ethyl-4-dimethylaminobenzoate And combinations such as 2-ethylhexyl-4-dimethylaminobenzoate Although but can be used, especially in order to ensure transparency in the visible region, that the maximum wavelength peak of light absorption of 400nm or less, or it is desirable to rapidly absorbed intensity is attenuated by light irradiation.

In the present invention, the means for coating the photocurable resin for forming the intermediate layer on a transparent plastic substrate such as polycarbonate is not particularly limited, and a known or well-known method can be adopted. For example, dip method, flow coating method, spray method, bar coating method, gravure coating method, roll coating method, blade coating method, air knife coating method, spin coating method, slit coating method, micro gravure coating method, etc. are adopted. it can.
In addition, after application of the photocurable resin coating liquid, if the coated coating liquid material contains a solvent, it is dried to remove the solvent, and then irradiated with active energy rays such as ultraviolet rays. And cured to form an intermediate layer such as an acrylic resin.

  In the present invention, in order to obtain a particularly high scratch-resistant and wear-resistant film, it is sufficient to cure the acrylic resin of the resin cured film layer as an intermediate layer and then perform plasma CVD at normal pressure. When a silicon oxide film is formed by applying an oxygen to form an organic silicon compound into a plasma, silicon / silicon oxide microcrystals are formed in the amorphous silicon oxide film, and the resulting microcrystals have a wear resistance effect. It was able to be elucidated that it was fully demonstrated. This is because the cured resin layer of the intermediate layer functions as a cushion to disperse the local load during the wear test, and the silicon / silicon oxide microcrystals in the outermost silicon oxide film are collectively wear resistant. It is inferred that it has become possible to demonstrate its sexuality.

  The silicon oxide compound used for forming the outer layer silicon oxide film in the present invention is an organoalkoxysilane compound containing no amino group, epoxy group, or isocyanate group. Bifunctional alkoxysilane, trifunctional alkoxysilane, and tetrafunctional alkoxysilane are preferable. Furthermore, a partial condensate (that is, a polyorganoalkoxysilane compound) in which these compounds are bonded by a siloxane bond (Si—O bond) can also be used. In addition, these compounds may be used independently and may be used in combination of multiple.

For example, as trifunctional alkoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, methyl-tris (2-methoxyethoxy) silane, ethyltrimethoxysilane, ethyltriethoxysilane , Ethyltripropoxysilane, ethyltributoxysilane, ethyl-tris (2-methoxyethoxy) silane, hexyltrimethoxysilane, hexyltriethoxysilane, hexyltripropoxysilane, hexylriboxysilane, decyltrimethoxysilane, decyltri Fluorinated alkyls such as ethoxysilane, decyltripropoxysilane, decyltributoxysilane, and trifluoropropyltrimethoxysilane with a fluorine atom introduced as a substituent Shi) silane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, .gamma.-methacryloxypropyltrimethoxysilane, and the like. Moreover, methyldimethoxy (ethoxy) silane, ethyl diethoxy (methoxy) silane, etc. which have two types of alkoxy groups are mentioned.

  Furthermore, examples of the bifunctional alkoxysilane include dimethyldimethoxysilane, dimethyldiethoxysilane, bis (2-methoxyethoxy) dimethylsilane, diethyldiethoxysilane, diphenyldimethoxysilane, and diphenyldiethoxysilane. Examples of the organic silicon compound to be used include tetraethoxysilane (TEOS), tetramethoxysilane (TMOS), hexamethyldisiloxane (HMDSO), and the like. These organosilicon compounds are preferable because they have a high vapor pressure and are easily converted to discharge plasma under normal pressure.

The cured resin film of the intermediate layer of the present invention may be filled with silica particles. This has the effect of increasing the hardness of the intermediate layer due to the presence of silica particles and improving the scratch resistance. The average particle size of silica is preferably 1 to 100 nm, particularly preferably 1 to 50 nm, from the viewpoints of transparency and dispersibility.
As the silica particles to be used, unless the object of the present invention is impaired, the silica surface may be modified with hydrolyzable silicon groups or silanol groups, and the dispersion medium of the silica particles is not particularly limited. The colloidal colloidal silica may be dispersed and used, and the content of the colloidal silica, that is, the concentration is arbitrary, but is preferably 15 to 50% by mass.

