WO2013128697A1 - Stratifié de résine résistant aux rayures, matériau de revêtement avant pour des dispositifs d'affichage, et dispositif d'affichage d'image - Google Patents

Stratifié de résine résistant aux rayures, matériau de revêtement avant pour des dispositifs d'affichage, et dispositif d'affichage d'image Download PDF

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Publication number
WO2013128697A1
WO2013128697A1 PCT/JP2012/075181 JP2012075181W WO2013128697A1 WO 2013128697 A1 WO2013128697 A1 WO 2013128697A1 JP 2012075181 W JP2012075181 W JP 2012075181W WO 2013128697 A1 WO2013128697 A1 WO 2013128697A1
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Prior art keywords
resin
resin layer
scratch
acrylic
curable
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PCT/JP2012/075181
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English (en)
Japanese (ja)
Inventor
佐藤記央
河野正彦
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三菱樹脂株式会社
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Application filed by 三菱樹脂株式会社 filed Critical 三菱樹脂株式会社
Priority to KR1020137009511A priority Critical patent/KR101413900B1/ko
Priority to JP2012544990A priority patent/JP5237506B1/ja
Priority to KR1020147006664A priority patent/KR20140118976A/ko
Priority to KR1020137010983A priority patent/KR20140118692A/ko
Priority to CN201280003820.5A priority patent/CN103402765B/zh
Publication of WO2013128697A1 publication Critical patent/WO2013128697A1/fr
Priority to HK14104521.4A priority patent/HK1191295A1/xx

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/022—Mechanical properties
    • 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
    • G02B1/14—Protective coatings, e.g. hard coatings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays

Definitions

  • the present invention is a surface protection panel used by being arranged on the front side (viewing side) of an image display device.
  • the present invention relates to a conductive resin laminate.
  • glass has been widely used from the viewpoint of hardness, heat resistance, and transparency in the fields of display covers for electronic devices.
  • glass is easily broken by impact and the weight of the glass itself is heavy, an alternative to plastic is being studied.
  • acrylic resins are widely used because of their high transparency and excellent surface hardness.
  • acrylic resins are very brittle, the processing method is generally performed by cutting, and it cannot be said that the productivity is high.
  • an acrylic resin when it comes into contact with a hard material such as steel wool, there is a problem that the matrix resin portion has a low scratch resistance and is easily damaged.
  • Patent Document 1 an acrylic resin layer mainly composed of an acrylic resin having a thickness of 10 to 40 ⁇ m is laminated on both surfaces or one surface of a resin sheet composed of a resin material mainly composed of a polycarbonate resin,
  • a polycarbonate resin laminated sheet for punching which has a total thickness of 0.2 to 2.0 mm by laminating a hard coat layer on an acrylic resin layer.
  • Such a resin laminated sheet has the properties of high productivity and excellent scratch resistance by having excellent punching processability.
  • the thickness of the layer containing the acrylic resin which comprises the laminated body containing polycarbonate resin, and the total thickness of this laminated body are controlled to a specific range, and also on the layer containing an acrylic resin, or the layer containing an acrylic resin
  • a laminate including a polycarbonate resin suitable for a liquid crystal display cover having a balanced surface hardness, particularly pencil hardness, and impact resistance has been proposed by performing a hard coat treatment on a substrate including a polycarbonate resin.
  • a method of laminating a hard coat layer composed of an ultraviolet curable resin or the like with a predetermined thickness is generally used.
  • surface hardness such as scratch resistance and abrasion resistance is improved by the laminated scratch-resistant resin layer.
  • Patent Document 3 a scratch-resistant resin layer having a thickness of 1 to 5 ⁇ m is laminated on a substrate composed of an acrylic resin as a thermoplastic matrix resin containing a hard dispersed phase. Resin laminates have been proposed. This scratch-resistant resin laminate has the property that even if the base material composed of an acrylic resin is different from the resin material, warping, undulation, peeling, etc. do not occur with the curing and shrinkage of the resin. .
  • the scratch-resistant resin disclosed in Patent Document 3 has a configuration in which a thermoplastic resin, which is a matrix resin, includes a hard resin obtained by radical polymerization as a dispersed phase. This disperse phase improves the scratch resistance of the resin molded body, but there is still room for improvement from the viewpoint of surface hardness such as pencil hardness.
  • an object of the present invention is to provide a scratch-resistant resin laminate having a scratch-resistant function as a high surface hardness while solving the problems of warping and waviness.
  • the present invention comprises a structure in which a curable resin layer (B) containing an organic / inorganic hybrid hard coating agent is laminated on both sides or one side of an acrylic resin layer (A) containing an acrylic resin as a main component.
  • a characteristic scratch-resistant resin laminate is proposed.
  • the present invention also provides an organic / inorganic hybrid system on at least one surface of a resin laminate in which an acrylic resin layer (A) containing an acrylic resin as a main component is laminated on both surfaces or one surface of a resin substrate (C). Proposed is a scratch-resistant resin laminate comprising a structure in which a curable resin layer (B) containing a hard coating agent is laminated.
