WO2015122485A1 - 透明樹脂積層体及び前面板 - Google Patents
透明樹脂積層体及び前面板 Download PDFInfo
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- WO2015122485A1 WO2015122485A1 PCT/JP2015/053920 JP2015053920W WO2015122485A1 WO 2015122485 A1 WO2015122485 A1 WO 2015122485A1 JP 2015053920 W JP2015053920 W JP 2015053920W WO 2015122485 A1 WO2015122485 A1 WO 2015122485A1
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- 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
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/288—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyketones
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- 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
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- 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
-
- 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
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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- 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
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
-
- 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
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
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- 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
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- 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
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- 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
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- 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
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- 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
- B32B2250/00—Layers arrangement
- B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
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- 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
- B32B2255/00—Coating on the layer surface
- B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
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- 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
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
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- 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
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/10—Inorganic fibres
- B32B2262/101—Glass fibres
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- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
- B32B2307/202—Conductive
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- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/412—Transparent
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- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/546—Flexural strength; Flexion stiffness
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- 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 provides a transparent resin laminate having a high light transmittance in a wide wavelength range such that the total light transmittance is 80% or more, the light transmittance at 550 nm is 80% or more, and the light transmittance at 400 nm is 60% or more. About.
- Transparent resin films or sheets typified by polymethyl methacrylate (PMMA), polycarbonate (PC), and polyethylene terephthalate (PET) are widely used as optical materials for electrical and electronic equipment such as liquid crystal displays and mobile phones.
- PMMA polymethyl methacrylate
- PC polycarbonate
- PET polyethylene terephthalate
- the front panel (front plate) of portable display devices such as mobile phone terminals, portable electronic play equipment, and personal digital assistants (PDAs) has transparency and visibility, weather resistance that can be used outdoors, and finger
- characteristics such as scratch resistance for preventing damage when contacting and carrying, and impact resistance and rigidity for preventing damage due to impact and load.
- Candidates for front plate materials for display devices include films and sheets composed of polymethyl methacrylate (PMMA) and polycarbonate (PC), and polyester films in which fine particles as fillers are uniformly dispersed in polyester (Patent Document 1). ), A laminate (Patent Document 2) in which an acrylic resin layer (PMMA layer) is provided on at least one surface of a polycarbonate resin layer (PC layer), and a silicone resin molded article obtained by radical copolymerization of a silicone resin composition ( Patent Document 3), a laminate (Patent Document 4) in which a biaxially stretched PET film is bonded to a PC have been proposed.
- PMMA polymethyl methacrylate
- PC polycarbonate
- polymethylmethacrylate has a low glass transition temperature and is prone to cracking, so it is inferior in workability.
- Polycarbonate (PC) has a glass transition temperature as good as about 145 ° C., but its surface hardness and rigidity are inferior, making it difficult to employ as a front panel for a display or the like.
- PET polyethylene terephthalate
- the biaxially stretched one has a softening temperature of 200 ° C. or higher and a good surface hardness, but it is difficult to increase the plate thickness, and it is difficult to cope with thick film applications (Patent Document 1).
- Patent Document 2 Research on a laminate having a PMMA layer and a PC layer has also been made (Patent Document 2), and some of them have been used, but have problems such as workability problems due to warpage during heat treatment and lack of rigidity. Yes.
- This invention aims at providing the transparent resin laminated body which solved the said subject.
- the inventors have obtained transparency by providing a transparent layer (B) containing a glass fiber cloth and a resin composition containing a sulfur compound on both sides of the transparent resin layer (A).
- the inventors have found that a transparent resin laminate excellent in rigidity can be obtained, and have reached the present invention. That is, one form of the present invention provides the following transparent resin laminate and display front plate.
- the difference between the refractive index of the resin composition in the transparent layer (B) and the refractive index of the glass fiber cloth is 0.01 or less, according to any one of (1) to (12).
- Transparent resin laminate (14) The transparent resin laminate according to any one of (1) to (13), wherein the resin composition in the transparent layer (B) contains a polymer of a thiol compound and an epoxy resin. (15) The transparent resin laminate according to any one of (1) to (14), wherein the refractive index of the glass fiber cloth in the transparent layer (B) is greater than 1.55. (16) The transparent resin laminate according to any one of (1) to (15), wherein the glass fiber cloth of the transparent layer (B) is an E glass cloth.
- the transparent resin laminate described in 1. (18) The transparent resin laminate according to (17), wherein the resin component in the transparent resin layer (A) contains polycarbonate. (19) The transparent resin laminate according to any one of (1) to (18), wherein a polyethylene terephthalate film layer is disposed on at least one outer side of the transparent layer (B). (20) The transparent resin laminate according to (19), wherein a hard coat layer is further disposed on at least one outer side of the polyethylene terephthalate film layer. (21) The transparent resin laminate according to (19) or (20), wherein a transparent conductive film layer is disposed on at least one outer side of the polyethylene terephthalate film layer. (22) A display front plate using the transparent resin laminate according to any one of (1) to (21).
- the following display front plate comprising a transparent resin laminate (C) in which a transparent layer (B) formed of a resin composition containing a glass fiber cloth and a sulfur compound is disposed on both sides of the transparent resin layer (A).
- Front plate (2) The display front plate according to (1), wherein the transparent resin layer (A) has a thickness of 100 ⁇ m to 2000 ⁇ m, and the transparent layer (B) has a thickness of 20 ⁇ m to 300 ⁇ m.
- the resin composition containing a sulfur compound in the transparent layer (B) contains a polymer of a thiol compound and an epoxy resin, as described in any one of (1) to (6) Front plate for display.
- the resin component in the transparent resin layer (A) is at least one member selected from the group consisting of polycarbonate, polyethylene terephthalate, polybutylene terephthalate, and polymethyl methacrylate.
- the following display front plate is provided.
- a transparent layer formed of a photocurable resin composition containing a glass fiber cloth and a compound (a) having a thiol group and a compound (b) having an alkenyl group on both surfaces of the transparent resin layer (A) ( A display front plate comprising a transparent resin laminate (C) in which B) is disposed.
- the display front plate according to claim 1. The display front plate according to any one of (1) to (8), wherein a polyethylene terephthalate film layer is disposed on at least one outer side of the transparent resin laminate (C).
- the following transparent laminated bodies are provided.
- a transparent layer (B) in which a glass fiber cloth is impregnated with a curable resin having a tensile modulus of elasticity of 10 MPa or more when cured at a thickness of 1 mm is disposed on both surfaces of the polycarbonate resin layer (A).
- a hard coat layer is further disposed on at least one outer side of the polyethylene terephthalate film layer.
- the following transparent laminated bodies are provided.
- a transparent layer (B) having a tensile elastic modulus of 10 GPa or more by impregnating and curing a glass fiber cloth with a curable resin is tensile elastic at the time of curing at a thickness of 1 mm.
- the transparent resin laminate of the present invention is suitable as a substitute for glass because it is excellent in transparency and rigidity and excellent in workability.
- 1 is a schematic cross-sectional view showing a display front plate according to an embodiment of the present invention.
- 1 is a schematic cross-sectional view showing a display front plate according to an embodiment of the present invention.
- 2 is a cross-sectional photograph of a transparent resin laminate according to an embodiment of the present invention, which is a cross-sectional photograph of the transparent resin laminate produced in Example A-2.
- One embodiment of the present invention is a transparent resin laminate in which a transparent layer (B) containing a glass fiber cloth and a resin composition containing a sulfur compound is disposed on both sides of the transparent resin layer (A).
- the transparent resin laminate of the present invention is transparent and excellent in rigidity, and excellent in workability and impact resistance. Therefore, the transparent resin laminate is used as a transparent substrate material, a transparent protective material, and the like, and particularly preferably used as a substitute for glass for various glazing materials, substrate materials, and front plate materials such as a display front plate.
- the “transparent resin laminate” is also simply referred to as “transparent laminate” or “laminate”.
- the term “transparent” means that the total light transmittance is 80% or more.
- the light transmittance at 550 nm which is a general wavelength in the visible light region, is preferably 80% or more, and the light transmittance at 400 nm is preferably 60% or more.
- the light transmittance at 400 nm is important from the viewpoint of image contrast and color reproducibility, and it is preferable to increase the light transmittance in the wavelength region.
- the total light transmittance and the light transmittances of 400 nm and 550 nm can be measured by the methods described in Examples described later.
- FIG. 1 is a schematic cross-sectional view illustrating a display front plate according to an embodiment of the present invention.
- the display front plate 10 shown in FIG. 1 has an adhesive layer 3 on both surfaces of a transparent resin layer (A) 1 and a transparent layer (B) 2 containing a glass fiber cloth and a resin composition containing a sulfur compound. It consists of the transparent resin laminated body (C) laminated
- FIG. 2 is a schematic cross-sectional view showing a display front plate according to another embodiment of the present invention.
- the display front plate 10 shown in FIG. 2 is a transparent resin laminate in which a transparent layer (B) 2 containing a glass fiber cloth and a resin composition containing a sulfur compound is disposed on both sides of the transparent resin layer (A) 1. (C).
- the transparent layer (B) 2 is directly disposed on the transparent resin layer (A).
- the transparent resin layer (A) and the transparent layer (B) may not be bonded, but more preferably, the transparent resin layer (A) and the transparent layer (B) are bonded from a highly rigid surface. Yes. That is, in one embodiment of the present invention, the transparent resin layer (A) and the transparent layer (B) are directly bonded or bonded via the adhesive layer 3.
- FIG. 3 is a cross-sectional photograph of the transparent resin laminate according to one embodiment of the present invention, and corresponds to a cross-sectional photograph of the transparent resin laminate produced in Example A-2 below.
- the transparent resin laminate shown in FIG. 3 is formed by sequentially laminating a GC reinforced film as a transparent layer (B) 2 and a polyethylene terephthalate film layer 4 as a resin layer on both sides of a PC plate as a transparent resin layer (A) 1. It has become.
- the layer 5 in FIG. 3 is a sheet
- FIG. 1 is a sheet
- the transparent layer (B) is composed of a GC reinforced film formed from a glass fiber cloth 21, a resin composition 22 comprising a compound having a thiol group and a compound having an epoxy group.
- the glass fiber cloth 21 is an E glass cloth, and is formed by knitting warp yarns and weft yarns (glass yarns) (white portion in the figure).
- the transparent layer (B) 2 is formed by impregnating and curing the resin composition in the glass cloth.
- a transparent layer (B) containing a glass fiber cloth and a resin composition containing a sulfur compound has higher rigidity (such as tensile elastic modulus) than the transparent resin layer (A).
- rigidity such as tensile elastic modulus
- the rigidity of the layer containing the glass fiber cloth is reflected by arranging the high rigidity layer (B) containing the glass fiber cloth on both surfaces of the relatively low rigidity layer (A).
- the rigidity of can be increased.
- the rigidity (bending elastic modulus) is 2.6 GPa, but the rigidity can be improved by arranging the layers containing glass fiber cloth on both sides.
- the transparent resin laminate (C) includes a transparent resin layer (A), a transparent layer (B), and an adhesive layer, a resin layer (smoothing layer), a hard coat layer, and a transparent conductive film layer that are arranged as necessary.
- the transparent resin layer (A) is a transparent layer (film / sheet) mainly composed of resin.
- the thickness of the transparent resin layer (A) is not particularly limited, but is preferably 100 ⁇ m to 2000 ⁇ m, and more preferably 200 ⁇ m to 1000 ⁇ m. If the thickness of the transparent resin layer (A) is within this range, the rigidity becomes high, and an increase in the mass of the entire transparent resin laminate (C) can be suppressed.
- the resin (resin component) used in the transparent resin layer (A) is not particularly limited, but polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polymethyl methacrylate, cyclic cycloolefin resin, norbornene resin, acrylic resin, polystyrene, polyethersal Examples include phon, polyarylate, polyester resin, polyacetal resin, polyvinyl butyral, polyvinyl alcohol, and urethane resin.
- polycarbonate, polyethylene terephthalate, polybutylene terephthalate, and polymethyl methacrylate are selected from the viewpoint of transparency and rigidity. At least one kind is preferable, and polycarbonate resin is particularly preferable from the viewpoint of transparency and punchability. These resins may be used alone or in combination.
- the transparent resin layer (A) is processed into a layer mainly by molding.
- the molding method is not particularly limited, and for example, a general extrusion method such as a thermoplastic resin film forming method, a melt casting method, a calendering method, or the like can be used.
- the transparent resin layer (A) is made of a layered polycarbonate resin.
- a layered polycarbonate resin By using a layered polycarbonate resin, a laminate having excellent transparency, rigidity, impact resistance, flexibility, and punchability can be obtained.
- a layered polycarbonate resin for example, Iupilon NF-2000 from Mitsubishi Gas Chemical Co., Ltd. can be preferably used.
- the total light transmittance of the transparent resin layer (A) molded to the thickness used when forming the transparent resin laminate is 80% or more. If it is 80% or more, the transmittance
- the transparent resin layer (A) can contain various additives in addition to the resin without departing from the spirit of the present invention.
- Additives include heat stabilizers, antioxidants, flame retardants, flame retardant aids, UV absorbers, mold release agents, colorants, antistatic agents, fluorescent whitening agents, antifogging agents, fluidity improvers, Examples include plasticizers, dispersants, and antibacterial agents. These may be used singly or in combination of two or more.
- heat stabilizers include phenol-based, phosphorus-based, and sulfur-based heat stabilizers.
- phosphorus oxo acids such as phosphoric acid, phosphonic acid, phosphorous acid, phosphinic acid, polyphosphoric acid
- acidic pyrophosphate metal salts such as acidic sodium pyrophosphate, acidic potassium pyrophosphate, acidic calcium pyrophosphate
- potassium phosphate Sodium phosphate, cesium phosphate, zinc phosphate, etc.
- Group 1 or Group 10 metal phosphates organic phosphate compounds, organic phosphite compounds, organic phosphonite compounds, and the like.
- a phosphite compound (a), phosphorous acid (b) and phosphorous ester compound esterified with phenol and / or phenol having at least one alkyl group having 1 to 25 carbon atoms in at least one ester in the molecule Mention may be made of at least one selected from the group of tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylene-di-phosphonite (c). These may be used alone or in combination of two or more.
- the addition ratio of the heat stabilizer is, for example, 0.001 part by mass or more, preferably 0.01 part by mass or more, more preferably 0.03 part by mass or more, with respect to 100 parts by mass of the resin component. Moreover, it is 1 mass part or less, Preferably it is 0.7 mass part or less, More preferably, it is 0.5 mass part or less. If the amount of the heat stabilizer is too small, the heat stabilizing effect may be insufficient. If the amount of the heat stabilizer is too large, the effect may reach a peak and may not be economical.
- antioxidants examples include phenolic antioxidants, hindered phenolic antioxidants, bisphenolic antioxidants, polyphenolic antioxidants, and the like.
- the addition ratio of the antioxidant is, for example, 0.001 part by mass or more, preferably 0.01 part by mass or more, and 1 part by mass or less, preferably 0 with respect to 100 parts by mass of the resin component. .5 parts by mass or less. If the addition ratio of the antioxidant is below the lower limit, the effect as an antioxidant may be insufficient, and if the addition ratio of the antioxidant exceeds the upper limit, the effect reaches a peak and is economical. There is a possibility of disappearing.
- Examples of flame retardants include organic sulfonic acid metal salts.
- Examples of the organic sulfonic acid metal salts include aliphatic sulfonic acid metal salts and aromatic sulfonic acid metal salts. These may be used alone or in combination of two or more.
