JP2009279778A - Laminate with hard coat layers - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminate with hard coat layers which has a high film hardness and excellent in smoothness, scratch resistance, and adhesion and has a lamination structure. <P>SOLUTION: In the laminate with the hard coat layers in which two or more hard coat layers containing inorganic particles and a metal oxide layer are laminated in the turn on at least one side of a resin substrate, the mean particle sizes of the inorganic particles contained in each of the two or more hard coat layers are different from each other, and the mean particle sizes of the inorganic particles are decreased toward the metal oxide layer in this layer construction. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a laminate with a hard coat layer having a laminated structure having high film hardness and excellent smoothness, scratch resistance, and adhesion. The present invention relates to the surface of a display such as a cathode ray tube (CRT), a liquid crystal display (LCD), a plasma display panel (PDP), a field emission display (FED), a touch panel such as a home appliance, various windows, for example, a house window, a show. It can be used as a glass protective film for a window, a window for a vehicle, a windshield for a vehicle, an amusement machine, or a glass substitute resin product.

  In recent years, plastic products have been replaced with glass products from the viewpoint of processability and weight reduction, but since the surfaces of these plastic products are easily damaged, a hard coat film is used for the purpose of imparting scratch resistance. In addition, in the case of conventional glass products, plastic films are increasingly being bonded to prevent scattering, and in order to strengthen the hardness of these film surfaces, a hard coat layer is widely formed on the surface. It has been broken. However, the conventional hard coat film is not fully satisfactory because the hardness of the hard coat layer is insufficient and the thickness of the coating film is thin.

  Therefore, a technique in which an inorganic charge material is included in the hard coat layer is disclosed. For example, Patent Document 1 discloses a hard coat film obtained by coating a hard coat layer mainly composed of an active energy ray polymerizable resin on at least one surface of a transparent base film, and has a Mohs hardness of 6 on the hard coat layer. A hard coat film containing the above inorganic fine particles, fine particles having a Mohs hardness of 4 or less and / or fine particles having an elastic modulus E of 6 GPa or less is disclosed.

  Patent Document 2 discloses a hard coat film in which the transparent hard coat layer contains a synthetic resin and surface-coated metal oxide fine particles dispersed in the resin. .

  On the other hand, transparent plastic moldings such as polycarbonate resin and acrylic resin are also used as substrates in various fields as substitutes for glass. For example, it is used for various types of window glass substitutes, lenses represented by glasses, roofing materials, transparent soundproof walls, electric light protection materials, vehicle lighting, windshields, flat panel display members, and the like. Even in such a field, for example, in Patent Document 3, a compound having an isocyanate group or a blocked isocyanate group on the surface of a polycarbonate resin molded body contains a compound selected from colloidal silica to obtain a resin molded body having high hardness. Is disclosed.

However, in any of these techniques, if the hard coat layer contains only inorganic fine particles, it is hard and highly resistant to scratches, but cracks such as cracks hardly occur, and it can be satisfied as a hard coat film having excellent adhesion to the substrate. It was not a thing.
JP 2002-107503 A JP 2006-159853 A Japanese Patent Laid-Open No. 2006-8776

  The present invention has been made in view of the above problems, and an object of the present invention is to provide a laminate with a hard coat layer having a laminated structure having high film hardness and excellent smoothness, scratch resistance, and adhesion. is there.

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

  1. In a laminate with a hard coat layer in which two or more hard coat layers containing inorganic particles and a metal oxide layer are laminated in this order on at least one surface of a resin base material, the two or more hard coat layers A laminate with a hard coat layer, characterized in that the inorganic particles contained in each have different layer sizes and the average particle size of the inorganic particles is smaller toward the metal oxide layer.

  2. 2. The method according to 1, further comprising an intermediate layer containing no inorganic particles between the resin base material and the hard coat layer, between the two or more hard coat layers, or between the hard coat layer and the metal oxide layer. Laminate with hard coat layer.

  3. The laminate with a hard coat layer according to 1 or 2, wherein the two or more hard coat layers have a layer configuration in which a filling rate of inorganic particles increases toward the metal oxide layer.

  4). 4. The laminate with a hard coat layer according to any one of 1 to 3, wherein the inorganic particles are silicon oxide particles.

  5). 5. The laminate with a hard coat layer according to any one of 1 to 4, wherein an average particle size of inorganic particles contained in each layer of the hard coat layer is 5 nm or more and 1.0 μm or less.

  6). The laminate with a hard coat layer according to any one of 1 to 5, wherein the hard coat layer is formed by a wet coating method.

  7. 7. The laminate with a hard coat layer according to 6 above, wherein the wet coating method is a multilayer simultaneous coating method in which a plurality of layers are coated simultaneously.

  8). 8. The laminate with a hard coat layer according to any one of 1 to 7, wherein a main component of the metal oxide layer is silicon oxide.

  9. 9. The laminate with a hard coat layer according to any one of 1 to 8, wherein the metal oxide layer is formed by a plasma CVD method.

  10. 10. The laminate with a hard coat layer according to 9, wherein the plasma CVD treatment method for forming the metal oxide layer is an atmospheric pressure plasma CVD method in which plasma treatment is performed under atmospheric pressure or a pressure near atmospheric pressure. .

  According to the present invention, it was possible to provide a laminate with a hard coat layer having a laminated structure with high film hardness and excellent smoothness, scratch resistance and adhesion.

  Hereinafter, the best mode 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 inventor laminated two or more hard coat layers containing inorganic particles and a metal oxide layer in this order on at least one surface of the resin base material. In the laminate with a hard coat layer, the average particle diameter of the inorganic particles contained in each of the two or more hard coat layers is different, and the average particle diameter of the inorganic particles is small toward the metal oxide layer. The present invention finds that a laminate with a hard coat layer characterized in that a laminate with a hard coat layer having a laminated structure having high film hardness and excellent smoothness, scratch resistance and adhesion can be realized. It is up to you.

  Hereinafter, the detail of each component of the laminated body with a hard-coat layer of this invention is demonstrated.

[Hard coat layer]
In the laminate with a hard coat layer of the present invention, the hard coat layer unit is composed of two or more hard coat layers containing inorganic particles, and the average particle size of the inorganic particles contained in each hard coat layer is different. It is characterized by having a structure in which the average particle size of the contained inorganic particles decreases from the resin substrate toward the metal oxide layer.

(Configuration of hard coat layer)
As a result of studying the characteristics of a laminate with a hard coat layer in which a hard coat layer and a metal oxide layer are provided on a resin base material, the present inventor has obtained a predetermined composition composed of a uniform composition on the resin base material. When a hard coat layer having a film thickness is installed and a metal oxide layer is formed thereon, the rigidity of each material or the interface between the resin substrate and the hard coat layer or between the hard coat layer and the metal oxide layer Due to the difference in characteristics, for example, when it is stored for a long time in a harsh environment, peeling occurs at each interface, resulting in a decrease in adhesion, or when the laminate with a hard coat layer receives a severe impact, It has been found that when the composition of the two is greatly different at each interface, the fracture vibration does not propagate smoothly through the laminated constituent layers, resulting in film breakage.

  As a result of intensive studies on a method for solving the above-mentioned problems, the present inventor constituted a hard coat layer with a structure in which two or more inorganic particle-containing layers having different average particle diameters were laminated, and further formed a metal from a resin substrate. Structure toward the oxide layer, the average particle size of the inorganic particles contained is not small, that is, the average particle size of the inorganic particles contained in the upper hard coat layer is contained in the lower hard coat layer It has been found that by taking a configuration smaller than the average particle size of the inorganic particles, the effect intended by the present invention can be obtained.

  The hard coat layer according to the present invention is mainly composed of a resin binder, specifically an actinic ray curable resin described later and fine particles, but the inorganic particles having different average particle diameters referred to in the present invention are When the average particle diameter of one inorganic particle is r1 and the average particle diameter of the other inorganic particle is r2, it is defined that r1 / r2 satisfies the relationship of 1.2 or more.

  By setting it as the structure of the hard-coat layer prescribed | regulated by this invention, the adhesiveness of a resin base material and a hard-coat layer or the adhesiveness of a hard-coat layer and a metal oxide layer can be improved. In particular, by disposing a hard coat layer having a high hardness having the configuration according to the present invention at a position in contact with the metal oxide layer, extremely high hardness can be realized together with the metal oxide layer provided on the hard coat layer. Furthermore, on the surface of a hard coat layer having inorganic particles having a relatively large particle diameter, when inorganic particles are present in the vicinity of the surface or in the surface region, it is difficult to form a smooth surface due to the inorganic particle pattern. Thus, the planarity of the metal oxide layer disposed on the upper part of the metal oxide layer is impaired, or the adhesiveness is impaired. On the other hand, in the present invention, it was possible to achieve high flatness and adhesion by using inorganic particles having a smaller particle size as the hard coat layer according to the present invention located in contact with the metal oxide layer. .