  Hereinafter, operations for forming a silicon oxide film according to the present invention will be described with reference to the drawings.

FIG. 4 shows one mode of a manufacturing apparatus for carrying out the method for manufacturing a silicon oxide film according to the present invention.
In the manufacturing apparatus X, the chamber 7 is disposed and is cut off from the outside, and the flat lower electrode 1 made of a grounded (grounded) conductor moves left and right on the base 14 inside the chamber 7. It is arranged to be possible. A dielectric plate 2 is attached to the upper surface of the flat lower electrode 1, and two upper electrodes 3 are arranged above the dielectric plate 2 through the gap 5 so as to face the lower electrode 1. It is installed. Similarly to the lower electrode 1, the upper electrode 3 is attached to the lower surface of the upper electrode 3 so that the dielectric plate 4 covers the surface (lower surface) facing the lower electrode 1.

  In the manufacturing apparatus X of FIG. 4, a silicon oxide film is formed on the surface of the base material 13 by generating discharge plasma in the gap 5 formed between the lower electrode 1 and the upper electrode 3. In addition, examples of the constituent material of the upper electrode 3 and the lower electrode 1 include copper, aluminum, zinc, silver, gold, and tungsten.

  In order to efficiently form a silicon oxide film and to prevent the plastic sheet of the base material from becoming hot and deformed by the plasma gas, the lower electrode 1 under the base material is a constant temperature cooling pipe with circulating water. 15, the surface temperature of the substrate 13 is heated in the range of 60 to 120 ° C. When the surface temperature of the base material 13 is lower than 60 ° C., the vaporized precursor compound is reliquefied, and when the surface temperature of the base material 13 is higher than 120 ° C., the deformation temperature becomes higher than the deformation resistance temperature of the polycarbonate of the base material. May occur. The surface temperature of the substrate 13 is more preferably 80 to 100 ° C.

It is preferable that the upper electrode 3 is kept at a constant temperature with warm water or the like to prevent condensation of the introduced source gas (described later). In FIG. 4, the temperature of the upper electrode is maintained at a constant temperature via a holding member 17 that holds and fixes the upper electrode and the dielectric plate by two hot water tubes 16.
The two hot water pipes 16 have a constant temperature by the hot water sent from the hot water tank 18. The upper electrode 3 is preferably held at 80 to 250 ° C, more preferably 80 to 200 ° C.

  The dielectric plates 2 and 4 are plate-shaped and may be any solid dielectric that can select a material that can withstand the temperature of the generated plasma. For example, polytetrafluoroethylene, polyethylene terephthalate, polyethylene and other plastics, Glass, metal oxide, etc. can be used.

  A high frequency voltage is applied to the upper electrode 3 disposed for generating discharge plasma by an AC voltage device 19. The applied high-frequency voltage is preferably in the range of 10 to 20 kV, more preferably in the range of 10 to 15 kV, and the frequency is more preferably in the range of 5 to 20 kHz, and in the range of 10 to 15 kHz. Is more preferable.

  The waveform of the high-frequency voltage is not particularly limited, but is preferably a conventionally known waveform such as a rectangular wave, a triangular wave, or a sine wave. One of these waveforms may be used alone, or two or more thereof may be used in combination.

  The high-frequency voltage is preferably adjusted optimally according to the distance of the gap 5 where the plasma between the opposing dielectric plates 2 and 4 is generated. The distance of the gap 5 between the dielectric plates 2 and 4 is preferably 1 to 5 mm, particularly preferably 1 to 2 mm. What is necessary is just to set the distance of the gap | interval 5 so that the upper electrode 3 may not contact the said base material.

  At the center of the holding member 17 that holds the upper electrode 3, there is provided a slit-like opening 6a in which the gas introduction path 6 extends in the depth direction of the figure, and the vapor-like precursor compound and oxygen gas are mixed. The raw material gas is introduced into the gap 5 between the dielectric plates 2 and 4 where plasma discharge is performed through the slit-like opening 6a via the gas introduction path 6.

