JP5482651B2 - Laminate with hard coat layer - Google Patents

Description

  The present invention relates to a laminate with a hard coat layer having a laminated structure excellent in film adhesion, high film strength and scratch resistance. 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 scratch resistance. It is in.

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

  1. In the laminate with a hard coat layer having a hard coat layer composed of at least a resin and inorganic particles or a resin on at least one surface of the resin base material, the hard coat layer has two layers having different inorganic particle concentrations. 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, the surface of the hard coat layer is an A 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 when the A layer unit is composed of layers having different dry film thicknesses, the A layer unit The dry film thickness of each layer constituting the layer decreases toward the resin substrate, and when the B layer unit is composed of layers having different dry film thicknesses, the dryness of each layer constituting the B layer unit is dried. The thickness increases toward the resin substrate, and the total ΣAh of the dry film thickness of the A layer unit and the total ΣBh of the dry film thickness of the B layer unit satisfy the relationship ΣAh ≧ ΣBh Laminate with hard coat layer.

2. In a laminate with a hard coat layer in which a hard coat layer composed of at least a resin and inorganic particles or a resin and a metal oxide layer are laminated in this order on at least one surface of a resin base material, the hard coat layer is When the two layers having different inorganic particle concentrations are alternately stacked, 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 unit and the B layer unit is constituted by at least two layers having different dry film thicknesses, and when the A layer unit is constituted by layers having different dry film thicknesses, the A layer unit is constituted. The dry film thickness of each layer decreases toward the resin base material, and when the B layer unit is composed of layers having different dry film thicknesses, the dry film thickness of each layer constituting the B layer unit is The resin substrate Towards increasing the dry film total thickness ShigumaBh dried film thickness of total ShigumaAh and said B layer unit of the A layer unit, a hard coat layer with a laminate characterized by satisfying the relation of ΣAh ≧ ΣBh.

  3. The inorganic particle concentration of the A layer unit is 30.0% by volume or more and 70.0% by volume or less, and the inorganic particle concentration of the B layer unit is 0% by volume or more and 40.0% by volume or less. The laminate with a hard coat layer according to 1 or 2 above.

  4). The inorganic particle concentration of the A layer unit is 40.0% by volume or more and 60.0% by volume or less, and the inorganic particle concentration of the B layer unit is 0% by volume or more and 20.0% by volume or less. The laminate with a hard coat layer according to any one of 1 to 3 above.

5 . 3. The hardware according to 2 above, wherein a dry film thickness of a layer which is closest to the metal oxide layer among the layers constituting the A layer unit is 3.0 μm or more and 100 μm or less. Laminated body with coat layer.

6 . Among the layers constituting the B layer unit, the dry film thickness of the layer closest to the metal oxide layer is 0.1 μm or more and 2.0 μm or less, 2 or 5 above A laminate with a hard coat layer as described in 1.

7 . 7. The laminate with a hard coat layer according to any one of 1 to 6 , wherein the inorganic particles are silicon oxide particles.

8 . 8. The laminate with a hard coat layer according to any one of 1 to 7 , wherein an average particle size of the inorganic particles is 5.0 nm or more and 1.0 μm or less.

9 . 9. The laminate with a hard coat layer according to any one of 1 to 8 , wherein the hard coat layer is formed by a wet coating method.

10 . 10. The laminate with a hard coat layer according to 9 , wherein the wet coating method is a multilayer simultaneous coating method in which a plurality of layers are coated simultaneously.

11 . 7. The laminate with a hard coat layer according to 2 , 5, or 6, wherein a main component of the metal oxide layer is silicon oxide.

12 . 12. The laminate with a hard coat layer according to 2 , 5, 6, or 11 , wherein the metal oxide layer is formed by a plasma CVD method.

13 . 13. The laminate with a hard coat layer as described in 12 above, wherein the plasma CVD method is an atmospheric pressure plasma CVD method in which plasma treatment is performed under atmospheric pressure or a pressure near atmospheric pressure.

14 . The laminate with a hard coat layer according to 2 , 5, 6, or 11 , wherein the metal oxide layer is formed by a wet coating method using inorganic polysilazane.