  In addition, by adopting a structure of two or more hard coat layers containing inorganic particles having different average particle diameters according to the present invention, stress relaxation against external pressure can be smoothly performed, whereby the laminate with a hard coat layer is bent. It is possible to prevent the occurrence of cracks and the like of the thin film when it hits. In addition, the average particle diameter as used in the field of this invention means the average particle diameter of a primary particle.

  In the laminate with a hard coat layer of the present invention, an inorganic material is further provided between 1) a resin substrate and a hard coat layer, 2) two or more hard coat layers, or 3) a hard coat layer and a metal oxide layer. From the viewpoint that the effects of the present invention can be further exhibited by having an intermediate layer that does not contain particles, this is one preferred embodiment.

  Further, in the laminate with a hard coat layer of the present invention, two or more hard coat layers have a configuration in which the filling rate of inorganic particles increases from the resin base toward the metal oxide layer. From the viewpoint that the effects of the invention can be further exerted, one preferred embodiment is provided.

  Hereinafter, the layer structure of the hard coat layer according to the present invention will be described with reference to the drawings.

  FIG. 1 is a cross-sectional view showing an example of a conventional laminate with a hard coat layer having a single hard coat layer.

  A laminate 1 with a hard coat layer shown in FIG. 1 is composed of a hard coat layer 3 containing inorganic particles on a resin substrate 2 and a metal oxide layer 5 on the top.

  In the laminate 1 with a hard coat layer having a hard coat layer composed of a single inorganic particle as exemplified above, the filling rate of the inorganic particles is low, so that sufficient hardness and bending resistance cannot be obtained. In addition, since the shape profile of the inorganic particles appears on the surface of the surface S1 of the hard coat layer 3 and the interface S1 has an uneven shape, when the metal oxide layer 5 is formed thereon, the hard coat layer 3 has its hard profile. Since the profile of the coat layer surface S1 is reflected as it is, it becomes impossible to obtain a metal oxide surface with high smoothness, and the adhesiveness also decreases.

  FIG. 2 is a cross-sectional view showing an example of a laminate with a hard coat layer having a plurality of hard coat layers containing inorganic particles.

  A laminate 1 with a hard coat layer of the present invention shown in FIG. 2 has a structure in which hard coat layers 3A, 3B, and 3C are laminated in this order on a resin substrate 2, and a metal oxide layer 5 is formed thereon. Is provided.

  The hard coat layers 3A, 3B, and 3C contain inorganic particles 4A, 4B, and 4C, respectively, and the relationship between the average particle diameters of the inorganic particles is 4A> 4B> 4C.

  By adopting the hard coat layer constitution defined in the present invention, the hard coat layer located at the uppermost part contains the smallest inorganic particles, so that a hard coat layer with high hardness is formed and an inorganic located at the surface part is formed. Since the particles have a small particle size, the smoothness of the contact interface with the metal oxide layer is enhanced, and as a result, excellent film hardness, smoothness, scratch resistance, and adhesion can be obtained.

  In addition, it is possible to further enhance the above-mentioned effect that the filling rate (volume%) of the inorganic particles 3A, 3B, 3C in the hard coat layers 3A, 3B, 3C satisfies the relationship of 4A <4B <4C. ,preferable.

  FIG. 3 is a cross-sectional view showing another example of a laminate with a hard coat layer having a plurality of hard coat layers containing inorganic particles.

  The laminated body 1 with a hard-coat layer shown in FIG. 3 shows an example of the structure which further provided the intermediate | middle layer with respect to the laminated body 1 with a hard-coat layer shown in FIG.

  3A is a configuration in which an intermediate layer IL is provided between the resin base material 2 and the lowermost hard coat layer 4A, and the intermediate layer according to the present invention includes a resin binder, specifically, Is mainly composed of an actinic ray curable resin described later. The configuration shown in b) of FIG. 3 is a configuration example in which an intermediate layer IL is provided between three hard coat layers, and the configuration shown in c) of FIG. This is a configuration example in which an intermediate layer IL is provided between the hard coat layer 4A and between hard coat layers constituted by layers.

  As shown in FIG. 3, by providing an intermediate layer between the constituent layers constituting the laminate 1 with a hard coat layer, stress relaxation between the constituent layers can be effectively performed, and the layer breaks against external pressure. Etc. can be prevented.

(Constituent material of hard coat layer)
The hard coat layer according to the present invention is composed of inorganic particles and a resin binder, preferably an actinic ray curable resin.

<Actinic ray curable resin>
Typical examples of the actinic ray curable resin applicable to the present invention include an ultraviolet curable resin and an electron beam curable resin, but a resin that is cured by irradiation with active rays other than ultraviolet rays and electron beams may be used. Examples of the ultraviolet curable resin include an ultraviolet curable acrylic urethane resin, an ultraviolet curable polyester acrylate resin, an ultraviolet curable epoxy acrylate resin, an ultraviolet curable polyol acrylate resin, and an ultraviolet curable epoxy resin. I can do it.

  In general, UV-curable acrylic urethane-based resins are obtained by further reacting 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate (hereinafter referred to as acrylate, methacrylate) with a product obtained by reacting a polyester polyol with an isocyanate monomer or a prepolymer. Can be easily obtained by reacting an acrylate monomer having a hydroxyl group such as 2-hydroxypropyl acrylate (for example, see JP-A-59-151110).

  The UV curable polyester acrylate resin can be easily obtained by reacting polyester polyol with 2-hydroxyethyl acrylate or 2-hydroxy acrylate monomer (see, for example, JP-A-59-151112). .

  Specific examples of the ultraviolet curable epoxy acrylate resin include those obtained by reacting epoxy acrylate with an oligomer, a reactive diluent and a photoinitiator added thereto (for example, JP-A-1- No. 105738). As the photoreaction initiator, one or more kinds selected from benzoin derivatives, oxime ketone derivatives, benzophenone derivatives, thioxanthone derivatives and the like can be selected and used.

  Specific examples of ultraviolet curable polyol acrylate resins include trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, alkyl-modified dipentaerythritol pentaacrylate. Etc. can be mentioned.

  These resins are usually used together with known photosensitizers. Moreover, the said photoinitiator can also be used as a photosensitizer. Specific examples include acetophenone, benzophenone, hydroxybenzophenone, Michler's ketone, α-amyloxime ester, thioxanthone, and the like. Further, when using an epoxy acrylate photoreactant, a sensitizer such as n-butylamine, triethylamine, or tri-n-butylphosphine can be used. The photoreaction initiator or photosensitizer contained in the ultraviolet curable resin composition excluding the solvent component that volatilizes after coating and drying can be added in an amount of usually 1 to 10% by mass of the composition, and 2.5 to 6 It is preferable that it is mass%.

  Examples of the resin monomer include general monomers such as methyl acrylate, ethyl acrylate, butyl acrylate, vinyl acetate, benzyl acrylate, cyclohexyl acrylate, and styrene as monomers having one unsaturated double bond. In addition, monomers having two or more unsaturated double bonds include ethylene glycol diacrylate, propylene glycol diacrylate, divinylbenzene, 1,4-cyclohexane diacrylate, 1,4-cyclohexyldimethyl adiacrylate, and the above trimethylolpropane. Examples thereof include triacrylate and pentaerythritol tetraacryl ester.

  For example, as an ultraviolet curable resin, Adekaoptomer KR / BY series: KR-400, KR-410, KR-550, KR-566, KR-567, BY-320B (above, manufactured by Asahi Denka Kogyo Co., Ltd.) Or Koei hard A-101-KK, A-101-WS, C-302, C-401-N, C-501, M-101, M-102, T-102, D-102, NS-101, FT -102Q8, MAG-1-P20, AG-106, M-101-C (manufactured by Guangei Chemical Industry Co., Ltd.), Seika Beam PHC2210 (S), PHC X-9 (K-3), PHC2213, DP- 10, DP-20, DP-30, P1000, P1100, P1200, P1300, P1400, P1500, P1600, SCR900 (above Manufactured by Dainichi Seika Kogyo Co., Ltd.), or KRM7033, KRM7039, KRM7130, KRM7131, UVECRYL29201, UVECRYL29202 (above, Daicel UCB Corporation), or RC-5015, RC-5016, RC-5020, RC-5031, RC -5100, RC-5102, RC-5120, RC-5122, RC-5152, RC-5171, RC-5180, RC-5181 (manufactured by Dainippon Ink & Chemicals, Inc.) or Aulex No. 340 clear (manufactured by China Paint Co., Ltd.), or Sun Rad H-601 (manufactured by Sanyo Chemical Industries, Ltd.), SP-1509, SP-1507 (manufactured by Showa Polymer Co., Ltd.), or RCC-15C (Grace Japan Co., Ltd.) (Manufactured by company), Aronix M-6100, M-8030, M-8060 (above, manufactured by Toagosei Co., Ltd.) or other commercially available products.