  • the scratch-resistant resin laminate proposed by the present invention comprises a curable resin layer (B) containing an organic / inorganic hybrid hard coating agent, thereby eliminating the problems of warpage and undulation, and having a high surface hardness. It can have a scratch resistance function. More preferably, in the resin laminate having a specific configuration, by applying a curable resin layer (B) containing an organic / inorganic hybrid hard coating agent, a higher surface is provided while providing excellent punching workability. It can have a high scratch resistance function. Therefore, the scratch-resistant resin laminate can be suitably used as a front cover material for liquid crystal displays, particularly as a front cover material for mobile phones or liquid crystal pen tablets having a touch panel function.
  • the present resin laminate a scratch-resistant resin laminate as an example of an embodiment of the present invention will be described.
  • the present invention is not limited to this resin laminate.
  • This resin laminate has a configuration in which a curable resin layer (B) containing an organic / inorganic hybrid hard coating agent is laminated on both sides or one side of an acrylic resin layer (A) containing an acrylic resin as a main component. . More preferably, the present resin laminate has at least one surface on a resin laminate in which an acrylic resin layer (A) containing an acrylic resin as a main component is laminated on both sides or one side of the resin base material (C). And a curable resin layer (B) containing an organic / inorganic hybrid hard coating agent.
  • the acrylic resin layer (A) is a layer containing an acrylic resin as a main component.
  • the monomer constituting the acrylic resin include methyl methacrylate, methacrylic acid, acrylic acid, benzyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl ( (Meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, glycidyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2-methoxyethyl (meth) Acrylate, 2-ethoxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate
  • the acrylic resin layer (A) is preferably composed of a hard resin layer (a) having a pencil hardness of 3H or more. By forming the acrylic resin layer (A) with such a high surface hardness, it is possible to obtain advantages such as imparting extremely high surface hardness to the resin laminate.
  • the pencil hardness of the acrylic resin layer (A) is more preferably 4H or more, and further preferably 5H or more.
  • the acrylic resin layer (A) is composed of a hard resin layer (a) containing and dispersed in the acrylic resin a hard dispersed phase material that has better heat resistance or scratch resistance than the acrylic resin.
  • the method of forming is mentioned.
  • thermosetting resins examples include thermosetting resins. Specifically, polycondensation such as phenol resin, amino resin, epoxy resin, silicone resin, thermosetting polyimide resin, and thermosetting polyurethane resin.
  • addition polymerization resins such as thermosetting acrylic resins, vinyl ester resins, unsaturated polyester resins, diallyl phthalate resins, and the like can be given. However, it is not limited to these. You may use a thermosetting resin individually or in combination of 2 or more types. Moreover, you may use combining these thermoplastic resins and the thermoplastic resin which has an unsaturated bond which can be bridge
  • Examples of the shape of the hard dispersed phase include particles, spheres, lines, fibers, and the like. From the viewpoint of being easily dispersed evenly in the acrylic resin that is a thermoplastic matrix resin, a sphere is preferable. However, it is not limited to this.
  • the particle size of the hard dispersed phase is appropriately set according to the purpose and application of the present resin laminate, but is preferably 0.1 to 1000 ⁇ m.
  • the blending amount of the hard dispersed phase in the acrylic resin layer (A) is appropriately set depending on the purpose and application of the resin laminate, but is preferably 0.1 to 60% by weight.
  • thermosetting resin material constituting a hard dispersed phase is added to the acrylic resin material.
  • a hard dispersed phase can be formed by causing phase separation and crosslinking.
  • the thermosetting resin may be molded into a particulate form in advance, added to the acrylic resin, and kneaded and molded at a temperature at which the thermosetting resin does not dissolve.
  • the thickness of the acrylic resin layer (A) is preferably 40 ⁇ m or more.
  • the thickness of the acrylic resin layer (A) is 40 ⁇ m or more, there is no possibility that the effect of improving the scratch resistance due to the contribution of the acrylic resin layer cannot be obtained.
  • the thickness of the acrylic resin layer (A) is more preferably 50 ⁇ m or more.
  • the thickness of the acrylic resin layer (A) is preferably 200 ⁇ m or less, and more preferably 100 ⁇ m or less.
  • This resin laminated body has a curable resin layer (B).
  • the curable resin layer (B) includes an organic / inorganic hybrid hard coating agent, and is a layer that plays a role of imparting high scratch resistance to the resin laminate without causing warpage or undulation.
  • the curable resin layer (B) can be formed, for example, by laminating it as a coating film on another layer using a paint containing an organic / inorganic hybrid hard coating agent. However, it is not limited to this method. A known method is used as a method of laminating with other layers.
  • laminating method using cover film, dip coating method, natural coating method, reverse coating method, comma coater method, roll coating method, spin coating method, wire bar method, extrusion method, curtain coating method, spray coating method, The gravure coat method etc. are mentioned.
  • a method of laminating the curable resin layer (B) on another layer using a transfer sheet in which the curable resin layer (B) is bonded to the release layer may be employed.
  • organic / inorganic hybrid coating agent examples include those composed of a curable resin composition containing an inorganic component having a reactive functional group.