  According to the present invention, it is possible to provide a laminate with a hard coat layer that can be easily produced, has excellent film adhesion, and has high film strength and 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 A1-A3, B1-B3 Hard-coat layer 3 Metal oxide layer 10, 30 Plasma discharge processing apparatus 11 1st electrode 12 2nd electrode 14 Processing position 21, 41 1st power supply 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 Square 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-mentioned problems, the present inventor has a hard coat layer-attached laminate having a hard coat layer composed of at least a resin and inorganic particles or a resin on at least one surface of the resin base material, or In a laminate with a hard coat layer in which a hard coat layer composed of at least a resin and inorganic particles or a resin and a metal oxide layer are laminated in this order on at least one surface of a resin base material, the hard coat layer is When the two layers having different inorganic particle concentrations are alternately stacked, 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 unit and the B layer unit is composed of at least two layers having different dry film thicknesses, and the total ΣAh of the dry film thicknesses of the A layer unit and the B layer unit The laminate with hard coat layer is characterized in that the total dry film thickness ΣBh satisfies the relationship of ΣAh ≧ ΣBh. It can be easily manufactured, has excellent film adhesion, and has high film strength and scratch resistance. It has been found that an excellent laminate with a hard coat layer can be realized, and has reached the present invention.

[Hard coat layer]
In the laminate with a hard coat layer of the present invention, the hard coat layer 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 is designated as an A layer unit and an inorganic particle concentration. When a layer group having a low A 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 of the A layer unit is The sum of ΣAh and the total dry film thickness ΣBh of the B layer unit is ΣAh ≧ ΣBh.

  Furthermore, in the laminate with a hard coat layer of the present invention, the total ΣAh of the dry film thickness of the A layer unit is not particularly limited, but is approximately 1.0 μm or more and 100 μm or less, preferably 5.0 μm. Above, it is 50 micrometers or less, More preferably, they are 5.0 micrometers or more and 20 micrometers or less. Further, the total dry thickness ΣBh of the B layer unit is not particularly limited, but is approximately 1.0 μm or more and 100 μm or less, preferably 3.0 μm or more and 50 μm or less, and more preferably 3.0 μm. As mentioned above, it is 20 micrometers or less.

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

  As a result of intensive studies on a method for solving the above problems, the present inventor constituted a hard coat layer with a structure in which two layers having different inorganic particle concentrations were alternately laminated, and further, an A layer having a high inorganic particle concentration. At least one layer unit of the unit and the B layer unit having a low inorganic particle concentration is composed of at least two layers having different dry film thicknesses, and the total dry film thickness of the A layer unit ΣAh ≧ the total dry film thickness of the B layer unit ΣBh The present inventors have found that the effect intended by the present invention can be obtained by satisfying the above condition.

  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 in the present invention, it is composed of an actinic ray curable resin and inorganic particles. In the inorganic particle-containing layer, the inorganic particle concentration contained in each layer is different, and the inorganic particle concentration contained in each layer constituting the A layer unit is higher than the inorganic particle concentration contained in each layer constituting the B layer unit. It is characterized by doing.

  More preferably, the inorganic particle concentration of each layer constituting the A layer unit is 30% by volume or more and 70% by volume or less, and the inorganic particle concentration of each layer constituting the B layer unit is 0% by volume or more and 40% by volume or less. More preferably, the inorganic particle concentration of each layer constituting the A layer unit is 40% by volume or more and 60% by volume or less, and the inorganic particle concentration of each layer constituting the B layer unit is 0% by volume or more and 20% by volume. % Or less.

  In the hard coat layer according to the present invention, the layer constituting the A layer unit may be a single layer or may be composed of two or more layers. For example, the B layer unit is a single layer. The A layer unit is composed of two or more layers. Further, the layer constituting the B layer unit may be a single layer or may be composed of two or more layers. For example, when the A layer unit is a single layer, the B layer unit has 2 layers. Each layer is composed of layers or more, and each layer constituting the A layer unit having different inorganic particle concentrations and each layer constituting the B layer unit are alternately laminated.

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

  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 three inorganic particle-containing layers having different inorganic particle concentrations are laminated.

  FIG. 1A shows an example in which an A layer unit having a high inorganic particle concentration is composed of two layers A1 and A2, and a B layer unit having a low inorganic particle concentration is composed of a single layer of B1.