<Inorganic particles>
As the inorganic particles applicable to the hard coat layer according to the present invention, for example, metal oxide fine particles selected from Si, Ti, Mg, Ca, Zr, Sn, Sb, As, Zn, Nb, In, and Al are preferable. Specifically, silicon oxide, titanium oxide, aluminum oxide, tin oxide, indium oxide, ITO, zinc oxide, zirconium oxide, magnesium oxide, calcium carbonate, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, Mention may be made of hydrated calcium silicate, aluminum silicate, magnesium silicate and calcium phosphate. In particular, in the present invention, it is preferable to use silicon oxide as the inorganic particles.

  As silicon oxide that can be preferably applied to the present invention, for example, preferably used silicon oxide particles are: Silicia manufactured by Fuji Silysia Chemical Co., Ltd., Nippon Sil E manufactured by Nippon Silica Co., Ltd., manufactured by Nippon Aerosil Co., Ltd. Aerosil series of etc. can be applied.

  The inorganic particles applied to the hard coat layer according to the present invention preferably have an average particle size in the range of 5 nm or more and 1.0 μm or less, and further, the average particle size of the inorganic particles A having the largest average particle size. Is r1, and the average particle diameter of the inorganic particle B having the smallest average particle diameter is r2, r1 / r2 is preferably 1.2 or more, and the inorganic particle B having the smallest average particle diameter is 5 nm or more. The inorganic particle A having the largest average particle diameter is preferably 50 nm or more and 500 nm or less.

  The average particle diameter of the inorganic particles in the present invention refers to the average particle diameter value of the primary particles. For example, the inorganic particles are observed with an electron microscope to determine the particle diameter of 100 arbitrary primary particles, and the simple average value ( (Number average). Here, each particle diameter is expressed by a diameter assuming a circle equal to the projected area.

  In the hard coat layer according to the present invention, it is preferable that two or more hard coat layers have a configuration in which the filling rate of the inorganic particles increases from the resin base toward the metal oxide layer. In the hard coat layer located in the lowermost layer portion where the filling rate (volume%) of the inorganic particles is the lowest, the filling rate is preferably 5% by volume or more and 40% by volume or less. In the hard coat layer located in the uppermost layer portion having the highest), the filling rate is preferably 50% by volume or more and 70% by volume or less.

  In the present invention, the filling rate (volume%) of the inorganic particles in the hard coat layer is obtained by, for example, cutting out a cross section of the laminate with a hard coat layer, measuring the distribution state of the inorganic particles using an electron microscope, It can obtain | require by measuring the total volume ratio of the inorganic particle with respect to a film thickness.

<Method for forming hard coat layer>
In the present invention, as a method for forming two or more hard coat layers according to the present invention on a resin substrate, a known method for forming a thin film can be applied, and in particular, a wet coating method is used. It is preferable to do.

  The wet coating method is, for example, an actinic ray curable resin dissolved in a solvent, for example, hydrocarbons, alcohols, ketones, esters, glycol ethers, and other solvents, and then inorganic particles are added to the inorganic particles. In this method, a containing layer coating solution is prepared, and a wet thin film is formed on the resin substrate using the coating solution.

  Examples of coating methods used in such wet coating methods include spin coating, dip coating, extrusion coating, roll coating coating spray coating, gravure coating, wire bar coating, air knife coating, slide popper coating, and curtain coating. A coating method (coating apparatus) using a known solution can be applied.

  In addition, as a wet coating method for forming a laminated hard coat layer according to the present invention, for example, in the configuration shown in FIG. It is preferable from a viewpoint obtained.

  As a coating apparatus applicable to the multilayer simultaneous coating method, a supply port or a supply slit capable of supplying a plurality of coating liquids is provided, and the supply amount of the coating liquid to each supply port or the supply slit so as to obtain a desired dry film thickness For example, a coating apparatus such as extrusion coating, slide popper coating, or curtain coating can be applied.

The hard coat layer (inorganic particle-containing layer) formed on the resin substrate by the above coating method is irradiated with actinic rays for the purpose of curing the film. As a light source for forming a cured film layer by a photo-curing reaction of an actinic ray curable resin, any light source that generates ultraviolet rays can be used. For example, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, A high pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, etc. can be mentioned. The irradiation conditions vary depending on individual lamps, but the amount of light irradiated may be any degree 20~10000mJ / cm ^2, preferably from 50~2000mJ / cm ^2. It can be used by using a sensitizer having an absorption maximum in the near ultraviolet region to the visible light region.

  The UV curable resin composition is applied and dried, and then irradiated with UV light from a light source. The irradiation time is preferably 0.5 seconds to 5 minutes, and 3 seconds to 2 from the curing efficiency and work efficiency of the UV curable resin. Minutes are more preferred.

[Middle layer]
In the laminate with a hard coat layer of the present invention, inorganic particles are contained between 1) a resin substrate and a hard coat layer, 2) two or more hard coat layers, or 3) a hard coat layer and a metal oxide layer. It is preferable to have an intermediate layer that does not.

  The intermediate layer according to the present invention is composed of a resin binder used for forming the hard coat layer, preferably an actinic ray curable resin.

  The intermediate layer is preferably formed by a wet coating method, and more preferably by a multilayer simultaneous coating method using two or more hard coat layers using a wet coating method. .

[Metal oxide layer]
After forming the hard-coat layer on a resin base material according to the said method, the laminated body with a hard-coat layer of this invention can be obtained by forming a metal oxide layer on it.

  The metal oxide layer according to the present invention is preferably composed of a metal oxide as a main component of the constituent material from the viewpoint of forming an outermost layer having high hardness.

  The main component referred to in the present invention is that 80% by mass or more of the metal oxide layer is composed of a metal oxide, preferably 90% by mass or more is composed of a metal oxide, Particularly preferably, 95% by mass or more is composed of a metal oxide.

  The metal oxide constituting the metal oxide layer according to the present invention is not particularly limited, and examples thereof include silicon oxide, silicon oxynitride, silicon nitride, titanium oxide, titanium oxynitride, titanium nitride, boron oxide, and aluminum oxide. Among these, a silicon oxide film is particularly preferable from the viewpoint of obtaining a surface layer having high hardness.

  The metal oxide layer according to the present invention may be formed by, for example, spraying a raw material, a spin coating method, a sputtering method, an ion assist method, a plasma CVD method, an atmospheric pressure plasma CVD method under atmospheric pressure or a pressure near atmospheric pressure, or the like. Can be formed by applying.

  However, in wet coating methods such as spraying and spin coating, it is difficult to obtain molecular level (nm level) smoothness, and since a solvent is used, the resin substrate applied to the present invention is an organic material. For this reason, there is a drawback in that the usable resin base material or solvent is limited. Therefore, in the laminate with a hard coat layer of the present invention, it is preferable to apply a plasma CVD method as a method for forming an oxide layer, and in particular, atmospheric pressure plasma CVD under atmospheric pressure or pressure near atmospheric pressure. The method is preferable from the viewpoint that a decompression chamber or the like is unnecessary, a high-speed film formation is possible, and the productivity is high. This is because by forming the metal oxide layer according to the present invention by the atmospheric pressure plasma CVD method, it is possible to relatively easily form a film having a uniform and smooth surface. The details of the layer formation conditions of the atmospheric pressure plasma CVD method will be described later.

  The metal oxide layer obtained by the plasma CVD method, or the plasma CVD method under atmospheric pressure or a pressure near atmospheric pressure, is a raw material (also referred to as a raw material) organometallic compound, decomposition gas, decomposition temperature, input power, etc. Is preferable because various metal oxides having various characteristics can be generated. For example, when a silicon compound is used as a raw material compound and oxygen is used as a decomposition gas, silicon oxide 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 promoted very rapidly in the plasma space, and the elements present in the plasma space are heated. This is because it is converted into a mechanically stable compound in a very short time.

  As such an inorganic material, as long as it has a typical or transition metal element, 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. Moreover, you may dilute and use with a solvent and organic solvents, such as methanol, ethanol, n-hexane, and these mixed solvents can be used for a solvent. Since these diluted solvents are decomposed into molecular and atomic forms during the plasma discharge treatment, the influence can be almost ignored.