- a metal salt an alkali metal salt and an alkaline-earth metal salt are preferable.
- the added mass of the flame retardant with respect to 100 parts by mass of the resin component is, for example, 0.005 parts by mass to 0.1 parts by mass, preferably 0.01 parts by mass to 0.1 parts by mass, and more preferably 0.03 parts by mass. Parts by mass to 0.09 parts by mass.
- a silicone compound can be added as a flame retardant aid.
- a silicone compound what has a phenyl group in a molecule
- numerator is preferable. By having a phenyl group, the dispersibility of the silicone compound in a resin component (particularly polycarbonate) is improved, and the transparency and flame retardancy are excellent.
- the addition ratio of the flame retardant aid is, for example, 0.1 parts by mass or more, preferably 0.2 parts by mass or more, and 7.5 parts by mass or less with respect to 100 parts by mass of the resin component. Preferably it is 5 mass parts or less. If the addition rate of flame retardant aid is below the lower limit, flame retardancy may be insufficient, and if the addition rate of flame retardant aid exceeds the upper limit, appearance defects such as delamination will occur and transparency , The flame retardancy reaches its peak, and it may not be economical.
- UV absorbers include benzotriazole compounds, benzophenone compounds, salicylate compounds, cyanoacrylate compounds, triazine compounds, oxanilide compounds, malonic ester compounds, hindered amine compounds, phenyl salicylates
- organic ultraviolet absorbers such as compounds. Of these, benzotriazole-based and benzophenone-based organic ultraviolet absorbers are preferred.
- the addition ratio of the ultraviolet absorber is, for example, 0.01 parts by mass or more, preferably 0.1 parts by mass or more, and 3 parts by mass or less, preferably 1 with respect to 100 parts by mass of the resin component. It is below mass parts. If the addition ratio of the UV absorber is below the lower limit, the effect of improving the weather resistance may be insufficient, and if the addition ratio of the UV absorber exceeds the upper limit, mold deposits, etc. will occur and mold contamination (Cooling roll contamination) may occur.
- release agent examples include carboxylic acid esters, polysiloxane compounds, and paraffin wax (polyolefin type). Two or more of these may be used in combination.
- the addition ratio of the release agent is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, and 2 parts by mass or less, based on 100 parts by mass of the resin component. Preferably it is 1 mass part or less. If the addition ratio of the release agent is below the lower limit value, the effect of the release property may not be sufficient, and if the addition ratio of the release agent exceeds the upper limit value, hydrolysis resistance decreases, gold during injection molding Mold contamination may occur.
- dyes and pigments as colorants include inorganic pigments, organic pigments, and organic dyes.
- inorganic pigments for example, sulfide pigments such as carbon black, cadmium red and cadmium yellow; silicate pigments such as ultramarine blue; titanium oxide, zinc white, petal, chromium oxide, iron black, titanium yellow, zinc-iron -Based brown, titanium-cobalt green, cobalt-green, cobalt-blue, copper-chromium-based black, copper-iron-based black and other oxide pigments; yellow lead, molybdate orange and other chromic pigments; bitumen and other ferrocyanians And pigments.
- inorganic pigments for example, sulfide pigments such as carbon black, cadmium red and cadmium yellow; silicate pigments such as ultramarine blue; titanium oxide, zinc white, petal, chromium oxide, iron black, titanium yellow, zinc-iron -Based brown, titanium-cobalt green, cobalt-green
- organic pigments and organic dyes as colorants include phthalocyanine dyes such as copper phthalocyanine blue and copper phthalocyanine green; azo dyes such as nickel azo yellow; thioindigo, perinone, perylene, and quinacridone And condensed polycyclic dyes such as dioxazine, isoindolinone, and quinophthalone; quinoline, anthraquinone, heterocyclic, and methyl dyes.
- phthalocyanine dyes such as copper phthalocyanine blue and copper phthalocyanine green
- azo dyes such as nickel azo yellow
- thioindigo perinone, perylene, and quinacridone
- condensed polycyclic dyes such as dioxazine, isoindolinone, and quinophthalone
- quinoline, anthraquinone, heterocyclic, and methyl dyes are preferable from the viewpoint of thermal stability.
- 1 type may contain the dye / pigment, and 2 or more types may contain it by arbitrary combinations and a ratio.
- dyes and pigments may be used as masterbatches with polystyrene resins, polycarbonate resins, and acrylic resins for the purpose of improving handling during extrusion and improving dispersibility in the resin composition. Good.
- the proportion of the colorant added is, for example, 1 part by mass or less, preferably 0.5 parts by mass or less, more preferably 0.1 parts by mass or less, relative to 100 parts by mass of the resin component. If the addition ratio of the colorant is too large, the impact resistance may not be sufficient.
- the transparent layer (B) includes a glass fiber cloth and a resin composition containing a sulfur compound.
- the transparent layer (B) is made transparent by adjusting so that the Abbe number of the resin composition containing the sulfur compound and the glass fiber cloth matches the refractive index of 589 nm.
- the thickness of the transparent layer (B) is preferably 20 ⁇ m to 300 ⁇ m, and more preferably 50 ⁇ m to 200 ⁇ m. When the thickness of the transparent layer (B) is within this range, rigidity and transparency tend to be improved.
- the sulfur compound is not particularly limited as long as the transparency and rigidity of the transparent layer (B) can be secured.
- the sulfur compound include a sulfur atom-containing resin selected from the group consisting of a thermoplastic resin containing a sulfur atom, a thermosetting resin containing a sulfur atom, and a photocurable resin containing a sulfur atom. .
- a thermosetting resin or a photocurable resin containing a sulfur atom is preferable from the viewpoint of optical characteristics (transparency).
- thermoplastic resin containing a sulfur atom is not particularly limited, and examples thereof include thermoplastic resins such as polythiocarbonate resin, polythioester resin, polyoxothioester resin, polythioether resin, and sulfur-containing cyclic polyolefin resin.
- thermosetting resin containing a sulfur atom is not particularly limited, and examples thereof include a thermosetting resin formed by a thermosetting reaction of a composition containing an epoxy resin and a polyfunctional thiol compound.
- the photocurable resin containing a sulfur atom is not particularly limited, but light formed by photocuring a photocurable resin composition containing a compound having a carbon-carbon double bond and a (polyfunctional) thiol compound. Photocurable resin formed by carrying out photocuring reaction of the photocurable resin composition containing curable resin, an epoxy resin, and a polyfunctional thiol compound is mentioned.
- the actinic ray used for curing the photocurable resin composition of the transparent layer (B) is not limited as long as it is used for curing the photocurable resin composition.
- Ultraviolet light, visible light, near infrared light, or the like can be used. From the viewpoint that side reactions hardly occur, it is preferable to use ultraviolet rays.
- the light source for irradiating the ultraviolet light include a metal halide type and a high-pressure mercury lamp lamp.
- the resin composition of the transparent layer (B) contains a curable resin.
- a curable resin is included, it is preferable in terms of refractive index adjustment and processability.
- the resin composition of the transparent layer (B) includes a curable resin having a tensile elastic modulus at the time of curing at a thickness of 1 mm of 10 MPa or more. That is, the transparent resin laminate of one embodiment of the present invention is made of a resin composition containing a curable resin having a tensile elastic modulus of 10 MPa or more when cured at a thickness of 1 mm on both surfaces of the transparent resin layer (A).
- a transparent layer (B) formed by impregnating a fiber cloth is provided.
- the transparent resin layer (A) is a polycarbonate resin layer because it is excellent in transparency, rigidity, impact resistance, flexibility, and punchability.
- the “tensile modulus at curing” means the tensile modulus of the resin after thermosetting or photocuring.
- the present inventors made the curable resin used for the layer (B) having high rigidity transparent and have a tensile elastic modulus of 10 MPa or more when cured at a thickness of 1 mm, so that the layer as a whole becomes rigid. It was found that an excellent laminate (preferably having a flexural modulus of 5 GPa or more) was obtained, and a laminate suitable for a display front (protection) plate was obtained. If it is less than 10 MPa, the flexural modulus as a whole transparent laminate may rather be lower than the flexural modulus (2.6 GPa) of the polycarbonate resin layer (A).
- the tensile elastic modulus at the time of curing of the curable resin used for the transparent layer (B) is more preferably 70 MPa or more, further preferably 100 MPa or more, and particularly preferably 500 MPa or more.
- the tensile modulus of the curable resin is preferably 5 GPa or less.
- the curable resin having such characteristics for example, an epoxy resin, an acrylic resin, a polyimide resin, a benzoxazine resin, an oxetane resin, or the like can be used.
- the resin composition contains a polymer of a thiol compound and an epoxy resin, and particularly preferably the resin composition contains a polymer obtained by thermosetting reaction of the thiol compound and the epoxy resin.
- the transparent layer (B) is obtained by impregnating and curing a glass fiber cloth with a resin composition containing a curable resin, and when the transparent layer (B) is cured (after curing).
- a resin composition containing a curable resin has a tensile modulus of 10 GPa or more.
- a method for obtaining a transparent layer (B) having a tensile modulus of 10 GPa or more a method using a specific curable resin can be mentioned.
- the curable resin having such characteristics is not particularly limited, and an epoxy resin, an acrylic resin, a polyimide resin, a benzoxazine resin, an oxetane resin, or the like can be used, but depending on the type of the curable resin used, it is transparent.
- the tensile modulus of the layer (B) may be less than 10 GPa, and it is not preferable to use such a curable resin.
- the transparent resin layer (A) is a polycarbonate resin layer because it is excellent in transparency, rigidity, impact resistance, flexibility, and punchability.
- the total light transmittance of the transparent layer (B) is preferably 80% or more, more preferably 85% or more. If the total light transmittance of a transparent layer (B) is this range, the transparency of the whole transparent resin laminated body can be made favorable, and it is preferable as a front plate for a display.
- the difference between the Abbe number of the resin composition constituting the transparent layer (B) and the glass fiber cloth is preferably 15 or less, more preferably 10 or less, in order to obtain high transparency.
- the lower limit of the Abbe number difference is not particularly limited, and is preferably as small as possible from the viewpoint of obtaining high transparency, and is most preferably 0.
- the Abbe number of a resin composition means the Abbe number after hardening, when a resin composition contains curable resin.
- the obtained transparent layer (B) has a high light transmittance at a short wavelength near 400 nm, which is preferable as a display front plate.
- the Abbe number is an index of the wavelength dependence of the refractive index of visible light.
- glass has a value larger than that of resin, and it is more difficult to match the larger the refractive index.
- a resin composition containing a sulfur compound By using a resin composition containing a sulfur compound, the Abbe number of the resin approaches the Abbe number of the glass fiber cloth, the light transmittance in a wide wavelength region is improved, and high transparency is obtained.
- the refractive index difference of the resin composition constituting the transparent layer (B) and the refractive index of the glass fiber cloth is preferably 0.01 or less, more preferably 0.005 or less in order to obtain high transparency.
- the refractive index difference of the D line (589 nm) between the resin composition and the glass fiber cloth is preferably 0.01 or less, and more preferably 0.005 or less.
- the lower limit of the refractive index difference of the D line (589 nm) is not particularly limited, and is preferably as small as possible from the viewpoint of obtaining high transparency, and is most preferably 0.
- the refractive index of a resin composition means the refractive index after hardening, when a resin composition contains curable resin so that it may mention later.
- the transmittance of the obtained transparent layer (B) becomes high, which is preferable as a display front plate.
- a resin having a difference in refractive index between the glass fiber cloth and the D line of 0.01 or less is used alone. It may be used, or a resin having a higher refractive index of the D line and a lower resin than the glass fiber cloth may be used in combination.
- the total light transmittance of the transparent layer (B) is 80% or more, which is a general wavelength in the visible light region of 550 nm. It is preferable that the light transmittance at 70 is 70% or more.
- a plurality of reactive monomers (curable resins) and a curing agent are used.
- the method or the method (2) is preferred.
- “matching the refractive index” means that the refractive index difference is 0.01 or less, preferably 0.005 or less. Further, that the Abbe numbers coincide with each other means that the Abbe number difference is 15 or less, preferably 10 or less.
- the resin containing sulfur atoms can be used as it is.
- the refractive index can be configured to match that of the glass fiber by adjusting the types and amounts of monomers and curing agents that constitute the copolymer resin and the curable resin.
- examples of such a resin include at least one sulfur atom-containing resin selected from a thermoplastic resin containing a sulfur atom, a thermosetting resin containing a sulfur atom, and a photocurable resin containing a sulfur atom. Is mentioned. In this case, only one type of resin containing sulfur atoms may be used, or two or more types may be used in combination.
- the glass type of the glass fiber cloth is E glass (Abbe number 58, refractive index 1.56).
- a thermoplastic copolymer resin such as a copolymer of polythioester and polyester, a thermosetting resin such as an episulfide resin, and the like.
- a thermoplastic copolymer resin such as a copolymer of polythioester and polyester or an episulfide resin is used.
- a thermosetting resin etc. are mentioned.
- the refractive index and the Abbe number depend on the ratio of the sulfur compound (sulfur atom-containing compound) to be copolymerized and the compound not containing sulfur, and the smaller the sulfur compound, the lower the refractive index.
- the amount used depends on the glass type.
- the refractive index and Abbe number of the episulfide resin vary depending on the sulfur content in the episulfide resin, and the smaller the sulfur content, the lower the refractive index. When an S glass or T glass is used, an episulfide resin having a sulfur content corresponding to that is used.
- the curability formed by a curing reaction between a reactive monomer of a curable resin and a curing agent containing a sulfur atom can also be used.
- a method of adjusting by combining a curing agent containing a sulfur atom having a refractive index higher than that of glass fiber cloth and a reactive monomer (resin monomer containing no sulfur atom) of a resin having a refractive index lower than that of glass fiber cloth is preferable. .
- the sulfur atom-containing curable resin a thermosetting resin or a photocurable resin composed of an epoxy resin as a reactive monomer and a curing agent containing a sulfur compound, an alkenyl group as a reactive monomer.
- a photo-curable resin comprising a compound having a sulfur and a curing agent containing a sulfur compound.
- a sulfur atom-containing curing agent having a refractive index higher than that of the glass fiber cloth and a reactive monomer of a curable resin having a low refractive index are mixed one by one or two or more, respectively.
- the method of hardening with active energy, such as light is mentioned.
- a method of curing a resin for example, an epoxy resin
- a sulfur atom-containing compound for example, a polyfunctional thiol compound
- a curable resin composed of an epoxy resin and a sulfur atom-containing curing agent is preferable from the viewpoint of transparency.
- Examples of the sulfur atom-containing curing agent include polyfunctional thiol compounds having a refractive index higher than that of glass fiber cloth.
- the polyfunctional thiol compound having a higher refractive index than that of the glass fiber cloth is not particularly limited, but 1,2-ethanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 1,6-hexanedithiol 2,2′-oxybis (1-mercaptoethane), 2,2′-thiobis (1-mercaptoethane), 1,4-dimercaptobutane-2,3-diol, ethylene glycol bis (1-mercaptoethane) , Ethylene glycol bis (2-mercaptoacetate), ethylene glycol bis (3-mercaptopropionate), ethylene glycol bis (2-mercaptopropionate), ethylene glycol bis (3-mercaptobutanoate), butanediol bis ( 2-mercaptoacetate), butanedi
- pentaerythritol tetrakis (3-mercaptopropionate) and 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane are preferable from the viewpoint of refractive index adjustment.
