WO2013153648A1 - Stratifié de résine transparente - Google Patents

Stratifié de résine transparente Download PDF

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Publication number
WO2013153648A1
WO2013153648A1 PCT/JP2012/059984 JP2012059984W WO2013153648A1 WO 2013153648 A1 WO2013153648 A1 WO 2013153648A1 JP 2012059984 W JP2012059984 W JP 2012059984W WO 2013153648 A1 WO2013153648 A1 WO 2013153648A1
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Prior art keywords
refractive index
layer
hard coat
transparent resin
mass
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PCT/JP2012/059984
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English (en)
Japanese (ja)
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昌宏 斉藤
秀人 橋口
哲平 板本
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フクビ化学工業株式会社
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Application filed by フクビ化学工業株式会社 filed Critical フクビ化学工業株式会社
Priority to PCT/JP2012/059984 priority Critical patent/WO2013153648A1/fr
Priority to CN201280072334.9A priority patent/CN104220903B/zh
Priority to JP2014509981A priority patent/JP5973555B2/ja
Publication of WO2013153648A1 publication Critical patent/WO2013153648A1/fr

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    • G02B1/105—
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G02B1/111—Anti-reflection coatings using layers comprising organic materials
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings

Definitions

  • the present invention relates to a transparent resin laminate having high antireflection performance and excellent scratch resistance, particularly surface hardness.
  • an antireflection film has been widely used on front panels of display devices such as CRTs, LCDs, and plasma displays in order to prevent reflection on the surface and make the screen easier to see.
  • a transparent resin laminate having antireflection ability in which a multilayer film is formed on a plastic substrate is also known, for example, on a plastic substrate having translucency, a high refractive index layer, an antireflection layer, a coating layer,
  • a transparent resin laminate having excellent wear resistance, scratch resistance, adhesion, and translucency, which are sequentially laminated, is known (Patent Document 1).
  • electronic devices such as mobile phones and digital cameras have been remarkably advanced, and a display such as a small liquid crystal or organic EL is provided as a display device.
  • the display is usually provided with a transparent resin laminate, and the transparent resin laminate is required to have various characteristics as described below.
  • the transparent resin laminate is required to have various characteristics as described below.
  • transparency and antireflection performance are high.
  • mechanical strength impact resistance, scratch resistance, and high hardness are required.
  • an antistatic ability is required to prevent adverse effects on the equipment due to dust adhesion and charging.
  • the properties of impact resistance, scratch resistance, and high hardness related to mechanical strength are not necessarily side by side, for example, those having high impact resistance and being hard to break may have surface hardness, There was a problem that the scratch resistance was insufficient and the film was easily damaged.
  • Patent Documents 2 and 3 development of an impact-resistant transparent resin laminate having high hardness and excellent scratch resistance has been made (Patent Documents 2 and 3).
  • the surface hardness of the grade that satisfies “4H and no scratch” can be achieved in the pencil hardness test.
  • mobile terminals such as mobile phones, smart (future) phones, tablets, etc. may be subjected to harsh usage environments such as dropping, stepping on, rubbing, etc., having higher surface hardness and anti-reflection ability Transparent resin laminates that are superior to the above have become necessary.
  • An object of the present invention is to solve the above-mentioned problems and to provide a transparent resin laminate having excellent scratch resistance and surface hardness in addition to high impact resistance and antireflection ability.
  • the present inventors have provided a multilayer hard coat layer between the resin substrate and the antireflection layer, and the substrate.
  • a specific silica sol in the hard coat monolayer located on the side it was found that the pencil hardness test expressed a surface hardness of “no scratch at 7H” and other characteristics could be satisfied, The present invention has been completed.
  • the hard coat layer (B) is composed of a hard coat layer I (B1) located on the transparent resin substrate side and a hard coat layer II (B2) located on the antireflection layer side,
  • the hard coat layer I (B1) has a layer thickness of 5 to 20 ⁇ m, and (a) a multifunctional urethane acrylate having 6 or more (meth) acryloyl groups in one molecule, and the multifunctional urethane acrylate 100 (B) a cured product of a curable composition comprising 40 to 200 parts by mass of a surface-treated silica sol with respect to parts by mass
  • the hard coat layer II (B2) has a layer thickness of 1 to 10 ⁇ m, (a) a multifunctional urethane acrylate having 6 or more (meth) acryl
  • the antireflection layer (C) is composed of two layers of the low refractive index layer (C1) and the middle refractive index layer (C2) located on the transparent resin substrate side, and the middle refractive index layer (C2)
  • the refractive index is 1.50 or more and less than 1.75, and the thickness is 50 to 200 nm.
