JP5663875B2 - Laminate with hard coat layer - Google Patents

Description

  The present invention relates to a laminate with a hard coat layer having a laminate structure having high hardness, excellent scratch resistance, and excellent 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 that can be easily produced, has excellent film adhesion, and has high film strength and excellent scratch resistance. There is.

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

1. In a laminate with a hard coat layer in which a hard coat layer and a metal oxide layer are laminated in this order on at least one surface of a resin substrate, the hard coat layer contains two or more inorganic particles having different inorganic particle concentrations. The inorganic particle concentration is higher in the region in contact with the resin base material than in the region in contact with the resin substrate. The hard coat layer has a structure in which two layers having different inorganic particle concentrations are alternately laminated. A layer group having a high inorganic particle concentration is an A layer unit, and a layer group having a low inorganic particle concentration is a B layer unit. Then, at least one layer unit of the A layer unit and the B layer unit is composed of at least two layers having different dry film thicknesses, and the total dry film thickness ΣAh of the A layer unit and the dry film of the B layer unit The sum ShigumaBh of a hard coat layer with a laminate characterized by satisfying the relation of ΣAh ≧ ΣBh.

2 . 2. The inorganic particle concentration of the A layer unit is 30% by volume or more and 70% by volume or less, and the inorganic particle concentration of the B layer unit is 0% by volume or more and 40% by volume or less. Laminate with hard coat layer.

3 . 2. The inorganic particle concentration of the A layer unit is 40% by volume or more and 60% by volume or less, and the inorganic particle concentration of the B layer unit is 0% by volume or more and 20% by volume or less. Laminate with hard coat layer.

4 . The laminate with a hard coat layer according to any one of 1 to 3 , wherein the inorganic particles contained in the inorganic particle-containing layer 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 diameter of the inorganic particles contained in the inorganic particle-containing layer is 5 nm or more and 1.0 μm or less.

6 . 6. The laminate with a hard coat layer according to any one of 1 to 5 , wherein the inorganic particle-containing layer contains an ultraviolet curable resin as a binder.

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

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.

1 0 . 10. The laminate with a hard coat layer according to 9 , wherein the plasma 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 in the vicinity of atmospheric pressure.

  According to the present invention, it was possible to provide a laminate with a hard coat layer that can be easily produced, has excellent film adhesion, has high film strength, and has excellent scratch resistance.

It is sectional drawing which shows an example of the typical layer structure of the laminated body with a hard-coat layer of this invention. 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 Hard-coat layer unit 3-1, 3-2 Inorganic particle content layer 4 Metal oxide layer 10, 30 Plasma discharge processing apparatus 11 1st electrode 12 2nd electrode 14 Processing position 21, 41 First power source 22, 42 Second power source 32 Discharge space (between counter 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

  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 inventors have found that in a laminate with a hard coat layer in which a hard coat layer and a metal oxide layer are laminated in this order on at least one surface of a resin base material, The coating layer is a layer with a hard coat layer, characterized in that it is an inorganic particle-containing layer of two or more layers having different inorganic particle concentrations or an inorganic particle-containing layer in which the inorganic particle concentration is continuously different in the film thickness direction. It has been found that a laminate with a hard coat layer having excellent uniformity and film adhesion and having high film strength and excellent scratch resistance can be realized.

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

[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.

[Hard coat layer]
In the laminate with a hard coat layer of the present invention, two or more inorganic particle-containing layers having different inorganic particle concentrations or inorganic particle-containing layers having different inorganic particle concentrations continuously in the film thickness direction are provided on the resin substrate. It is characterized by.

(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 stored for a long time in a harsh environment, when adhesion deteriorates due to peeling at each interface, 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 inventors have found that in a laminate with a hard coat layer in which a hard coat layer and a metal oxide layer are laminated on a resin substrate, the resin substrate and the hard coat layer It has been found that the above problems can be achieved by optimizing the inorganic particle concentration at the interface and the interface between the hard coat layer and the metal oxide layer.

  That is, the constitution of the hard coat layer is characterized in that two or more inorganic particle-containing layers having different inorganic particle concentrations or inorganic particle-containing layers having different inorganic particle concentrations continuously in the film thickness direction are used.

  The hard coat layer according to the present invention is mainly composed of an actinic ray curable resin, which will be described later, or an actinic ray curable resin and fine particles, but two or more inorganic layers having different inorganic particle concentrations referred to in the present invention. The particle-containing layer is a structure in which two or more inorganic particle-containing layers composed of actinic ray curable resin and inorganic particles are laminated, and represents that the inorganic particle concentration (content) of each inorganic particle-containing layer is different. It is.