- a cyclic carboxylic acid anhydride having a refractive index lower than that of the glass fiber cloth can be used in addition to the polyfunctional thiol compound.
- Such cyclic carboxylic acid anhydrides are not particularly limited, but for example, maleic anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, nadic anhydride, glutaric anhydride, tetrahydrophthalic anhydride, methyl Tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride, methyl nadic anhydride, dodecenyl succinic anhydride, dichlorosuccinic anhydride, benzophenone tetracarboxylic anhydride and chlorendic anhydride Thing etc.
- tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride are preferable from the viewpoint of transparency, and hexahydrophthalic anhydride is more preferable from the viewpoint of transparency.
- Examples of the epoxy resin having a refractive index lower than that of the glass fiber cloth combined with a curing agent containing a sulfur atom include an epoxy resin containing no aromatic ring.
- Such an epoxy resin is not particularly limited, but hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin, triazine skeleton-containing epoxy resin, linear aliphatic epoxy resin, cyclohexane oxide skeleton-containing epoxy resin, cyclohexane Examples include polyether skeleton-containing epoxy resins, glycidylamine-type epoxy resins, dicyclopentadiene skeleton-containing epoxy resins, and the like. These may be used alone or in combination of two or more.
- the combination of a polyfunctional thiol compound having a refractive index higher than that of the glass fiber cloth and an epoxy resin not containing an aromatic ring having a low refractive index is not particularly limited.
- the glass fiber cloth has a higher Abbe number than a general resin having a close refractive index, the difference between the Abbe number and a resin containing an aromatic ring or a resin having a large amount of carbonyl bonds tends to increase.
- a combination of a thiol compound such as pentaerythritol tetrakis (3-mercaptopropionate) and / or 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane and a cyclohexane oxide skeleton-containing epoxy resin may be used. preferable.
- the total content of thiol functional groups contained in the polyfunctional thiol compound is preferably 1 equivalent to the epoxy group of an epoxy resin that is a cured plastic resin. It is preferably 0.5 to 1.0 equivalent, more preferably 0.7 to 1.0 equivalent. If the content is within this range, curability does not decrease, and odor due to residual thiol functional groups can be suppressed.
- the thiol functional group contained in the polyfunctional thiol compound and the carboxylic acid anhydride functional group contained in the cyclic carboxylic acid anhydride is preferably 0.5 to 1.0 equivalent, more preferably 0.7 to 1.0 equivalent, based on 1 equivalent of the epoxy group of the epoxy resin which is a cured plastic resin. If the content is within this range, curability does not decrease, and odor due to residual thiol functional groups can be suppressed.
- the polyfunctional thiol compound and the cyclic carboxylic acid anhydride as a curing agent for a curable resin are used in combination, the polyfunctional thiol compound and the cyclic carboxylic acid anhydride as a curing agent, and The compounding ratio of the epoxy resin is adjusted depending on the glass fiber cloth used.
- the compounding ratio of the polyfunctional thiol compound having a high refractive index is increased to match the refractive index with the glass fiber cloth.
- T glass fiber cloth with low refractive index, S glass fiber cloth, NE glass fiber cloth, etc. as said glass fiber cloth, the compounding ratio of resin containing a high refractive index sulfur compound is decreased, and glass fiber is used. Match the refractive index with the cloth.
- a sulfur atom-containing resin having a refractive index identical to that of the glass fiber cloth of (1) a composition containing a compound having a carbon-carbon double bond and a (polyfunctional) thiol compound is subjected to a photocuring reaction.
- a photocurable resin may be used.
- a photocurable resin formed from a photocurable resin composition containing the compound (a) having a thiol group and the compound (b) having an alkenyl group hereinafter referred to as “thiol-ene photocurable resin”
- thiol-ene photocurable resin is preferable.
- Such a thiol-ene photocurable resin has a thiol group and an alkenyl group in the same molecule.
- a glass fiber cloth on both surfaces of the transparent resin layer (A), a glass fiber cloth and a resin composition containing a compound (a) having a thiol group and a compound (b) having an alkenyl group. It is a transparent resin laminate (C) in which the formed transparent layer (B) is arranged.
- the transparent layer (B) is obtained by impregnating a glass fiber cloth with a photocurable resin composition containing a compound (a) having a thiol group and a compound (b) having an alkenyl group. , Processed into layers.
- the photocurable resin composition as described above allows a reaction between a thiol group and an alkenyl group by an actinic ray (thiol-ene reaction) due to the thiol group of the compound having a thiol group and the alkenyl group of the compound having an alkenyl group.
- thiol-ene reaction an actinic ray
- the advantages of the photocurable resin produced by the thiol-ene reaction are that the reaction proceeds easily with active light regardless of the presence or absence of a polymerization initiator, the reaction is not inhibited by oxygen, and the curing shrinkage is small.
- the point that the resin after hardening has a high weather resistance is mentioned, and the hardened
- the photo-curable resin composition that generates a thiol-alkenyl reaction has a ratio of reactive functional groups in the molecule, that is, compared with a thiol-epoxy reaction that can produce a curable resin using a similar photo-curing reaction, that is, It is not necessary to adjust the ratio between the thiol group and the epoxy group, and the refractive index of the resin is easily adjusted.
- the compound having a thiol group is not particularly limited as long as it is a compound having a thiol group, but as mentioned above, a polyfunctional thiol having a higher refractive index than the glass fiber cloth used as a sulfur atom-containing curing agent.
- System compounds can be used. These may be used individually by 1 type and may use 2 or more types together.
- the thiol compound in the thiol-alkenyl reaction is preferably pentaerythritol tetrakis (3-mercaptopropionate), 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane from the viewpoint of adjusting the refractive index. is there.
- the compound having an alkenyl group is not particularly limited as long as it is a compound having an alkenyl group.
- 2-methacryloyloxyethylphthalic acid methoxypolyethylene glycol methacrylate, 1,9-nonanediol dimethacrylate, neopentyl glycol diester.
- the compound (a) having a thiol group and the compound (b) having an alkenyl group described above are combined, and the Abbe number and refractive index of the cured photocurable resin are the Abbe of the glass fiber cloth.
- the number and refractive index should be matched.
- a compound having a higher refractive index than that of the glass fiber cloth and a compound having a lower refractive index are mixed to be transparent. At that time, in order to obtain high transparency, it is preferable to precisely match the refractive index of the resin and the glass fiber cloth. Therefore, the compound (a) having a thiol group having a refractive index higher than that of the glass fiber cloth and the glass fiber cloth.
- the method of mixing and adjusting the photocurable resin containing the compound (b) having an alkenyl group having a lower refractive index than that is preferable.
- a photocurable resin containing a compound (a) having a thiol group having a higher refractive index than the glass fiber cloth and a compound (b) having an alkenyl group having a lower refractive index than the glass fiber cloth One type may be mixed, or two or more types may be used.
- the E glass fiber cloth when E glass cloth is used as the glass fiber cloth, the E glass fiber cloth has a higher Abbe number than a general resin having a refractive index close to that of a resin containing an aromatic ring or a resin having a large amount of carbonyl bonds. The numbers do not match. Therefore, pentaerythritol tetrakisthioglycolate and / or 4-mercaptomethyl-3,6-dithia-1,8-octanedithiol is used as the compound having a thiol group, and tricyclodecane dimethanol is used as the compound having an alkenyl group. It is preferable to combine using diacrylate.
- Method (2) If the refractive index of the resin containing the sulfur compound and the glass fiber cloth do not match, adjust by mixing a resin with a higher refractive index than the glass fiber cloth and another resin with a lower refractive index than the glass fiber cloth. be able to.
- the resin composition constituting the transparent layer (B) include, for example, a thermoplastic resin containing a sulfur atom, a thermosetting resin containing a sulfur atom, and a light containing a sulfur atom.
- the structure containing at least 1 sort (s) of sulfur atom containing resin selected from curable resin and other resin (sulfur atom non-containing resin) from which a refractive index differs from the said sulfur atom containing resin is mentioned.
- the refractive index of the resin composition of the transparent layer (B) is a resin containing a sulfur atom having a refractive index higher than that of the glass fiber cloth and another resin having a refractive index lower than that of the glass fiber cloth (a sulfur atom-free resin). And a method of adjusting by mixing.
- resin containing sulfur atoms with higher refractive index than glass fiber cloth (sulfur atom-containing resin) and resin with lower refractive index (other resins) sulfur atom-containing resin and other resins (not containing sulfur atoms)
- One type of resin may be mixed, or two or more types may be used.
- the resin containing a sulfur atom is a thermoplastic resin
- the resin containing a sulfur atom has a higher refractive index than a glass fiber cloth, such as a polythiocarbonate resin, a polythioester resin, or a polyoxo.
- a glass fiber cloth such as a polythiocarbonate resin, a polythioester resin, or a polyoxo.
- examples include thioester resins, polythioether resins, sulfur-containing cyclic polyolefin resins, and the like.
- resins having a refractive index lower than that of glass fiber cloth (other resins; sulfur atom-free resins) combined with the sulfur atom-containing resin include cyclic cycloolefin resins, polymethyl methacrylate resins, acrylic resins, polyacetals. Examples thereof include resins.
- a sulfur atom-containing resin having a higher refractive index than the glass fiber cloth and another resin having a lower refractive index as long as the refractive index difference between the glass fiber cloth and the resin composition can be adjusted to a desired range, It is not limited.
- the glass fiber cloth generally has a higher Abbe number than a general resin having a similar refractive index, the difference between the Abbe number and a resin containing an aromatic ring or a resin having a large amount of carbonyl bonds increases.
- a combination of cyclic cycloolefin resins is preferred.
- the resin containing a sulfur atom is a curable resin
- the resin containing a sulfur atom is a thermosetting resin or a photocurable resin comprising an epoxy resin and a curing agent containing a sulfur compound, a compound having an alkenyl group And a curing agent containing a sulfur compound, more preferably a thermosetting resin or a photocurable resin consisting of an epoxy resin and a curing agent containing a sulfur compound.
- the curing agent containing a sulfur atom include a polyfunctional thiol compound having a refractive index higher than that of the glass fiber cloth, and the polyfunctional thiol compound as the sulfur atom-containing curing agent in the method (1) is used in the same manner. be able to.
- a cyclic carboxylic acid anhydride having a refractive index lower than that of the glass fiber cloth as mentioned in the method (1) is used. Can do.
- the amount of the resin with respect to the transparent layer (B) is appropriately selected according to the purpose of use, but is usually 10 to 80% by mass, preferably 20 with respect to the total mass (100% by mass) of the transparent layer (B). It is in the range of ⁇ 70% by mass. If the amount of the resin is too small, the resin may be insufficient and the transparency may decrease. Conversely, if the amount of the resin is too large, the rigidity may be insufficient.
- thermoplastic resin there is a method in which the resin to be used is heated and mixed using a kneading apparatus such as a lab plast mill, a twin screw extruder, a Banbury mixer, and a vessel.
- a thermosetting resin the resin composition can be adjusted according to a conventional method. If the resin composition containing the resin to be used and other optional components can be obtained uniformly, the adjustment can be made.
- the method is not particularly limited.
- a resin composition can be easily adjusted by blending a polyfunctional thiol compound and an epoxy resin that does not contain an aromatic ring and stirring sufficiently.
- a known process for uniformly dissolving or dispersing each component can be performed.
- the above stirring, mixing, and kneading treatment can be appropriately performed using, for example, a known device such as a ball mill, a bead mill or the like for mixing, or a revolution / spinning type mixing device.
- the resin composition constituting the transparent layer (B) may further contain an inorganic filler as long as desired properties are not impaired.
- inorganic fillers include silica-based inorganic fillers such as quartz, fumed silica, precipitated silica, silicic anhydride, fused silica, crystalline silica, and ultrafine powder amorphous silica, alumina, zircon, zinc oxide, and oxidation.
- the said inorganic filler can be used individually by 1 type or in combination of 2 or more types as appropriate.
- the resin composition of the transparent layer (B) may contain a curing accelerator for adjusting the curing rate as needed when adjusting the resin composition.
- a curing accelerator for adjusting the curing rate as needed when adjusting the resin composition.
- examples of such compounds include imidazole compounds, benzoyl peroxide, lauroyl peroxide, acetyl peroxide, parachlorobenzoyl peroxide, organic peroxides exemplified by di-tert-butyl-di-perphthalate, Azobisnitrile azo compound, N, N-dimethylbenzylamine, N, N-dimethylaniline, N, N-dimethyltoluidine, 2-N-ethylanilinoethanol, tri-n-butylamine, pyridine, quinoline, N -Tertiary amines such as methylmorpholine, triethanolamine, triethylenediamine, tetramethylbutanediamine, N-methylpiperidine, phenol
- the resin composition containing the sulfur compound that forms the transparent layer (B) may contain an organic solvent, if necessary. That is, the transparent layer (B) can be used as an embodiment (varnish) in which at least a part or all of the above-described resin is dissolved or compatible with an organic solvent. Any known organic solvent can be used as long as it can dissolve or be compatible with at least a part, preferably all of the resin monomer, and the kind thereof is not particularly limited.
- Specific examples thereof include, for example, benzene, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone (2-butanone), acetone, methanol, ethanol, isopropyl alcohol, 2-butanol, ethyl acetate, butyl acetate, propylene glycol monomethyl ether, propylene Examples include glycol monomethyl ether acetate, diacetone alcohol, N, N′-dimethylformamide, N, N′-dimethylacetamide, acetonitrile, and the like, but are not particularly limited thereto.
- An organic solvent can be used individually by 1 type or in combination of 2 or more types as appropriate.
- the solid content concentration of the solution is usually preferably 10 to 99% by mass, and preferably 20 to 90% by mass. Is more preferable. If the solution concentration is too low, the impregnation resin may be insufficient and the transparency may be lowered. Conversely, if the solution concentration is high, the solution viscosity may be increased, resulting in poor impregnation.
- a diluent such as a monoepoxy compound is added so as not to impair the reaction in order to improve workability and workability after curing the epoxy resin. It is preferable to add.
- a diluent is added, workability and processability are improved by lowering the monomer viscosity, and flexibility can be imparted to the cured epoxy resin, and the flexibility of the transparent layer (B) , Impact resistance, toughness and the like can be improved.
- Diluents include styrene oxide, cyclohexene oxide, propylene oxide, methyl glycidyl ether, ethyl glycidyl ether, n-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, cresyl glycidyl ether, sec-butylphenyl glycidyl ether, cardanol glycidyl ether, Glycidyl methacrylate, phenyl glycidyl ether, allyl glycidyl ether, octylene oxide, dodecene oxide, 1,6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, glycerin Triglycidyl ether
- the amount of the diluent is preferably less than 100 parts by mass and more preferably 15 parts by mass or less with respect to 100 parts by mass of the epoxy resin. If the amount of the diluent is within this range, the tensile elastic modulus of the transparent layer (B) is 15 GPa or more, and the bending elastic modulus of the transparent resin laminate as a whole can be 5 GPa or more.
- a resin composition containing the compound (a) having a thiol group and the compound (b) having an alkenyl group is used as an ultraviolet ray or the like.
- a photopolymerization initiator that generates radicals may be added to the resin composition. Examples of such photopolymerization initiators include benzophenone, N, N′-tetraethyl-4,4′-diaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 2,2-diethoxyacetophenone, benzoin, and benzoin methyl.