  • the antireflection layer (C) is composed of the low refractive index layer (C1), the middle refractive index layer (C2 ) And a high refractive index layer (C3) provided between the low refractive index layer and the middle refractive index layer.
  • the high refractive index layer (C3) has a refractive index of 1 .60 or more and less than 2.00, the thickness is 50 to 200 nm, and the refractive index of the high refractive index layer (C3) is larger than the refractive index of the middle refractive index layer (C2).
  • a (meth) acryloyl group-modified silica sol or a vinyl group-modified silica sol is preferred.
  • the transparent resin laminate of the present invention is excellent in mechanical strength in addition to high antireflection performance, and in particular, the surface hardness can achieve “7H with no scratch”. Therefore, it can be suitably used as a front panel of not only a general display device but also a device requiring high hardness, such as a mobile phone, a smart (future) phone, and a tablet.
  • the transparent resin laminate of the present invention has a basic structure in which a transparent resin substrate (A), a hard coat layer (B), and an antireflection layer (C) are laminated in this order. Further, these layers (B and C) are characterized by being composed of the specified structure, physical properties and components.
  • the transparent resin substrate is not particularly limited as long as it is a transparent resin that has excellent impact strength and does not obstruct visual field. From the viewpoint of transparency and impact strength, a substrate made of aromatic polycarbonate resin or polymethyl methacrylate resin is preferred. A laminated substrate of an aromatic polycarbonate resin and a polymethyl methacrylate resin may be used. The thickness of the substrate is designed by appropriately selecting from the required transparency and impact strength, but is usually selected from the range of 0.2 to 2.0 mm.
  • Hard coat layer (B) A hard coat layer (B) is laminated on a transparent resin substrate, and the layer (B) includes a hard coat layer I (B1) and a hard coat layer II (B2).
  • the hard coat layer I (B1) and the hard coat layer II (B2) are such that the hard coat layer I (B1) is located on the substrate side, and an antireflection layer (C described later) is formed on the hard coat layer II (B2). ) are stacked.
  • the hard coat layer I (B1) is a layer mainly contributing to hardness, and its film thickness is 5 to 20 ⁇ m, preferably 10 to 20 ⁇ m. If it is less than 5 ⁇ m, the hardness is insufficient, and if it exceeds 20 ⁇ m, appearance defects and post-workability become difficult.
  • the layer comprises (a) a polyfunctional urethane acrylate having 6 or more (meth) acryloyl groups in one molecule (hereinafter also referred to as polyfunctional urethane acrylate) and 100 parts by mass of the polyfunctional urethane acrylate.
  • it is a layer obtained by curing (b) a curable composition comprising 40 to 200 parts by mass of a surface-treated silica sol (hereinafter also referred to as B1 composition).
  • the polyfunctional urethane acrylate is a polymerizable compound obtained by a polyaddition reaction between a diisocyanate compound and a (meth) acrylate compound having a plurality of hydroxyl groups, and particularly has 6 or more (meth) acryloyl groups. It is essential.
  • a dense layer having a high surface hardness can be formed.
  • a compound having less than 6 (meth) acryloyl groups has insufficient surface hardness and poor scratch resistance.
  • diisocyanate compound used as a raw material for the polyaddition reaction examples include aromatic diisocyanates such as tolylene diisocyanate and diphenylmethane diisocyanate, and aliphatic diisocyanates such as 1,6-hexamethylene diisocyanate and 1,3-bis (isocyanatomethyl) cyclohexane.
  • aromatic diisocyanates such as tolylene diisocyanate and diphenylmethane diisocyanate
  • aliphatic diisocyanates such as 1,6-hexamethylene diisocyanate and 1,3-bis (isocyanatomethyl) cyclohexane.
  • the Examples of the (meth) acrylate compound as one raw material include trimethylolpropane (meth) acrylate and pentaerythritol (meth) acrylate. These both raw materials can be used in a quantitative ratio such that the (meth) acryloyl group is 6-fold mol
  • the surface-treated silica sol is a component that imparts extremely high hardness to the transparent resin substrate of the present invention by combining with a polyfunctional urethane acrylate. Therefore, it is important to blend at a ratio of 40 to 200 parts by mass with respect to 100 parts by mass of the polyfunctional urethane acrylate.