  Specifically, in the laminate 1 with a hard coat layer, the A1 of the A layer unit having a high inorganic particle concentration is disposed on the resin base material 2, and then the B1 of the B layer unit having a low inorganic particle concentration is stacked. It is a laminate with a hard coat layer in which the A2 of the A layer unit having a high inorganic particle concentration is disposed thereon, and the metal oxide layer 3 is further formed thereon. At this time, the total dry film thickness of the two layers A1 and A2 constituting the A layer unit is designed to be larger than the dry film thickness of B1 constituting the B layer unit.

  Furthermore, in the A layer unit composed of two layers A1 and A2, it is preferable that the dry film thickness is increased in the order of A1 and A2 toward the metal oxide layer 3.

  Further, in the hard coat layer according to the present invention, among the layers constituting the A layer unit, the dry film thickness of the layer (A2) in the layer closest to the metal oxide layer 3 (a in FIG. 1) is: It is preferable that it is 3 micrometers or more and 100 micrometers or less.

  Furthermore, in the hard coat layer according to the present invention, among the layers constituting the B layer unit, the dry film thickness of the layer (B1) in the layer closest to the metal oxide layer 3 (a in FIG. 1) is: It is preferable that they are 0.1 micrometer or more and 2 micrometers or less.

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

  FIG. 1b shows an example in which the A layer unit having a high inorganic particle concentration is constituted by a single layer of only A1, and the B layer unit having a low inorganic particle concentration is constituted by two layers B1 and B2.

  Specifically, in the laminate 1 with a hard coat layer, the B1 of the B layer unit having a low inorganic particle concentration is disposed on the resin base material 2, and then the A1 of the A layer unit having a high inorganic particle concentration is stacked. It is a laminated body with a hard coat layer in which B2 of a B layer unit having a low inorganic particle concentration is disposed thereon, and a metal oxide layer 3 is further formed thereon. At this time, the dry film thickness of A1 constituting the A layer unit is designed to be thicker than the total dry film thickness of B1 and B2 constituting the B layer unit.

  Furthermore, in the B layer unit composed of two layers B1 and B2, it is preferable that the dry film thickness is decreased in the order of B1 and B2 toward the metal oxide layer 3.

  Furthermore, in the hard coat layer according to the present invention, among the layers constituting the A layer unit, the dry film thickness of A1) in the layer closest to the metal oxide layer 3 (b in FIG. 1) is: It is preferable that it is 3 micrometers or more and 100 micrometers or less.

  Furthermore, in the hard coat layer according to the present invention, among the layers constituting the B layer unit, the dry film thickness of the layer (B2) in the layer closest to the metal oxide layer 3 (b in FIG. 1) is: It is preferable that they are 0.1 micrometer or more and 2 micrometers or less.

  FIG. 1 c) is a cross-sectional view of a laminate with a hard coat layer in which the A layer unit and the B layer unit having different inorganic particle concentrations are each composed of three layers and are alternately laminated.

  In c) of FIG. 1, an example in which the A layer unit having a high inorganic particle concentration is composed of three layers A1, A2, and A3, and the B layer unit having a low inorganic particle concentration is composed of three layers B1, B2, and B3. Is shown.

  Specifically, in the laminate 1 with a hard coat layer, the B1 of the B layer unit having a low inorganic particle concentration is disposed on the resin base material 2, and then the A1 of the A layer unit having a high inorganic particle concentration is stacked. Next, the laminate with a hard coat layer is obtained by alternately laminating B2, A2, B3, and A3 in this order, and further forming the metal oxide layer 3 thereon. At this time, the total dry film thickness of the three layers A1, A2, and A3 constituting the A layer unit is designed to be thicker than the total dry film thickness of the three layers B1, B2, and B3 constituting the B layer unit. And

  Furthermore, in the A layer unit composed of three layers of A1, A2, and A3, it is preferable to increase the dry film thickness in the order of A1, A2, and A3 toward the metal oxide layer 3.

  Furthermore, in the hard coat layer according to the present invention, among the layers constituting the A layer unit, the dry film thickness of the layer (A3) in the layer closest to the metal oxide layer 3 (c in FIG. 1) is: It is preferable that it is 3 micrometers or more and 100 micrometers or less.

  Furthermore, in the B layer unit composed of three layers B1, B2, and B3, it is preferable that the dry film thickness is decreased in the order of B1, B2, and B3 toward the metal oxide layer 3.