- Ether benzoinpropyl ether, benzoin isobutyl ether, benzyldimethyl ketal, ⁇ -hydroxyisobutylphenone, thioxanthone, 2-chlorothioxanthone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2 -Morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-dimethylamino-2- (4-methyl-benzyl) -1- (4 -Morph Phosphorin-4-yl-phenyl) -butan-1-one, 2,6-dimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, t-butylanthraquinone, 1-chloroanthraquinon
- the said photoinitiator can be used individually by 1 type or in combination of 2 or more types as appropriate.
- Examples of commercially available photopolymerization initiators include Darocur 1173, Irgacure 651, Irgacure 184, Irgacure 907, and Lucilin TPO (all trade names manufactured by BASF).
- the content in the resin composition in the case of using the photopolymerization initiator may be an amount that can be appropriately cured, and is, for example, 0.8% relative to a total of 100 parts by mass of compounds having two or more alkenyl groups.
- the content is preferably 01 to 2 parts by mass, more preferably 0.02 to 1 part by mass, and most preferably 0.1 to 0.5 parts by mass.
- a storage stabilizer that suppresses the thiol-ene reaction can be blended in order to improve the storage stability before curing.
- the photopolymerization initiator mentioned above since the storage stability of the resin composition tends to be lowered, it is preferable to use such a storage stabilizer in combination.
- Examples of such storage stabilizers include phosphorus compounds such as triphenylphosphine and triphenyl phosphite; p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, t-butylcatechol, cuprous chloride, 2,6-di-t-butyl-p-cresol, 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t -Butylphenol), radical polymerization inhibitors such as N-nitrosophenylhydroxylamine aluminum salt, diphenylnitrosamine; benzyldimethylamine, 2- (dimethylaminomethyl) phenol, 2,4,6-tris (diaminomethyl) phenol, Tertiary amines such as diazabicycloundecene; 2-methylimidazole, 2-ethyl-4-methyli Examples thereof include imidazoles such as midazole, 2-e
- glass fiber cloth used for the transparent layer (B) is not particularly limited, for example, from among publicly known ones used for various transparent fiber reinforced resins, appropriately selected and used depending on the intended use and performance Can do.
- glass fiber cloths such as E glass, S glass, T glass, NE glass, L glass, D glass, Q glass, UN glass, are mentioned.
- the refractive index of the glass fiber cloth is preferably larger than 1.55, and E glass fiber cloth (preferably E glass cloth) is more preferable from the viewpoints of transparency, rigidity, workability and cost.
- the thickness of the glass fiber cloth is usually preferably 10 ⁇ m to 200 ⁇ m, and more preferably 40 ⁇ m to 150 ⁇ m. Moreover, only one sheet of these glass fiber cloths may be used, and a plurality of sheets may be used in a stacked manner. Moreover, the thing surface-treated with the silane coupling agent etc., and the thing which performed the fiber opening process physically in the woven fabric (cloth) can be used suitably from the surface of moisture absorption heat resistance.
- the method for producing the transparent layer (B) used in the display front plate of the present embodiment may be a method of processing the resin composition used for the transparent layer (B) and a glass fiber cloth together to form a layer. If it does not specifically limit.
- the resin containing the sulfur atom is a thermoplastic resin
- the glass fiber cloth is immersed in a solution in which the resin containing the sulfur compound is dissolved and impregnated with the resin containing the sulfur compound, and then heated with a dryer or the like. Thus, the solvent can be volatilized and removed. Thereafter, the resin may be heated to a temperature equal to or higher than the softening temperature of the resin containing the sulfur compound and may be compression-molded, or may be rolled using a metal roll.
- the resin containing a sulfur atom is a curable resin
- the glass fiber cloth after impregnating the glass fiber cloth with the curable resin-soluble composition, the glass fiber cloth is dried as necessary, and pressed or laminated with another base material to increase the thickness. It is prepared by a method of adjusting, crosslinking and curing the curable resin composition by at least one of heating and irradiation with actinic rays.
- the curable resin composition here refers to a mixed liquid of a curable resin monomer and a curing accelerator.
- the glass fiber cloth when the resin containing sulfur atoms is a thermosetting resin, the glass fiber cloth may be immersed in a resin composition containing a sulfur compound having fluidity at room temperature or under heating. Alternatively, the glass fiber cloth may be immersed in a solution in which a resin containing sulfur atoms is dissolved to impregnate the resin containing sulfur atoms. After impregnating the resin composition containing the sulfur compound, it is dried if necessary, pressed or laminated with another substrate, the thickness is adjusted, and the resin composition containing the sulfur compound is crosslinked by heating, A curing method is possible.
- the resin composition containing a sulfur compound represents a composition containing a resin monomer before curing.
- the resin containing sulfur atoms is a photocurable resin
- a glass fiber cloth is immersed in a photocurable resin composition containing a compound (a) having a thiol group and a compound (b) having an alkenyl group.
- a base material such as SUS plate, glass plate, polyethylene terephthalate, etc.
- actinic rays such as ultraviolet light are irradiated.
- the method for producing the transparent resin laminate (C) of the present embodiment is not particularly limited.
- the transparent layer (B) is formed on the transparent resin layer (A) via an adhesive layer.
- adhering the transparent resin layer (A) and the transparent layer (B), the transparent resin layer (A) and the transparent layer (B) are prepared using a transparent adhesive as a method for producing the transparent resin laminate. If it sticks together, it will not be specifically limited.
- the transparent layer (B) is laminated and transparently bonded. The method of hardening an agent is mentioned.
- the type and method of the transparent adhesive for laminating the transparent resin layer (A) and the transparent layer (B) are not particularly limited, but various types such as a photocurable adhesive, a thermosetting adhesive, and a room temperature curable adhesive.
- An adhesive can be used.
- an adhesive containing a solvent is used, bubbles may be generated at the time of curing, and the transparency of the entire transparent laminate may be lowered.
- the adhesive may be a one-component type or a two-component type.
- the transparent adhesive that bonds the transparent resin layer (A) and the transparent layer (B) include, for example, an epoxy adhesive, an acrylic adhesive, and a urethane adhesive.
- a transparent adhesive may be used individually by 1 type, or multiple may be mixed and used for it.
- Daikin Industries, Ltd.'s optodyne series acrylic UV adhesives for example, Optodyne UV-2000, Optodyne UV-3000, etc.
- Henkel's Loctite series acrylic UV adhesives eg, Loctite 3193HS
- World Lock series modified acrylate UV adhesive for example, World Lock XVL-90, World Lock 8807, World Lock HRJ-21, etc.
- Acrylic UV adhesive for example, GLX18-73N, etc.
- Acrylic adhesives such as Unidic V-9500 series urethane adhesives such as Unidic V-9520, Unidic V-9540, etc. manufactured by DIC; Daikin Industries Optodyne series epoxy UV adhesives (for example, Optodyne UV-1000, Optodyne UV-4000, etc.), EA series epoxy thermosetting adhesives, Sanyu Rec Co., Ltd. (EA-409, EA-415, etc.)
- epoxy adhesives such as ADEKA OPTMER KR series epoxy photo-curing adhesives (such as KR-401) manufactured by ADEKA Corporation.
- the adhesive for laminating the transparent resin layer (A) and the transparent layer (B) has a tensile elastic modulus of 1 MPa or more at the time of curing (after curing) at a thickness of 1 mm and at the time of curing.
- a tensile elastic modulus of 1 MPa or more at the time of curing (after curing) at a thickness of 1 mm and at the time of curing Use something that is transparent. The reason is as follows. In order to demonstrate the properties generally required of adhesives that make it difficult to peel off the object to be bonded even when bending or bending force is applied, tensile elasticity at the time of curing of the adhesive is high.
- the adhesive layer will be deformed when bending or bending force is applied, and the hardness of the transparent layer (B) will be in the entire transparent laminate. It is presumed not to be reflected. Therefore, in this embodiment, a certain degree of tensile elastic modulus is ensured in the adhesive layer, and the transparent resin layer (B) is bonded to both sides of the transparent resin layer (A), whereby the transparent resin layer ( A) Higher rigidity can be exhibited compared to the single case.
- the tensile elastic modulus at the time of curing (after curing) at a thickness of 1 mm of the adhesive is preferably 10 MPa or more, more preferably 20 MPa or more.
- the tensile modulus of the adhesive is preferably 4 GPa or less, more preferably 2 GPa or less.
- Examples of transparent adhesive application methods include dip coating, spray coating, spinner coating, bead coating, wire bar coating, blade coating, roller coating, curtain coating, slit die coater, and gravure.
- Examples include a coater method, a slit reverse coater method, a micro gravure method, and a comma coater method.
- the transparent layer (B) is laminated on both sides of the transparent resin layer (A), and light is emitted from one side. By irradiating, light reaches the other surface and both surfaces can be cured simultaneously.
- the thickness of the adhesive layer is preferably 1 ⁇ m to 100 ⁇ m, more preferably 5 ⁇ m to 50 ⁇ m. If the adhesive layer is too thick, the rigidity of the entire transparent laminate is lowered, and if it is too thin, the adhesiveness is lowered. When the thickness is in the above range, the rigidity and adhesiveness of the entire transparent resin laminate are improved.
- the viscosity at 23 ° C. before curing of the adhesive is preferably 10000 mPa ⁇ s or less, more preferably 5000 mPa ⁇ s or less.
- the coating film of the adhesive layer does not become too thick and is controlled to a desired thickness, so that a decrease in rigidity of the transparent resin laminate can be suppressed.
- the lower limit of the viscosity is not particularly limited as long as a good coating film is formed, but is preferably 1 mPa ⁇ s or more in terms of workability at the time of application.
- the viscosity of the adhesive before curing can be measured according to JIS7117-1: 1999 using a rotary B-type viscometer.
- the total light transmittance of the adhesive layer is preferably 80% or more, and more preferably 85% or more. If it is 80% or more, the transparency is high and it is suitable as a display front plate.
- the curing shrinkage rate of the adhesive is preferably small.
- the cure shrinkage is preferably 10% or less, and more preferably 8% or less.
- the adhesive is preferably fast-curing from the viewpoint of productivity.
- a photo-curing adhesive an adhesive that cures with an integrated light quantity of 5000 mJ / cm 2 or less is preferable.
- the transparent layer (B) when the transparent layer (B) is laminated directly on the transparent resin layer (A) and the transparent resin layer (A) and the transparent layer (B) are bonded, for example, transparent
- the resin composition forming the layer (B) contains a curable resin
- the resin composition before curing of the transparent layer (B) was applied to both sides of the transparent resin layer (A) to form a coating film.
- the coating film is cured by active energy such as heat or light, and thereby the transparent resin layer (A) and the transparent layer (B) are bonded.
- the resin composition forming the transparent layer (B) contains a thermosetting resin such as an epoxy resin
- the transparent layer (B) before curing is superimposed on both sides of the transparent resin layer (A).
- the layers may be laminated while being cured by heating to the required temperature while pressing with a hot platen.
- the resin composition which forms a transparent layer (B) contains a thermoplastic resin
- the softened transparent layer (B) There is a method in which the transparent resin layer (A) and the transparent layer (B) are adhered by solidifying by cooling to a temperature below the softening point while applying pressure on both sides of the transparent resin layer (A).
- the resin composition forming the transparent layer (B) contains a photocurable resin
- a glass fiber is used as the photocurable resin composition containing the compound (a) having a thiol group and the compound (b) having an alkenyl group.
- a method of photocuring a photocurable resin composition after laminating a coating film (transparent layer (B)) immersed in a cloth onto the transparent resin layer (A), a compound (a) having a thiol group and alkenyl A method of photocuring a coating film (transparent layer (B)) obtained by immersing a photocurable resin composition containing a group-containing compound (b) in a glass fiber cloth while adhering to the transparent resin layer (A). Is mentioned.
- the transparent resin laminate (C) used in the display front plate of this embodiment is transparent as a laminate because the transparent resin layer (A) and the transparent layer (B) are transparent. Moreover, also when laminating
- the flexural modulus of the transparent resin laminate (C) used in the display front plate of the present embodiment is preferably 5 GPa or more, more preferably 7 GPa or more, and more preferably 8 GPa or more. If the flexural modulus of the transparent resin laminate is 5 GPa or more, the rigidity is improved and it is suitably used as a display front plate.
- a transparent resin laminate having a bending elastic modulus of 5 GPa or more can be obtained by arranging a transparent layer (B) having a tensile elastic modulus of 10 GPa or more on both surfaces of a polycarbonate resin layer (A) having a bending elastic modulus of 2.6 GPa. And you can use it.
- a transparent layer (B) containing a curable resin having a tensile elastic modulus of 10 MPa or more at a thickness of 1 mm is disposed on both surfaces of a polycarbonate resin layer (A) having a flexural modulus of 2.6 GPa.
- a transparent resin laminate having an elastic modulus of 5 GPa or more is obtained and can be used.
- the flexural modulus of the transparent resin laminate is 5 GPa or more, the rigidity is improved and it is suitably used as a display front plate.
- the transparent resin laminate according to an embodiment of the present invention is a transparent resin layer (A) having a tensile elastic modulus of 10 GPa or more by impregnating and curing a glass fiber cloth with a resin composition containing a curable resin on both sides of the transparent resin layer (A). It is a transparent laminated body which bonded together the layer (B) with the transparent adhesive whose tensile elasticity modulus after hardening in thickness 1mm is 1 Mpa or more.
- a transparent layer (B) of a transparent layer (B) having a tensile elastic modulus of 10 GPa or more is bonded to both surfaces of the polycarbonate resin layer (A) with the transparent adhesive, so that it is transparent and excellent in rigidity as a whole.
- the body can be obtained.
- This transparent laminate can be suitably used as a display front plate from the viewpoint of transparency and rigidity.
- the tensile elastic modulus of the transparent layer (B) is smaller than 10 GPa, even if it is bonded to both surfaces of the polycarbonate resin layer (A) with a transparent adhesive having a tensile elastic modulus of 1 MPa or more when cured at a thickness of 1 mm, As a result, a transparent laminate having a bending elastic modulus of 5 GPa or more may not be obtained.
- the total light transmittance of the transparent resin laminate (C) used in the display front plate of the present embodiment is 80% or more, preferably 85% or more. When it is 80% or more, the transparency is high and it is suitably used as a display front plate. Further, from the viewpoint of image contrast and color reproducibility, the light transmittance at 400 nm of the transparent resin laminate (C) is preferably 60% or more, more preferably 70% or more, and particularly preferably 75%. That's it.
- a resin layer (smoothing layer) is provided on at least one surface of the transparent layer (B).
- the resin layer is more preferably a polyethylene terephthalate film layer.
- the resin layer improves the surface smoothness and makes it easy to provide functionality. That is, in the transparent resin laminate of one embodiment of the present invention, a polyethylene terephthalate film layer is disposed on at least one outer side of the transparent layer (B).
- the polyethylene terephthalate film requires surface hardness
- the scratch resistance is improved, and it is suitably used as a front plate for a display.
- a polyethylene terephthalate film as a hard coat layer that has been subjected to a hard coat treatment may be bonded together, or after a polyethylene terephthalate film is bonded, a hard coat treatment may be performed.
- a hard coat layer may be formed. That is, in the transparent resin laminate of one embodiment of the present invention, a hard coat layer is disposed on at least one outer side of the resin layer (for example, a polyethylene terephthalate film layer).
- the polyethylene terephthalate film When used as a front plate for a display, the polyethylene terephthalate film is preferably subjected to a transparent conductive film to form an electrode layer integrated material.
- a transparent conductive film layer By using an electrode layer-integrated material, an electrode layer becomes unnecessary, and material costs and process costs can be suppressed. That is, in the transparent resin laminate of one embodiment of the present invention, a transparent conductive film layer is disposed on at least one outer side of a resin layer (for example, a polyethylene terephthalate film layer).