  In the present invention, the configuration of the hard coat layer is preferably a mode in which the inorganic particle concentration in the region in contact with the metal oxide layer is higher than the inorganic particle concentration in the region in contact with the resin substrate. That is, as described above, when taking a form in which two or more inorganic particle-containing layers having different inorganic particle concentrations are stacked, the inorganic particle-containing layer group with respect to the inorganic particle concentration of the inorganic particle-containing layer in contact with the resin substrate It means that the inorganic particle concentration of the inorganic particle-containing layer in the uppermost layer is high, and more specifically, the inorganic particle concentration of the inorganic particle-containing layer located in the upper part is the inorganic particle concentration in the lower part. It is preferable to have a configuration that is higher than the inorganic particle concentration of the particle-containing layer, and taking a configuration in which the inorganic particle concentration is increased stepwise from the lower inorganic particle-containing layer to the upper inorganic particle-containing layer is It is preferable from the viewpoint of achieving the intended effect.

  In addition, the provision of an inorganic particle-containing layer in which the inorganic particle concentration is continuously different in the film thickness direction in the present invention means that an inorganic concentration profile is formed by stacking the inorganic particle-containing layers having different inorganic particle concentrations described above. In contrast, this is a method of forming a hard coat layer with an inorganic particle-containing layer having a distribution of inorganic particles within a single layer. The inorganic particle-containing layer having the distribution of inorganic particles in such a layer may be composed of a single layer, or may be composed of two or more layers having such an inorganic concentration pattern. In the present invention, the difference between the upper and lower inorganic particle concentrations in the inorganic particle-containing layer in which the inorganic particle concentration is continuously different in the film thickness direction is preferably 2% by volume or more, more preferably 5% by volume or more. It is. The upper and lower inorganic particle concentrations in the inorganic particle-containing layer are the average inorganic particle concentration in the region up to 5% in the depth direction from the layer surface when the total film thickness of the inorganic particle-containing layer is 100%. Similarly, the average inorganic particle concentration in the region from the bottom of the layer to a thickness of 5% was defined as the inorganic particle concentration in the lower part. In addition, each inorganic particle density | concentration can be calculated | required by the method mentioned later.

  FIG. 1 shows a typical sectional view of a laminate with a hard coat layer of the present invention, but the present invention is not limited to the configuration exemplified here.

  FIG. 1 a is a cross-sectional view of a laminate with a hard coat layer in which two inorganic particle-containing layers having different inorganic particle concentrations are laminated.

  In a) of FIG. 1, the laminated body 1 with a hard-coat layer is on the resin base material 2, the 1st inorganic particle content layer 3-2 with a low inorganic particle density | concentration, and the 2nd inorganic particle with a high inorganic particle density | concentration. The hard coat layer unit 3 is formed by laminating the containing layer 3-1, and the metal oxide layer 4 is further formed thereon.

  At this time, as the inorganic particle distribution profile in the entire hard coat layer, as shown in the schematic graph on the right side, the inorganic particle concentration of the first inorganic particle-containing layer 3-2 on the side in contact with the resin substrate 2 is It is preferable that the inorganic particle concentration of the second inorganic particle-containing layer 3-1 on the side in contact with the metal oxide layer 4 at the upper part is increased.

  In the laminate 1 with a hard coat layer of the present invention, all the layers constituting the hard coat layer unit 3 may contain inorganic particles, and each may be composed of inorganic particle-containing layers having different concentrations. A layer containing no inorganic particles may be provided as a layer.

  FIG. 1 b) shows an example in which a layer 3-3 that does not contain any inorganic particles is provided in the lowermost layer in the configuration of FIG. Even in such a configuration, the inorganic particle concentration of the first inorganic particle-containing layer 3-2 positioned above the layer 3-3 not containing inorganic particles is set higher on the side in contact with the resin base material 2 than the layer 3-3. In addition, the inorganic particle concentration of the second inorganic particle-containing layer 3-1 on the side in contact with the metal oxide layer 4 positioned on the upper side is higher than that of the first inorganic particle-containing layer 3-2. It is preferable to do.

  FIG. 1 c) shows that the hard coat layer unit 3 is composed of a multilayered inorganic particle-containing layer and an inorganic particle-free layer (an example of an eight-layer structure is shown in FIG. 1 c), and the inorganic particles are sequentially formed. The concentration change may be designed as a more precise profile.

  On the other hand, FIG. 1 d) shows a configuration example in which the hard coat layer 3 ′ is a single layer and the inorganic particle concentration distribution is continuously changed in the single layer. Even in such a configuration, it is preferable that the inorganic particle concentration profile in the region in contact with the metal oxide layer is higher than the inorganic particle concentration in the region in contact with the resin base material.