  • Such an organic / inorganic hybrid coating agent utilizes an inorganic component having a reactive functional group.
  • the inorganic component is copolymerized and crosslinked with a radical polymerizable monomer, whereby an inorganic component is added to the organic binder.
  • curing shrinkage hardly occurs and high scratch resistance can be exhibited.
  • an organic / inorganic hybrid coating agent containing ultraviolet-reactive silica as an inorganic component having a reactive functional group can be mentioned. More preferable examples include organic / inorganic hybrid coating agents containing ultraviolet-reactive colloidal silica. Moreover, polyfunctional (meth) acrylate is mentioned as a radically polymerizable monomer.
  • bifunctional (meth) acrylate ethylene oxide-modified diacrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di ( (Meth) acrylate, bisphenol A ethylene oxide modified diacrylate, dimethylol-tricyclodecane di (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, epoxy (meth) diacrylate, urethane ( And (meth) diacrylate.
  • trifunctional or higher polyfunctional (meth) acrylates include pentaerythritol hexaacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol ethoxytetraacrylate, trimethylolpropane tri (meth) acrylate, and trimethylolpropane triethoxy (meth).
  • examples include acrylate, urethane tri (meth) acrylate, urethane tetra (meth) acrylate, urethane hexa (meth) acrylate, polyester tetra (meth) acrylate, and polyester hexa (meth) acrylate.
  • monofunctional (meth) acrylates can be added as appropriate for the purpose of adjusting the cure shrinkage and viscosity and improving the solubility of a small amount of additives in the hard coat.
  • Monofunctional (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, tert-butyl (meth) acrylate, isobornyl (meth) acrylate, octyl (meth) acrylate, isodecyl (meth) acrylate, methoxypolyethylene (Meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, phenoxyethyl (meth) acrylate, etc. are mentioned.
  • the content of the inorganic component having a reactive functional group in the organic / inorganic hybrid coating agent is preferably 5% by mass or more and less than 65% by mass for reasons such as surface hardness, transparency, and punchability.
  • the content is more preferably 10% by weight or more and less than 50% by weight, and most preferably 15% by weight or more and less than 50% by weight.
  • a curable resin layer (B) contains a leveling agent as a surface adjustment component.
  • the leveling agent include silicone leveling agents and acrylic leveling agents.
  • those having a reactive functional group at the terminal are preferable, and those having a reactive functional group having two or more functionalities are more preferable. preferable.
  • polyether-modified polydimethylsiloxane having an acrylic group having double bonds at both ends for example, “BYK-UV 3500” and “BYK-UV 3530” manufactured by Big Chemie Japan Co., Ltd.
  • polyester-modified polydimethylsiloxane having an acrylic group having two double bonds at the end (“BYK-UV 3570” manufactured by BYK Japan).
  • polyester-modified polydimethylsiloxane having an acrylic group that has a stable haze value and contributes to improvement of scratch resistance is particularly preferable.
  • the curable resin layer (B) preferably contains a lubricant.
  • the lubricant include silicon compounds, fluorine compounds, and mixed compounds thereof. By adding these, slipperiness can be improved.
  • the curable resin layer (B) may contain, for example, an ultraviolet absorber, a light stabilizer, an antioxidant, and an antistatic agent as necessary.
  • the thickness of the curable resin layer (B) is preferably in the range of 5 to 15 ⁇ m. When the thickness is 5 ⁇ m or more, the effect of improving the scratch resistance by the curable resin layer (B) is sufficiently obtained. On the other hand, when the thickness is 15 ⁇ m or less, the ultraviolet curing that constitutes the curable resin layer (B). There is no risk of warping, undulation, peeling or the like accompanying the curing / shrinking of the functional resin. Furthermore, there is no possibility that the transparency is remarkably impaired by the ultraviolet curable resin layer.
  • the present resin laminate can achieve high hardness even with a thin resin laminate due to the synergistic effect of the acrylic resin layer (A) containing the hard dispersed phase and the curable resin layer (B).
  • the thickness of the acrylic resin layer (A) is 200 ⁇ m, which is the upper limit of the above preferred range, and the thickness of the curable resin layer (B) is less than 5 ⁇ m, High hardness cannot be achieved.
  • the thickness of the acrylic resin layer (A) is 40 ⁇ m, which is the lower limit of the above preferred range, and the thickness of the curable resin layer (B) exceeds 15 ⁇ m, There is a risk of warping and swell.
  • the thickness of the acrylic resin layer (A) is 50 ⁇ m or more and 200 ⁇ m or less as a lamination ratio, and the curable resin layer (B). It is particularly preferable that the thickness of the film is 5 to 15 ⁇ m.
  • the curable resin layer shrinks upon curing, and may cause curling when laminated with other layers. Since the shrinkage ratio of the curable resin layer tends to be proportional to the thickness of the curable resin layer, it is not practical from the viewpoint of curling to achieve high hardness only by the thickness of the curable resin layer.
  • the curl accompanying the curing shrinkage of the resin laminate is preferably 3 mm or less, and more preferably 2 mm or less.
  • a resin base material (C) is a layer which plays the role which provides punching workability to this resin laminated body.