- a transparent electrode film When a transparent electrode film is applied to the above polyethylene terephthalate film, a polyethylene terephthalate film that has been subjected to a transparent electrode film in advance may be bonded, or a transparent electrode film may be applied after the polyethylene terephthalate film has been bonded.
- patterning the film it may be performed after the polyethylene terephthalate film is bonded, or may be performed after the polyethylene terephthalate film is bonded.
- the method for attaching the polyethylene terephthalate film (layer) to the transparent layer (B) is not particularly limited.
- a photocurable resin is formed on both sides of the transparent layer (B) constituting the transparent resin laminate (C),
- An example is a method in which a suitable transparent adhesive made of a thermosetting resin, a hot melt resin, or the like is applied, and then a polyethylene terephthalate film is laminated to cure the transparent adhesive.
- the transparent layer (B) before hardening is laminated
- the sulfur atom-containing resin forming the transparent layer (B) is a thermoplastic resin
- the polyethylene terephthalate film may be laminated while being cured by heating to a required temperature while pressing with a heating plate.
- the transparent layer (B) is preheated to a temperature at which it softens, it is stacked on both sides of the transparent resin layer (A), and a polyethylene terephthalate film as a resin layer is further stacked on the outside of the transparent layer (B). You may laminate
- An epoxy-type adhesive agent an acrylic adhesive agent, and a urethane type adhesive agent can be used.
- the transparent resin laminate (C) of this embodiment is formed into the shape of a display front plate by punching the transparent resin laminate (C) as necessary as a display front plate, and is used as a liquid crystal display device, organic electro -It is attached to the surface mainly for the purpose of protecting a display device of a flat display device such as a luminescence (organic EL) device.
- the angle of the weave of the glass fiber cloth of the display front plate includes a method of giving an inclination of 1 ° or more with respect to the pixel portion row of the display element in order to prevent moire.
- the present invention will be specifically described by way of examples, but the present invention is not limited thereto.
- the light transmittance, the Abbe number, and the elasticity modulus were measured by the method shown below.
- Total light transmittance and light transmittance of each wavelength The total light transmittance is measured using a haze meter NDH-2000 (manufactured by Nippon Denshoku Industries Co., Ltd.), and the light transmittance at each wavelength is measured using a spectrophotometer MULTISPEC-1500 (manufactured by Shimadzu Corporation). It was measured.
- the Abbe number of E glass fiber cloth was measured by the following method. Using contact liquids (manufactured by Shimadzu Device Manufacturing Co., Ltd.) having different refractive indexes, a liquid having a refractive index of 589 nm and a refractive index of 1.535 to 1.570 is adjusted in increments of 0.001 to obtain an E glass fiber cloth (3313 53 S101S (manufactured by Nitto Boseki Co., Ltd.) and sandwiched in a slide glass with a 100 ⁇ m slit to produce a 100 ⁇ m-thick contact liquid-impregnated E glass fiber cloth, and a spectrum measurement is performed using a spectrophotometer It was.
- contact liquids manufactured by Shimadzu Device Manufacturing Co., Ltd.
- a liquid having a refractive index of 589 nm and a refractive index of 1.535 to 1.570 is adjusted in increments of 0.001 to obtain an E glass fiber cloth (3313 53 S101S (manu
- the Abbe number was derived from the refractive index of D line (589 nm), F line (486 nm), and C line (656 nm) of E glass fiber cloth.
- the tensile elastic modulus was measured using a dynamic viscoelasticity measuring device DMS6100 (manufactured by SII Nano Technology Co., Ltd.). The test length was 20 mm and the frequency was 1 Hz.
- the tensile elastic modulus in the present invention means a storage elastic modulus at 20 ° C.
- Example A-1 54 parts by mass of a cyclohexane oxide skeleton-containing epoxy resin (Celoxide 2021P, manufactured by Daicel Corp., refractive index 1.51), which is a resin having a lower refractive index than E glass fiber cloth, and sulfur having a higher refractive index than E glass fiber cloth 43 parts by mass of pentaerythritol tetrakisthiopropionate (hereinafter referred to as PETP, manufactured by Sakai Chemical Co., Ltd., refractive index 1.60), 4-mercaptomethyl-3,6-dithia-1, which is a resin containing a compound , 8-octanedithiol (hereinafter referred to as GST, synthesized according to Japanese Patent No.
- a cyclohexane oxide skeleton-containing epoxy resin (Celoxide 2021P, manufactured by Daicel Corp., refractive index 1.51), which is a resin having a lower refractive index than
- the monomer mixed solution is put into a vat, and an E glass fiber cloth (3313, 53, S101S, manufactured by Nitto Boseki Co., Ltd., refractive index 1.56) is immersed in the monomer mixed solution to complete the mold release treatment.
- an E glass fiber cloth 3313, 53, S101S, manufactured by Nitto Boseki Co., Ltd., refractive index 1.56
- a transparent epoxy adhesive KR-401 (manufactured by ADEKA Co., Ltd.) is applied to a polycarbonate resin plate (Iupilon NF-2000 manufactured by Mitsubishi Gas Chemical Co., Ltd., thickness 700 ⁇ m) with a bar coater to a thickness of about 30 ⁇ m, and air bubbles
- the transparent layer 1 was stacked so as not to enter.
- the other surface was coated with an adhesive, and the transparent layer 1 was layered thereon, irradiated with UV at 1000 mJ / cm 2 using a UV irradiation device, and turned over to be irradiated with 1000 mJ / cm 2 and cured.
- a three-layer transparent resin laminate of transparent layer / transparent resin layer (PC) / transparent layer was formed to produce a display front plate.
- the thickness of the display front plate was 913 ⁇ m.
- light also reached the other transparent layer 1 by irradiation from one side, and both adhesive surfaces of the transparent resin layer (PC) were cured simultaneously, but light was also irradiated from the other side just in case.
- Example A-2 The monomer mixture prepared in Example A-1 was placed in a vat, and E glass fiber cloth (3313 53 S101S, manufactured by Nitto Boseki Co., Ltd.) was immersed in the monomer mixture so that the monomer mixture was immersed in the polycarbonate resin. It was sandwiched between a plate (thickness 700 ⁇ m) and a 50 ⁇ m stretched polyethylene terephthalate film. This was placed in a blown oven and held at 40 ° C. for 5 hours, then heated to 120 ° C. at 0.5 ° C./min, cured by holding at 120 ° C.
- Tetrabutylphosphonium O, O-Diethyl Phosphodithioate By Wako Pure Chemical Pure Chemical Industries Co., Ltd. 0.8 parts by mass was added and stirred for 5 minutes with a magnetic stirrer, was a monomer mixture solution.
- E monomer fiber solution (3313 53 S101S, manufactured by Nitto Boseki Co., Ltd., refractive index 1.56) is immersed in the above monomer mixed solution and heated at 130 ° C. for 4 minutes to remove the solvent and resin. Semi-cured to prepare a prepreg. Then, this single prepreg is sandwiched between surface-treated SUS plates, set in a hot and cold press VH2-1630 (manufactured by Kitagawa Seiki Co., Ltd.), heated to 200 ° C. at 3 ° C./min, and at 200 ° C. for 1 hour. Holding and hardening, the transparent layer 2 was obtained.
- the light transmittance at 550 nm and the flexural modulus were measured.
- Example B-1 Tricyclodecane dimethanol diacrylate of an alicyclic resin having an alkenyl group, which is a resin having a lower refractive index than the E glass fiber cloth used (hereinafter referred to as A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.) 1.53) 83 parts by mass and 4-mercaptomethyl-3,6-dithia-1,8-octanedithiol (hereinafter referred to as GST) which is a resin having a thiol group having a higher refractive index than the E glass fiber cloth used.
- A-DCP a resin having a lower refractive index than the E glass fiber cloth used
- GST 4-mercaptomethyl-3,6-dithia-1,8-octanedithiol
- the monomer mixed solution is put into a pad, and an E glass fiber cloth (3313 53 S101S, manufactured by Nitto Boseki Co., Ltd., refractive index 1.56) is immersed therein to allow the monomer mixed solution to be immersed therein.
- an E glass fiber cloth 3313 53 S101S, manufactured by Nitto Boseki Co., Ltd., refractive index 1.56
- a transparent epoxy adhesive KR-401 (manufactured by ADEKA Co., Ltd.) is applied to a polycarbonate resin plate (Iupilon NF-2000, manufactured by Mitsubishi Gas Chemical Co., Ltd., thickness 800 ⁇ m) with a bar coater to a thickness of about 30 ⁇ m.
- the transparent fiber reinforced resin 1 is layered so that bubbles do not enter, and ultraviolet light is irradiated at 1000 mJ / cm 2 using an ultraviolet light irradiation device (eye ultraviolet curing device, manufactured by Eye Graphics Co., Ltd.). / Cm 2 irradiation and curing.
- Comparative Example B-1 70 parts by mass of A-DCP (made by Shin-Nakamura Chemical Co., Ltd., refractive index 1.53) of an alicyclic resin having an alkenyl group, which is a resin having a refractive index lower than that of the used E glass fiber cloth, was used.
- Shin-Nakamura Chemical, 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene hereinafter referred to as A-BPEF
- A-BPEF 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene
- the monomer mixed solution is put into a pad, and an E glass fiber cloth (3313 53 S101S, manufactured by Nitto Boseki Co., Ltd., refractive index 1.56) is immersed therein to allow the monomer mixed solution to be immersed therein.
- an E glass fiber cloth 3313 53 S101S, manufactured by Nitto Boseki Co., Ltd., refractive index 1.56
- Example C-1 51 parts by mass of a cyclohexane oxide skeleton-containing epoxy resin (Celoxide 2021P, manufactured by Daicel Corporation, refractive index 1.51), which is a resin having a lower refractive index than E glass cloth, and a cyclohexane oxide skeleton-containing epoxy resin (Celoxide 2000Z, ( Co., Ltd., manufactured by Daicel Corporation, refractive index 1.50) 3 parts by mass, pentaerythritol tetrakisthiopropionate (hereinafter referred to as PETP, manufactured by Sakai Chemical Co., Ltd.), which is a resin having a higher refractive index than the E glass cloth used.
- a cyclohexane oxide skeleton-containing epoxy resin (Celoxide 2021P, manufactured by Daicel Corporation, refractive index 1.51), which is a resin having a lower refractive index than E glass cloth
- Refractive index 1.60 43 parts by mass, 4-mercaptomethyl-3,6-dithia-1,8-octanedithiol (hereinafter referred to as GST, synthesized in accordance with Japanese Patent No. 3048929, refractive index 1.70) 3 parts by mass
- the parts were mixed and stirred with a magnetic stirrer for 5 minutes. Further, 1 part by mass of Tetrabutylphosphonium O, O-Diethyl Phosphodithioate (Wako Pure Chemical Industries, Ltd.) was added as a curing accelerator, and the mixture was stirred for 5 minutes with a magnetic stirrer to obtain a monomer mixture.
- the monomer mixed solution is put into a vat, and E glass cloth (3313 53 S101S, manufactured by Nitto Boseki Co., Ltd., refractive index 1.56) is immersed in the monomer mixed solution so that the release treatment has been completed. It was sandwiched between polyethylene terephthalate films. This was placed in a blown oven and held at 40 ° C. for 5 hours, then heated to 120 ° C. at 0.5 ° C./min and cured by holding at 120 ° C. for 5 hours to obtain a transparent layer. The total thickness of the transparent layer was 186 ⁇ m (single side: 93 ⁇ m).
- a transparent epoxy adhesive KR-401 (manufactured by ADEKA Co., Ltd.) was applied to a polycarbonate resin plate (Iupilon NF-2000, manufactured by Mitsubishi Gas Chemical Co., Ltd., thickness 800 ⁇ m) with a bar coater to a thickness of about 20 ⁇ m.
- the transparent layer was layered so that no bubbles could enter.
- the other surface was coated with an adhesive, and a transparent layer was laminated thereon.
- UV was irradiated at 1000 mJ / cm 2 , and turned over to be irradiated at 1000 mJ / cm 2 to be cured.
- Example C-2 Transparent layer / polycarbonate resin layer / transparent in the same manner as in Example 1 except that 48 parts by mass of Celoxide 2021P, 6 parts by mass of Celoxide 2000Z, 43 parts by mass of PETP, and 3 parts by mass of GST were mixed to obtain a monomer mixture. A three-layer transparent laminate of layers was obtained. The total thickness of this transparent layer was 178 ⁇ m (one side: 89 ⁇ m), and the thickness of the transparent laminate was 1028 ⁇ m.
- Example C-3 Transparent layer / polycarbonate resin layer in the same manner as in Example C-1, except that 42 parts by mass of Celoxide 2021P, 12 parts by mass of Celoxide 2000Z, 41 parts by mass of PETP, and 5 parts by mass of GST were mixed to obtain a monomer mixture. / A three-layer transparent laminate of transparent layers was obtained. The total thickness of this transparent layer was 182 ⁇ m (single side: 91 ⁇ m), and the thickness of the transparent laminate was 1037 ⁇ m.
- Example C-4 Transparent layer / polycarbonate resin layer in the same manner as in Example C-1, except that 36 parts by mass of Celoxide 2021P, 18 parts by mass of Celoxide 2000Z, 42 parts by mass of PETP, and 4 parts by mass of GST were mixed to obtain a monomer mixture. / A three-layer transparent laminate of transparent layers was obtained. The total thickness of the transparent layer was 172 ⁇ m (one side: 86 ⁇ m), and the thickness of the transparent laminate was 1045 ⁇ m.
- Example C-5 Transparent layer / polycarbonate resin layer in the same manner as in Example C-1, except that 27 parts by mass of Celoxide 2021P, 27 parts by mass of Celoxide 2000Z, 40 parts by mass of PETP, and 6 parts by mass of GST were mixed to obtain a monomer mixture. / A three-layer transparent laminate of transparent layers was obtained. The total thickness of the transparent layer was 210 ⁇ m (single side: 105 ⁇ m), and the thickness of the transparent laminate was 1016 ⁇ m.
- the tensile modulus of the curable resin for the transparent layer was measured by the following method.
- a SUS frame (thickness 1 mm) with a hole of 2 cm ⁇ 4 cm is placed on a release-treated glass plate, filled with each monomer mixture into the hole, covered with the release-treated glass plate, and UV irradiation device
- the sample was irradiated with UV at 1000 mJ / cm 2 , further turned over, and cured by irradiation at 1000 mJ / cm 2 to obtain a curable resin test piece.
- the tensile elasticity modulus was measured by said method.
- the total light transmittance of the transparent layer was 80% or more in all Examples.
- the flexural modulus of the polycarbonate resin layer (thickness 800 ⁇ m) as the transparent resin layer (A layer) was 2.6 GPa. As shown in Table C2, in Examples C-1 to C-4, the flexural modulus of the transparent laminate was all 5 GPa or more. From this, it is confirmed that the rigidity (bending elastic modulus) of the laminate can be further improved by including a curable resin having a tensile elastic modulus of 10 MPa or more in the transparent layer.
- Example D-1 Preparation of transparent resin laminate> [Example D-1] (Preparation of transparent layer (B-1)) E glass fiber cloth (3313 53 S101S, manufactured by Nitto Boseki Co., Ltd.) was used as the glass fiber cloth. 54 parts by mass of a cyclohexane oxide skeleton-containing epoxy resin (Celoxide 2021P, manufactured by Daicel Corporation, refractive index 1.51), which is a resin having a lower refractive index than the used E glass fiber cloth, is refracted more than the used E glass cloth.