In the operation of forming these multi-layered silicon oxide films, discharge plasma is performed under normal pressure.
In the present invention, “normal pressure” includes a pressure in the vicinity of atmospheric pressure, and specifically means a range of, for example, 0.008 to 0.012 Pa in absolute pressure.
The figure shows a general pressure range that occurs when the atmosphere is replaced with an inert gas such as nitrogen while air is sucked with the rotary pump 20 within a few seconds.

  In the inside of the chamber 7 in the manufacturing apparatus shown in FIG. 4, the introduction pipe 8 connected to the nitrogen gas introduction part 21 for replacing the atmospheric gas with air from an atmospheric inert gas, particularly inexpensive nitrogen, is quickly replaced. A rotary pump exhaust port 9 connected to the rotary pump 20 for performing the operation is disposed, and the inside of the chamber or the periphery of the gap where the discharge plasma is formed is maintained at normal pressure.

  In the present invention, an inert gas such as nitrogen gas or argon gas can be used as a dilution gas for diluting the raw material compound and generating steam, which is inexpensive and stabilizes the plasma discharge under normal pressure. It is preferable to use nitrogen gas having an effect. When nitrogen gas is used as a dilution gas, the nitrogen gas is preferably pure nitrogen that does not contain moisture or other impurities. Furthermore, the raw material compound vapor may be supplied only by the vapor pressure of the raw material compound, or may be vaporized by mixing oxygen gas and the raw material compound.

  A predetermined amount of the precursor compound is sent from the precursor compound introduction unit 22 to the steam generator (evaporator) 10 by a metering pump (not shown), and is supplied to the steam generator 10 by the dilution gas introduced from the dilution gas introduction unit 23. It is heated while being diluted to become a vapor-form precursor compound mixed with a diluent gas. Such a vapor precursor compound is mixed with the oxygen gas introduced from the oxygen gas introduction section 24 to become a raw material gas, and is introduced into the gap 5 between the dielectric plates 2 and 4 that generate plasma as described above. The

  The above-mentioned apparatus is used to form a multi-layered silicon oxide film, which is the object of the present invention, on the surface of a base material having a predetermined area. (Hereinafter referred to as scanning). A plurality of unit silicon oxide films can be formed by repeating the scanning once in one direction and then repeating the movement of the lower electrode 1 in the opposite direction. For example, 2 to 20 unit silicon oxide films can be formed by performing scanning 20 to 20 times. The thickness of the unit silicon film can be controlled to a desired thickness (0.2 to 1 μm) by changing the scanning speed.

  In the first scan, the unit silicon oxide film 103 is first formed on the resin cured film 102 of the intermediate layer, and then in step A, an inert gas atmosphere (nitrogen atmosphere) that comes out of the plasma gas and contains a very small amount of moisture. The unit silicon oxide film 103 is further formed on the unit silicon oxide film 103 which has been held for a certain period of time and then scanned again in the plasma gas as the B process. It is necessary that the combination is repeated at a certain period.

The operation of forming the unit silicon oxide film is schematically described in detail with reference to FIGS.
FIG. 5 shows the first stage in which the silicon oxide film is formed on the intermediate resin cured film by the plasma blown out from the slit of the plastic substrate, and FIG. 6 shows that the substrate further moves out of the plasma. FIG. 7 shows the state in which water molecules are adsorbed to a depth of 10 to 50 nm from the film surface by being exposed to moisture containing atmospheric gas (nitrogen) (step A). ), Water molecules adsorbed on the membrane surface are activated by plasma, hydrogen is bonded to silicon oxide on the membrane surface, the hydrogen content is increased, and conversely the density is lowered. FIG. It is a schematic diagram which respectively shows the state which moves and the next silicon oxide film is formed.

That is, FIG. 5 shows the initial stage of formation of the unit silicon oxide film. When plasma of the source gas is introduced into the electrode gap, the unit oxidation is further performed on the resin cured film existing as an intermediate layer on the plastic substrate. Silicon is formed. At this time, unit silicon oxide is gradually formed by scanning the plastic substrate (rightward in FIG. 5).
FIG. 6 shows the state when the plastic substrate goes out of the plasma region, and the surface of the unit silicon oxide is brought into contact with the nitrogen gas containing water vapor on the surface of the unit silicon oxide formed. The state in which water vapor in nitrogen gas is gradually adsorbed is shown.