  • the resin substrate (C) includes polycarbonate (PC) resin, triacetyl cellulose (TAC) resin, polyethylene terephthalate (PET) resin, polymethyl methacrylate (PMMA) resin, methyl methacrylate-styrene copolymer (MS) resin, polysulfone resin, norbornene resin and cycloolefin resin are preferably formed from a resin composition containing at least one of them.
  • a resin base material (C) is comprised from transparent resin.
  • the resin base material (C) is particularly preferably formed from a polycarbonate resin in view of transparency, impact resistance, heat resistance and the like.
  • the polycarbonate resin can be obtained, for example, by an interfacial polymerization method in which an aromatic dihydroxy compound or a small amount of a polyhydroxy compound is reacted with phosgene.
  • the aromatic dihydroxy compound include bisphenol A synthesized from bisphenol and acetone.
  • other bisphenol A can be produced by a transesterification method, a pyridine method or the like using a raw material as a raw material.
  • polyester carbonates obtained by copolymerization of bisphenol A and dicarboxylic acid derivatives such as tere (iso) phthalic acid dichloride, bisphenol A derivatives such as those obtained by polymerization of tetramethylbisphenol A and the like. can do.
  • the molecular weight of the polycarbonate-based resin is preferably a molecular weight that can produce a sheet by ordinary extrusion molding.
  • the viscosity average molecular weight is 15000 to 40000, preferably 20000 to 35000, and more preferably 22000 to 30000. It is. If the molecular weight is smaller than this, the impact strength of the sheet obtained from the composition is lowered, which is not preferable. On the other hand, if the molecular weight is larger than this, the fluidity is lowered and the extrusion moldability may be deteriorated.
  • the resin laminate needs to have an acrylic resin layer (A) and a curable resin layer (B) containing an organic / inorganic hybrid coating agent. Further preferably, a resin base material (C) is further provided. More specifically, (B) / (A), (B) / (A) / (B), (B) / (A) / (C), (B) / (A) / (C) / (B), (B) / (C) / (A) / (B), (B) / (A) / (C) / (A) and (B) / (A) / (C) / (A ) / (B).
  • FIG. 1 illustrates the configuration of an embodiment of the present resin laminate.
  • the resin laminate 12 has an acrylic resin layer 13 laminated on one side of the resin base material 12.
  • a scratch-resistant resin laminate 15 having a configuration in which a curable resin layer 14 is laminated on one side is illustrated.
  • the synergistic effect of the acrylic resin layer 13 and the curable resin layer 14 has an advantage that high surface hardness can be exhibited even when the thickness of the curable resin layer is as thin as 5 to 15 ⁇ m.
  • FIG. 1B the scratch-resistant resin laminate 11 having a structure in which a curable resin layer 14 is laminated on both surfaces of a resin laminate in which an acrylic resin layer 13 is laminated on one surface of a resin substrate 12 is shown.
  • the method for producing the resin laminate is not particularly limited, and a known method can be adopted.
  • the apparatus for producing the resin laminate is constituted by, for example, one main extruder that extrudes a polycarbonate resin and a sub-extruder that extrudes an acrylic resin that constitutes an acrylic resin layer.
  • the sub-extruder is smaller than the main extruder.
  • the temperature condition of the main extruder is usually 230 to 290 ° C, preferably 240 to 280 ° C, and the temperature condition of the sub-extruder is usually 220 to 270 ° C, preferably 230 to 260 ° C.
  • a known method such as a feed block method or a multi-manifold method can be used.
  • the molten resin laminated in the feed block is guided to a sheet forming die such as a T die, and after being formed into a sheet shape, flows into a forming roll (metal elastic roll or polishing roll) whose surface is mirror-finished.
  • a forming roll metal elastic roll or polishing roll
  • the sheet-like molded product is mirror-finished and cooled while passing through the molding roll, thereby forming a laminate.
  • the molten resin laminated in the die is similarly formed into a sheet inside the die, and then surface-finished and cooled by a forming roll to form a laminated body.
  • the temperature of the die is usually 210 to 300 ° C., preferably 230 to 280 ° C.
  • the molding roll temperature is usually 100 to 190 ° C., preferably 110 to 180 ° C.
  • a vertical roll or a horizontal roll can be appropriately used.
  • This resin laminate is useful as a front cover material for a surface protection panel used by being arranged on the front side (viewing side) of an image display device, particularly a mobile phone or a liquid crystal pen tablet having a touch panel function.
  • film refers to a thin flat product that is extremely small compared to its length and width and whose maximum thickness is arbitrarily limited, and is usually supplied in the form of a roll (Japan) Industrial standard JISK6900), and in general, “sheet” refers to a product that is thin by definition in JIS and generally has a thickness that is small instead of length and width.
  • sheet refers to a product that is thin by definition in JIS and generally has a thickness that is small instead of length and width.
  • main component in the present specification includes the meaning of allowing other components to be contained within a range that does not hinder the function of the main component unless otherwise specified.
  • the main component (when two or more components are main components, the total amount thereof) is 50% by mass or more, preferably 70% in the composition. It occupies at least 90% by mass, particularly preferably at least 90% by mass (including 100%).