- a cyclohexane oxide skeleton-containing epoxy resin (Celoxide 2021P, manufactured by Daicel Corporation, refractive index 1.51), which is a resin having a lower refractive index than the used E glass fiber cloth, is refracted more than the used E glass cloth.
- Tetrabutylphosphonium O, O-Diethyl Phosphorodithioate (Wako Pure Chemical Industries, Ltd.) was added as a curing accelerator and stirred with a magnetic stirrer for 5 minutes to obtain a curable resin composition.
- the curable resin composition was placed in a vat, and an E glass fiber cloth was immersed therein to infiltrate the curable resin composition, and was sandwiched between release-treated PET films. This was placed in a blown oven and held at 40 ° C. for 5 hours, then heated to 120 ° C. at 0.5 ° C./min, cured by holding at 120 ° C. for 5 hours, and a transparent layer (B -1) was obtained. The tensile modulus of the transparent layer (B-1) was 19 GPa.
- the other surface was coated with an adhesive, and the transparent layer (B-1) was layered thereon, irradiated with UV at 1000 mJ / cm 2 using a UV irradiation device, and turned over to be irradiated with 1000 mJ / cm 2 and cured.
- a three-layer transparent laminate of transparent layer (B-1) / polycarbonate resin layer (A) / transparent layer (B-1) was obtained.
- the thickness of this transparent laminate was 1013 ⁇ m. Note that light from one side also reached the other transparent layer (B-1), and both adhesive surfaces of the polycarbonate resin layer (A) were cured at the same time. did.
- Example D-2 (Preparation of transparent layer (B-2)) E glass fiber cloth (3313 53 S101S, Nittobo Co., Ltd.) was used as the glass fiber cloth in the same manner as in Example 1.
- 83 parts by mass of tricyclodecane dimethanol diacrylate (made by Shin-Nakamura Chemical Co., Ltd., refractive index 1.53) of an alicyclic acrylate resin which is a resin having a lower refractive index than the E glass fiber cloth used 17 parts by mass of GST, which is a resin having a higher refractive index than the conventional E glass fiber cloth, was mixed and stirred for 5 minutes with a magnetic stirrer.
- a curable resin composition 0.5 part by mass of Irgacure 184 was added as a photopolymerization initiator and stirred for 5 minutes with a magnetic stirrer to obtain a curable resin composition.
- the curable resin composition was placed in a pad, and an E glass fiber cloth was immersed therein to infiltrate the curable resin composition, and was sandwiched between the release-treated PET films. This was irradiated with UV at 1000 mJ / cm 2 using a UV irradiation apparatus, turned over, and irradiated with 1000 mJ / cm 2 to be cured to obtain a transparent layer (B-2) having a thickness of 119 ⁇ m.
- the tensile modulus of the transparent layer (B-2) was 18 GPa.
- Example D-3 A transparent layer (B-1) / polycarbonate resin layer (in the same manner as in Example D-1) except that GLX18-73N (manufactured by Guru Labs, tensile elastic modulus at a thickness of 1 mm is 26 MPa) was used as an adhesive. A three-layer transparent laminate of A) / transparent layer (B-1) was obtained. The thickness of this transparent laminate was 1058 ⁇ m.
- Example D-4 A transparent layer (B) was prepared in the same manner as in Example D-1, except that Worldlock HRJ-21 (manufactured by Kyoritsu Chemical Industry Co., Ltd., tensile elastic modulus at a thickness of 1 mm was 0.32 MPa) was used as an adhesive. -1) A three-layer transparent laminate of polycarbonate resin layer (A) / transparent layer (B-1) was obtained. The thickness of this transparent laminate was 1061 ⁇ m.
- a transparent epoxy adhesive KR-401 is applied to a polycarbonate resin plate (Iupilon NF-2000, manufactured by Mitsubishi Gas Chemical Co., Ltd., thickness 700 ⁇ m) with a bar coater at a thickness of about 30 ⁇ m, and polyethylene is used to prevent bubbles from entering.
- a terephthalate (PET) resin film (thickness: 100 ⁇ m) was stacked.
- PET terephthalate
- the other surface was coated with an adhesive, overlapped with a PET resin film, irradiated with UV at 1000 mJ / cm 2 using a UV irradiation device, and further turned over and irradiated with 1000 mJ / cm 2 to be cured.
- a three-layer transparent laminate of PET resin film / polycarbonate resin layer / PET resin film was obtained.
- the thickness of this transparent laminate was 1014 ⁇ m.
- the total light transmittance and bending elastic modulus of the transparent resin laminate; the tensile elastic modulus of the adhesive; and the tensile elastic modulus of the transparent layer (B) were evaluated by the evaluation methods described above. .
- the tensile modulus of the adhesive was measured by the following method.
- the total light transmittance of the transparent layer was 80% or more in all Examples.
- the transparent laminate has a flexural modulus of 5 GPa or more, and is used for front plate materials such as various glazing materials, substrate materials, and display front plates as a substitute for glass. Therefore, a preferable rigidity can be obtained. From this, the rigidity (bending elastic modulus) of the laminate can be further improved by using an adhesive having a tensile elastic modulus of the transparent layer (B) of 10 GPa or more and an elastic modulus of 1 MPa or more. It is confirmed.
- Comparative Example D-1 in which a film having a tensile modulus of 10 GPa or less was used for the transparent layer (B), an adhesive having an elastic modulus of 1 MPa or less was used, but the flexural modulus of the transparent laminate was 5 GPa or less. It was.
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Abstract
Description
(2) 透明樹脂層(A)の両面に、ガラス繊維布と、チオール基を有する化合物(a)及びアルケニル基を有する化合物(b)を含有する樹脂組成物で形成された透明層(B)が配された、(1)に記載の透明樹脂積層体。
(3) 透明樹脂層(A)の両面に、厚さ1mmにおける硬化時の引張弾性率が10MPa以上である硬化性樹脂を含む、樹脂組成物をガラス繊維布に含浸させてなる透明層(B)が配された、(1)または(2)に記載の透明樹脂積層体。
(4) 前記透明樹脂層(A)と前記透明層(B)との間に透明接着剤を含む接着剤層を有する、(1)~(3)のいずれか一項に記載の透明樹脂積層体。
(5) 前記接着剤層の厚みが、1μm~100μmである、(4)に記載の透明樹脂積層体。
(6) 前記透明接着剤の厚さ1mmにおける硬化時の引張弾性率が、1MPa以上である、(4)または(5)に記載の透明樹脂積層体。
(7) 透明樹脂層(A)の両面に、硬化性樹脂を含む樹脂組成物をガラス繊維布に含浸及び硬化させて引張弾性率を10GPa以上とした透明層(B)を、厚さ1mmにおける硬化時の引張弾性率が1MPa以上の透明接着剤で貼り合わせた、(1)~(6)のいずれか一項に記載の透明樹脂積層体。
(8) 前記透明接着剤は、アクリル系接着剤、エポキシ系接着剤、およびウレタン系接着剤からなる群から選択される少なくとも一種である、(4)~(7)のいずれか一項に記載の透明樹脂積層体。
(9) 前記透明樹脂積層体の曲げ弾性率が、5GPa以上である、(1)~(8)のいずれか一項に記載の透明樹脂積層体。
(10) 前記透明樹脂層(A)の厚みが、100μm~2000μm、かつ前記透明層(B)の厚みが20μm~300μmである、(1)~(9)のいずれか一項に記載の透明樹脂積層体。
(11) 全光線透過率が80%以上である、(1)~(10)のいずれか一項に記載の透明樹脂積層体。
(12) 前記透明層(B)における樹脂組成物の硬化時におけるアッベ数と、ガラス繊維布のアッベ数との差が15以下である、(1)~(11)のいずれか一項に記載の透明樹脂積層体。
(13) 前記透明層(B)における樹脂組成物の屈折率と、ガラス繊維布の屈折率との差が0.01以下である、(1)~(12)のいずれか一項に記載の透明樹脂積層体。
(14) 前記透明層(B)における樹脂組成物が、チオール化合物とエポキシ樹脂との重合物を含有する、(1)~(13)のいずれか一項に記載の透明樹脂積層体。
(15) 前記透明層(B)におけるガラス繊維布の屈折率が、1.55より大きい、(1)~(14)のいずれか一項に記載の透明樹脂積層体。
(16) 前記透明層(B)のガラス繊維布がEガラスクロスである、(1)~(15)のいずれか一項に記載の透明樹脂積層体。
(17) 前記透明樹脂層(A)における樹脂成分が、ポリカーボネート、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリメチルメタクリレートなる群から選択される少なくとも一種を含む、(1)~(16)のいずれか一項に記載の透明樹脂積層体。
(18) 前記透明樹脂層(A)における樹脂成分が、ポリカーボネートを含む、(17)に記載の透明樹脂積層体。
(19) 前記透明層(B)の少なくとも一方の外側にポリエチレンテレフタレートフィルム層が配された、(1)~(18)のいずれか一項に記載の透明樹脂積層体。
(20) 前記ポリエチレンテレフタレートフィルム層のさらに少なくとも一方の外側にハードコート層が配された、(19)に記載の透明樹脂積層体。
(21) 前記ポリエチレンテレフタレートフィルム層のさらに少なくとも一方の外側に透明導電膜層が配された、(19)または(20)に記載の透明樹脂積層体。
(22) (1)~(21)のいずれか一項に記載の透明樹脂積層体を用いた、ディスプレイ用前面板。
(1) 透明樹脂層(A)の両面に、ガラス繊維布及び硫黄化合物を含有する樹脂組成物で形成された透明層(B)が配された透明樹脂積層体(C)からなる、ディスプレイ用前面板。
(2) 前記透明樹脂層(A)の厚みが、100μm~2000μm、かつ前記透明層(B)の厚みが20μm~300μmである、(1)に記載のディスプレイ用前面板。
(3) 前記透明樹脂積層体(C)の曲げ弾性率が、5GPa以上である、(1)又は(2)に記載のディスプレイ用前面板。
(4) 全光線透過率が80%以上である、(1)~(3)のいずれか一項に記載のディスプレイ用前面板。
(5) 前記透明層(B)における、硫黄化合物を含有する樹脂組成物の硬化時におけるアッベ数と、ガラス繊維布のアッベ数の差が15以下である、(1)~(4)のいずれか一項に記載のディスプレイ用前面板。
(6) 前記透明層(B)における、硫黄化合物を含有する樹脂組成物の硬化時における屈折率と、ガラス繊維布の屈折率の差が0.01以下である、(1)~(5)のいずれか一項に記載のディスプレイ用前面板。
(7) 前記透明層(B)における、硫黄化合物を含有する樹脂組成物が、チオール化合物とエポキシ樹脂の重合物を含有するものである、(1)~(6)のいずれか一項に記載のディスプレイ用前面板。
(8) 前記透明層(B)におけるガラス繊維布の屈折率が、1.55より大きいものである、(1)~(7)のいずれか一項に記載のディスプレイ用前面板。
(9) 前記透明樹脂層(A)における樹脂成分が、ポリカーボネート、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリメチルメタクリレートから選ばれる群のうち、いずれか一種以上である、(1)~(8)のいずれか一項に記載のディスプレイ用前面板。
(10) 前記透明樹脂積層体(C)のさらに少なくとも一方の外側にポリエチレンテレフタレートフィルム層が配された、(1)~(9)のいずれか一項に記載のディスプレイ用前面板。
(11) 前記ポリエチレンテレフタレートフィルム層のさらに少なくとも一方の外側にハードコート層が配された、(10)に記載のディスプレイ用前面板。