Further, FIG. 7 shows that when the silicon oxide film is returned to the original position (scanned in the left direction in FIG. 7), the unit silicon oxide film and the plasma-forming source gas come into contact with each other again on the silicon oxide film. A hydrogen bonded layer is formed, which forms a low density layer.
Further, when the plastic base material on which the low-density unit silicon oxide film is formed is scanned in the right direction, a new unit silicon oxide film is formed by contact with the plasma source gas.
As the outermost silicon oxide film of the laminate of the present invention, a multilayer structure is formed by repeating the above steps.

The laminate of the present invention is in a state in which a large number of unit silicon oxide films are laminated on the outermost layer. In order to confirm this, the X-ray reflectance spectrum measured is shown in FIG. The solid line) and the spectrum of the result of the simulation (dotted line) for calculating the density gradient of each layer are shown.
The X-ray reflectivity spectrum in FIG. 9 shows that when X-rays are incident on the silicon oxide thin film formed as the outermost layer at a very shallow angle, the X-rays reflected at the interface of each unit silicon thin film interfere with each other. It was obtained by.

FIG. 10A shows the hydrogen content profile in the depth direction of the laminated silicon oxide film of the outermost layer of the 10-layer structure of the present invention by secondary ion mass spectrometry (SIMS). FIG. 10B is a density profile in the depth direction of the silicon oxide film obtained by simulation from the X-ray reflectance spectrum of FIG. 9, and is shown in correspondence with the hydrogen content profile shown in FIG. 10A in the depth direction. Is.
That is, it shows the presence of a large number of unit silicon oxide films formed as the outer layer in FIG. 10B (however, the gray portion layer in contact with the vertical axis is a cured resin film as a primer). It is composed of a density core layer and a low-density layer having a gradient characteristic, and the hydrogen content in each low-density layer has a structure in which it gradually increases toward the surface.

9 and 10A and 10B, the unit silicon oxide film is composed of a low density layer having a thickness in the range of 10 to 50 nm in the depth direction from the outer surface and a high density layer having the remaining thickness, The density of the high-density layer is in the range of 2.4 to 2.8 g / cm ³ , and the density of the low-density layer is continuously 0.2 to 0.00 from the boundary with the high-density layer toward the outer surface. In view of the hydrogen content profile, the high-density layer contains hydrogen atoms in the range of 0.3 to 0.8 atomic%, and the low-density layer is reduced in the range of 8 g / cm ^3. It was confirmed that the hydrogen atom concentration continuously increased from the boundary with the high-density layer toward the outer surface, and contained 1 to 1.5 atomic% of hydrogen atoms on the outermost surface.

  In addition, since the unit silicon oxide film of the outermost layer was not exposed to the plasma gas after being formed, a gradient structure of density and hydrogen content was not found. However, after forming the outermost silicon oxide film, it is possible to impart a gradient structure of density and hydrogen content to the outermost silicon oxide film by treating it with an inert gas, oxygen, nitrogen, etc. in a plasma gas atmosphere. In this case, further improvement in wear resistance can be expected.

  In the plasma gas in the above apparatus, the surface temperature of the cured resin film or silicon oxide film formed on the surface of the base material is compared with the base material base (maintained at 80 to 120 ° C. by circulating constant temperature water). As a result of being exposed to atmospheric pressure plasma gas (200 to 300 ° C.), the temperature of the base material is maintained at around 80 ° C., although the temperature rises up to about 50 to 100 ° C. during the formation of the silicon oxide film in plasma gas Therefore, there is no damage due to the temperature of the substrate.

In the cooling process in which the substrate comes out of the plasma and comes out in a nitrogen gas atmosphere containing a small amount of moisture, the substrate surface is in contact with moisture in a hot state and moisture penetrates to a depth of 10 to 50 nm of the substrate surface, The base temperature drops to 80 ° C. Next, when entering the plasma gas again, the temperature becomes high, hydrogen is taken into the unit silicon oxide film from the permeated moisture, and the density of the surface layer is inclined 0.2 to 0.8 g / cm ³ toward the surface. A low density layer having a thickness in the range of 10 to 50 nm in the depth direction from the outer surface is formed.