  • X is preferably greater than X” and “preferably Y”, with the meaning of “X to Y” unless otherwise specified. It means “smaller”.
  • X or more when expressed as “X is an arbitrary number), it means “preferably larger than X” unless otherwise specified, and “Y or less” (Y is an arbitrary number). ) Includes the meaning of “preferably smaller than Y” unless otherwise specified.
  • a cured resin layer was formed by a method similar to the method described in each example and comparative example, using 125 ⁇ m of A4 size PET film (trade name “Diafoil”, manufactured by Mitsubishi Plastics) as a resin base material. A central portion of each sample was cut into a 10 cm square and used as a test sample. In the evaluation, the warpage of the four corners was measured with a ruler, and the average value of the four points was taken as the curl value in the test sample.
  • Example 1 A layer composed of a mixture of 80 parts by mass of polycarbonate resin (trade name “Iupilon S1000” manufactured by Mitsubishi Engineering Plastics) and 20 parts by mass of PCTG (trade name “SKYGREEN J2003”) as a base resin, hard A layer made of an acrylic resin (trade name “Altoglas HT121” manufactured by Arkema Co., Ltd.) having a conductive dispersed phase is extruded using an extruder, and the thickness of the base resin layer is 560 ⁇ m and the thickness of the acrylic resin layer is 140 ⁇ m.
  • the laminate a was formed by coextrusion so that the thickness of the body was 700 ⁇ m.
  • Organic / inorganic hybrid UV curable hard coating agent (trade name “EKS1105”, manufactured by DIC Corporation, content of inorganic component (silica) having UV reactive functional group) on the surface of the acrylic resin layer of the laminate a: 15 to 25 mass%)
  • EKS1105 organic / inorganic hybrid UV curable hard coating agent
  • a mixed solution of 10 parts by mass, Irgacure 184 (manufactured by Ciba Japan), and 2 parts by mass of MEK was applied using a bar coater, dried at 70 ° C. for 3 minutes, and then 500 mJ / cm 2.
  • the resin laminate 1 having a thickness of the curable resin layer after drying of 5 ⁇ m was obtained.
  • Organic / inorganic hybrid UV-curable hard coating agent (trade name “UVHC7800”, product name “UVHC7800”, ultraviolet ray-reactive functional group, manufactured by Momentive, Inc.) on the surface of the acrylic resin layer of the laminate a: 40 to 50 % By weight) is applied using a bar coater, dried at 90 ° C. for 1 minute, exposed at an exposure amount of 500 mJ / cm 2 , and a resin laminate 2 having a curable resin layer thickness of 6 ⁇ m after drying is obtained. Obtained.
  • Example 3 Except for adding 5 parts of 100 parts hard coating agent to polyester-modified polydimethylsiloxane having an acrylic group (trade name “BYK-UV3570”, manufactured by Big Chemie Japan Co., Ltd.) as a leveling agent. In the same manner as in Example 2, a resin laminate 3 having a dried curable resin layer thickness of 6 ⁇ m was obtained.
  • Organic / inorganic hybrid UV curable hard coating agent (trade name “EXCRATE RUA-069VE”, an inorganic component (silica) content having UV reactive functional group on the surface of the acrylic resin layer of laminate a : 5 to 15% by mass) using a bar coater, dried at 90 ° C. for 1 minute, exposed at an exposure amount of 500 mJ / cm 2 , and a curable resin layer having a thickness of 6 ⁇ m after drying.
  • a laminate 4 was obtained.
  • Organic / inorganic hybrid UV-curable hard coating agent (trade name “UVHC7300”, manufactured by Momentive, Inc., trade name “UVHC7300”) on the surface of the acrylic resin layer of the laminate a Content: 10 to 20 Mass%) is applied using a bar coater, dried at 90 ° C. for 1 minute, exposed at an exposure amount of 500 mJ / cm 2 , and a resin laminate 5 having a dried curable resin layer thickness of 6 ⁇ m is obtained. Obtained.
  • a laminate b composed of an acrylic resin layer having a thickness of 700 ⁇ m was molded from an acrylic resin having a hard dispersed phase (trade name “Altglas HT121” manufactured by Arkema Co., Ltd.) with an extruder.
  • An organic / inorganic hybrid ultraviolet curable hard coating agent (trade name “UVHC7800”, an inorganic component (silica) content having an ultraviolet reactive functional group: 40 to 50% by mass) manufactured by Momentive, Inc.) on one side of the laminate b, It applied using a bar coater, dried at 90 ° C. for 1 minute, and then exposed at an exposure amount of 500 mJ / cm 2 to obtain a resin laminate 6 having a dried curable resin layer thickness of 6 ⁇ m.
  • Ultraviolet curable hard coating agent of main component urethane acrylate (trade name “EXCERATE RUA-066VE”) 10 parts by mass, Irgacure 184 (Ciba Japan Co., Ltd.) 0 .02 parts by mass and MEK 15 parts by mass are mixed using a bar coater, dried at 70 ° C. for 5 minutes, exposed at an exposure amount of 500 mJ / cm 2 , and the thickness of the curable resin layer after drying. Of 7 ⁇ m was obtained.