(12) 前記ポリエチレンテレフタレートフィルム層のさらに少なくとも一方の外側に透明導電膜層が配された、(10)に記載のディスプレイ用前面板。
(1) 透明樹脂層(A)の両面に、ガラス繊維布及びチオール基を有する化合物(a)及びアルケニル基を有する化合物(b)を含有する光硬化性樹脂組成物で形成された透明層(B)が配された、透明樹脂積層体(C)からなるディスプレイ用前面板。
(2) 前記透明樹脂層(A)の厚みが、100μm~2000μm、かつ前記透明層(B)の厚みが20μm~300μmである、(1)に記載のディスプレイ用前面板。
(3) 前記透明樹脂積層体(C)の曲げ弾性率が、5GPa以上である、(1)又は(2)に記載のディスプレイ用前面板。
(4) 全光線透過率が80%以上である、(1)~(3)のいずれか一項に記載のディスプレイ用前面板。
(5) 前記透明層(B)における、光硬化性樹脂組成物の硬化時におけるアッベ数と、ガラス繊維布のアッベ数の差が15以下である、(1)~(4)のいずれか一項に記載のディスプレイ用前面板。
(6) 前記透明層(B)における、光硬化性樹脂組成物の硬化時における屈折率と、ガラス繊維布の屈折率の差が0.01以下である、(1)~(5)のいずれか一項に記載のディスプレイ用前面板。
(7) 前記透明層(B)におけるガラス繊維布の屈折率が、1.55より大きいものである、(1)~(6)のいずれか一項に記載のディスプレイ用前面板。
(8) 前記透明樹脂層(A)における樹脂成分が、ポリカーボネート、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリメチルメタクリレートから選ばれる群のうち、いずれか一種以上である、(1)~(7)のいずれか一項に記載のディスプレイ用前面板。
(9) 前記透明樹脂積層体(C)のさらに少なくとも一方の外側にポリエチレンテレフタレートフィルム層が配された、(1)~(8)のいずれか一項に記載のディスプレイ用前面板。
(10) 前記ポリエチレンテレフタレートフィルム層のさらに少なくとも一方の外側にハードコート層が配された、(9)に記載のディスプレイ用前面板。
(11) 前記ポリエチレンテレフタレートフィルム層のさらに少なくとも一方の外側に透明導電膜層が配された、(10)に記載のディスプレイ用前面板。
(1) ポリカーボネート樹脂層(A)の両面に、厚さ1mmにおける硬化時の引張弾性率が10MPa以上である硬化性樹脂にガラス繊維布を含浸させた透明層(B)が配された、透明積層体であって、全体としての曲げ弾性率が5GPa以上である、透明積層体。
(2) 前記ポリカーボネート樹脂層(A)の厚みが、100μm~2000μm、かつ前記透明層(B)の厚みが20μm~300μmである、(1)に記載の透明積層体。
(3) 前記透明層(B)の硬化性樹脂が、エポキシ樹脂を含有するものである、(1)又は(2)に記載の透明積層体。
(4) 前記透明層(B)のガラス繊維布がEガラスクロスである、(1)~(3)のいずれか一項に記載の透明積層体。
(5) 前記透明層(B)の全光線透過率が80%以上である、(1)~(4)のいずれか一項に記載の透明積層体。
(6) (1)~(5)のいずれか一項に記載の透明積層体のさらに少なくとも一方の外側にポリエチレンテレフタレートフィルム層が配された、透明積層体。
(7) 前記ポリエチレンテレフタレートフィルム層のさらに少なくとも一方の外側にハードコート層が配された、(6)に記載の透明積層体。
(8) 前記ポリエチレンテレフタレートフィルム層のさらに少なくとも一方の外側に透明導電膜層が配された、(6)に記載の透明積層体。
(9) (1)~(8)のいずれか一項に記載の透明積層体を用いたディスプレイ用前面板。
である。
(1) ポリカーボネート樹脂層(A)の両面に、硬化性樹脂をガラス繊維布に含浸及び硬化させて引張弾性率を10GPa以上とした透明層(B)を、厚さ1mmにおける硬化時の引張弾性率が1MPa以上の透明接着剤で貼り合わせた透明積層体であって、全体としての曲げ弾性率が5GPa以上である、透明積層体。
(2) 全光線透過率が80%以上である、(1)に記載の透明積層体。
(3) 前記ポリカーボネート樹脂層(A)の厚みが100μm~2000μm、かつ前記透明層(B)の厚みが20μm~300μmである、(1)又は(2)に記載の透明積層体。
(4) (1)~(3)のいずれか一項に記載の透明積層体の少なくとも一方の外側にポリエチレンテレフタレートフィルム層が配された、透明積層体。
(5) 前記ポリエチレンテレフタレートフィルム層のさらに少なくとも一方の外側にハードコート層が配された、(4)に記載の透明積層体。
(6) 前記ポリエチレンテレフタレートフィルム層のさらに少なくとも一方の外側に透明導電膜層が配された、(4)に記載の透明積層体。
(7) (1)~(6)のいずれかに記載の透明積層体を用いた、ディスプレイ用前面板。
(1)ガラス繊維布のアッベ数、屈折率に合った硫黄原子を含有する樹脂を選択する方法、
(2)ガラス繊維布よりも屈折率の高い樹脂とガラス繊維布よりも屈折率の低い樹脂とを組み合わせることにより硫黄化合物を含有する樹脂組成物のアッベ数、屈折率をガラス繊維布と一致させる方法等が採用され得る。高い透明性を得るためには樹脂組成物とガラス繊維布の屈折率とを精密に一致させることが好ましいため、(1)の方法において複数の反応性モノマー(硬化性樹脂)および硬化剤を用いる方法または(2)の方法が好ましい。なお、本明細書において、屈折率が一致するとは、屈折率差が0.01以下、好ましくは0.005以下であることを意味する。また、アッベ数が一致するとは、アッベ数差が15以下、好ましくは10以下であることを意味する。
前記硫黄原子を含有する樹脂の屈折率とガラス繊維布の屈折率が一致している場合は、硫黄原子を含有する樹脂をそのまま使用することができる。例えば、共重合樹脂や硬化性樹脂を構成するモノマーや硬化剤の種類や量を調整することで、屈折率がガラス繊維と一致するように構成することができる。このような樹脂としては、例えば、硫黄原子を含有する熱可塑性樹脂、硫黄原子を含有する熱硬化性樹脂、および硫黄原子を含有する光硬化性樹脂から選択される少なくとも1種の硫黄原子含有樹脂が挙げられる。この場合、硫黄原子を含有する樹脂を1種類のみを用いても良いし、2種類以上を組み合わせて用いてもよい。屈折率の異なる複数の硫黄原子含有樹脂(モノマー)を混合させることで樹脂組成物とガラス繊維布の屈折率とを精密に一致させることができ、高い透明性を達成し得る。
硫黄化合物を含有する樹脂とガラス繊維布の屈折率が一致していない場合は、ガラス繊維布よりも屈折率の高い樹脂とガラス繊維布よりも屈折率の低い他の樹脂と混合して調節することができる。このような透明層(B)を構成する樹脂組成物の具体的な構成としては、例えば、硫黄原子を含有する熱可塑性樹脂、硫黄原子を含有する熱硬化性樹脂、および硫黄原子を含有する光硬化性樹脂から選択される少なくとも1種の硫黄原子含有樹脂と、前記硫黄原子含有樹脂とは屈折率の異なる他の樹脂(硫黄原子非含有樹脂)とを含む構成が挙げられる。例えば、透明層(B)の樹脂組成物の屈折率は、ガラス繊維布よりも屈折率の高い硫黄原子を含有する樹脂とガラス繊維布よりも屈折率の低い他の樹脂(硫黄原子非含有樹脂)とを混合して調節する方法が好ましい。ガラス繊維布よりも屈折率の高い硫黄原子を含有する樹脂(硫黄原子含有樹脂)と屈折率の低い樹脂(他の樹脂)を混合する場合、硫黄原子含有樹脂および他の樹脂(硫黄原子非含有樹脂)はそれぞれ1種類ずつを混合しても良いし、2種類以上を用いても良い。
(硬化収縮率の測定方法)
接着剤の液比重をJIS K 7232:1986の3.1(1)から求め、接着剤の硬化体の比重をJIS K 7232の3.2(1)から求め、以下の式より硬化収縮率を測定する。
(硬化収縮率)=(硬化体比重-液比重)/(硬化体比重)×100(%)
ヘーズメーターNDH-2000(日本電色工業株式会社製)を用いて、全光線透過率を測定し、分光光度計MULTISPEC-1500(株式会社島津製作所製)を用いて、各波長における光線透過率を測定した。
(透明層(B))
多波長アッベ屈折計DR-M4(株式会社アタゴ製)を用いて、屈折率およびアッベ数を測定した
Eガラス繊維布のアッベ数は以下の方法で測定した。屈折率の異なる接触液(島津デバイス製造製)を用いて589nmの屈折率が1.535~1.570の屈折率の液を屈折率差0.001刻みで調整し、Eガラス繊維布(3313 53 S101S、日東紡績株式会社製)に含浸させて、100μmのスリットを付けたスライドガラスに挟み込み、厚さ100μmの接触液含浸Eガラス繊維布を作製し、分光光度計を用いてスペクトル測定を行った。
精密万能試験機AG-5000B(株式会社島津製作所製)を用いて3点曲げ試験で測定した。支点間距離は20mm、ストローク速度は1mm/minとした。ロードセルについては1kNのものを使用した。
動的粘弾性測定装置DMS6100(エスアイアイ・ナノテクノロジー株式会社製)を用いて、引張弾性率を測定した。試長は20mm、周波数は1Hzとした。本発明における引張弾性率とは、20℃における貯蔵弾性率を意味する。
[実施例A-1]
Eガラス繊維布よりも屈折率の低い樹脂であるシクロヘキサンオキサイド骨格含有エポキシ樹脂(セロキサイド2021P(株)ダイセル製、屈折率1.51)54質量部と、Eガラス繊維布よりも屈折率の高い硫黄化合物を含有する樹脂であるペンタエリスリトールテトラキスチオプロピオネート(以下、PETPと称する、淀化学(株)製、屈折率1.60)43質量部、4-メルカプトメチル-3,6-ジチア-1,8-オクタンジチオール(以下GSTと呼称する、特許第3048929号公報に従い合成、屈折率1.70)3質量部を混合し、マグネチックスターラーで5分間撹拌した。さらに硬化促進剤としてTetrabutylphosphonium O,O-Diethyl Phosphorodithioate(和光純薬純薬工業(株))1質量部を加え、マグネチックスターラーで5分間撹拌し、モノマー混合液とした。
実施例A-1で作製したモノマー混合液をバットに入れ、そこにEガラス繊維布(3313 53 S101S、日東紡績(株)製)を浸漬して上記モノマー混合液を浸み込ませ、ポリカーボネート樹脂板(厚さ700μm)と50μmの延伸ポリエチレンテレフタレートフィルムで挟んだ。これを送風式オーブンに入れ、40℃で5時間保持した後、0.5℃/minで120℃まで昇温し、120℃で5時間保持して硬化し、延伸ポリエチレンテレフタレートフィルム/透明層/透明樹脂層(PC)/透明層/延伸ポリエチレンテレフタレートフィルムの五層透明樹脂積層体を形成して、ディスプレイ用前面板を作成した。このディスプレイ用前面板の厚みは990μmであった。
Eガラス繊維布よりも屈折率の低い樹脂であるトリアジン骨格含有エポキシ樹脂(TEPIC-S(日産化学工業(株)製、屈折率1.54)47質量部と、Eガラス繊維布よりも屈折率の高い硫黄を含まない樹脂であるエポキシ樹脂(テクモアVG3101(株)プリンテック製、屈折率1.61)21質量部及び、硬化剤(リカシッドMH700(4-メチルヘキサヒドロ無水フタル酸/ヘキサヒドロ無水フタル酸=70/30)(新日本理化(株)製、屈折率1.49))32質量部を混合し、2-ブタノンで50wt%になるように希釈した後にマグネチックスターラーで10分間撹拌した。さらに硬化促進剤としてTetrabutylphosphonium O,O-Diethyl Phosphorodithioate(和光純薬純薬工業(株))を0.8質量部加え、マグネチックスターラーで5分間撹拌し、モノマー混合溶液とした。
以上のようにして作製した透明樹脂積層体について、上記に示す評価方法により、透明層またはガラス繊維布の屈折率、全光線透過率およびアッベ数;ならびに透明樹脂積層体の全光線透過率、400nmまたは550nmの光線透過率、および曲げ弾性率を測定した。
[実施例B-1]
用いたEガラス繊維布よりも屈折率の低い樹脂であるアルケニル基を有する脂環式樹脂のトリシクロデカンジメタノールジアクリレート(以下、A-DCPと称する、新中村化学工業(株)製、屈折率1.53)83質量部と、用いたEガラス繊維布よりも屈折率の高いチオール基を有する樹脂である4-メルカプトメチル-3,6-ジチア-1,8-オクタンジチオール(以下、GSTと称する、三井化学(株)製、1.70)17質量部を混合し、マグネチックスターラーで5分間攪拌した。さらに、光重合開始剤としてイルガキュア184を樹脂質量部に対して0.5質量部加え、マグネチックスターラーで5分間攪拌し、モノマー混合液とした。
用いたEガラス繊維布よりも屈折率の低い樹脂であるアルケニル基を有する脂環式樹脂のA-DCP(新中村化学工業(株)製、屈折率1.53)70 質量部と、用いたEガラス繊維布よりも屈折率の高いアルケニル基を有する芳香族系樹脂である9,9-ビス[4-(2-アクリロイルオキシエトキシ)フェニル]フルオレン(以下、A-BPEFと称する、新中村化学工業(株)製、屈折率1.62)30質量部を混合し、マグネチックスターラーで、50℃、30分間攪拌した。さらに、光重合開始剤としてイルガキュア184を樹脂質量部に対して0.5質量部加え、マグネチックスターラーで、50℃、5分間攪拌し、モノマー混合液とした。
以上のようにして作製した透明樹脂積層体について、上記に示す評価方法により、透明層(透明繊維強化樹脂層)またはガラス繊維布の屈折率、全光線透過率およびアッベ数;ならびに透明樹脂積層体の全光線透過率、400nmまたは550nmの光線透過率、および曲げ弾性率を測定した。
[実施例C-1]
Eガラスクロスよりも屈折率の低い樹脂であるシクロヘキサンオキサイド骨格含有エポキシ樹脂(セロキサイド2021P、(株)ダイセル製、屈折率1.51)51質量部と、シクロヘキサンオキサイド骨格含有エポキシ樹脂(セロキサイド2000Z、(株)ダイセル製、屈折率1.50)3質量部、用いたEガラスクロスよりも屈折率の高い樹脂であるペンタエリスリトールテトラキスチオプロピオネート(以下、PETPと称する、淀化学(株)製、屈折率1.60)43質量部、4-メルカプトメチル-3,6-ジチア-1,8-オクタンジチオール(以下GSTと呼称する、特許第3048929号公報に従い合成、屈折率1.70)3質量部を混合し、マグネチックスターラーで5分間撹拌した。さらに硬化促進剤としてTetrabutylphosphonium O,O-Diethyl Phosphorodithioate(和光純薬純薬工業(株))1質量部を加え、マグネチックスターラーで5分間撹拌し、モノマー混合液とした。
セロキサイド2021Pを48質量部、セロキサイド2000Zを6質量部、PETPを43質量部、GSTを3質量部混合し、モノマー混合液とした以外は実施例1と同様にして透明層/ポリカーボネート樹脂層/透明層の三層透明積層体を得た。この透明層の厚みは合計で178μm(片面:89μm)であり、透明積層体の厚みは1028μmであった。
セロキサイド2021Pを42質量部、セロキサイド2000Zを12質量部、PETPを41質量部、GSTを5質量部混合し、モノマー混合液とした以外は実施例C-1と同様にして透明層/ポリカーボネート樹脂層/透明層の三層透明積層体を得た。この透明層の厚みは合計で182μm(片面:91μm)であり、透明積層体の厚みは1037μmであった。
セロキサイド2021Pを36質量部、セロキサイド2000Zを18質量部、PETPを42質量部、GSTを4質量部混合し、モノマー混合液とした以外は実施例C-1と同様にして透明層/ポリカーボネート樹脂層/透明層の三層透明積層体を得た。この透明層の厚みは合計で172μm(片面:86μm)であり、透明積層体の厚みは1045μmであった。
セロキサイド2021Pを27質量部、セロキサイド2000Zを27質量部、PETPを40質量部、GSTを6質量部混合し、モノマー混合液とした以外は実施例C-1と同様にして透明層/ポリカーボネート樹脂層/透明層の三層透明積層体を得た。この透明層の厚みは合計で210μm(片面:105μm)であり、透明積層体の厚みは1016μmであった。
以上のようにして作製した透明積層体について、上記に示す評価方法により、透明層の全光線透過率および引張弾性率;透明層(B)に用いた硬化性樹脂の引張弾性率、ならびに透明樹脂積層体の曲げ弾性率を測定した。
[実施例D-1]
(透明層(B-1)の作製)
ガラス繊維布としてEガラス繊維布(3313 53 S101S、日東紡績(株)製)を用いた。用いたEガラス繊維布よりも屈折率の低い樹脂であるシクロヘキサンオキサイド骨格含有エポキシ樹脂(セロキサイド2021P、(株)ダイセル製、屈折率1.51)54質量部と、用いたEガラスクロスよりも屈折率の高い硫黄化合物を含有する樹脂であるペンタエリスリトールテトラキスチオプロピオネート(淀化学(株)製、屈折率1.60)43質量部と、4-メルカプトメチル-3,6-ジチア-1,8-オクタンジチオール(以下、GSTと呼称する、特許第3048929号公報に従い合成、屈折率1.70)3質量部を混合し、マグネチックスターラーで5分間撹拌した。さらに硬化促進剤としてTetrabutylphosphonium O,O-Diethyl Phosphorodithioate(和光純薬純薬工業(株))を1質量部加え、マグネチックスターラーで5分間撹拌し、硬化性樹脂組成物とした。
ポリカーボネート樹脂板(ユーピロンNF-2000、三菱ガス化学(株)製、厚さ700μm、曲げ弾性率は2.6GPa)にバーコーターで透明エポキシ系接着剤KR-401((株)ADEKA製、厚さ1mmにおける引張弾性率は1593MPa)を30μmの薄さで塗布し、気泡が入らないように透明層(B-1)を重ねた。もう一方の面も同様に接着剤を塗布し透明層(B-1)を重ね、UV照射装置を用いてUVを1000mJ/cm2照射し、さらに裏返して1000mJ/cm2照射し硬化した。これにより、透明層(B-1)/ポリカーボネート樹脂層(A)/透明層(B-1)の三層透明積層体を得た。この透明積層体の厚みは1013μmであった。なお、片面からの照射により他方の透明層(B-1)にも光が届き、ポリカーボネート樹脂層(A)の両方の接着面が同時に硬化したが、念のため他方の面からも光を照射した。
(透明層(B-2)の作製)
ガラス繊維布として実施例1と同様にEガラス繊維布(3313 53 S101S、日東紡績(株))を用いた。用いたEガラス繊維布よりも屈折率の低い樹脂である脂環式アクリレート樹脂のトリシクロデカンジメタノールジアクリレート(新中村化学工業(株)製、屈折率1.53)83質量部と、用いたEガラス繊維布よりも屈折率の高い樹脂であるGST17質量部を質量混合し、マグネチックスターラーで5分間攪拌した。さらに、光重合開始剤としてイルガキュア184を0.5質量部加え、マグネチックスターラーで5分間攪拌し、硬化性樹脂組成物とした。硬化性樹脂組成物をバッドに入れ、そこにEガラス繊維布を浸漬して硬化性樹脂組成物を浸み込ませ、離型処理済みのPETフィルムで挟んだ。これをUV照射装置を用いてUVを1000mJ/cm2照射し、さらに裏返して1000mJ/cm2照射し硬化し、厚さ119μmの透明層(B-2)を得た。透明層(B-2)の引張弾性率は18GPaであった。