  Furthermore, in the hard coat layer according to the present invention, among the layers constituting the B layer unit, the dry film thickness of the layer (B3) in the layer closest to the metal oxide layer 3 (FIG. 1c) is: It is preferable that they are 0.1 micrometer or more and 2 micrometers or less.

(Constituent material of hard coat layer)
It is preferable that each layer of the A layer unit and the B layer unit constituting the hard coat layer according to the present invention is mainly composed 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 Chemical Industries, Ltd.), SP-1509, SP-1507 (manufactured by Showa Polymer Co., Ltd.), or RCC-15C (Grace Japan Co., Ltd.) (Manufactured by company), Aronix M-6100, M-8030, M-8060 (above, manufactured by Toagosei Co., Ltd.) or other commercially available products.

<Inorganic particles>
In the hard coat layer according to the present invention, as described above, the inorganic particle concentration of each layer constituting the A layer unit is 30% by volume or more and 70% by volume or less, and the inorganic particle concentration of each layer constituting the B layer unit is 0 volume. Preferably, the inorganic particle concentration of each layer constituting the A layer unit is 40% by volume or more and 60% by volume or less, and the inorganic particle concentration of each layer constituting the B layer unit is It is preferable to set it to 0 volume% or more and 20 volume% or less. That is, the layer constituting the B layer unit according to the present invention includes a case that does not contain any inorganic particles and is composed only of an actinic ray curable resin.

  Examples of inorganic particles applicable to the constituent layer of the hard coat layer according to the present invention include oxidation of a metal selected from Si, Ti, Mg, Ca, Zr, Sn, Sb, As, Zn, Nb, In, and Al. In particular, 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 Mention may be made of calcium silicate, hydrated calcium silicate, aluminum silicate, magnesium silicate and calcium phosphate. In particular, in the present invention, it is preferable to use silicon oxide as the inorganic particles.

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

  In the hard coat layer according to the present invention, the content of the inorganic particles in the inorganic particle-containing layer is not particularly limited as long as it satisfies the conditions defined in the present invention.

<Method for forming inorganic particle-containing layer>
In the present invention, the layers constituting the A layer unit and the layers constituting the B layer unit are alternately laminated on the resin base material, and each constituent layer is formed on the resin base material. As a method for forming the thin film, 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. For preparing a layer coating solution containing no or an inorganic particle obtained by dissolving an actinic radiation curable resin in a solvent, and forming a wet thin film on a resin substrate using the coating solution It is.

  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.

  When the layer constituting the A layer unit and the layer constituting the B layer unit according to the present invention are alternately laminated, the first layer (for example, FIG. After applying B1) in c) of 1 and then irradiating with actinic rays, after applying a second layer (for example, A1) in c of FIG. 1 on the first layer, Irradiate with actinic rays. In the case of the configuration shown in FIG. 1 c), B2, A2, B3, and A3 can be similarly applied and cured so as to have predetermined film thicknesses.

  In addition, as a wet coating method for forming a laminated hard coat layer according to the present invention, for example, in the configuration shown in FIG. 1 c), it is high to apply a multilayer simultaneous coating method in which a total of six layers are coated simultaneously. It is preferable from the viewpoint of obtaining productivity.

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

[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 includes, for example, a dry film formation by 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, a sol-gel method, and a silazane. It can be formed by applying a wet coating by a method.

  In the laminated body with a hard coat layer of the present invention, it is preferable to apply a plasma CVD method as a method for forming a metal oxide layer by dry film formation, and in particular, a high pressure under atmospheric pressure or a pressure near atmospheric pressure. The atmospheric pressure plasma CVD method is preferable because it does not require a decompression chamber or the like and can form a film at a high speed and has high productivity. 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.

  Further, in the laminate with a hard coat layer of the present invention, as a method for forming a metal oxide layer by wet coating, it is preferable to apply a sol-gel method or a silazane method, and in particular, a silazane method using an inorganic silazane, From the viewpoint of obtaining a coating film having a relatively low temperature and a high hardness. Examples of the inorganic polysilazane applicable to the present invention include inorganic polysilazanes described in paragraph numbers (0097) to (0104) of JP-A No. 11-240103. Moreover, as polysilazane (perhydropolysilazane), it can obtain as a commercial item as AQUAMICA NAX120-20, NP110, NP140, etc. by AZ Electronic Materials.