  • the surface-treated silica sol the surface of silica particles known per se is treated with a silane coupling agent having an alkoxysilyl group at the terminal, such as 3-methacryloxypropyltriethoxysilane or 3-acryloxypropyltrimethoxysilane (methacrylate).
  • the surface treatment method is not particularly limited, and a conventionally known method is employed.
  • the silane coupling agent is dissolved in an organic solvent containing water, such as methyl alcohol, toluene, methyl isobutyl ketone, methyl isobutyl butyl ketone, to obtain a solution, and silica sol is added to the solution. Heat to about 150 ° C. and stir for about 5 to 30 hours to react.
  • the B1 composition is a composition that becomes the hard coat layer I by being cured, and is contained in a proportion of 40 to 200 parts by mass of the surface-treated silica sol with respect to 100 parts by mass of the polyfunctional urethane acrylate.
  • arbitrary additives can be added in the range which does not impair the objective for the purpose of viscosity adjustment or easy coating property.
  • the thermal polymerization initiator or the photopolymerization initiator is usually a catalytic amount, usually a solid in the composition. Based on the total amount, 0.01 to 20% by mass is added.
  • This polymerization initiator does not substantially affect the properties of the hard coat layer I obtained by curing the B1 composition.
  • the polymerization initiator 2,2′-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy, which acts by ultraviolet rays or electron beams, from the viewpoint of preventing deformation of the transparent resin substrate due to heat.
  • Photopolymerization initiators such as -cyclohexyl-phenyl-ketone, camphorquinone and benzyl are preferred.
  • ⁇ Formation of hard coat layer I> Each of the above essential components (a) and (b) and further optional components are dissolved in the following solvent to form a solution of the B1 composition. After applying this solution to the transparent resin substrate, the solvent is dried at 50 ° C. or higher. And then cured by ultraviolet irradiation to form the hard coat layer I.
  • the thickness of the layer is set in the range of 5 to 20 ⁇ m, preferably 10 to 20 ⁇ m.
  • Solvents used include alcohol solvents such as ethyl alcohol and (iso) propyl alcohol; aromatic solvents such as toluene and xylene; acetate solvents such as (iso) butyl acetate; methyl ethyl ketone (MEK) and methyl isobutyl ketone A ketone solvent such as (MIBK) is suitable. These solvents are removed by evaporation when the hard coat layer I is formed.
  • alcohol solvents such as ethyl alcohol and (iso) propyl alcohol
  • aromatic solvents such as toluene and xylene
  • acetate solvents such as (iso) butyl acetate
  • MEK methyl ethyl ketone
  • MIBK methyl isobutyl ketone solvent
  • the above components constituting the B1 composition are usually mixed with a solvent in any order at room temperature and stirred to form a solution.
  • the coating method of this solution on the transparent resin substrate is not particularly limited, and dip coating method, roll coating method, die coating method, flow coating method, spraying method, etc. are adopted, but appearance quality and film thickness control are adopted. In view of the above, the dip coating method is preferable.
  • the hard coat layer II (B2) is a layer mainly contributing to adhesion with the antireflection layer laminated thereon, and has a film thickness of 1 to 10 ⁇ m. If it is less than 1 ⁇ m, the adhesion is insufficient, and if it exceeds 10 ⁇ m, it is difficult to maintain the appearance.
  • the layer has (c) an average particle diameter of 5 to 30 nm and a refractive index of 1.44 to 1.50 with respect to (a) the polyfunctional urethane acrylate and 100 parts by mass of the polyfunctional urethane acrylate.
  • a curable composition comprising 1 to 50 parts by weight of silica sol, (d) 1 to 30 parts by weight of a silane coupling compound or a hydrolyzate thereof, and (e) 0.1 to 3.0 parts by weight of a metal chelate compound It is a layer made of a cured product (hereinafter also referred to as B2 composition).
  • B2 composition a cured product
  • the silica sol contained in the hard coat layer II (B2) is a particle that contributes to the improvement of scratch resistance, and has an average particle size of 5 to 30 nm and a refractive index of 1.44 to 1.50. When the average particle size is out of the above range, the crack resistance is deteriorated.