  • ⁇ Comparative example 2> A UV curable hard coating agent (product name “UVHC1101”, manufactured by Momentive Co., Ltd.) of the main component urethane acrylate is applied to the surface of the acrylic resin layer of the laminate a using a bar coater and dried at 90 ° C. for 1 minute. The resin laminate 8 was exposed with an exposure amount of 500 mJ / cm 2 and the thickness of the curable resin layer after drying was 8 ⁇ m.
  • An organic / inorganic hybrid ultraviolet curable hard coating agent (product name “UVHC7800”, an inorganic component (silica) content having an ultraviolet reactive functional group: 40 to 50% by mass) manufactured by Momentive, Inc.) on one side of the resin sheet c, It apply
  • UVHC7800 an inorganic component (silica) content having an ultraviolet reactive functional group: 40 to 50% by mass
  • a single layer resin sheet d having a thickness of 700 ⁇ m was formed using an acrylic resin (trade name “Acrypet VH001” manufactured by Mitsubishi Rayon Co., Ltd.) having no hard dispersed phase.
  • a UV curable hard coating agent (manufactured by Asia Industry Co., Ltd., trade name “EXCERATE RUA-066VE”) of the main component urethane acrylate was applied to one side of the resin sheet d using a bar coater, dried at 70 ° C. for 5 minutes, It exposed with the exposure amount of 500 mJ / cm ⁇ 2 >, and obtained the resin laminated body 10 whose thickness of the curable resin layer after drying is 6 micrometers.
  • ⁇ Curl test 2> A cured resin layer was formed by the same method as that described in each example and comparative example, using the following laminate d as a resin substrate. A central portion of each sample was cut into a 10 cm square and used as a test sample. In the evaluation, the warpage of the four corners was measured with a ruler, and the average value of the four points was taken as the curl value in the test sample. The curl value is a value including the thermal expansion of the original fabric.
  • ⁇ Haze> It measured using NDH5000 (made by Nippon Denshoku Industries Co., Ltd.) as a test apparatus with respect to the test sample of the resin laminated body 5cm square of an Example and a comparative example. The test was performed according to JIS K 7136, and the average value was taken as the haze value in the test sample.
  • Example 7 A layer composed of a mixture of 80 parts by mass of a polycarbonate resin (manufactured by Sumika Stylon, trade name “CALIBER 301-4”) and 20 parts by weight of PCTG (trade name “SKYGREEN J2003”) as a base resin, a hard A layer made of an acrylic resin (trade name “Altglas HT121” manufactured by Arkema Co., Ltd.) having a conductive disperse phase is extruded using an extruder and the thickness of the base resin layer is 240 ⁇ m and the thickness of the acrylic resin layer is 60 ⁇ m.
  • the laminate d was formed by coextrusion so that the thickness of the body was 300 ⁇ m.
  • Organic / inorganic hybrid ultraviolet curable hard coating agent (trade name “EKS1105”, manufactured by DIC Corporation, content of inorganic component (silica) having an ultraviolet reactive functional group) on the surface of the acrylic resin layer of the laminate d: 15 to 25 mass%)
  • EKS1105 organic / inorganic hybrid ultraviolet curable hard coating agent
  • a mixed solution of 10 parts by mass, Irgacure 184 (manufactured by Ciba Japan), and 2 parts by mass of MEK was applied using a bar coater, dried at 70 ° C. for 3 minutes, and then 500 mJ / cm 2.
  • the resin laminate 11 having a thickness of the curable resin layer after drying of 12 ⁇ m was obtained.
  • Organic / inorganic hybrid UV-curable hard coating agent (trade name “UVHC7800”, product name “UVHC7800”, ultraviolet ray-reactive functional group, manufactured by Momentive, Inc.) on the surface of the acrylic resin layer of the laminate d: 40 to 50 Mass%) is applied using a bar coater, dried at 90 ° C. for 1 minute, exposed at an exposure amount of 500 mJ / cm 2 , and a resin laminate 12 having a dried curable resin layer thickness of 12 ⁇ m is obtained. Obtained.
  • Example 9 Except for adding 5 parts of 100 parts hard coating agent to polyester-modified polydimethylsiloxane having an acrylic group (trade name “BYK-UV3570”, manufactured by Big Chemie Japan Co., Ltd.) as a leveling agent. In the same manner as in Example 2, a resin laminate 13 having a dried curable resin layer thickness of 12 ⁇ m was obtained.
  • Organic / inorganic hybrid UV curable hard coating agent (trade name “EXCRATE RUA-069VE”, inorganic component (silica) content having a UV-reactive functional group on the surface of the acrylic resin layer of the laminate d) : 5 to 15% by mass) using a bar coater, dried at 90 ° C. for 1 minute, exposed at an exposure amount of 500 mJ / cm 2 , and a curable resin layer having a thickness of 12 ⁇ m after drying.
  • a laminate 14 was obtained.