  Furthermore, as a result of observing the cross section of each unit silicon oxide film with a transmission electron microscope (TEM), it was confirmed that silicon / silicon oxide microcrystals of 2 to 10 nm were dispersed in the amorphous silicon oxide film. did it. This silicon / silicon oxide-based microcrystal is contained in an amorphous silicon oxide film in an amount of about 10% by volume, and can be obtained only in a silicon oxide film formed by normal pressure, and not formed by a low pressure plasma CVD method. . The formation of the silicon / silicon oxide microcrystals improves the scratch resistance.

  In the production of the laminate of the present invention, in order to synthesize the silicon oxide film by the discharge plasma, the amount of oxygen for mixing the necessary oxygen gas as the raw material gas is the amount of the vapor precursor compound. Oxygen is mixed with silicon contained in the vapor at a ratio of 360 to 800 atoms (as an atomic ratio, silicon / oxygen = 1/360 to 1/800). By mixing in such a range, the silicon dioxide component increases and the required hardness can be obtained. The ratio of silicon and oxygen is particularly preferably silicon / oxygen = 1/500 to 1/800 as an atomic ratio.

  The source gas supplied to the gap 5 is turned into plasma by applying a high frequency voltage to the upper electrode 3, and a silicon oxide film is formed on the surface of the base material 13 placed on the dielectric plate 2 covering the upper surface of the lower electrode 1. And the excess source gas is sucked by the blower 12 from the slits 11 provided at both ends of the upper electrode 3 and removed to the outside.

  Note that the carbon-containing silicon oxide film formed by the vaporized precursor compound and oxygen source gas that has been converted into plasma in the gap 5 is formed in a slit shape in the gas introduction path 6 disposed in the holding member 17 that holds the upper electrode 3. Since the film forming speed is the fastest immediately below the opening 6a, the base material is scanned back and forth perpendicularly to the slit together with the movable lower electrode 1 so that a film is uniformly formed on the surface of the base material 13. It is preferable.

EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated in detail, this invention is not limited to this Example at all.
Table 1 below shows the process conditions, Table 2 shows the state of the film structure, and Table 3 shows the measurement results.

The example which produces the laminated body made into the objective of this invention using the apparatus of FIG. 4 is shown.
(Substrate 13)
As the base material on which the carbon-containing silicon oxide film is provided, polycarbonate (PC) (a polycarbonate sheet manufactured by Mitsubishi Gas Chemical Company, trade name Iupilon sheet, model number NF2000, length 100 mm, width 100 mm, thickness 1 mm) was used.

(Operation for forming the intermediate layer)
On the surface of the polycarbonate base material 13, a photo base resin (UV curable acrylic resin, manufactured by Momentive Performance Materials, UVHC3000) is used as a plastic base material using a bar coater (manufactured by Matsuo Sangyo Co., Ltd., bar coater). And the thickness after curing of the intermediate layer was adjusted to 2 μm, 5 μm, 10 μm, and 20 μm, respectively. After heating and drying at 60 ° C. for 10 minutes, a UV lamp (manufactured by Mario Network, 600 mW / cm ² ) was used, and the UV-A irradiation doses were 1.2, 3, 6 for film thicknesses of 2 μm, 5 μm, 10 μm and 20 μm, respectively. UV irradiation was performed so as to be 9 J / cm ² .

(Unit silicon oxide film formation operation)
Next, a unit silicon oxide film was laminated on the polycarbonate substrate coated with the photocurable resin layer (intermediate layer) by the following operation using the production apparatus shown in FIG.