  • the silica sol is a single particle, a non-hollow particle having a dense inside and no space inside, and has a density of usually 1.9 g / cm 3 or more. Since the silica sol is known per se and commercially available, a commercially available product satisfying the above average particle diameter and refractive index may be selected and used. Since the silica sol is usually provided in a state of being dispersed in a solvent, this solvent is inevitably mixed in the curable composition solution for forming the hard coat layer II and behaves in the same manner as other solvents. .
  • silane coupling compound or hydrolyzate thereof The silane coupling compound or its hydrolyzate itself hydrolyzes to form a dense siliceous film.
  • this silane coupling compound a well-known thing can be used without a restriction
  • the silane coupling compound is a decomposition product that has been previously hydrolyzed with a dilute acid or the like.
  • the method of hydrolyzing in advance is not particularly limited, and a method of hydrolyzing a part using an acid catalyst such as acetic acid is common.
  • the metal chelate compound is contained for the purpose of increasing the denseness and strength of the layer and further the hardness.
  • the metal chelate compound is a compound in which a chelating agent having a bidentate ligand as a representative example is coordinated to a metal such as titanium, zirconium, or aluminum.
  • Hexafluorophosphate chelate compounds Diethoxy mono (acetylacetonato) aluminum, monoethoxy bis (acetylacetonato) aluminum, di-i-propoxy mono (acetylacetonato) aluminum, monoethoxy bis (ethylacetoacetate) aluminum, diethoxy mono (Ethylacetoacetate) Aluminum chelate compounds such as aluminum can be mentioned.
  • the B2 composition is a curable composition containing the components (a), (c), (d) and (e) as essential components, and is blended at the following specific ratio.
  • the silica sol is blended in an amount of 1 to 50 parts by mass with respect to 100 parts by mass of the polyfunctional urethane acrylate. If the amount is less than 1 part by mass, the scratch resistance does not appear, and if it exceeds 50 parts by mass, the film adhesion deteriorates.
  • the silane coupling compound or the hydrolyzate thereof is blended in an amount of 1 to 30 parts by mass with respect to 100 parts by mass of the polyfunctional urethane acrylate.
  • the metal chelate compound is blended in an amount of 0.1 to 3.0 parts by mass with respect to 100 parts by mass of the polyfunctional urethane acrylate. Outside this range, the adhesion with the antireflection layer C formed on the hard coat film II becomes poor.
  • any additive component can be added in the same manner as the B1 composition. Usually, a polymerization initiator is added for the purpose of accelerating curing, and a solvent is used for the purpose of coating. The preparation method of B2 composition is also performed according to that of B1 composition.
  • the hard coat layer II is directly laminated on the hard coat layer I laminated on the transparent resin substrate to form a two-layer hard coat layer.
  • the hard coat layer II is formed in the same manner as the hard coat layer I in terms of the coating method and the curing method.
  • the thickness of the layer to be formed is set in the range of 1 to 10 ⁇ m.
  • the antireflection layer (C) is directly laminated on the hard coat layer laminated on the transparent resin substrate.
  • the antireflection layer (C) is composed of a low refractive index layer (C1) having a refractive index of less than 1.50 and a thickness of 50 to 200 nm.
  • the low refractive index layer is an antireflection layer that becomes the outermost layer (viewing side).
  • the low refractive index layer (C1) does not exhibit a sufficient antireflection function when the refractive index is 1.50 or more.
  • the low refractive index layer (C1) comprises (f) a silica sol having an average particle diameter of 5 to 150 nm and a refractive index of 1.44 or less, (d) a silane coupling compound or a hydrolyzate thereof, and (e) (F) silica sol is compounded in an amount of 10 to 50% by mass, and (d) the compounding ratio of the silane coupling compound or a hydrolyzate thereof and (e) the metal chelate compound is 60 to 50%. 99% by mass: a layer composed of a cured product of a curable composition (C1 composition) of 40 to 1% by mass.
  • the silica sol contained in the low refractive index layer (C1) is a particle for controlling the refractive index of the layer, and has an average particle diameter of 5 to 150 nm and a refractive index of 1.44 or less.
  • the average particle size is out of the above range, the reflection performance is lowered or the haze ratio is increased.
  • the refractive index exceeds 1.44 the reflection performance decreases.
  • silica sol particles having a hollow interior are suitable.
  • the silica sol is also usually provided in a state of being dispersed in a solvent, the solvent behaves in the same manner as in the case of the (c) silica sol.