  • Organic / inorganic hybrid ultraviolet curable hard coating agent (trade name “UVHC7300”, manufactured by Momentive, Inc., trade name “UVHC7300”) on the surface of the acrylic resin layer of the laminate d Content: 10 to 20 Mass%) is applied using a bar coater, dried at 90 ° C. for 1 minute, exposed at an exposure amount of 500 mJ / cm 2 , and a resin laminate 15 having a dried curable resin layer thickness of 12 ⁇ m is obtained. Obtained.
  • Ultraviolet curable hard coating agent of main component urethane acrylate (trade name “EXCRATE RUA-066VE”, manufactured by Asia Kogyo Co., Ltd.) 10 parts by mass on the surface of the acrylic resin layer of laminate d, Irgacure 184 (Ciba Japan Co., Ltd.) 0 .02 parts by mass and MEK 15 parts by mass are mixed using a bar coater, dried at 70 ° C. for 5 minutes, exposed at an exposure amount of 500 mJ / cm 2 , and the thickness of the curable resin layer after drying. Of 12 ⁇ m was obtained.
  • main component urethane acrylate trade name “EXCRATE RUA-066VE”, manufactured by Asia Kogyo Co., Ltd.
  • Irgacure 184 Ciba Japan Co., Ltd.
  • MEK 15 parts by mass are mixed using a bar coater, dried at 70 ° C. for 5 minutes, exposed at an exposure amount of 500 mJ / cm 2
  • UV curable hard coating agent product name “UVHC1101”, manufactured by Momentive Co., Ltd.
  • UVHC1101 manufactured by Momentive Co., Ltd.
  • the resin laminate 17 was exposed at an exposure amount of 500 mJ / cm 2 and the thickness of the curable resin layer after drying was 12 ⁇ m.
  • Example 12 A layer composed of a mixture of 80 parts by mass of a polycarbonate resin (manufactured by Sumika Stylon, trade name “CALIBER 301-4”) and 20 parts by weight of PCTG (trade name “SKYGREEN J2003”) as a base resin, a hard A layer made of an acrylic resin (trade name “Altglas HT121” manufactured by Arkema Co., Ltd.) having a conductive dispersed phase is extruded using an extruder, and the thickness of the base resin layer is 105 ⁇ m and the thickness of the acrylic resin layer is 20 ⁇ m.
  • the laminate e was formed by coextrusion so that the thickness of the body was 125 ⁇ m.
  • Organic / inorganic hybrid ultraviolet curable hard coating agent (trade name “UVHC7800F” manufactured by MOMENTIVE, inorganic component having an ultraviolet reactive functional group (silica)) on the surface of the acrylic resin layer of the laminate e: 30-40% by mass) using a bar coater, dried at 90 ° C. for 1 minute, exposed at an exposure amount of 500 mJ / cm 2 , and a curable resin layer having a thickness of 10 ⁇ m after drying. Body 18 was obtained.
  • Ultraviolet curable hard coating agent of main component urethane acrylate (trade name “EXCRATE RUA-066VE”, manufactured by Asia Kogyo Co., Ltd.) 10 parts by mass, Irgacure 184 (Ciba Japan Co., Ltd.) 0 .02 parts by mass and MEK 15 parts by mass are mixed using a bar coater, dried at 70 ° C. for 5 minutes, exposed at an exposure amount of 500 mJ / cm 2 , and the thickness of the curable resin layer after drying. Of 10 ⁇ m was obtained.
  • main component urethane acrylate trade name “EXCRATE RUA-066VE”, manufactured by Asia Kogyo Co., Ltd.
  • Irgacure 184 Ciba Japan Co., Ltd.
  • MEK 15 parts by mass are mixed using a bar coater, dried at 70 ° C. for 5 minutes, exposed at an exposure amount of 500 mJ / cm 2 , and the thickness of the curable resin layer after drying

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)
  • Paints Or Removers (AREA)

Abstract

La présente invention porte sur un stratifié en résine résistant aux rayures qui a une fonction de résistance aux rayures, sous la forme d'une dureté de surface élevée, tout en résolvant les problèmes de gauchissement, de productivité, et analogues. L'invention porte sur un stratifié de résine résistant aux rayures, lequel stratifié a une configuration dans laquelle une couche de résine durcissable (B) qui contient un agent de revêtement dur hybride organique-minéral est stratifié sur les deux surfaces ou sur une surface d'une couche de résine acrylique (A) qui contient une résine acrylique comme composant principal. Ce stratifié de résine résistant aux rayures est caractérisé en ce que : la couche de résine acrylique (A) est une résine dure (a) qui a une phase dispersée dure dans une matrice de couche de résine acrylique; l'agent de revêtement dur hybride organique-minéral est constitué par une composition de résine durcissable qui contient un composant minéral ayant un groupe fonctionnel réactif; la couche de résine durcissable (B) a une épaisseur à l'intérieur de la plage de 5 à 15 µm; et la surface sur laquelle la couche de résine durcissable (B) est stratifiée a une dureté de surface de 7 H ou plus.