(Constituent material of hard coat layer)
The inorganic particle-containing layer constituting the hard coat layer according to the present invention is preferably composed mainly of an actinic ray curable resin and fine particles.

<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 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 Kasei Kogyo Co., Ltd.), or SP-1509, SP-1507 (manufactured by Showa Polymer 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.

  The inorganic silicon oxide particles are appropriately selected from colloidal silica, wet silica, dry silica, and the like, but are not limited thereto. Moreover, you may use the inorganic particle by which the surface was modified by organic group etc. and various surface treatments.

  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 average particle diameter of the inorganic particles that can be applied to the hard coat layer according to the present invention is preferably 5 nm or more and 1.0 μm or less, more preferably 5 nm or more and 500 nm or less. The average particle diameter of the inorganic particles is obtained as a simple average value (number average) by observing the inorganic particles with an electron microscope, determining the particle diameter of 100 arbitrary primary particles. Here, each particle diameter is expressed by a diameter assuming a circle equal to the projected area.

  The hard coat layer according to the present invention has a structure in which two layers having different inorganic particle concentrations are alternately laminated, and a layer group having a high inorganic particle concentration (A layer unit) and a layer group having a low inorganic particle concentration (B layer). Unit), and the inorganic particle concentration of the A layer unit is preferably 30% by volume or more and 70% by volume or less, and the inorganic particle concentration of the B layer unit is preferably 0% by volume or more and 40% by volume or less. Preferably, the inorganic particle concentration of the A layer unit is 40% by volume or more and 60% by volume or less, and the inorganic particle concentration of the B layer unit is 0% by volume or more and 20% by volume or less.

  The hard coat layer according to the present invention is characterized in that the inorganic particle concentration in the region in contact with the metal oxide layer is higher than the inorganic particle concentration in the region in contact with the resin substrate. The layer in contact is at least one layer of the B layer unit, and the layer in contact with the metal oxide layer is at least one layer constituting the A layer unit.

<Other additives>
In addition to the constituent materials described above, various additives can be used in the hard coat layer according to the present invention as long as the object effects of the present invention are not impaired.

  In preparing the hard coat layer coating solution, an organic solvent can be used. For example, hydrocarbons (toluene, xylene), alcohols (methanol, ethanol, isopropanol, butanol, cyclohexanol), ketones (acetone) , Methyl ethyl ketone, methyl isobutyl ketone), esters (methyl acetate, ethyl acetate, methyl lactate), glycol ethers, other organic solvents, or a mixture thereof. Propylene glycol monoalkyl ether (1 to 4 carbon atoms of the alkyl group) or propylene glycol monoalkyl ether acetate ester (1 to 4 carbon atoms of the alkyl group) is 5% by mass or more, more preferably 5 to 80%. It can be contained by mass%.

  In preparing the hard coat layer coating solution, it is preferable to add a silicon compound. For example, polyether-modified silicone oil is preferably added.

  Further, the hard coat layer may contain fine particles of an inorganic compound or an organic compound in order to adjust the scratch resistance, slipperiness and refractive index.

  Examples of inorganic fine particles used in the hard coat layer include silicon oxide, titanium oxide, aluminum oxide, tin oxide, indium oxide, ITO, zinc oxide, zirconium oxide, magnesium oxide, calcium carbonate, calcium carbonate, talc, clay, and calcined kaolin. And calcined calcium silicate, hydrated calcium silicate, aluminum silicate, magnesium silicate and calcium phosphate. In particular, silicon oxide, titanium oxide, aluminum oxide, zirconium oxide, magnesium oxide and the like are preferably used.

  Organic particles include polymethacrylic acid methyl acrylate resin powder, acrylic styrene resin powder, polymethyl methacrylate resin powder, silicon resin powder, polystyrene resin powder, polycarbonate resin powder, benzoguanamine resin powder, melamine resin powder. An ultraviolet curable resin composition such as polyolefin resin powder, polyester resin powder, polyamide resin powder, polyimide resin powder, or polyfluoroethylene resin powder can be added. Particularly preferred are cross-linked polystyrene particles (for example, SX-130H, SX-200H, SX-350H, manufactured by Soken Chemical), polymethyl methacrylate-based particles (for example, MX150, MX300, manufactured by Soken Chemical), and fluorine-containing acrylic resin fine particles. .

  In order to increase the heat resistance of the hard coat layer, an antioxidant that does not inhibit the photocuring reaction can be selected and used. Examples include hindered phenol derivatives, thiopropionic acid derivatives, phosphite derivatives, and the like. Specifically, for example, 4,4′-thiobis (6-tert-3-methylphenol), 4,4′-butylidenebis (6-tert-butyl-3-methylphenol), 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) mesitylene, di-octadecyl-4- Examples thereof include hydroxy-3,5-di-tert-butylbenzyl phosphate.