  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.

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

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

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

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

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

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

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

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

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

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

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

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

  A gas G is introduced 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 rectangular tube-shaped fixed electrode group (second electrode) 36. A second high-frequency electric field having a current I ₂ is applied.

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

In the present invention, the roll rotation electrode 35 may be the second electrode, and the rectangular tube-shaped fixed electrode group 36 may be the first electrode. In any case, the first power source is connected to the first electrode, and the second power source is connected to the second electrode. The first power supply preferably applies a higher high-frequency electric field strength (V ₁ > V ₂ ) than the second power supply. Further, the frequency has the ability to satisfy ω ₁ <ω ₂ .

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

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

  The 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, the roll electrode 35a and the 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 power applied between the electrodes facing each other is such that power (power density) of 1 W / cm ² or more is supplied to the second electrode (second high-frequency electric field) to excite the discharge gas to generate plasma. The energy is applied to the thin film forming gas to form a thin film. The upper limit value of the power supplied to the second electrode is preferably 50 W / cm ² , more preferably 20 W / cm ² . The lower limit is preferably 1.2 W / cm ² . In addition, discharge area (cm < ² >) points out the area of the range which discharge occurs in an electrode.

Further, by supplying power (output density) of 1 W / cm ² or more to the first electrode (first high frequency electric field), the output density is improved while maintaining the uniformity of the second high frequency electric field. I can do it. Thereby, a further uniform high-density plasma can be generated, and a further improvement in film forming speed and an improvement in film quality can be achieved. Preferably it is 5 W / cm ² or more. The upper limit value of the power supplied to the first electrode is preferably 50 W / cm ² .

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

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

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

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

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

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

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

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

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

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

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

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

  The resin base exemplified above can be obtained as a commercial product, such as ZEONEX or ZEONOR (manufactured by Nippon Zeon Co., Ltd.), an amorphous cyclopolyolefin resin film ARTON (manufactured by JSR Corporation), polycarbonate. Examples include a pure ace film (manufactured by Teijin Ltd.) and a cellulose triacetate film Konica Katak KC4UX, KC8UX (manufactured by Konica Minolta Opto Co., Ltd.).

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

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

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

  EXAMPLES Hereinafter, 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 >>
[Preparation of Sample 1]
(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 liquid 1A 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 1A for A layer unit. The ratio of the inorganic particles (silicon oxide) to the solid content (components other than methyl ethyl ketone as the solvent) in the coating liquid 1A for the A layer unit is about 40% by volume, but the active energy ray curable resin is active. Since it shrinks simultaneously with curing in the polymerization reaction caused by irradiation with energy rays, the filling rate of inorganic particles in the dry film, determined by the filling rate measurement method (volume analysis method) shown below, was 50% by volume.

−Filling rate measurement method (volume analysis method) −
The filling rate of the inorganic particles in the dried film was measured by the following method. After forming the hard coat layer using the coating liquid 1A for the A layer unit, the hard coat layer is peeled off from the resin base material to measure the total volume, and then the volume of the inorganic particles is measured by dissolving the resin component. And obtained from these measured values.

<Preparation of coating liquid 1B 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 1B for a B layer unit. The ratio (solid content ratio) of inorganic particles (silicon oxide) to the solid content (components other than methyl ethyl ketone as a solvent) in the coating liquid 1B for the B layer unit is 0% by volume.

(Formation of hard coat layer)
Using the coating liquid 1A for the A layer unit on the resin base material, coating with a wire bar under the condition that the dry film thickness is 3.0 μm, and drying at 90 ° C. 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 1B for the B layer unit, a wire bar was applied under 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 1A for the A layer unit, a coating is applied with a wire bar under the condition that the dry film thickness is 6.0 μm, and drying 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.

[Preparation of Samples 2 to 27]
In the preparation of Sample 1, the hard coat layer is formed by the following conditions: the number of layers alternately stacked in the A layer unit and the B layer unit, and the thickness of each sensitive layer (μm); The addition rate of active energy ray curable resin, photoreaction initiator, inorganic particle dispersion and methyl ethyl ketone is adjusted as appropriate so that the filling rate (volume%) of silicon) is reached, and the filling rates shown in Tables 1 and 2 are obtained. Samples 2 to 27 were produced in the same manner except that the changes were made.