Using the apparatus shown in FIG. 4, the process conditions in Table 1 (the number of scans of the silicon oxide film, the conveyance speed, the amount of moisture in the nitrogen gas, and the silicon oxide film synthesis pressure) were changed to The surface of the dielectric plate 2 was placed on the dielectric plate 2 so that the temperature of the surface of the dielectric plate 2 could be maintained at 80 ° C. by the liquid temperature control means (constant temperature water circulation coil) 15. The upper electrode 3 was heated to 85 ° C. by two hot water pipes 16 to prevent the source gas from condensing.
The “number of scans of the silicon oxide film” is the total number of scans for the first time for forming the unit silicon oxide film on the resin cured film and the subsequent scan (step B in the claims). Is the moving speed of the pedestal 14, “the amount of water in the nitrogen gas” is the amount of water in the nitrogen gas at the time of cooling, and “the silicon oxide film synthesis pressure” is in the chamber 7 and the electrode gap 5 (plasma generation region). Indicates the pressure.

In a state where the substrate 13 is placed, a dilute gas composed of nitrogen gas and a precursor compound are mixed by a steam generator (evaporator) 10 to form a vapor precursor compound, and the vapor precursor compound and oxygen gas are mixed. Is introduced into the gap 5 via the gas introduction part 6, and a high frequency voltage is applied to the upper electrode 3 to form discharge plasma, and the material gas converted to discharge plasma is brought into contact with the surface of the substrate 13. Thus, a carbon-containing silicon oxide film was formed on the surface of the substrate 13. Tetramethoxysilane (TMOS) was used as the precursor compound. The flow rate of TMOS is 0.3 g / min, and the oxygen flow rate is 8 L / min. Pure nitrogen was used as a dilution gas for converting TMOS into steam, and adjustment was made so that a predetermined amount of TMOS steam was generated.
In the examples, plasma discharge was performed at 95 kPa (0.095 MPa) as a normal pressure condition, and the pressure inside the chamber (including the pressure in the gap 5) was maintained at the same pressure.

Under the above conditions, as Comparative Example 1, only one scan for forming the unit silicon oxide film on the first resin cured film was performed, and the lower electrode 1 was formed with one unit silicon oxide film at a rate of 5 mm / min only in one way. As a comparative example 2, the lower electrode 1 was scanned 10 times at a speed of 12 mm / min so that the total thickness of 10 layers was greater than 1 μm. Furthermore, as Comparative Example 3, the scan of the lower electrode was reciprocated 10 times at a speed of 250 mm / min to make the total thickness of the 10 layers thinner than 0.1 μm. Furthermore, as Comparative Example 4, a silicon oxide film was formed without forming a resin cured film as an intermediate layer.
Further, as Comparative Examples 5 and 6, the pressure at the time of plasma discharge was set to 13 Pa which is usually used in the conventional low pressure CVD method.
Further, nitrogen gas containing 2.5 ppm of water vapor was used as an atmospheric gas for keeping the inside of the chamber at normal pressure. Nitrogen gas (Comparative Example 7) containing 20 ppm of water vapor as the atmospheric gas and nitrogen gas (Comparative Example 8) having a water vapor content of 0.1 ppm or less using a moisture adsorption device were used as comparative examples.

  The application condition of the high frequency voltage is a negative peak voltage of 14 kV, a peak width of 10 microseconds at 20 kHz. Moreover, the inside of the chamber 7 of the manufacturing apparatus X was made into the normal pressure conditions substituted by the nitrogen gas of the pressure of 95 kPa. The upper electrode 3 was made of copper, and the lower electrode 1 was made of aluminum. The opposing surfaces were covered with alumina dielectric plates 2 and 4 having a thickness of 1 mm.

  The slit-like gas inlet 6 for introducing gas into the upper electrode 3 has a length of 120 mm, a gap of 1 mm, and the distance between the opposing dielectric plates 2 and 4 is 1.5 mm. During film formation, the lower electrode 1 is scanned at a moving distance of 100 mm at a speed of 10 to 100 mm / min (in the comparative example, 12 mm / min and 250 mm / min) perpendicular to the slit width direction of the upper electrode 3. A film can be formed on the surface of the material 13 with a uniform thickness. Each time a single unit silicon oxide film is formed by a single scan, the unit exits from the discharge plasma and is exposed to nitrogen gas containing moisture so that moisture is adsorbed on the outermost surface.