  • the (d) silane coupling compound or a hydrolyzate thereof and the (e) metal chelate compound those described above can be used in the same manner.
  • the C1 composition is a curable composition containing the components (f), (d), and (e) as essential components, and is blended at the following specific ratio.
  • the compounding ratio of (d) the silane coupling compound or its hydrolyzate and (e) the metal chelate compound is 60 to 99% by mass: 40 to 1% by mass.
  • the low refractive index layer is laminated on the hard coat layer, specifically, the hard coat II layer laminated on the transparent resin substrate.
  • the low refractive index layer is formed in accordance with the formation of the hard coat layer by applying a solution of the C1 composition onto the hard coat II layer, which is a cured product, and then drying and heating and curing at 70 to 120 ° C. Do it.
  • the thickness of the layer is set in the range of 50 to 200 nm from the viewpoint of antireflection performance.
  • the antireflection layer is composed of two layers of a medium refractive index layer and a low refractive index layer, which will be described later, the medium refractive index layer is first formed on the hard coat II layer, and then on the layer. A low refractive index layer is formed. Furthermore, when the antireflective layer is composed of three layers of a medium refractive index layer, a high refractive index layer, and a low refractive index layer, the medium refractive index layer is first formed on the hard coat II layer, Next, a high refractive index layer is formed on the layer, and a low refractive index layer is formed thereon.
  • the transparent resin laminate of the present invention preferably has a two-layer structure in which an intermediate refractive index layer is laminated on the substrate surface side of the low refractive index layer in order to further enhance the antireflection effect.
  • the medium refractive index layer is preferably a layer having a refractive index of 1.50 or more and less than 1.75 and a thickness of 50 to 200 nm.
  • This medium refractive index layer is typically added to the above-mentioned (d) silane coupling compound or its hydrolyzate 20 to 80 parts by mass and (e) 0.1 to 2 parts by mass of a metal chelate compound, (G) Curing containing 20 to 80 parts by mass of metal oxide particles having a refractive index of 1.70 or more and 2.80 or less ⁇ with the total amount of (d), (e) and (g) being 100 parts by mass ⁇
  • the adhesive composition is cured to form.
  • the middle refractive index layer can contain a thermosetting resin as a binder.
  • thermosetting resins examples include phenol-formaldehyde resins, silane-modified phenol resins, furan-formaldehyde resins, xylene-formaldehyde resins, ketone-formaldehyde resins, urea formaldehyde resins, melamine-formaldehyde resins, alkyd resins, and unsaturated polyester resins.
  • the said thermosetting resin used as a binder has the advantage that it has tolerance with respect to the oxidation by photoactivity.
  • (G) Metal oxide particles are contained for the purpose of satisfying that the refractive index of the medium refractive index layer is 1.50 or more and less than 1.75. Typically, the average particle diameter is 10 to 100 nm. Metal oxide particles having a refractive index of 1.70 or more and 2.80 or less.
  • the middle refractive index layer is laminated on the hard coat layer, specifically, the hard coat II layer laminated on the transparent resin substrate.
  • the medium refractive index layer is formed in the same manner as the low refractive index layer, and the thickness of the layer is set in the range of 50 to 200 nm from the viewpoint of antireflection performance.
  • the transparent resin laminate of the present invention has a three-layer structure in which a high refractive index layer (C3) is laminated between a low refractive index layer (C1) and a middle refractive index layer (C2) in order to exhibit an extremely high antireflection effect.
  • a layer structure is particularly preferable.
  • the high refractive index layer is preferably a layer having a refractive index of 1.60 or more and less than 2.00 and a thickness of 50 to 200 nm.
  • it is essential that the refractive index of the high refractive index layer is higher than the refractive index of the medium refractive index layer.
  • This high refractive index layer is typically composed of the above-mentioned (d) silane coupling compound or its hydrolyzate 10 to 50 parts by mass, and (g) 50 to 90 parts by mass of metal oxide particles ⁇ (d) And the total amount of (g) is 100 parts by mass ⁇ is formed by curing.
  • the metal oxide particles are selected from the above metal oxide particles or a combination thereof so that the refractive index of the high refractive index layer is 1.60 or more and less than 2.00.
  • a thermosetting resin can be contained as a binder.
  • the high refractive index layer is laminated on the medium refractive index layer laminated on the hard coat layer, and then the low refractive index layer is laminated on the high refractive index layer to form a three-layer structure.