PCT/JP2012/075181 2012-02-28 2012-09-28 Stratifié de résine résistant aux rayures, matériau de revêtement avant pour des dispositifs d'affichage, et dispositif d'affichage d'image WO2013128697A1 (fr)

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KR1020137009511A KR101413900B1 (ko) 2012-02-28 2012-09-28 내찰상성 수지 적층체, 디스플레이의 프론트 커버재 및 화상 표시 장치
JP2012544990A JP5237506B1 (ja) 2012-02-28 2012-09-28 耐擦傷性樹脂積層体、ディスプレイのフロントカバー材及び画像表示装置
KR1020147006664A KR20140118976A (ko) 2012-02-28 2012-09-28 내찰상성 수지 적층체, 디스플레이의 프론트 커버재 및 화상 표시 장치
KR1020137010983A KR20140118692A (ko) 2012-02-28 2012-09-28 내찰상성 수지 적층체, 디스플레이의 프론트 커버재 및 화상 표시 장치
CN201280003820.5A CN103402765B (zh) 2012-02-28 2012-09-28 耐擦伤性树脂叠层体、显示器的前板材料及图像显示装置
HK14104521.4A HK1191295A1 (en) 2012-02-28 2014-05-14 Abrasion-resistant resin laminate, material for front cover of display and image display device

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WO2015040931A1 (fr) * 2013-09-20 2015-03-26 リケンテクノス株式会社 Film multicouche transparent contenant une couche de résine à base de poly(méth)acrylimide, et procédé pour produire ledit film multicouche transparent
WO2015146565A1 (fr) * 2014-03-24 2015-10-01 リケンテクノス株式会社 Procédé de production d'un article à partir d'un objet stratifié à revêtement dur, et article formé à partir d'un objet stratifié à revêtement dur comprenant une couche de résine à base de polyméthacrylimide
JP2015182273A (ja) * 2014-03-24 2015-10-22 リケンテクノス株式会社 ハードコート積層体からなる物品の製造方法
US10450431B2 (en) 2013-07-10 2019-10-22 Riken Technos Corporation Poly(meth)acrylimide film, easy-adhesion film using same, and method for manufacturing such films
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JP6276211B2 (ja) 2014-05-30 2018-02-07 リケンテクノス株式会社 透明樹脂積層体
JP6908083B2 (ja) * 2014-07-14 2021-07-21 三菱ケミカル株式会社 積層体
JP6693041B2 (ja) * 2014-07-14 2020-05-13 三菱ケミカル株式会社 積層体
JP6153977B2 (ja) 2014-10-02 2017-06-28 リケンテクノス株式会社 粘着フィルム
US10428194B2 (en) * 2015-02-25 2019-10-01 Mitsui Chemicals, Inc. Modified acrylic resin cured product, and laminate thereof, and production methods therefor
JP6508330B2 (ja) * 2015-03-31 2019-05-08 三菱ケミカル株式会社 積層体
JP6430342B2 (ja) * 2015-08-11 2018-11-28 Ｔｏｗａ株式会社 樹脂成形装置及び樹脂成形方法並びに成形型
KR102373615B1 (ko) 2015-08-24 2022-03-15 삼성디스플레이 주식회사 윈도우 부재를 포함하는 표시장치 및 윈도우 부재의 제조방법
JP6669477B2 (ja) * 2015-11-27 2020-03-18 リケンテクノス株式会社 活性エネルギー線硬化性樹脂組成物、及びこれを用いたハードコート積層フィルム
JP6862183B2 (ja) 2016-01-18 2021-04-21 リケンテクノス株式会社 ハードコート積層フィルム
KR102604087B1 (ko) 2016-06-24 2023-11-21 삼성디스플레이 주식회사 윈도우 및 이를 포함하는 표시 장치
JP6718340B2 (ja) * 2016-09-08 2020-07-08 株式会社ダイセル ハードコート積層体並びに成形体及びその製造方法
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WO2015040931A1 (fr) * 2013-09-20 2015-03-26 リケンテクノス株式会社 Film multicouche transparent contenant une couche de résine à base de poly(méth)acrylimide, et procédé pour produire ledit film multicouche transparent
JP2015083370A (ja) * 2013-09-20 2015-04-30 リケンテクノス株式会社 ポリ（メタ）アクリルイミド系樹脂透明多層フィルム、及びその製造方法
JP2016153232A (ja) * 2013-09-20 2016-08-25 リケンテクノス株式会社 ポリ（メタ）アクリルイミド系樹脂透明多層フィルム、及びその製造方法
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US10576498B2 (en) 2014-03-21 2020-03-03 Riken Technos Corporation Method for producing multilayer coated film
WO2015146565A1 (fr) * 2014-03-24 2015-10-01 リケンテクノス株式会社 Procédé de production d'un article à partir d'un objet stratifié à revêtement dur, et article formé à partir d'un objet stratifié à revêtement dur comprenant une couche de résine à base de polyméthacrylimide
JP2015182273A (ja) * 2014-03-24 2015-10-22 リケンテクノス株式会社 ハードコート積層体からなる物品の製造方法
US10173392B2 (en) 2014-03-24 2019-01-08 Riken Technos Corporation Process for producing article from layered hardcoat object, and article formed from layered hardcoat object including poly(meth)acrylimide-based resin layer

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KR20130108582A (ko) 2013-10-04
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