  Further, the hard coat layer preferably contains a silicon surfactant or a polyoxyether compound. As the silicon-based surfactant, polyether-modified silicon is preferable. Specifically, BYK-UV3500, BYK-UV3510, BYK-333, BYK-331, BYK-337 (manufactured by BYK-Chemical Japan), TSF4440, TSF4445, TSF4446, TSF4452, TSF4460 (manufactured by GE Toshiba Silicon), KF-351, KF-351A, KF-352, KF-353, KF-354, KF-355, KF-615, KF-618, KF-945, KF- 6004 (polyether-modified silicone oil; manufactured by Shin-Etsu Chemical Co., Ltd.) and the like are exemplified, but not limited thereto.

  The hard coat layer may contain a fluorine-siloxane graft polymer. The fluorine-siloxane graft polymer refers to a copolymer polymer obtained by grafting polysiloxane containing siloxane and / or organosiloxane alone and / or organopolysiloxane to at least a fluorine-based resin.

<Method for forming inorganic particle-containing layer>
In the present invention, as a method for forming the inorganic particle-containing layer on the resin substrate, a known method for forming a thin film can be applied, but it is particularly preferable to form the thin film by a wet coating method.

  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.

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.

  In the laminate with a hard coat layer of the present invention, the total thickness of the hard coat layer is preferably 1.0 μm or more and 100 μm or less, more preferably 2.0 μm or more and 50 μm or less.

  In a case where two or more inorganic particle-containing layers having different inorganic particle concentrations are laminated so as to have the inorganic particle constitution defined in the present invention, the first inorganic particles are formed on the resin substrate by a wet coating method. It can be formed by coating the containing layer and then irradiating with actinic rays, and then coating the second inorganic particle-containing layer on the first inorganic particle-containing layer and then irradiating with actinic rays. Moreover, the hard-coat layer unit which consists of a structure as shown to b of FIG. 1 and c of FIG. 1 can be formed using the several inorganic particle content layer coating liquid from which inorganic particle content differs.

  In addition, as shown in FIG. 1 d), when forming an inorganic particle-containing layer in which the concentration of inorganic particles continuously changes in a single layer, for example, it is possible to apply multiple layers simultaneously by wet-on-wet Using a coater such as a slide hopper type coater or curtain coater, a plurality of inorganic particle-containing layer coating liquids having different inorganic particle concentrations are used, and the lowest layer is an inorganic particle-containing layer coating liquid having the lowest inorganic particle concentration. As a coating liquid composition in which the concentration of inorganic particles rises as it becomes an upper layer in sequence, after applying multiple layers simultaneously on a resin substrate, after a certain period of time, and mixing some layers between layers It can be obtained by curing by irradiating with ultraviolet light from a light source.

  In the laminate with a hard coat layer of the present invention, it is preferable that the inorganic particle concentration in the region in contact with the metal oxide layer is higher than the inorganic particle concentration in the region in contact with the resin substrate.

  In the present invention, the region in contact with the metal oxide layer or the region in contact with the resin substrate is a region up to 5% in depth of the hard coat layer thickness from the surface in contact with the metal oxide layer or the resin substrate, respectively. Say. The concentration of inorganic particles in this region is determined by observing the cross section of the laminate with a hard coat layer with a high-magnification electron microscope and counting the number of inorganic particles in the region, using a microtome from the interface, etc. And a method of quantifying inorganic particles in the obtained ultrathin slice or a method of quantifying silicon atoms up to a predetermined depth region using ESCA or the like.

[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. Here, the vicinity of atmospheric pressure represents a pressure of 20 kPa to 110 kPa, but 93 kPa to 104 kPa is preferable in order to preferably obtain the effects described in the present invention.

  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). Although the ratio of the discharge gas and the reactive gas varies depending on the properties of the film to be obtained, the reactive gas is supplied with the ratio of the discharge gas being 50% or more with respect to the entire mixed gas.

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

  In the laminate with a hard coat layer of the present invention, the thickness of the metal oxide layer is preferably 10 nm or more and 1.0 μm or less, more preferably 100 nm or more and 500 nm or less. The film thickness ratio of the hard coat layer to the metal oxide layer (hard coat layer: metal oxide layer) is preferably in the range of 10,000: 1 to 1: 1, more preferably 500: 1 to 1. The range is 4: 1.