  • the high refractive index layer is formed in the same manner as the low refractive index layer, and the thickness of the layer is set in the range of 50 to 200 nm from the viewpoint of antireflection performance.
  • the transparent resin laminate of the present invention is not limited to the one having the above layer structure.
  • an overcoat layer can be provided for the purpose of protecting the antireflection layer.
  • examples of such an overcoat layer include organic polysiloxane materials and fluororesin coat layers that impart wear resistance and scratch resistance.
  • an adhesive layer made of an acrylic, rubber, or silicone adhesive can be provided on the back side of the transparent resin laminate.
  • a hard coat layer (B) and an antireflection layer (C) may be laminated on both the front and back surfaces of the transparent resin substrate.
  • the transmitted light means light transmitted through the transparent resin laminate, and the reflected light means light reflected on the surface of the laminate.
  • ⁇ No flaws were observed when observed with either transmitted light or reflected light.
  • ⁇ Several scratches were observed when observed with transmitted light, but not with reflected light.
  • ⁇ Several scratches were confirmed when observed with either transmitted light or reflected light.
  • ⁇ Ten or more scratches were confirmed when observed with either transmitted light or reflected light.
  • Example 1 On the PMMA side of a laminated resin substrate (PC layer thickness 0.93 mm, PMMA layer thickness 0.07 mm) of 1 mm thick aromatic polycarbonate resin (PC) and polymethyl methacrylate resin (PMMA), the following method is used. A hard coat layer and an antireflection layer were further formed thereon.
  • PC aromatic polycarbonate resin
  • PMMA polymethyl methacrylate resin
  • a laminated resin substrate was dip-coated using a hard coat layer I forming solution having the above composition, dried at 60 ° C. for 5 minutes, and UV cured to form a hard coat layer I having a thickness of 12 ⁇ m.
  • the substrate having the hard coat layer I was dip coated with the solution for forming the hard coat layer II having the above composition, dried at 60 ° C. for 5 minutes, and UV cured to form a hard coat layer II having a thickness of 3 ⁇ m.
  • the substrate having the hard coat layer was dip-coated with an antireflection layer forming solution and heat-treated at 80 ° C. for 20 minutes to form an antireflection layer (low refractive index layer) having a thickness of 100 nm.
  • Example 2 A transparent resin laminate was prepared in the same manner as in Example 1 except that the hard coat layer I forming solution, the hard coat layer II forming solution, and the antireflection layer forming solution shown in Table 1 were used. Measurements were performed in the same manner. The results are shown in Tables 1 and 2.
  • Comparative Examples 1-5 A transparent resin laminate was prepared in the same manner as in Example 1 except that the hard coat layer I forming solution, the hard coat layer II forming solution, and the antireflection layer forming solution shown in Table 2 were used. Measurements were performed in the same manner. The results are shown in Table 3.
  • Example 1 As a result of comparison between Example 1 and Comparative Example 1, if the hard coat layer I contains (A) surface-treated silica sol in an amount of less than 50 parts by mass with respect to 100 parts by mass of the polyfunctional urethane acrylate, the hardness performance deteriorates. I understand that. Further, from Comparative Example 2, when the thickness of the hard coat layer I is not 5 ⁇ m or more, the hardness performance is poor and the scratch resistance is extremely poor. Furthermore, from Comparative Example 3, when the silane coupling agent is not included in the hard coat layer II, both the hardness performance and the scratch resistance are insufficient. From Comparative Example 4, when no silica sol is contained in the hard coat layer II, the scratch resistance is insufficient. From Comparative Example 5, when the hard coat layer II is not present, the hardness performance is insufficient and the scratch resistance is extremely poor.
  • Examples 7-9 It consists of two or three layers by the following method using a solution for forming a low refractive index layer, a solution for forming a medium refractive index layer, and a solution for forming a high refractive index layer as necessary, as shown in Table 3.
  • a transparent resin laminate having an antireflection film was prepared and evaluated. The results are shown in Table 4.
  • the substrate having the hard coat layer was dip coated on the medium refractive index layer forming solution, and heat-treated at 90 ° C. for 30 minutes.
  • a medium refractive index layer having a thickness of 85 nm was formed.
  • the substrate was dip-coated with a solution for forming a low refractive index layer, and heat-treated at 80 ° C. for 20 minutes to form a low refractive index layer having a thickness of 100 nm.