(Evaluation method of membrane)
(transparency)
Using a spectrophotometer (U-2810 manufactured by Hitachi High-Technologies Corporation), an average value of transmittance at a wavelength of 400 to 700 nm was defined as visible light transmittance.
(Abrasion resistance)
A Taber abrasion test specified in JIS K7204 was performed. Using a Model 503 type Taber abrasion tester manufactured by Taber, using a CS-10F wheel at a load of 500 g, the change rate (ΔH) of the haze value before and after the Taber abrasion test was measured and evaluated at 1000 revolutions.
(Pencil hardness)
The pencil hardness test prescribed | regulated to JISK5600-5-4 was implemented.
(X-ray reflectivity measurement)
Film density and film thickness were measured by RTP-300RC manufactured by Rigaku Corporation.
(SIMS measurement)
Elemental analysis in the depth direction was performed with PHI ADEPT 1010 manufactured by ULVAC-PHI.

The measurement results are shown in Table 3. The film thickness was sufficient when the lower electrode 1 had a single unit silicon oxide film (Comparative Example 1) with only one scan at a speed of 5 mm / min. Both the abrasion test and the pencil hardness were insufficient. This is because the silica oxide film is a single layer and does not have a laminated structure, so there is no interface in the film, and there are no barriers to slip deformation or microcrack growth. It seems that it was insufficient.
In addition, when the lower electrode 1 is scanned 10 times at a speed of 12 mm / min and the total thickness of 10 layers is greater than 1 μm (Comparative Example 2), 10 silicon oxide films are peeled off at the time of measurement, and cannot be tested. It became.
Further, when the lower electrode is scanned 10 times at a speed of 250 mm / min and the total thickness of 10 layers is thinner than 0.1 μm (Comparative Example 3), the film thickness of the silicon oxide film is not sufficient and the pencil hardness is low. Above, the Taber abrasion test could not be maintained.
In addition, the silicon oxide film (Comparative Example 4) formed without forming the cured resin film of the intermediate layer had a low pencil hardness and a poor Taber abrasion test. Moreover, the results of the Taber abrasion test were insufficient when the plasma discharge was changed to a general decompression condition of 13 Pa (Comparative Example 5 and Comparative Example 6).
In addition, in the case of using nitrogen gas containing 20 ppm of water vapor as the atmospheric gas for maintaining the inside of the chamber at normal pressure (Comparative Example 7), although the microcrystalline silicon oxide exists, the Taber abrasion test result was bad.
Further, in the case of using nitrogen gas having a water vapor content of 0.1 ppm or less using a moisture adsorption device (Comparative Example 8), the film was peeled off during the test.
In addition, the transparency of Examples 7-9 had no problem at all.

[Summary]
As a result of the above embodiment, it is appropriate that the silicon oxide film is formed from a multilayer unit silicon oxide film by CVD plasma on the intermediate layer, and in this formation, nitrogen gas having a moisture concentration of 1 to 10 ppm is used. Alternatively, moisture is adsorbed on the surface of the unit silicon oxide film under an atmospheric pressure of an inert gas, and then the unit silicon oxide film on which the moisture is adsorbed is put into the plasma again, and the plasma source gas is converted into the unit silicon oxide film. It was found that it was necessary to form a multilayer by a process of increasing the hydrogen content in the range of 10 to 50 nm from the outermost surface of the unit silicon oxide film and overlapping the unit silicon oxide film on the surface of the unit silicon oxide film.
Furthermore, it was confirmed that it is preferable to form 2 to 20 layers of the unit silicon oxide film.

X Silicon oxide film forming apparatus 1 of the present invention Lower electrode 2 Dielectric plate 3 Upper electrode 5 Electrode gap 6 Gas introduction path 6a Slit-shaped opening 7 Chamber 10 Steam generator 13 Plastic substrate 14 Base 16 Hot water pipe 17 Upper electrode holding member 18 Hot water tank 19 AC voltage generator 21 Nitrogen gas introduction part 23 Dilution gas introduction part 101 Plastic base material 102 Photo-curing resin 103 Unit silicon oxide film 104 Silicon oxide film 105 Silicon / silicon oxide system microcrystal 106 Low density layer 107 High density layer

Claims (14)