  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 general, in the 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. That's it. 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. 2 or FIG. 3 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. 2 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. 2 (shown in FIG. 3 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 output from the first electrode 11 between the counter electrodes. A first high frequency electric field having electric field strength V ₁ and current I ₁ is applied, and a second high frequency electric field having frequency ω ₂ , electric field strength 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 into the space (discharge space) 13 between the first electrode 11 and the second electrode 12 from a gas supply means as shown in FIG. 3 to be described later, 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 desired 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. 3 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. 3 shows a thin film formed by subjecting the base material F to plasma discharge treatment between the opposed 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 square tube fixed electrode group (second electrode) 36. A second high-frequency electric field of 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 either method, 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 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 base material F is unwound from the original winding (not shown) and is transported or is transported from the previous process, and the air and the like that is entrained by the base material by the nip roll 65 through the guide roll 64 is blocked. 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. 4 is a perspective view showing an example of the structure of the conductive metallic base material of the roll rotating electrode shown in FIG. 3 and the dielectric material coated thereon.

  In FIG. 4, 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. 5 is a perspective view showing an example of the structure of a conductive metallic base material of a rectangular tube electrode and a dielectric material coated thereon.

  In FIG. 5, a rectangular tube type electrode 36a has a coating of a dielectric 36B similar to FIG. 4 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. 5 may be a cylindrical electrode, but the rectangular tube electrode has an effect of widening the discharge range (discharge area) as compared with the cylindrical electrode, and thus is preferably used in the present invention. .

  4 and 5, 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. 3, it is preferable to cover both side surfaces (up to the vicinity of the substrate surface) of both parallel electrodes 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 electric power applied between the electrodes facing each other supplies power (power density) of 1 W / cm ² or more 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 . The discharge area (cm ² ) refers to an area in a range where discharge occurs in the 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 less, more preferably 5 × 10 ⁻⁶ / ° C. or less, and further preferably 2 × 10 ⁻⁶ / ° C. or less. 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. .

  Further, the hardness of the metal oxide layer formed according to the above method is preferably 5 GPa or more and 10 GPa or less, more preferably 7 GPa or more and 10 GPa or less, as measured by a nanoindentation method.

  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.

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

Example 1
<< 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 is prepared, filtered through a polypropylene filter having a pore size of 0.4 μm, coated on the resin substrate using a micro gravure coater, dried at 90 ° C., and then subjected to an ultraviolet lamp. The illuminance of the used irradiation part was 100 mW / cm ² , the irradiation amount was 80 mJ / cm ² , the coating layer was cured, and a hard coat layer 1 having a thickness of 3 μm was formed.

<Hardcoat layer coating solution 1>
Dipentaerythritol hexaacrylate 100 parts by mass Photoinitiator (Irgacure 184 (Ciba Specialty Chemicals Co., Ltd.))
5 parts by mass Ethyl acetate 120 parts by mass Propylene glycol monomethyl ether 120 parts by mass Silicon compound (BYK-307 (manufactured by Big Chemie Japan)) 0.4 parts by mass Cross-linked polystyrene particles (SX350H by Soken Chemical, refractive index 1.6, particles (Diameter 3.5μm)
10 parts by mass Silicon oxide particles (Aerosil R972V (manufactured by Nippon Aerosil Co., Ltd.), primary average particle diameter 16 nm) 2 parts by mass (formation of metal oxide layer)
Using a roll electrode type discharge treatment apparatus shown in FIG. 3 carried a 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: 5% of oxygen gas to 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: 13.56 MHz, 10 W / cm ²
[Preparation of Sample 2]
In the preparation of Sample 1, the addition amount of silicon oxide particles in hard coat layer coating solution 1 is 2 parts by mass (concentration of 2.0% by mass with respect to dipentaerythritol hexaacrylate) is 7.5 parts by mass (dipenta Sample 2 was produced in the same manner except that the hard coat layer coating solution 2 was changed to a concentration of 7.5% by mass with respect to erythritol hexaacrylate.

[Preparation of Sample 3]
Sample 3 was prepared in the same manner as in the preparation of Sample 1, except that the method for forming the hard coat layer was changed as follows.

<Formation of hard coat layer>
After coating, drying and curing on the resin base material using the above-mentioned coating liquid 1 for hard coat layer in the same manner as for sample 1 under the condition that the dry film thickness is 1.5 μm, the hard coating layer is further coated thereon. The coating layer coating solution 2 is applied, dried, and cured in the same manner as in Sample 2 under the condition that the dry film thickness is 1.5 μm, and the silicon oxide concentrations having the structure shown in FIG. A hard coat layer unit having a total film thickness of 3.0 μm in which two inorganic particle-containing layers were laminated was formed.

[Preparation of Sample 4]
Sample 4 was prepared in the same manner as in the preparation of Sample 1, except that the method for forming the hard coat layer was changed as follows.