[Preparation of Sample 28]
Sample 28 was prepared in the same manner as in the preparation of Sample 1, except that the silicon oxide particles used for forming the A layer unit of the hard coat layer were changed to titanium oxide particles having a primary average particle diameter of 15 nm.

[Preparation of Sample 29]
Sample 29 was prepared in the same manner as in the preparation of Sample 1, except that the silicon oxide particles used for forming the A layer unit of the hard coat layer were changed to zirconium oxide particles having a primary average particle diameter of 15 nm.

[Production of Samples 30 to 33]
In the production of Sample 1, the silicon oxide particles (primary average particle diameter of 15 nm) used for forming the A layer unit of 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. Samples 29 to 33 were prepared in the same manner except that.

[Preparation of Sample 34]
In the preparation of the sample 9, each coating solution 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 34 was produced in the same manner as in the method described in the sample 1, except that the hard coat layer unit was formed by drying and curing.

  The following Tables 1 and 2 show details of the laminates with hard coat layers prepared above.

<< Evaluation of laminate with hard coat layer >>
The following evaluation was performed about the produced laminated body with a hard-coat layer (samples 1-34).

[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, 2 cm × 2 cm) with a friction tester HEIDON-14DR, the load (9.8 N, movement) was performed on the surface of each laminate (hard coat layer forming surface side) produced above. Speed: After carrying out the rubbing treatment 20 times under the condition of 15 mm / min, the rubbing range was observed with a loupe, and the rubbing 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. 25 or less xx: Scratches generated 26 or more (Evaluation 3: Scratch resistance evaluation 2)
As a result of the evaluation 2, the samples marked with “◎” were evaluated again under the condition that the steel wool was changed and the flaws were easily damaged in order to evaluate the scratch resistance in more detail.

Friction tester HEIDON-14DR
Steel wool (Bonster # 0, 2cm x 2cm)
Load: 9.8N
Moving speed: 15 mm / min 20 rubbing treatments After the rubbing treatment, the rubbing range was observed with a magnifying glass, and the scratch resistance was evaluated according to the following criteria.

5: No generation of scratches is observed 4: Generation of scratches is 1 or more and 5 or less 3: Generation of scratches is 6 or more and 15 or less 2: Generation of scratches is 16 or more, The number is 25 or less. 1: The number of scratches is 26 or more. Table 3 shows the results obtained.

  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 having a layer structure defined in the present invention is more resistant to pencil hardness test and scratch resistance than the comparative example. It turns out that it is excellent and has 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, 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 1 for A layer unit. The ratio (solid content ratio) of the inorganic particles (silicon oxide) to the solid content (components other than methyl ethyl ketone as the solvent) in the coating liquid 1 for layer A unit is about 40% by volume. Since it shrinks simultaneously with curing in the polymerization reaction caused by irradiation with energy rays, the filling rate of inorganic particles in the dry film, determined by the filling rate measurement method (volume analysis method) shown below, was 50% by volume.

−Filling rate measurement method (volume analysis method) −
The filling rate of the inorganic particles in the dried film was measured by the following method. After forming the hard coat layer using the coating liquid 1 for the A layer unit, the hard coat layer is peeled off from the resin base material to measure the total volume, and then the volume of the inorganic particles is measured by dissolving the resin component. And obtained from these measured values.

<Preparation of coating solution 1 for layer B unit: second layer>
Active energy ray curable resin (dipentaerythritol hexaacrylate) 100g
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 1 for B layer unit. The ratio (solid content ratio) of inorganic particles (silicon oxide) to the solid content (components other than methyl ethyl ketone as a solvent) in the coating liquid 1 for the B layer unit is 0% by volume.

(Formation of hard coat layer)
On the resin base material, using the coating liquid 1 for the A layer unit, after applying with a wire bar under the condition that the dry film thickness is 3.0 μm and drying at 90 ° C., an irradiation part is used using 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 1 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 . Then, using the coating liquid 1 for the A layer unit, a coating with a wire bar was performed under the condition that the dry film thickness was 6.0 μm, and the coating 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)
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, and raw materials (the following discharge gases, reaction gases 1 and 2) and electric power are supplied to each electrode portion. 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
[Preparation of Samples 102 to 130]
In the preparation of the sample 101, the hard coat layer was formed by the following conditions: the number of layers alternately stacked in the A layer unit and the B layer unit, and the thickness of each sensitive layer (μm); The addition rate of active energy ray-curable resin, photoreaction initiator, inorganic particle dispersion and methyl ethyl ketone is adjusted as appropriate so that the filling rate (volume%) of silicon) is obtained, and the filling rates shown in Tables 4 and 5 are obtained. Samples 102 to 130 were produced in the same manner except that the changes were made.