In the present invention, the organometallic compound used for forming the metal oxide is
Examples of the silicon compound include silane, tetramethoxysilane, tetraethoxysilane (TEOS), tetra n-propoxysilane, tetraisopropoxysilane, tetra n-butoxysilane, tetrat-butoxysilane, dimethyldimethoxysilane, and dimethyldiethoxy. Silane, 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) carbodiimi , Diethylaminotrimethylsilane, 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, phenyltrimethylsila , Propargyltrimethylsilane, 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 titanium compound include titanium methoxide, titanium ethoxide, titanium isopropoxide, titanium tetraisoporooxide, titanium n-butoxide, titanium diisopropoxide (bis-2,4-pentanedionate), titanium. Examples thereof include diisopropoxide (bis-2,4-ethylacetoacetate), titanium di-n-butoxide (bis-2,4-pentanedionate), titanium acetylacetonate, and butyl titanate dimer.

  Zirconium compounds include zirconium n-propoxide, zirconium n-butoxide, zirconium t-butoxide, zirconium tri-n-butoxide acetylacetonate, zirconium di-n-butoxide bisacetylacetonate, zirconium acetylacetonate, zirconium acetate, Zirconium hexafluoropentanedioate and the like can be mentioned.

  Examples of the aluminum compound include aluminum ethoxide, aluminum triisopropoxide, aluminum isopropoxide, aluminum n-butoxide, aluminum s-butoxide, aluminum t-butoxide, aluminum acetylacetonate, and triethyl dialumonium tri-s-butoxide. Can be mentioned.

  The boron compounds include diborane, tetraborane, boron fluoride, boron chloride, boron bromide, borane-diethyl ether complex, borane-THF complex, borane-dimethyl sulfide complex, boron trifluoride diethyl ether complex, triethylborane, trimethoxy. Examples include borane, triethoxyborane, tri (isopropoxy) borane, borazole, trimethylborazole, triethylborazole, triisopropylborazole, and the like.

  Examples of tin compounds include tetraethyltin, tetramethyltin, di-n-butyltin diacetate, tetrabutyltin, tetraoctyltin, tetraethoxytin, methyltriethoxytin, diethyldiethoxytin, triisopropylethoxytin, diethyltin, Dimethyltin, diisopropyltin, dibutyltin, diethoxytin, dimethoxytin, diisopropoxytin, dibutoxytin, tin dibutyrate, tin diacetoacetonate, ethyltin acetoacetonate, ethoxytin acetoacetonate, dimethyltin diacetoacetonate Examples of tin halides such as tin hydrogen compounds include tin dichloride and tin tetrachloride.

  Other organometallic compounds include, for example, antimony ethoxide, arsenic triethoxide, barium 2,2,6,6-tetramethylheptanedionate, beryllium acetylacetonate, bismuth hexafluoropentanedionate, dimethylcadmium, calcium 2,2,6,6-tetramethylheptanedionate, chromium trifluoropentanedionate, cobalt acetylacetonate, copper hexafluoropentanedionate, magnesium hexafluoropentanedionate-dimethyl ether complex, gallium ethoxide, tetraethoxygermane , Tetramethoxygermane, hafnium t-butoxide, hafnium ethoxide, indium acetylacetonate, indium 2,6-dimethylaminoheptanedionate Ferrocene, lanthanum isopropoxide, lead acetate, tetraethyl lead, neodymium acetylacetonate, platinum hexafluoropentanedionate, trimethylcyclopentadienylplatinum, rhodium dicarbonylacetylacetonate, strontium 2,2,6,6-tetramethyl Examples include heptanedionate, tantalum methoxide, tantalum trifluoroethoxide, tellurium ethoxide, tungsten ethoxide, vanadium triisopropoxide oxide, magnesium hexafluoroacetylacetonate, zinc acetylacetonate, and diethylzinc.

  Examples of the decomposition gas for decomposing a raw material gas containing these metals to obtain a metal oxide include hydrogen gas, methane gas, acetylene gas, carbon monoxide gas, carbon dioxide gas, and nitrogen gas.

  Various metal oxides can be obtained by appropriately selecting a source gas containing a metal element and a decomposition gas.

  A discharge gas that tends to be in a plasma state is mixed with these reactive gases, and the gas is sent to the plasma discharge generator.

  As such a discharge gas, nitrogen gas and / or 18th group atom of the periodic table, specifically, helium, neon, argon, krypton, xenon, radon, etc. are used. Among these, nitrogen, helium, and argon are preferably used, and nitrogen is particularly preferable because of low cost.

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

  As described above, various inorganic thin films can be formed by using the source gas as described above together with the discharge gas.

(Plasma CVD method)
Next, the plasma CVD method and the atmospheric pressure plasma CVD method that can be suitably used for forming the metal oxide layer according to the present invention in the method for producing a laminate with a hard coat layer of the present invention will be described in more detail.

  The plasma CVD method according to the present invention will be described.

  In the plasma CVD method (chemical vapor deposition method), a volatilized / sublimated organometallic compound adheres to the surface of a high-temperature substrate, a thermal decomposition reaction occurs, and a thermally stable inorganic thin film is generated. Is. Such a normal CVD method (also referred to as a thermal CVD method) normally requires a substrate temperature of 500 ° C. or higher, and is difficult to use for film formation on a plastic substrate.

  On the other hand, in the plasma CVD method, an electric field is applied to the space in the vicinity of the substrate to generate a space (plasma space) where a gas in a plasma state exists, and a volatilized / sublimated organometallic compound is introduced into the plasma space. After the decomposition reaction occurs, the metal oxide thin film is formed by being sprayed on the substrate. In the plasma space, a high percentage of gas is ionized into ions and electrons, and although the temperature of the gas is kept low, the electron temperature is very high, so this high temperature electron or low temperature Is in contact with an excited state gas such as ions and radicals, so that the organometallic compound as the raw material of the inorganic film can be decomposed even at a low temperature. Therefore, the temperature of the resin base material on which the metal oxide is formed can be lowered, and the film forming method can sufficiently form the film on the resin base material.

  However, in the plasma CVD method, it is necessary to apply an electric field to the gas to ionize it to be in a plasma state. Therefore, since the film was normally formed in a reduced pressure space of about 0.10 kPa to 10 kPa, a large area film When forming a film, the equipment is large, the operation is complicated, and there is a problem of productivity.

  On the other hand, the plasma CVD method near atmospheric pressure does not need to be reduced in pressure and has higher productivity than the plasma CVD method under vacuum, and has a high film density because the plasma density is high. Faster, and even under high pressure conditions under atmospheric pressure, compared to the normal conditions of CVD, the mean free path of gas is very short, so that a very flat film is obtained. The optical properties are good. From the above, in the present invention, it is more preferable to apply the atmospheric pressure plasma CVD method than the plasma CVD method under vacuum.

  Further, according to this method, a thin film having a dense performance and a stable performance can be obtained when the metal oxide film is formed on the resin substrate, more specifically, on the hard coat layer. Further, it is characterized in that a metal oxide film having a residual stress as a compressive stress in a range of 0.01 MPa or more and 100 MPa or less can be obtained stably.

  Hereinafter, a method for forming a metal oxide layer using an atmospheric pressure plasma CVD method at or near atmospheric pressure will be described.

  First, an example of a plasma film forming apparatus used for forming a metal oxide layer according to the present invention will be described with reference to FIGS. In the figure, symbol F is a long film as an example of a base resin having a hard coat layer.

  In the plasma discharge processing apparatus described in FIG. 4 or FIG. 5 and the like, the source gas containing the metal and the decomposition gas are appropriately selected from the gas supply means, and these reactive gases are mainly in a plasma state. The ceramic film can be obtained by mixing discharge gas that tends to be mixed and feeding the gas to a plasma discharge generator.

  As the discharge gas, nitrogen gas and / or 18th group atom of the periodic table, specifically helium, neon, argon, krypton, xenon, radon, etc. are used as described above. Among these, nitrogen, helium, and argon are preferably used, and nitrogen is particularly preferable because of low cost.

  FIG. 4 shows a jet-type atmospheric pressure plasma discharge processing apparatus. In addition to the plasma discharge processing apparatus and electric field applying means having two power sources, it is not shown in FIG. 4 (shown in FIG. 5 described later). Is an apparatus having gas supply means and electrode temperature adjustment means.

The plasma discharge processing apparatus 10 has a counter electrode composed of a first electrode 11 and a second electrode 12, and the frequency ω ₁ from the first power supply 21 is connected from the first electrode 11 between the counter electrodes. A first high-frequency electric field having electric field intensity V ₁ and current I ₁ is applied, and a second high-frequency electric field having frequency ω ₂ , electric field intensity V ₂ , and current I ₂ from second power source 22 is applied from second electrode 12. Is applied. The first power source 21 can apply a higher frequency electric field strength (V ₁ > V ₂ ) than the second power source 22, and the first frequency ω ₁ of the first power source 21 is higher than the second frequency ω ₂ of the second power source 22. A low frequency can be applied.