  Using the following hard coat layer coating solution 0 that does not contain any inorganic particles (silicon oxide) on the resin substrate, coating and drying in the same manner as for sample 1 under the condition that the dry film thickness is 1.0 μm, After curing, the hard coat layer coating solution 1 is then applied, dried and cured on the condition that the dry film thickness is 1.0 μm in the same manner as in Sample 1, and further hard coated thereon. The layer coating solution 2 is applied, dried, and cured in the same manner as Sample 2 under the condition that the dry film thickness is 1.0 μm, and does not contain any silicon oxide having the structure shown in FIG. A hard coat layer unit having a total film thickness of 3.0 μm was formed by laminating a layer and two inorganic particle-containing layers having different silicon oxide concentrations.

<Coating solution for hard coat layer 0>
Dipentaerythritol hexaacrylate 100 parts by mass Photoinitiator (Irgacure 184 (Ciba Specialty Chemicals Co., Ltd.))
5 parts by mass Ethyl acetate 120 parts by mass Propylene glycol monomethyl ether 120 parts by mass Silicon compound (BYK-307 (manufactured by Big Chemie Japan)) 0.4 parts by mass Cross-linked polystyrene particles (SX350H by Soken Chemical, refractive index 1.6, particles (Diameter 3.5μm)
10 parts by mass [Preparation of Sample 5]
In the preparation of Sample 4, the coating, drying, and curing are sequentially repeated on the resin base material using the following coating liquids for hard coat layers having different silicon oxide concentrations with respect to the eight types of dipentaerythritol hexaacrylate. Sample 5 was prepared in the same manner except that a hard coat layer unit having a total film thickness of 3.0 μm composed of the eight layers shown in c) of FIG. 1 was formed. The dry film thickness of each layer was 0.375 μm.

First layer: silicon oxide concentration = 0 mass% (coating solution for hard coat layer 0)
Second layer: silicon oxide concentration = 1.0 mass%
Third layer: silicon oxide concentration = 2.0 mass% (hard coat layer coating solution 1)
Fourth layer: silicon oxide concentration = 4.0% by mass
Fifth layer: silicon oxide concentration = 5.5% by mass
Sixth layer: silicon oxide concentration = 7.5 mass% (hard coat layer coating solution 2)
Seventh layer: silicon oxide concentration = 8.5% by mass
Eighth layer: silicon oxide concentration = 10 mass%
[Preparation of Sample 6]
In the preparation of the sample 5, each of the first to eighth layer coating liquids is applied on a resin base material using a slide hopper type coating apparatus capable of simultaneous application of eight layers, and the state is maintained for 10 seconds. Thereafter, drying and curing were performed in the same manner as described in Sample 1, and Sample 6 was similarly prepared except that a hard coat layer having different silicon oxide concentrations shown in FIG. Produced.

[Preparation of Sample 7]
Sample 7 was prepared in the same manner as in the preparation of Sample 4, except that the silicon oxide particles used for forming the hard coat layer were changed to titanium oxide particles having a primary average particle diameter of 16 nm.

[Preparation of Sample 8]
Sample 8 was prepared in the same manner as in the preparation of Sample 4, except that the silicon oxide particles used for forming the hard coat layer were changed to zirconium oxide particles having a primary average particle diameter of 16 nm.

[Preparation of Samples 9 to 12]
In the production of Sample 4, the silicon oxide particles (primary average particle diameter 16 nm) used for forming the hard coat layer were changed to silicon oxide particles having primary average particle diameters of 7 nm, 200 nm, 450 nm, and 850 nm, respectively. Thus, Samples 9 to 12 were produced.

[Preparation of Sample 13]
In the production of the sample 4, 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 13 was produced in the same manner except that the sample was changed to.

[Preparation of Sample 14]
Sample 14 was prepared in the same manner as in the preparation of Sample 4 except that the following plasma CVD method was used instead of the atmospheric pressure plasma CVD method as a method for forming the metal oxide layer.

  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: 0.3 torr
Reaction gas: tetraethoxysilane (TEOS) 5 sccm (standard cubic centimeter per minute)
Power: 100W at 13.56MHz
Substrate holding temperature: 120 ° C
<< Evaluation of laminate with hard coat layer >>
About the produced said laminated body with a hard-coat layer (samples 1-14), each following evaluation was performed.

[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, and the ratio of the area where the laminated film is peeled to the tape area affixed 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.

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: of the peeled layer The area was 10% or more and less than 20% 1: The area of the peeled layer was 20% or more [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. Table 1 shows the results obtained as described above.