  • the substrate before forming the low refractive index layer, that is, after forming the middle refractive index layer, the substrate was dip coated with the solution for forming the high refractive index layer, and then at 80 ° C. for 20 minutes. Then, heat treatment was performed to form a high refractive index layer having a thickness of 80 nm.

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  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Surface Treatment Of Optical Elements (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention porte sur un stratifié de résine transparente auquel une fonction anti-réflets avancée est ajoutée pour d'excellentes propriétés mécaniques telles qu'une résistance à la rayure et une dureté et qui, en particulier, est apte à atteindre « aucune rayure à 7 H » de dureté de surface. Une double couche de revêtement dur est disposée entre un substrat de résine transparente de PC et de polyméthacrylate de métyle (PMMA) ou similaire, et une couche anti-reflets constituée par une couche de réflectance faible qui est formée sur le substrat de manière à avoir une réflectance inférieure à 1,50 et une épaisseur d'entre 50 nm et 200 nm, et une monocouche de revêtement dur placée sur le côté substrat contient un sol de silice à surface traitée de manière à atteindre une dureté de surface élevée.
PCT/JP2012/059984 2012-04-12 2012-04-12 Stratifié de résine transparente WO2013153648A1 (fr)

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PCT/JP2012/059984 WO2013153648A1 (fr) 2012-04-12 2012-04-12 Stratifié de résine transparente
CN201280072334.9A CN104220903B (zh) 2012-04-12 2012-04-12 透明树脂层叠板
JP2014509981A JP5973555B2 (ja) 2012-04-12 2012-04-12 透明樹脂積層板

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Cited By (10)

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JP2016085451A (ja) * 2014-10-22 2016-05-19 Dic株式会社 ハードコートフィルム及び情報表示装置
JP2016081004A (ja) * 2014-10-22 2016-05-16 Dic株式会社 ハードコートフィルム及び情報表示装置
KR102542685B1 (ko) 2015-11-06 2023-06-12 린텍 가부시키가이샤 투명 도전층 적층용 필름, 그 제조 방법, 및 투명 도전성 필름
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JP2017132833A (ja) * 2016-01-25 2017-08-03 アイカ工業株式会社 紫外線硬化型樹脂組成物及びハードコートフィルム
WO2018084179A1 (fr) * 2016-11-07 2018-05-11 フクビ化学工業株式会社 Substrat transparent antiréflechissant et antiréflechissant et son procédé de fabrication
JP2018077279A (ja) * 2016-11-07 2018-05-17 フクビ化学工業株式会社 防眩性および反射防止性を有する透明基板とその製造方法
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KR102460223B1 (ko) * 2016-11-07 2022-11-01 후구비카가구코오교우가부시끼가이샤 방현성 및 반사 방지성을 가지는 투명 기판과 그 제조 방법
EP3505979A4 (fr) * 2016-11-07 2020-04-08 Fukuvi Chemical Industry Co., Ltd. Substrat transparent antiréflechissant et antiréflechissant et son procédé de fabrication
KR20190100259A (ko) * 2016-12-22 2019-08-28 후구비카가구코오교우가부시끼가이샤 투명 수지 기판
KR102438893B1 (ko) 2016-12-22 2022-08-31 후구비카가구코오교우가부시끼가이샤 투명 수지 기판
JPWO2018117018A1 (ja) * 2016-12-22 2019-10-24 フクビ化学工業株式会社 透明樹脂基板
US11498315B2 (en) 2016-12-22 2022-11-15 Fukuvi Chemical Industry Co., Ltd. Transparent resin substrate
WO2018117018A1 (fr) * 2016-12-22 2018-06-28 フクビ化学工業株式会社 Substrat en résine transparente
US20210103073A1 (en) * 2018-04-19 2021-04-08 Fukuvi Chemical Industry Co., Ltd. Antireflection plate
US11796717B2 (en) * 2018-04-19 2023-10-24 Fukuvi Chemical Industry Co., Ltd. Antireflection plate
WO2022153825A1 (fr) * 2021-01-18 2022-07-21 フクビ化学工業株式会社 Substrat antireflet
JP7389765B2 (ja) 2021-01-18 2023-11-30 フクビ化学工業株式会社 反射防止基板
WO2023058454A1 (fr) * 2021-10-05 2023-04-13 フクビ化学工業株式会社 Stratifié antireflet

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