[Preparation of Sample 131]
A sample 131 was prepared in the same manner as in the preparation of the sample 101 except that the silicon oxide particles used for forming the A layer unit of the hard coat layer were changed to titanium oxide particles having a primary average particle diameter of 15 nm.

[Preparation of Sample 132]
A sample 132 was produced in the same manner as in the production of the sample 101 except that the silicon oxide particles used for forming the A layer unit of the hard coat layer were changed to zirconium oxide particles having a primary average particle diameter of 15 nm.

[Production of Samples 133 to 136]
In the preparation of the sample 101, the silicon oxide particles (primary average particle diameter of 15 nm) used for forming the A layer unit of 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. Samples 133 to 136 were produced in the same manner except that.

[Preparation of Sample 137]
In the preparation of the sample 127, each of the first to sixth layer coating liquids was applied onto a resin base material using a slide hopper type coating apparatus capable of simultaneously coating six layers, and the state was maintained for 10 seconds. After the maintenance, a sample 137 was produced in the same manner except that the hard coat layer unit was formed by drying and curing in the same manner as described in the sample 101.

[Preparation of Sample 138]
In the preparation of the sample 101, 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 138 was produced in the same manner except that the sample was changed to.

[Preparation of Sample 139]
A sample 139 was produced in the same manner as in the production of the sample 101 except that the metal oxide layer was formed by the following plasma CVD method instead of the atmospheric pressure plasma CVD method.

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

  The film forming conditions are as follows.

Oxygen pressure: 40 Pa
Reaction gas: tetraethoxysilane (TEOS) 5 sccm (standard cubic centimeter per minute)
Power: 100W at 13.56MHz
Substrate holding temperature: 120 ° C
[Production of Sample 140]
A sample 140 was prepared in the same manner as in the preparation of 137 except that the formation of the metal oxide layer was changed to the wet coating method (silazane method) using polysilazane shown below instead of the atmospheric pressure plasma CVD method. did.

<Silazane method>
A dibutyl ether solution of a perhydropolysilazane containing a low-temperature curable metal catalyst (solid content 20% by mass, manufactured by AZ Electronic Materials, trade name: Aquamica NAX120-20) is 4 times in volume ratio using dibutyl ether. The diluted solution is applied to the hard coat layer by a wet coating method so as to have a wet film thickness of 6.0 μm, dried, and then kept in a hot air circulating oven at 120 ° C. for 60 hours. Then, heat treatment was performed. Next, the metal oxide layer was sufficiently cured by leaving it for 3 days in an environment of 25 ° C. and 50% relative humidity.

  Tables 4 and 5 below show details of the laminates with hard coat layers prepared above.

<< Evaluation of laminate with hard coat layer >>
The following evaluation was performed about the produced laminated body with a hard-coat layer (samples 101-140).

[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. . Paste a commercially available cellophane tape on this grid, peel one end vertically by hand, measure the ratio of the area where the metal oxide layer was peeled off to the tape area pasted from the score line, and Adhesion was evaluated according to the evaluation criteria. 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 6 shows the results obtained as described above.

  As is clear from the results shown in Table 6, the laminate with a hard coat layer of the present invention having a hard coat layer having an inorganic particle-containing layer structure 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.

Example 3
The samples 107, 137, and 140 prepared in Example 2 were evaluated for wear resistance according to the method described below, and the results obtained are shown in Table 4.

[Evaluation of wear resistance]
Haze value after applying 500 g load to each of two CS-10F wear wheels and rotating the surface of the metal oxide layer of each sample by 500 rotation and 1000 rotation by an abrasion resistance test method according to JIS R3212 Was measured using a haze meter NDH2000 (manufactured by Nippon Denshoku Kogyo Co., Ltd.). The haze value was measured at four locations on the wear cycle orbit of the CS-10F wear wheel, and the average value thereof was determined and used as the haze value.