  As is clear from the results shown in Table 1, the sample of the present invention having a hard coat layer having an inorganic particle-containing layer structure defined in the present invention is a resin base and a hard coat layer, or hard It can be seen that the film has excellent adhesion between the coat layer and the metal oxide layer, and has excellent pencil hardness test and scratch resistance on the outermost surface and high hardness.

Example 2
<< Production of laminate with hard coat layer >>
[Preparation of Sample 101]
(Resin base material)
A polycarbonate resin film (manufactured by Teijin Chemicals Ltd.) having a thickness of 100 μm was used as the resin base material.

(Preparation of coating solution for hard coat layer)
<Preparation of coating solution 1 for layer A unit: first layer>
Active energy ray curable resin (dipentaerythritol hexaacrylate)
20.0g
Photoinitiator (Irgacure 184 (Ciba Specialty Chemicals Co., Ltd.))
1.0g
108 g of inorganic particle dispersion (containing 30% by mass of silicon oxide, methyl ethyl ketone-dispersed silica sol (manufactured by Nissan Chemical Co., Ltd., trade name MEK-ST), average particle size: 15 nm)
Methyl ethyl ketone 10.0g
The above additives were sequentially mixed and stirred for 30 minutes, and then filtered through a polypropylene filter having a pore size of 1 μm to prepare a coating solution 1 for A layer unit. The filling rate (solid content ratio) of inorganic particles (silicon oxide) in the A layer unit formed using the coating liquid 1 for A layer unit is 50% by volume.

  In addition, the filling rate of the inorganic particles was determined by measuring the total volume by peeling the hard coat layer from the resin base material after forming the hard coat layer using the coating liquid 1 for the A layer unit according to the following method. The resin component was dissolved, the volume of the inorganic particles was measured, and the measured value was obtained.

(Formation of hard coat layer)
On the resin base material, using the coating liquid 1 for the A layer unit, the coating was applied with a wire bar under the condition that the dry film thickness was 12.0 μm, dried at 90 ° C., and then irradiated with an ultraviolet lamp. Was cured at an illuminance of 100 mW / cm ² and an irradiation amount of 80 mJ / cm ² to form a first layer (A layer unit) of the hard coat layer.

(Formation of metal oxide layer)
Using the roll electrode type discharge treatment apparatus shown in FIG. 3, the film thickness is 150 nm and only SiO ₂ is formed on the third layer of the sample in which the hard coat layer is formed on the resin substrate by the atmospheric pressure plasma discharge treatment. The metal oxide layer 1 comprised by this was formed, and the sample 1 which is a laminated body with a hard-coat layer was produced.

  The discharge treatment apparatus shown in FIG. 3 has a plurality of rod-shaped electrodes placed in parallel to the film transport direction so as to face the roll electrode. It has a structure that can be charged.

  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
[Production of Sample 102]
<Preparation of coating solution 2 for layer A unit: first layer, third layer>
Active energy ray curable resin (dipentaerythritol hexaacrylate)
20.0g
Photoinitiator (Irgacure 184 (Ciba Specialty Chemicals Co., Ltd.))
1.0g
108 g of inorganic particle dispersion (containing 30% by mass of silicon oxide, methyl ethyl ketone-dispersed silica sol (manufactured by Nissan Chemical Co., Ltd., trade name MEK-ST), average particle size: 15 nm)
Methyl ethyl ketone 10.0g
The above additives were sequentially mixed and stirred for 30 minutes, and then filtered through a polypropylene filter having a pore size of 1 μm to prepare a coating solution 2 for layer A unit. The filling rate (solid content ratio) of inorganic particles (silicon oxide) in the A layer unit formed using the coating liquid 2 for A layer unit is 50% by volume.

<Preparation of coating liquid 2 for layer B unit: second layer>
Active energy ray curable resin (dipentaerythritol hexaacrylate) 100 g
Photoinitiator (Irgacure 184 (Ciba Specialty Chemicals Co., Ltd.))
5.0g
Methyl ethyl ketone 10.0g
The above additives were sequentially mixed and stirred for 30 minutes, and then filtered through a polypropylene filter having a pore size of 1 μm to prepare a coating solution 2 for B layer unit. The solid content ratio of the inorganic particles (silicon oxide) in the B layer unit formed using the coating liquid 2 for B layer unit is 0% by volume.