  A first filter 23 is installed between the first electrode 11 and the first power source 21 to facilitate passage of current from the first power source 21 to the first electrode 11, and current from the second power source 22. Is designed so that the current from the second power source 22 to the first power source 21 is less likely to pass through.

  In addition, a second filter 24 is installed between the second electrode 12 and the second power source 22 to facilitate passage of current from the second power source 22 to the second electrode, and from the first power source 21. It is designed to ground the current and make it difficult to pass the current from the first power source 21 to the second power source.

  A gas G is introduced from a gas supply means as shown in FIG. 5 to be described later into the space (discharge space) 13 between the opposing electrodes of the first electrode 11 and the second electrode 12, and the first electrode 11 and the second electrode A processing space created between the lower surface of the counter electrode and the base material F by generating a discharge by applying a high-frequency electric field from 12 and blowing the gas G in a plasma state to the lower side of the counter electrode (the lower side of the paper). Is filled with plasma gas G ° and unwound from a base roll (unwinder) (not shown) to be transported, or processed onto the base material F transported from the previous process. A thin film is formed near position 14. During the thin film formation, 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 resin during the plasma discharge treatment, the physical properties, composition, etc. of the obtained metal oxide 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 the temperature unevenness of the base resin in the width direction or the longitudinal direction does not occur as much as possible.

  Since a plurality of jet-type atmospheric pressure plasma discharge treatment apparatuses can be connected in series and discharged in the same plasma state at the same time, it can be processed many times and processed at high speed. In addition, if each apparatus jets gas in a different plasma state, a laminated thin film having different layers can be formed.

  FIG. 5 is a schematic view showing an example of an atmospheric pressure plasma discharge processing apparatus of a system for processing a substrate between counter electrodes useful for the present invention.

  The atmospheric pressure plasma discharge processing apparatus according to the present invention is an apparatus having at least a plasma discharge processing apparatus 30, an electric field applying means 40 having two power supplies, a gas supply means 50, and an electrode temperature adjusting means 60.

  FIG. 5 shows a thin film formed by subjecting the substrate F to plasma discharge treatment between the opposing electrodes (discharge space) 32 between the roll rotating electrode (first electrode) 35 and the square tube type fixed electrode group (second electrode) 36. To do.

In the discharge space (between the counter electrodes) 32 between the roll rotating electrode (first electrode) 35 and the square tube type fixed electrode group (second electrode) 36, the roll rotating electrode (first electrode) 35 has a first power source. The first high-frequency electric field having frequency ω ₁ , electric field strength V ₁ and current I ₁ from 41, and the frequency ω ₂ and electric field strength V ₂ from the second power source 42 to the rectangular tube-shaped fixed electrode group (second electrode) 36. A second high-frequency electric field having a current I ₂ is applied.

  A first filter 43 is installed between the roll rotation electrode (first electrode) 35 and the first power supply 41, and the first filter 43 easily passes a current from the first power supply 41 to the first electrode. The current from the second power supply 42 is grounded so that the current from the second power supply 42 to the first power supply is difficult to pass. Further, a second filter 44 is provided between the square tube type fixed electrode group (second electrode) 36 and the second power source 42, and the second filter 44 is connected from the second power source 42 to the second electrode. It is designed so that the current from the first power supply 41 is grounded and the current from the first power supply 41 to the second power supply is difficult to pass.

In the present invention, the roll rotation electrode 35 may be the second electrode, and the rectangular tube-shaped 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 first power supply preferably applies a higher high-frequency electric field strength (V ₁ > V ₂ ) than the second power supply. Further, the frequency has the ability to satisfy ω ₁ <ω ₂ .

The current is preferably I ₁ <I ₂ . Current _{I 1} of the first high-frequency electric field is preferably ^{0.3mA / cm 2 ~20mA / cm 2} , more preferably at ^{1.0mA / cm 2 ~20mA / cm 2} . The current _{I 2} of the second high-frequency electric field is preferably ^{10mA / cm 2 ~100mA / cm 2} , more preferably ^{20mA / cm 2 ~100mA / cm 2} .

  The gas G generated by the gas generator 51 of the gas supply means 50 is introduced into the plasma discharge processing vessel 31 from the air supply port 52 while controlling the flow rate.

  The substrate F is unwound from the original winding (not shown) or conveyed from the previous process, or is conveyed from the previous process, and air or the like accompanying the substrate is blocked by the nip roll 65 via the guide roll 64. Then, while being wound while being in contact with the roll rotating electrode 35, it is transferred between the square tube fixed electrode group 36 and the roll rotating electrode (first electrode) 35 and the square tube fixed electrode group (second electrode) 36. An electric field is applied from both of them to generate discharge plasma between the counter electrodes (discharge space) 32. The base material F forms a thin film with a gas in a plasma state while being wound while being in contact with the roll rotating electrode 35. The base material F passes through the nip roll 66 and the guide roll 67 and is wound up by a winder (not shown) or transferred to the next process.

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

  In order to heat or cool the roll rotating electrode (first electrode) 35 and the rectangular tube type fixed electrode group (second electrode) 36 during the formation of the thin film, a medium whose temperature is adjusted by the electrode temperature adjusting means 60 is used as a liquid feed pump. P is sent to both electrodes through the pipe 61, and the temperature is adjusted 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. 6 is a perspective view showing an example of the structure of the conductive metallic base material of the roll rotating electrode shown in FIG. 5 and the dielectric material coated thereon.

  In FIG. 6, a roll electrode 35a is formed by covering a conductive metallic base material 35A and a dielectric 35B thereon. In order to control the electrode surface temperature during the plasma discharge treatment, a temperature adjusting medium (water, silicon oil or the like) can be circulated.

  FIG. 7 is a perspective view showing an example of the structure of the conductive metallic base material of the rectangular tube electrode and the dielectric material coated thereon.

  In FIG. 7, a rectangular tube electrode 36a has a coating of a dielectric 36B similar to FIG. 6 on a conductive metallic base material 36A, and the structure of the electrode is a metallic pipe. , It becomes a jacket so that the temperature can be adjusted during discharge.

  In addition, the number of the rectangular tube-shaped fixed electrodes is set in plural along the circumference larger than the circumference of the roll electrode, and the discharge area of the electrodes is a full square tube type facing the roll rotating electrode 35. It is represented by the sum of the area of the fixed electrode surface.

  The rectangular tube electrode 36a shown in FIG. 7 may be a cylindrical electrode. However, the rectangular tube electrode is preferably used in the present invention because it has an effect of expanding the discharge range (discharge area) as compared with the cylindrical electrode. .

  6 and 7, a roll electrode 35a and a rectangular tube electrode 36a are formed by spraying ceramics as dielectrics 35B and 36B on conductive metallic base materials 35A and 36A, respectively, and then sealing the inorganic compound. Is subjected to a sealing treatment. 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. Although titanium metal or a titanium alloy is particularly preferable for the reasons described later.

  When the dielectric is provided on one of the electrodes, 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 metal base material of the other electrode. Say that. 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 0.2 to 2 mm is particularly preferable.

  Details of the conductive metallic base material and dielectric useful in the present invention will be described later.

  The plasma discharge treatment vessel 31 is preferably a treatment vessel made of Pyrex (registered trademark) glass or the like, but can 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 the metal frame may be thermally sprayed to obtain insulation. In FIG. 5, it is preferable to cover both side surfaces of the parallel electrodes (up to the vicinity of the substrate surface) with an object made of the above-described material.

As the first power source (high frequency power source) installed in the atmospheric pressure plasma discharge processing apparatus of the present invention,
Applied power symbol Manufacturer Frequency Product name A1 Shinko Electric 3kHz SPG3-4500
A2 Shinko Electric 5kHz SPG5-4500
A3 Kasuga Electric 15kHz AGI-023
A4 Shinko Electric 50kHz SPG50-4500
A5 HEIDEN Research Laboratories 100kHz * PHF-6k
A6 Pearl Industry 200kHz CF-2000-200k
A7 Pearl Industry 400kHz CF-2000-400k
And the like, and any of them can be used.

As the second power source (high frequency power source),
Applied power supply symbol Manufacturer Frequency Product name B1 Pearl Industry 800kHz CF-2000-800k
B2 Pearl Industry 2MHz CF-2000-2M
B3 Pearl Industry 13.56MHz CF-5000-13M
B4 Pearl Industry 27MHz CF-2000-27M
B5 Pearl Industry 150MHz CF-2000-150M
And the like, and any of them can be preferably used.