  Table 4 shows the haze value (%) of the untreated sample before the wear resistance test as the initial haze value, and the wear resistance (%) after 500 rotations and 2000 rotations is expressed by the following equation. Asked.

      Abrasion resistance (%) = haze value after wear test (%)-initial haze value (%)

  As is clear from the results shown in Table 7, it can be seen that the laminate with a hard coat layer of the present invention is superior in wear resistance to the comparative example. Moreover, in the laminated body with a hard-coat layer of this invention, it turns out that the sample 140 which formed the metal oxide layer by the wet apply | coating method using inorganic polysilazane is somewhat excellent.

Claims (14)

  In the laminate with a hard coat layer having a hard coat layer composed of at least a resin and inorganic particles or a resin on at least one surface of the resin base material, the hard coat layer has two layers having different inorganic particle concentrations. 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, the surface of the hard coat layer is an A 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 when the A layer unit is composed of layers having different dry film thicknesses, the A layer unit The dry film thickness of each layer constituting the layer decreases toward the resin substrate, and when the B layer unit is composed of layers having different dry film thicknesses, the dryness of each layer constituting the B layer unit is dried. The thickness increases toward the resin substrate, and the total ΣAh of the dry film thickness of the A layer unit and the total ΣBh of the dry film thickness of the B layer unit satisfy the relationship ΣAh ≧ ΣBh Laminate with hard coat layer. In a laminate with a hard coat layer in which a hard coat layer composed of at least a resin and inorganic particles or a resin and a metal oxide layer are laminated in this order on at least one surface of a resin base material, the hard coat layer is When the two layers having different inorganic particle concentrations are alternately stacked, 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 unit and the B layer unit is constituted by at least two layers having different dry film thicknesses, and when the A layer unit is constituted by layers having different dry film thicknesses, the A layer unit is constituted. The dry film thickness of each layer decreases toward the resin base material, and when the B layer unit is composed of layers having different dry film thicknesses, the dry film thickness of each layer constituting the B layer unit is The resin substrate Towards increasing the dry film total thickness ShigumaBh dried film thickness of total ShigumaAh and said B layer unit of the A layer unit, a hard coat layer with a laminate characterized by satisfying the relation of ΣAh ≧ ΣBh.   The inorganic particle concentration of the A layer unit is 30.0% by volume or more and 70.0% by volume or less, and the inorganic particle concentration of the B layer unit is 0% by volume or more and 40.0% by volume or less. The laminate with a hard coat layer according to claim 1 or claim 2.   The inorganic particle concentration of the A layer unit is 40.0% by volume or more and 60.0% by volume or less, and the inorganic particle concentration of the B layer unit is 0% by volume or more and 20.0% by volume or less. The laminate with a hard coat layer according to any one of claims 1 to 3, wherein: Wherein among the layers constituting the A layer units, dry film thickness of a layer in the closest position to the metal oxide layer, 3.0 [mu] m or more, the range the second term of the claims, characterized in that at 100μm or less A laminate with a hard coat layer as described in 1. The dry film thickness of the layer which is the closest to the metal oxide layer among the layers constituting the B layer unit is 0.1 μm or more and 2.0 μm or less. Item 6. A laminate with a hard coat layer according to item 2 or item 5 . The laminate with a hard coat layer according to any one of claims 1 to 6 , wherein the inorganic particles are silicon oxide particles. The laminate with a hard coat layer according to any one of claims 1 to 7, wherein an average particle size of the inorganic particles is 5.0 nm or more and 1.0 µm or less. The laminate with a hard coat layer according to any one of claims 1 to 8 , wherein the hard coat layer is formed by a wet coating method. The laminate with a hard coat layer according to claim 9 , wherein the wet coating method is a multilayer simultaneous coating method in which a plurality of layers are coated simultaneously. The laminate with a hard coat layer according to any one of claims 2 , 5, and 6, wherein a main component of the metal oxide layer is silicon oxide. . The hard coat according to any one of claims 2 , 5, 6, and 11, wherein the metal oxide layer is formed by a plasma CVD method. Layered laminate. The laminate with a hard coat layer according to claim 12 , wherein the plasma CVD method 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. 12. The metal oxide layer according to any one of claims 2 , 5, 6, and 11, wherein the metal oxide layer is formed by a wet coating method using inorganic polysilazane. A laminate with a hard coat layer as described in 1.