透明層(B-1)を(B-2)とした以外は実施例1と同様に接着し、厚み1021μmの透明積層体を得た。
接着剤としてGLX18-73N((有)グルーラボ製、厚さ1mmにおける引張弾性率は26MPa)を用いた以外は実施例D-1と同様にして、透明層(B-1)/ポリカーボネート樹脂層(A)/透明層(B-1)の三層透明積層体を得た。この透明積層体の厚みは1058μmであった。
接着剤としてワールドロックHRJ-21(協立化学産業(株)製、厚さ1mmにおける引張弾性率は0.32MPa)を用いた以外は、実施例D-1と同様にして、透明層(B-1)/ポリカーボネート樹脂層(A)/透明層(B-1)の三層透明積層体を得た。この透明積層体の厚みは1061μmであった。
ポリカーボネート樹脂板(ユーピロンNF-2000、三菱ガス化学(株)製、厚さ700μm)にバーコーターで透明エポキシ系接着剤KR-401を30μm程度の薄さで塗布し、気泡が入らないようにポリエチレンテレフタレート(PET)樹脂フィルム(厚さ100μm)を重ねた。もう一方の面も同様に接着剤を塗布しPET樹脂フィルムを重ね、UV照射装置を用いてUVを1000mJ/cm2照射し、さらに裏返して1000mJ/cm2照射し硬化した。これにより、PET樹脂フィルム/ポリカーボネート樹脂層/PET樹脂フィルムの三層透明積層体を得た。この透明積層体の厚みは1014μmであった。
2cm×4cmの穴の開いたSUS製の枠(厚さ1mm)を離型処理済みのガラス板に載せ、各接着剤を穴に満たし、離型処理済みのガラス板を被せ、UV照射装置を用いてUVを1000mJ/cm2照射し、さらに裏返して1000mJ/cm2照射し硬化した。これを弾性率測定用の試料とし、上記に記載した引張弾性率の測定方法と同様に粘弾性測定装置DMS6100で引張弾性率を測定した。
2 透明層(B)
3 接着剤層
4 ポリエチレンテレフタレートフィルム層
5 シート
10 ディスプレイ用前面板
21 ガラス繊維布
22 樹脂組成物
Claims (22)
- 透明樹脂層(A)の両面に、ガラス繊維布と、硫黄化合物を含有する樹脂組成物とを含む透明層(B)が配された透明樹脂積層体。
- 透明樹脂層(A)の両面に、ガラス繊維布と、チオール基を有する化合物(a)及びアルケニル基を有する化合物(b)を含有する樹脂組成物とで形成された透明層(B)が配された、請求項1に記載の透明樹脂積層体。
- 透明樹脂層(A)の両面に、厚さ1mmにおける硬化時の引張弾性率が10MPa以上である硬化性樹脂を含む、樹脂組成物をガラス繊維布に含浸させてなる透明層(B)が配された、請求項1または2に記載の透明樹脂積層体。
- 前記透明樹脂層(A)と前記透明層(B)との間に透明接着剤を含む接着剤層を有する、請求項1~3のいずれか一項に記載の透明樹脂積層体。
- 前記接着剤層の厚みが、1μm~100μmである、請求項4に記載の透明樹脂積層体。
- 前記透明接着剤の厚さ1mmにおける硬化時の引張弾性率が、1MPa以上である、請求項4または5に記載の透明樹脂積層体。
- 透明樹脂層(A)の両面に、硬化性樹脂を含む樹脂組成物をガラス繊維布に含浸及び硬化させて引張弾性率を10GPa以上とした透明層(B)を、厚さ1mmにおける硬化時の引張弾性率が1MPa以上の透明接着剤で貼り合わせた、請求項1~6のいずれか一項に記載の透明樹脂積層体。
- 前記透明接着剤は、アクリル系接着剤、エポキシ系接着剤、およびウレタン系接着剤からなる群から選択される少なくとも一種である、請求項4~7のいずれか一項に記載の透明樹脂積層体。
- 前記透明樹脂積層体の曲げ弾性率が、5GPa以上である、請求項1~8のいずれか一項に記載の透明樹脂積層体。
- 前記透明樹脂層(A)の厚みが、100μm~2000μm、かつ前記透明層(B)の厚みが20μm~300μmである、請求項1~9のいずれか一項に記載の透明樹脂積層体。
- 全光線透過率が80%以上である、請求項1~10のいずれか一項に記載の透明樹脂積層体。
- 前記透明層(B)における樹脂組成物の硬化時におけるアッベ数と、ガラス繊維布のアッベ数との差が15以下である、請求項1~11のいずれか一項に記載の透明樹脂積層体。
- 前記透明層(B)における樹脂組成物の屈折率と、ガラス繊維布の屈折率との差が0.01以下である、請求項1~12のいずれか一項に記載の透明樹脂積層体。
- 前記透明層(B)における樹脂組成物が、チオール化合物とエポキシ樹脂との重合物を含有する、請求項1~13のいずれか一項に記載の透明樹脂積層体。
- 前記透明層(B)におけるガラス繊維布の屈折率が、1.55より大きい、請求項1~14のいずれか一項に記載の透明樹脂積層体。
- 前記透明層(B)のガラス繊維布がEガラスクロスである、請求項1~15のいずれか一項に記載の透明樹脂積層体。
- 前記透明樹脂層(A)における樹脂成分が、ポリカーボネート、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリメチルメタクリレートからなる群から選択される少なくとも一種を含む、請求項1~16のいずれか一項に記載の透明樹脂積層体。
- 前記透明樹脂層(A)における樹脂成分が、ポリカーボネートを含む、請求項17に記載の透明樹脂積層体。
- 前記透明層(B)の少なくとも一方の外側にポリエチレンテレフタレートフィルム層が配された、請求項1~18のいずれか一項に記載の透明樹脂積層体。
- 前記ポリエチレンテレフタレートフィルム層のさらに少なくとも一方の外側にハードコート層が配された、請求項19に記載の透明樹脂積層体。
- 前記ポリエチレンテレフタレートフィルム層のさらに少なくとも一方の外側に透明導電膜層が配された、請求項19または20に記載の透明樹脂積層体。
- 請求項1~21のいずれか一項に記載の透明樹脂積層体を用いた、ディスプレイ用前面板。
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KR1020167023322A KR20160122171A (ko) | 2014-02-17 | 2015-02-13 | 투명 수지 적층체 및 전면판 |
CN201580008806.8A CN106029374A (zh) | 2014-02-17 | 2015-02-13 | 透明树脂叠层体以及前面板 |
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KR (1) | KR20160122171A (ja) |
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Publication number | Priority date | Publication date | Assignee | Title |
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JP2017065105A (ja) * | 2015-09-30 | 2017-04-06 | グンゼ株式会社 | 透明積層体 |
JP2019014255A (ja) * | 2017-07-07 | 2019-01-31 | 三星電子株式会社Samsung Electronics Co., Ltd. | 積層フィルム、および積層フィルムを含む表示装置 |
KR20190029691A (ko) * | 2016-07-18 | 2019-03-20 | 쌩-고벵 글래스 프랑스 | 방호 및 패닉방지(antipanic) 특성을 갖는 투명한 방화글레이징 |
WO2019065912A1 (ja) * | 2017-09-28 | 2019-04-04 | 株式会社クラレ | 多層フィルムおよび繊維強化樹脂の加飾成形体 |
WO2019147915A1 (en) * | 2018-01-25 | 2019-08-01 | Corning Incorporated | Fiberglass composite cover for foldable electronic display and methods of making the same |
WO2019244395A1 (ja) * | 2018-06-22 | 2019-12-26 | 株式会社日立製作所 | 樹脂積層体及び樹脂積層体の製造方法 |
JP2020537185A (ja) * | 2017-10-11 | 2020-12-17 | コーニング インコーポレイテッド | 耐衝撃性及び曲げ抵抗を有する折り畳み式電子デバイスモジュール |
WO2023100828A1 (ja) * | 2021-11-30 | 2023-06-08 | Eneos株式会社 | 硬化性組成物およびその硬化物 |
EP4122696A4 (en) * | 2020-03-17 | 2024-04-17 | DIC Corporation | PRE-PREG AND MOLDED ARTICLE |
JP7533097B2 (ja) | 2020-10-06 | 2024-08-14 | Toppanホールディングス株式会社 | 壁面構造体及び壁面構造体の製造方法 |
JP7534691B2 (ja) | 2017-02-07 | 2024-08-15 | デクセリアルズ株式会社 | 画像表示装置の製造方法 |
Families Citing this family (2)
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CN108877517B (zh) * | 2018-06-26 | 2020-11-06 | 深圳市华星光电技术有限公司 | 一种柔性可拉伸基板及其制备方法 |
KR102534501B1 (ko) * | 2023-01-06 | 2023-05-30 | 차재현 | 자력을 이용한 무선충전의 효율을 향상시키는 스마트단말기의 글라스 보호커버 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007013329A1 (ja) * | 2005-07-28 | 2007-02-01 | Arakawa Chemical Industries, Ltd. | 硬化性樹脂組成物、当該硬化物、およびこれらから誘導される各種物品 |
JP2007203475A (ja) * | 2006-01-31 | 2007-08-16 | Sumitomo Bakelite Co Ltd | 透明樹脂積層シート |
JP2007220561A (ja) * | 2006-02-17 | 2007-08-30 | Daikin Ind Ltd | 不燃性照明カバー |
JP2009244757A (ja) * | 2008-03-31 | 2009-10-22 | Panasonic Electric Works Co Ltd | 透明基板 |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3457514B2 (ja) | 1997-08-08 | 2003-10-20 | 株式会社クラレ | 積層板およびその製造方法 |
JP2003026826A (ja) | 2001-07-23 | 2003-01-29 | Fuji Photo Film Co Ltd | 光学用ポリエステルフィルム、ハードコートフィルムおよびその製造方法 |
JP4409397B2 (ja) | 2004-09-27 | 2010-02-03 | 新日鐵化学株式会社 | シリコーン樹脂組成物及び成形体 |
JP2012183822A (ja) | 2011-02-14 | 2012-09-27 | Meihan Shinku Kogyo Kk | 光学ディスプレイ用透明積層体 |
JP2012031417A (ja) * | 2011-09-05 | 2012-02-16 | Mitsubishi Plastics Inc | 離型フィルム付中間膜用粘着シート及び透明積層体 |
JP5859926B2 (ja) * | 2011-11-25 | 2016-02-16 | ダイセル・オルネクス株式会社 | 層間充填用活性エネルギー線硬化性組成物 |
-
2015
- 2015-02-11 TW TW104104501A patent/TW201538328A/zh unknown
- 2015-02-13 KR KR1020167023322A patent/KR20160122171A/ko unknown
- 2015-02-13 JP JP2015562872A patent/JP6485363B2/ja active Active
- 2015-02-13 WO PCT/JP2015/053920 patent/WO2015122485A1/ja active Application Filing
- 2015-02-13 CN CN201580008806.8A patent/CN106029374A/zh active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007013329A1 (ja) * | 2005-07-28 | 2007-02-01 | Arakawa Chemical Industries, Ltd. | 硬化性樹脂組成物、当該硬化物、およびこれらから誘導される各種物品 |
JP2007203475A (ja) * | 2006-01-31 | 2007-08-16 | Sumitomo Bakelite Co Ltd | 透明樹脂積層シート |
JP2007220561A (ja) * | 2006-02-17 | 2007-08-30 | Daikin Ind Ltd | 不燃性照明カバー |
JP2009244757A (ja) * | 2008-03-31 | 2009-10-22 | Panasonic Electric Works Co Ltd | 透明基板 |
Cited By (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2017065105A (ja) * | 2015-09-30 | 2017-04-06 | グンゼ株式会社 | 透明積層体 |
KR20190029691A (ko) * | 2016-07-18 | 2019-03-20 | 쌩-고벵 글래스 프랑스 | 방호 및 패닉방지(antipanic) 특성을 갖는 투명한 방화글레이징 |
KR102188926B1 (ko) | 2016-07-18 | 2020-12-10 | 쌩-고벵 글래스 프랑스 | 방호 및 패닉방지(antipanic) 특성을 갖는 투명한 방화글레이징 |
JP7534691B2 (ja) | 2017-02-07 | 2024-08-15 | デクセリアルズ株式会社 | 画像表示装置の製造方法 |
JP7174545B2 (ja) | 2017-07-07 | 2022-11-17 | 三星電子株式会社 | 積層フィルム、および積層フィルムを含む表示装置 |
JP2019014255A (ja) * | 2017-07-07 | 2019-01-31 | 三星電子株式会社Samsung Electronics Co., Ltd. | 積層フィルム、および積層フィルムを含む表示装置 |
WO2019065912A1 (ja) * | 2017-09-28 | 2019-04-04 | 株式会社クラレ | 多層フィルムおよび繊維強化樹脂の加飾成形体 |
JPWO2019065912A1 (ja) * | 2017-09-28 | 2020-12-17 | 株式会社クラレ | 多層フィルムおよび繊維強化樹脂の加飾成形体 |
JP7094972B2 (ja) | 2017-09-28 | 2022-07-04 | 株式会社クラレ | 多層フィルムおよび繊維強化樹脂の加飾成形体 |
JP2020537185A (ja) * | 2017-10-11 | 2020-12-17 | コーニング インコーポレイテッド | 耐衝撃性及び曲げ抵抗を有する折り畳み式電子デバイスモジュール |
WO2019147915A1 (en) * | 2018-01-25 | 2019-08-01 | Corning Incorporated | Fiberglass composite cover for foldable electronic display and methods of making the same |
US11709291B2 (en) | 2018-01-25 | 2023-07-25 | Corning Incorporated | Fiberglass composite cover for foldable electronic display and methods of making the same |
WO2019244395A1 (ja) * | 2018-06-22 | 2019-12-26 | 株式会社日立製作所 | 樹脂積層体及び樹脂積層体の製造方法 |
EP4122696A4 (en) * | 2020-03-17 | 2024-04-17 | DIC Corporation | PRE-PREG AND MOLDED ARTICLE |
JP7533097B2 (ja) | 2020-10-06 | 2024-08-14 | Toppanホールディングス株式会社 | 壁面構造体及び壁面構造体の製造方法 |
WO2023100828A1 (ja) * | 2021-11-30 | 2023-06-08 | Eneos株式会社 | 硬化性組成物およびその硬化物 |
Also Published As
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JPWO2015122485A1 (ja) | 2017-03-30 |
JP6485363B2 (ja) | 2019-03-20 |
CN106029374A (zh) | 2016-10-12 |
KR20160122171A (ko) | 2016-10-21 |
TW201538328A (zh) | 2015-10-16 |
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