  Of the above power supplies, * indicates a HEIDEN Laboratory impulse high-frequency power supply (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 thin film forming gas to form a thin 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 1.2 W / cm ² . In addition, discharge area (cm < ² >) points out the area of the range which discharge occurs in an electrode.

Further, by supplying power (output density) of 1 W / cm ² or more to the first electrode (first high frequency electric field), the output density is improved while maintaining the uniformity of the second high frequency electric field. I can do it. Thereby, a further uniform high-density plasma can be generated, and a further improvement in film forming speed and an improvement in film quality can be achieved. 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.

  An electrode used in such a method for forming a thin film by atmospheric pressure plasma must be able to withstand severe conditions in terms of structure and performance. Such an electrode is preferably a metal base material coated with a dielectric.

In the dielectric-coated electrode used in the present invention, it is preferable that the characteristics match between various metallic base materials and dielectrics. One of the characteristics is linear thermal expansion between the metallic base material and the dielectric. The combination is such that the difference in coefficient is 10 × 10 ⁻⁶ / ° C. or less. It is preferably 8 × 10 ⁻⁶ / ° C. or lower, more preferably 5 × 10 ⁻⁶ / ° C. or lower, and further preferably 2 × 10 ⁻⁶ / ° C. or lower. The linear thermal expansion coefficient is a well-known physical property value of a material.

As a combination of a conductive metallic base material and a dielectric whose difference in linear thermal expansion coefficient is within this range,
1: Metal base material is pure titanium or titanium alloy, dielectric is ceramic spray coating 2: Metal base material is pure titanium or titanium alloy, dielectric is glass lining 3: Metal base material is stainless steel, Dielectric is ceramic spray coating 4: Metal base material is stainless steel, Dielectric is glass lining 5: Metal base material is a composite material of ceramics and iron, Dielectric is ceramic spray coating 6: Metal base material Ceramic and iron composite material, dielectric is glass lining 7: Metal base material is ceramic and aluminum composite material, dielectric is ceramic sprayed coating 8: Metal base material is ceramic and aluminum composite material, dielectric The body has glass lining. From the viewpoint of the difference in linear thermal expansion coefficient, the above 1 or 2 and 5 to 8 are preferable, and 1 is particularly preferable.

  In the present invention, titanium or a titanium alloy is particularly useful as the metallic base material from the above characteristics. By using titanium or a titanium alloy as the metal base material, the dielectric is used as described above, so that there is no deterioration of the electrode in use, especially cracking, peeling, dropping off, etc., and it can be used for a long time under harsh conditions. Can withstand.

  The atmospheric pressure plasma discharge treatment apparatus applicable to the present invention is described in, for example, Japanese Patent Application Laid-Open No. 2004-68143, 2003-49272, International Patent No. 02/48428, etc. in addition to the above description. And an atmospheric pressure plasma discharge treatment apparatus.

  According to the method as described above, the thickness of the metal oxide layer provided on the resin base material having the hard coat layer varies depending on the type of the metal oxide to be formed, but is generally preferably in the range of 50 to 2000 nm. .

  Moreover, as a hardness of the metal oxide layer formed according to the said method, it is preferable that the hardness measured by the nanoindentation method is 6 GPa or more and 10 GPa or less.

  By setting the hardness of the metal oxide layer within the above range, it is possible to suppress the occurrence of cracks on the surface, improve the adhesion between the hard coat layer and the metal oxide layer, and prevent cracking of the metal oxide layer. can do.

  Here, the hardness measurement method by the nanoindentation method is a method of measuring the relationship between the load and the indentation depth (displacement amount) while pushing a small diamond indenter into the thin film, and calculating the plastic deformation hardness from the measured value. is there. In particular, when measuring a thin film having a thickness of 1 μm or less, the film is not easily affected by the physical properties of the substrate, and the thin film is not easily cracked when pressed. Generally, it is used for measuring physical properties of a very thin thin film.

[Resin substrate]
The resin base material constituting the laminate with a hard coat layer of the present invention is not particularly limited, but may be a polyolefin (PO) resin such as a homopolymer or copolymer such as ethylene, propylene, or butene, or a cyclic polyolefin. Polyester resins such as amorphous polyolefin resin (APO), polyethylene terephthalate (PET), polyethylene 2,6-naphthalate (PEN), polyamide (PA) resin such as nylon 6, nylon 12, copolymer nylon, polyvinyl alcohol (PVA) resin, polyvinyl alcohol resin such as ethylene-vinyl alcohol copolymer (EVOH), polyimide (PI) resin, polyetherimide (PEI) resin, polysulfone (PS) resin, polyethersulfone (PES) resin , Polyetheretherketone (PEEK Resin, polycarbonate (PC) resin, acrylic resin, polystyrene resin, vinyl chloride resin, polyvinyl butyrate (PVB) resin, polyarylate (PAR) resin, ethylene-tetrafluoroethylene copolymer (ETFE), trifluorinated chloride Ethylene (PFA), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (FEP), vinylidene fluoride (PVDF), vinyl fluoride (PVF), perfluoroethylene-perfluoropropylene-perfluorovinyl ether-copolymer Fluororesin such as (EPA) can be used.

  In addition to the resins listed above, a resin composition comprising an acrylate compound having a radical-reactive unsaturated compound, a resin composition comprising an acrylate compound and a mercapto compound having a thiol group, epoxy acrylate, urethane acrylate It is also possible to use a photocurable resin such as a resin composition in which an oligomer such as polyester acrylate or polyether acrylate is dissolved in a polyfunctional acrylate monomer, and a mixture thereof.

  The resin bases exemplified above can be obtained as commercial products, such as ZEONEX and ZEONOR (manufactured by ZEON Corporation), amorphous cyclopolyolefin resin film ARTON (manufactured by GS Corporation), polycarbonate, and the like. Examples include a pure ace film (manufactured by Teijin Ltd.) and a cellulose triacetate film Konica Katak KC4UX, KC8UX (manufactured by Konica Minolta Opto Co., Ltd.).

  Furthermore, it is also possible to use what laminated | stacked 1 or 2 or more types of these resin by means, such as a lamination and a coating, as a resin film base material.

  The resin substrate according to the present invention may be in the form of a sheet, a film, or other forms, and the form is not particularly limited. The film thickness of the resin base material can be appropriately selected from a wide range according to various conditions such as the type of resin to be used and the intended use, but is usually in the range of 10 μm to 10 mm, preferably 100 μm to 5 mm.

[Application field]
The laminate with a hard coat layer produced according to the above method has characteristics of high hardness and durability (adhesiveness). For example, a cathode ray tube (CRT), a liquid crystal display (LCD), a plasma display panel ( PDP), surface materials for displays such as field emission displays (FEDs), touch panels for home appliances, various architectural windows such as residential windows, show windows, vehicle windows, vehicle windshields, game machines, etc. A glass protective film or a glass substitute resin product can be applied to a wide range of fields.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not limited to these. 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 laminate with hard coat layer >>
[Resin substrate]
A polycarbonate resin film (manufactured by Teijin Chemicals Ltd.) having a thickness of 100 μm was used as the resin base material.

[Preparation of Sample 1]
Sample 1 which is a laminate with a hard coat layer was produced according to the following method.

(Formation of hard coat layer)
The following hard coat layer coating solution 1 was prepared and filtered through a polypropylene filter having a pore size of 0.4 μm, and this was applied onto the resin substrate using an extrusion type coating device and dried at 90 ° C. Then, the illuminance of the irradiation part was 100 mW / cm ² using an ultraviolet lamp, the irradiation amount was 80 mJ / cm ² , and the coating layer was cured to form a 9 μm thick hard coat layer 1.

  The filling rate (volume%) of silicon oxide particles in the hard coat layer 1 is 25%.

<Hardcoat layer coating solution 1>
Dipentaerythritol hexaacrylate 100 parts by weight Photoinitiator (Irgacure 184 (manufactured by Ciba Japan)) 5 parts by weight Ethyl acetate 120 parts by weight Propylene glycol monomethyl ether 120 parts by weight Silicon compound (BYK-307 (BIC Chemie Japan) 0.4 parts by mass Silicon oxide particles (manufactured by Nippon Aerosil Co., Ltd., primary average particle size 30 nm) 53.9 parts by mass The filling rate (% by volume) is based on the actinic ray curable resin and the photoreaction initiator. The specific gravity of the silicon oxide particles was set to 1.0, the specific gravity of the silicon oxide particles was set to 2.2, and the actinic ray curable resin and the photoinitiator were calculated based on the experimental results that the volume decreased by 30% after curing. This calculation result shows that, after forming a hard coat layer using the coating liquid 1 for hard coat layer, the hard coat layer is peeled off from the resin base material and the total volume is measured, and then the resin component is dissolved to obtain inorganic particles. The volume was measured, and the results were almost identical to the results obtained from these measured values.