A plastic substrate, a resin cured film made of a photocurable resin as an intermediate layer, and a laminate having a silicon oxide film as an outermost layer,
The silicon oxide film is formed by laminating two or more unit silicon oxide films, and has a thickness of 0.2 to 1 μm.
The unit silicon oxide film is formed by laminating two or more unit silicon oxide films , and each unit silicon oxide film has a depth from the outer surface of the unit silicon oxide film in the outward direction with respect to the substrate. A low-density layer having a thickness of 10 to 50 nm and a remaining high-density layer excluding the low-density layer ,
The density of the high-density layer is in the range of 2.4 to 2.8 g / cm ³ ;
The low-density layer, and wherein the density toward the outer surface of the unit of silicon oxide film from the boundary between the dense layer is reduced in a range of inclination to 0.2 to 0.8 g / cm ³ Laminated body.   The unit silicon oxide film has a low-density layer having a thickness in the range of 10 to 50 nm in the depth direction from the outermost surface, except for at least one unit silicon oxide film located in the outermost layer, and the remaining thickness is high. The laminate according to claim 1, comprising a density layer. The laminate according to claim 1 or 2, wherein the unit silicon oxide film has a thickness of 20 to 100 nm. The laminate according to claim 1 or 2, wherein the unit silicon oxide film has a thickness of 25 to 250 nm. The high density layer contains hydrogen atoms in the range of 0.3 to 0.8 atomic%, and the low density layer has a hydrogen atom concentration continuously increasing from the boundary with the high density layer toward the outer surface. The laminate selected from any one of claims 1 to 4 , wherein the outermost surface contains 1 to 1.5 atomic percent of hydrogen atoms. The laminate selected from any one of claims 1 to 5 , wherein the cured resin film has a thickness of 2 to 10 µm. The silicon oxide film, any one of the claims 1-6, characterized in that silicon oxide crystal having an average particle diameter of 2~10nm the amorphous network structure consisting of silicon and oxygen are uniformly dispersed Laminate selected from Weight change in Taber abrasion test according to JIS K7204, CS-1OF wheel, change rate of haze value before and after test at 1000 rotations is 2% or less, and pencil hardness in pencil hardness test according to JIS K5600-5-4 is 5H laminate selected from any one of the claims 1-7, characterized in that at least. The laminate selected from any one of claims 1 to 8 , wherein the cured resin film and the silicon oxide film are disposed on at least one surface of a plastic substrate. The plastic substrate is a polycarbonate resin (PC) or polymethyl methacrylate laminate selected from either one of claims 1-9, wherein it is (PMMA). The photocurable resin is applied to the surface of the plastic substrate, the process you to cure the resin and cured resin film, and an organic silicon compound diluted gas and vaporized consisting inert gas or nitrogen gas are mixed, Furthermore, oxygen gas is mixed to obtain a raw material gas, a step of applying a high-frequency voltage under normal pressure to form discharge plasma, bringing the raw material gas converted to discharge plasma into contact with the resin cured film, A step of forming a unit silicon oxide film on the surface, and then removing the formed unit silicon oxide film from the plasma, and repeating the combination of the following step A and step B at least once to form two or more unit silicon oxide films. The manufacturing method of the laminated body characterized by comprising the process to do.
Step A: a step of adsorbing moisture on the surface of the unit silicon oxide film under an atmospheric pressure of nitrogen gas or inert gas having a moisture concentration of 1 to 10 ppm,
Step B: Next to Step A, the unit silicon oxide film on which moisture has been adsorbed is put into the plasma again, and the plasma source gas is brought into contact with the unit silicon oxide film so as to have a depth of 10 to 50 nm from the surface of the unit silicon oxide film. The process of increasing the hydrogen content within the range and further forming a unit silicon oxide film on the surface of the unit silicon oxide film The method for producing a laminate according to claim 11 , wherein the combination of the step A and the step B is performed 1 to 19 times to form 2 to 20 unit silicon oxide films. First to form a laminate in the manner described above on a transparent PC sheet substrate thickness 12～100Myuemu, according to claim 11 or 12 then characterized by pasting a laminate sheet to the transparent PC plate several mm A manufacturing method of a layered product. The method for producing a laminate selected from any one of claims 11 to 13, wherein the organosilicon compound is selected from tetraethoxysilane, tetramethoxysilane, and hexamethyldisiloxane.