(Formation of hard coat layer)
On the resin base material, using the coating liquid 2 for layer A unit, the coating was applied with a wire bar under the condition that the dry film thickness was 4.5 μm, dried at 90 ° C., and then irradiated with an ultraviolet lamp. Was cured at an illuminance of 100 mW / cm ² and an irradiation amount of 80 mJ / cm ² to form a first layer (A layer unit) of the hard coat layer. Next, using the coating liquid 2 for the B layer unit, a wire bar was applied on the condition that the dry film thickness was 3.0 μm, and the coating was dried at 90 ° C. Then, using an ultraviolet lamp, The second layer (B layer unit) of the hard coat layer was formed by curing with an illuminance of 100 mW / cm ² and an irradiation amount of 80 mJ / cm ² . Next, using the coating liquid 2 for the A layer unit, a wire bar was applied on the condition that the dry film thickness was 4.5 μm, and it was dried at 90 ° C. Then, using an ultraviolet lamp, Hardened with an illuminance of 100 mW / cm ² and an irradiation dose of 80 mJ / cm ² to form a third layer (A layer unit) of the hard coat layer, and a hard coat layer in which the A layer and the B layer are alternately laminated is produced. did.

(Formation of metal oxide layer)
A metal oxide layer was formed by a method similar to that used to manufacture the sample 101, so that a sample 102 was manufactured.

[Production of Samples 103 to 107]
In the preparation of the sample 102, the hard coat layer is formed under the following conditions: the number of layers alternately stacked in the A layer unit and the B layer unit, the thickness of each sensitive layer (μm), the inorganic particles in the A layer unit and the B layer unit (oxidation) The addition amount of active energy ray-curable resin, photoreaction initiator, inorganic particle dispersion and methyl ethyl ketone was appropriately adjusted so as to be a filling rate (volume%) of silicon), and changed to the filling rate shown in Table 2 Similarly, samples 103 to 107 were produced.

[Production of Sample 108]
In the preparation of the sample 105, each coating liquid of the first layer to the sixth layer was applied on a resin base material using a slide hopper type coating apparatus capable of simultaneous multilayer coating, and the state was maintained for 10 seconds. After the maintenance, the sample 108 was produced in the same manner as in the method described in the sample 105 except that drying and curing were performed to form a hard coat layer unit.

<< Evaluation of laminate with hard coat layer >>
The following evaluation was performed about the produced laminated body with a hard-coat layer (samples 101-108).

[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.

<Evaluation rank>
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: of the peeled layer The area 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 26 or more. Table 3 shows the results obtained as described above.

  As is clear from the results shown in Table 3, the laminate with a hard coat layer of the present invention having a hard coat layer composed of an inorganic particle-containing layer defined in the present invention is a resin substrate and a hard It can be seen that the coating layer or the adhesion between the hard coating layer and the metal oxide layer is excellent, the outermost pencil hardness test and the scratch resistance are excellent, and high hardness is provided.

Claims (10)

In a laminate with a hard coat layer in which a hard coat layer and a metal oxide layer are laminated in this order on at least one surface of a resin substrate, the hard coat layer contains two or more inorganic particles having different inorganic particle concentrations. The inorganic particle concentration is higher in the region in contact with the resin base material than in the region in contact with the resin substrate. ,
The hard coat layer has a structure in which two layers having different inorganic particle concentrations are alternately laminated. When the layer group having a high inorganic particle concentration is an A layer unit and the layer group having a low inorganic particle concentration is a B layer unit, At least one layer unit of the A layer unit and the B layer unit is composed of at least two layers having different dry film thicknesses, and the total dry film thickness ΣAh of the A layer unit and the dry film thickness of the B layer unit are A laminate with a hard coat layer, wherein the total sum ΣBh satisfies the relationship ΣAh ≧ ΣBh.   The inorganic particle concentration of the A layer unit is 30% by volume or more and 70% by volume or less, and the inorganic particle concentration of the B layer unit is 0% by volume or more and 40% by volume or less. The laminated body with a hard-coat layer as described in a term.   The inorganic particle concentration of the A layer unit is 40% by volume or more and 60% by volume or less, and the inorganic particle concentration of the B layer unit is 0% by volume or more and 20% by volume or less. The laminated body with a hard-coat layer as described in a term. The laminated body with a hard coat layer according to any one of claims 1 to 3, wherein the inorganic particles contained in the inorganic particle-containing layer are silicon oxide particles. The hard coat according to any one of claims 1 to 4, wherein an average particle diameter of the inorganic particles contained in the inorganic particle-containing layer is 5 nm or more and 1.0 µm or less. Layered laminate. The laminate with a hard coat layer according to any one of claims 1 to 5, wherein the inorganic particle-containing layer contains an ultraviolet curable resin as a binder. The laminate with a hard coat layer according to any one of claims 1 to 6 , wherein the hard coat layer is formed by a wet coating method. The laminate with a hard coat layer according to any one of claims 1 to 7 , 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. 10. The hard coat layer according to claim 9, wherein the plasma 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 in the vicinity of atmospheric pressure. Laminated body.