(Formation of metal oxide layer)
Using a roll electrode type discharge treatment apparatus shown in FIG. 5 conducted plasma discharge treatment, on the hard coat layer 1 of the sample to form a hard coat layer 1 on the resin substrate, the thickness is at 150 nm, SiO ₂ The metal oxide layer 1 comprised only by was formed. The discharge treatment apparatus has a structure in which a plurality of rod-shaped electrodes are installed in parallel to the film transport direction so as to face the roll electrode, and raw materials (the following discharge gases, reaction gases 1 and 2) and electric power can be input to each electrode portion. Have.

  Here, the dielectric covering each electrode was coated with a 1 mm thick single-sided ceramic sprayed one with both opposing electrodes. The electrode gap after coating was set to 1 mm. The metal base material coated with a dielectric has a stainless steel jacket specification having a cooling function by cooling water, and was performed while controlling the electrode temperature by cooling water during discharge. As the power source used here, a high frequency power source (80 kHz) manufactured by Applied Electric and a high frequency power source (13.56 MHz) manufactured by Pearl Industry were used. Other processing conditions are as follows.

<Formation conditions of metal oxide layer 1>
Discharge gas: N ₂ gas Reaction gas 1: Oxygen gas 5% of the total gas
Reaction gas 2: Tetraethoxysilane (TEOS) is 0.1% of the total gas
Low frequency side power supply power: 80 kHz, 10 W / cm ²
High frequency side power supply power: 13.56 MHz, 10 W / cm ²
[Preparation of Sample 2]
In the preparation of Sample 1, the silicon oxide particles (average particle size: 30 nm) in the hard coat layer coating solution 1 are changed to silicon oxide particles having an average particle size of 16 nm, and the filling rate is changed to 45% by volume. Sample 2 was prepared in the same manner except that the hard coat layer coating solution 2 was used.

[Preparation of Sample 3]
Sample 3 was prepared in the same manner as in the preparation of Samples 1 and 2 except that a hard coat layer having a two-layer structure was formed by sequentially laminating the first layer and the second layer by the following method.

After applying the coating liquid 2 for hard coat layer used for the preparation of Sample 2 on the resin base material with an extrusion-type coating apparatus under the condition that the dry film thickness is 4.5 μm, and drying at 90 ° C. Then, using an ultraviolet lamp, the irradiance of the irradiation part was 100 mW / cm ² and the irradiation amount was 80 mJ / cm ^{2 to} be cured to form the first hard coat layer. Next, the hard coat layer coating solution 1 used for the preparation of the sample 1 was applied thereon with an extrusion type coating apparatus under a condition that the dry film thickness was 4.5 μm, and dried at 90 ° C. Then, using an ultraviolet lamp, the illuminance of the irradiated portion was 100 mW / cm ² , the irradiation amount was cured to 80 mJ / cm ² , and the second layer of the hard coat layer was formed to prepare Sample 4.

[Preparation of Sample 4]
In the preparation of Sample 3, the same procedure was followed except that the first layer (4A), the second layer (4B), and the third layer (4C) were sequentially laminated and a three-layer hard coat layer was applied by the following method. Sample 4 was prepared.

(Formation of the first layer (4A))
<First-layer hard coat layer coating solution 4A>
According to the following method, the coating liquid 4A for hard coat layers for 1st layers whose filling rate (volume%) of a silicon oxide particle (7 nm) is 65 volume% was prepared.

Dipentaerythritol hexaacrylate 50 parts by mass Photoinitiator (Irgacure 184 (manufactured by Ciba Japan)) 2.5 parts by mass Ethyl acetate 120 parts by mass Propylene glycol monomethyl ether 120 parts by mass Silicon compound (BYK-307 (Bic 0.4 parts by mass Silicon oxide particles (manufactured by Nippon Aerosil Co., Ltd., primary average particle size 30 nm) 150 parts by mass The hard coat layer coating solution 4A was filtered through a polypropylene filter having a pore size of 0.4 μm. Then, this was coated on the resin substrate using an extrusion type coating apparatus, dried at 90 ° C., and then irradiated with an ultraviolet lamp at an irradiation part of 100 mW / cm ² and an irradiation amount of 80 mJ / The coating layer was cured as cm ² to form a hard coat layer 4A having a thickness of 3 μm.

(Formation of second layer (4B))
Next, the hard coat layer coating solution 2 (inorganic particles: 16 nm) used for the preparation of the sample 2 is applied thereon with an extrusion type coating apparatus under the condition that the dry film thickness is 3.0 μm. After drying at 90 ° C., a hard coat layer second layer (4B) having an irradiation intensity of 100 mW / cm ² and an irradiation amount of 80 mJ / cm ² is cured using an ultraviolet lamp, and the filling rate is 45% by volume. ) Was formed.

(Formation of third layer (4C))
Next, the hard coat layer coating solution 1 (inorganic particles: 30 nm) used for the preparation of the sample 1 is applied thereon with an extrusion type coating apparatus under the condition that the dry film thickness is 3.0 μm. After drying at 90 ° C., a hard coat layer third layer (4C) having an irradiance of 100 mW / cm ² and an irradiation amount of 80 mJ / cm ² with an ultraviolet lamp is used, and the filling rate is 25% by volume. ) Was formed.

[Preparation of Sample 5]
In the preparation of the sample 4, the first layer (4A), the second layer (4B), and the third layer (4C) are made of inorganic particles having the following average particle diameter, the added amount of inorganic particles, and the actinic ray curable resin. The sample was adjusted in the same manner except that the first layer (5A), the second layer (5B), and the third layer (5C) were changed to the following filling rate by adjusting the amount of addition of the photoreaction initiator. 5 was produced.

First layer (5A): silicon oxide particles (average particle size 30 nm), filling rate 10% by volume
Second layer (5B): silicon oxide particles (average particle size 16 nm), filling rate 25% by volume
Third layer (5C): silicon oxide particles (average particle size 7 nm), filling rate 40% by volume
[Preparation of Sample 6]
In the preparation of Sample 5, the same applies except that the filling rates of the first layer (5A), the second layer (5B), and the third layer (5C) were changed to 25% by volume, 45% by volume, and 65% by volume, respectively. Thus, Sample 6 was prepared.

[Preparation of Samples 7 and 8]
In preparation of the sample 5, the average particle diameter and filling rate of the silicon oxide particles used for the first layer (5A), the second layer (5B), and the third layer (5C) were changed as shown in Table 1, respectively. Samples 7 and 8 were produced in the same manner except that.

[Preparation of Sample 9]
As shown in FIG. 3 a), on the resin base material, the following intermediate layer coating solution was applied with an extrusion-type coating device under the condition that the dry film thickness was 1.0 μm, and at 90 ° C. After drying, using an ultraviolet lamp, the irradiation part has an illuminance of 100 mW / cm ² and is cured with an irradiation amount of 80 mJ / cm ² to form an intermediate layer. The first layer of the hard coat layer (silicon oxide particles (average particle size 30 nm), filling rate 25% by volume), the second layer (silicon oxide particles (average particle size 16 nm), filling rate 45% by volume), the third layer ( Silicon oxide particles (average particle size 7 nm, filling rate 65% by volume) were sequentially applied, cured, and dried to prepare Sample 9.

(Interlayer coating solution)
Dipentaerythritol hexaacrylate 100 parts by weight Photoinitiator (Irgacure 184 (manufactured by Ciba Japan)) 5 parts by weight Ethyl acetate 120 parts by weight Propylene glycol monomethyl ether 120 parts by weight Silicon compound (BYK-307 (BIC Chemie Japan) 0.4 mass part [Preparation of sample 10]
In the preparation of Sample 9, the intermediate layer is formed in the same manner except that the formation position of the intermediate layer is changed between the first and second layers of the hard coat layer and between the second and third layers as shown in FIG. Thus, Sample 10 was produced.

[Preparation of Sample 11]
In the preparation of Sample 10, Sample 11 was prepared in the same manner except that an intermediate layer was also provided between the resin substrate and the first layer as shown in FIG.

[Preparation of Sample 12]
In the preparation of the sample 6, each coating solution of the first layer to the third layer, which is a hard coat layer, is applied onto a resin substrate using an extrusion type coating apparatus that can apply three layers simultaneously, After maintaining the state for 10 seconds, Sample 12 was prepared in the same manner as in the method described in Sample 6, except that drying and curing were performed to form a hard coat layer.

[Preparation of Sample 13]
Sample 13 was prepared in the same manner as in Sample 6 except that the metal oxide layer was formed by the following plasma CVD method instead of the atmospheric pressure plasma CVD method.

  Film formation was performed using a plasma CVD apparatus Model PD-270STP manufactured by Samco as a thin film forming apparatus.

  The film forming conditions are as follows.

Oxygen pressure: 40 Pa
Reaction gas: tetraethoxysilane (TEOS) 5 sccm (standard cubic centimeter per minute)
Power: 100W at 13.56MHz
Substrate holding temperature: 120 ° C
[Preparation of Sample 14]
In the production of Sample 6, the raw material used for forming the metal oxide layer is changed to tetraisopropoxy titanium instead of tetraethoxysilane (silicon oxide film formation), and a metal oxide layer composed of titanium oxide Sample 14 was produced in the same manner except that the sample 14 was changed.

[Preparation of Sample 15]
Sample 15 was prepared in the same manner as in the preparation of Sample 6, except that the silicon oxide particles used for forming the first to third layers of the hard coat layer were changed to titanium oxide particles having the same average particle diameter. .

[Preparation of Sample 16]
Sample 16 was prepared in the same manner as in the preparation of Sample 6, except that the silicon oxide particles used for forming the first to third layers of the hard coat layer were changed to zirconium oxide particles having the same average particle diameter. .

  The details of each item described in abbreviations in Table 1 are as follows.

<Middle layer installation position>
* I: First layer of resin base material and hard coat layer (configuration shown by (a) in FIG. 3)
* II: First and second layers of hard coat layer and second and third layers (configuration shown by (b) in FIG. 3)
* III: The first layer of the resin base material and the hard coat layer, the first layer and the second layer, and the second layer and the third layer (configuration shown by (c) in FIG. 3)
<Method of applying hard coat layer>
A: Single layer coating B: Sequential coating method C: Three layer simultaneous coating method <Metal oxide layer forming method>
* 1: Atmospheric pressure plasma CVD method * 2: Plasma CVD method << Evaluation of laminate with hard coat layer >>
Each of the following evaluations was performed on samples 1 to 16, which are the laminates with a hard coat layer produced as described above.

[Evaluation of adhesion]
Each of the prepared laminates with a hard coat layer was evaluated for adhesion by a cross-cut test based on JIS K 5400.

On the surface on which each layer of each laminate with a hard coat layer was formed, a single blade razor blade was used to insert 11 incisions of 90 degrees with respect to the surface at 1 mm intervals vertically and horizontally to create 100 1 mm square grids. . A commercially available cellophane tape is affixed on the grid, and one end of the tape is peeled off vertically by hand, and the ratio of the area where the gas barrier layer is peeled to the affixed tape area from the score line is measured. The adhesion was evaluated according to Moreover, about the sample which raise | generated peeling, confirmation of the peeled layer was also performed simultaneously. Peeling position 5: No peeling was observed 4: The area of the peeled layer was 1% or more and less than 5% 3: The area of the peeled layer was 5% or more and less than 10% 2: Peeled The area of the layer was 10% or more and less than 20% 1: The area of the peeled layer was 20% or more <Peeling position>
a: Peeling occurred between the resin base material and the first layer of the hard coat layer b: Peeling occurred between the outermost layer of the hard coat layer and the metal oxide layer-: No peeling occurred [Evaluation of hardness]
(Evaluation 1: Pencil hardness test)
Using a test pencil specified by JIS S 6006, measurement was performed according to a pencil hardness evaluation method specified by JIS K 5400. For the test, a pencil hardness tester (HA-301 Clemens type scratch hardness tester) was used. As for the rank of hardness, 6B is the softest and 9H is the hardest in the order of (soft) 6B to B, HB, F, H to 9H (hard).

(Evaluation 2: Evaluation of scratch resistance)
Using the steel wool (Bonster # 0000), a friction tester HEIDON-14DR, the load (65 kPa) and the moving speed: 15 mm / min are applied to the surface of each of the laminates with the hard coat layer (the side on which the metal oxide layer is formed). Under the above conditions, after rubbing 20 times, the range of 1 cm × 1 cm was observed with a loupe, and the scratch resistance was evaluated according to the following criteria.

A: No generation of scratches is observed. O: Generation of scratches is 1 or more and 5 or less. Δ: Generation of scratches is 6 or more and 15 or less. X: Generation of scratches is 16 or more. It is 25 or less. XX: Generation of scratches is 25 or more [Evaluation of smoothness]
The surface condition of the surface of each of the prepared laminates with a hard coat layer (metal oxide layer forming surface side) was visually observed, and smoothness was evaluated according to the following criteria.

A: Extremely smooth surface B: Almost good flatness B: Slightly uneven shape is confirmed, but is a quality acceptable for practical use X: Uneven shape is confirmed on the surface, and smoothness is achieved XX: Inferior quality XX: Clear uneven shape is confirmed on the surface, and the quality is extremely inferior in smoothness [Evaluation of bending resistance]
Each of the produced laminates with a hard coat layer was cut into a size of 3 cm × 10 cm and conditioned for 24 hours in an environment of 10 ° C. and 15% RH. Each conditioned sample was wound around a 20mm diameter rod with the hard coat layer side outward and rewound, then the degree of surface cracking in the entire area was visually observed, and the crack resistance was evaluated according to the following criteria did.

◎: No cracks are observed. ○: Almost no cracks are observed. △: Some cracks are generated, but the film surface quality is acceptable for practical use. ×: Cracks are generated. Table 1 shows the results obtained as described above. XX: Quality in which many cracks are generated and the quality is not practical.

  As is clear from the results shown in Table 1, the sample of the present invention having the hard coat layer having the structure defined in the present invention is different from the comparative example in that the resin base material and the hard coat layer, or the hard coat layer and the metal are used. It can be seen that the adhesiveness between the oxide layers is excellent, the outermost pencil hardness test and the scratch resistance are excellent, and high hardness, excellent bending resistance and smoothness are provided.

It is a composition sectional view showing an example of a conventional layered product with a hard coat layer which has a single hard coat layer. It is a composition sectional view showing an example of a layered product with a hard coat layer which has a plurality of hard coat layers containing inorganic particles. It is a structure sectional view showing other examples of a layered product with a hard coat layer which has a plurality of hard coat layers containing inorganic particles. It is the schematic which showed an example of the atmospheric pressure plasma discharge processing apparatus of the jet system useful for this invention. 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 useful for this invention. 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.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Laminated body with a hard-coat layer 2 Resin base material 3, 3A, 3B, 3C Hard-coat layer 4, 4A, 4B, 4C Inorganic particle 5 Metal oxide layer IL Intermediate layer 10, 30 Plasma discharge processing apparatus 11 1st electrode 12 Second electrode 14 Processing position 21, 41 First power source 22, 42 Second power source 32 Discharge space (between opposing electrodes)
35 Roll rotating electrode (first electrode)
35a Roll electrode 35A Metal base material 35B, 36B Dielectric 36 Square tube type fixed electrode group (second electrode)
36a Rectangular tube electrode 36A Metal base material 40 Electric field applying means 50 Gas supply means 52 Air supply port 53 Air exhaust port F Base material G Gas G ° Gas in plasma state

Claims (10)

In a laminate with a hard coat layer in which two or more hard coat layers containing inorganic particles and a metal oxide layer are laminated in this order on at least one surface of a resin base material, the two or more hard coat layers A laminate with a hard coat layer, characterized in that the inorganic particles contained in each have different layer sizes and the average particle size of the inorganic particles is smaller toward the metal oxide layer. The intermediate layer which does not contain inorganic particles between the resin base material and the hard coat layer, between the two or more hard coat layers, or between the hard coat layer and the metal oxide layer. Laminated body with hard coat layer. The laminate with a hard coat layer according to claim 1 or 2, wherein the two or more hard coat layers have a layer structure in which a filling rate of inorganic particles increases toward the metal oxide layer. The laminate with a hard coat layer according to any one of claims 1 to 3, wherein the inorganic particles are silicon oxide particles. 5. The laminate with a hard coat layer according to claim 1, wherein an average particle diameter of inorganic particles contained in each layer of the hard coat layer is 5 nm or more and 1.0 μm or less. . The laminate with a hard coat layer according to any one of claims 1 to 5, wherein the hard coat layer is formed by a wet coating method. The laminate with a hard coat layer according to claim 6, wherein the wet coating method is a multilayer simultaneous coating method in which a plurality of layers are coated simultaneously. The laminate with a hard coat layer according to claim 1, wherein a main component of the metal oxide layer is silicon oxide. The laminate with a hard coat layer according to any one of claims 1 to 8, wherein the metal oxide layer is formed by a plasma CVD method. The plasma-coated CVD method for forming the metal oxide layer is an atmospheric pressure plasma CVD method in which plasma treatment is performed under atmospheric pressure or a pressure near atmospheric pressure. body.

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