WO2012026436A1 - 合成樹脂積層体 - Google Patents
合成樹脂積層体 Download PDFInfo
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- WO2012026436A1 WO2012026436A1 PCT/JP2011/068897 JP2011068897W WO2012026436A1 WO 2012026436 A1 WO2012026436 A1 WO 2012026436A1 JP 2011068897 W JP2011068897 W JP 2011068897W WO 2012026436 A1 WO2012026436 A1 WO 2012026436A1
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- synthetic resin
- resin
- structural unit
- styrene
- resin laminate
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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
- B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
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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
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (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
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (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
- B32B27/30—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
- 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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- G02B1/105—
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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
- G02B1/14—Protective coatings, e.g. hard coatings
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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
- B32B2250/24—All layers being polymeric
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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
- B32B2255/00—Coating on the layer surface
- B32B2255/26—Polymeric coating
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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
- B32B2270/00—Resin or rubber layer containing a blend of at least two different 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/402—Coloured
- B32B2307/4026—Coloured within the layer by addition of a colorant, e.g. pigments, dyes
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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
- B32B2307/408—Matt, dull surface
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/584—Scratch resistance
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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
- B32B2307/70—Other properties
- B32B2307/71—Resistive to light or to UV
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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
- B32B2307/70—Other properties
- B32B2307/712—Weather resistant
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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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31909—Next to second addition polymer from unsaturated monomers
- Y10T428/31928—Ester, halide or nitrile of addition polymer
Definitions
- the present invention relates to a synthetic resin laminate, and in particular, is used for a transparent substrate material and a protective material, and has transparency, low warpage, interlayer adhesion, and adhesion to a hard coat layer made of a photosensitive hard coat paint.
- the present invention relates to a synthetic resin laminate excellent in scratch resistance and weather resistance.
- Resin transparent plates are used in a wide variety of applications, including soundproof partitions, carports, signboards, and front plates of display units for office automation equipment and portable electronic devices.
- the front panel of portable display devices such as mobile phone terminals, portable electronic playground equipment, PDAs, etc.
- the intended scratch resistance is required.
- a method is generally used in which a photosensitive acrylic hard coat paint is applied to the surface of the front panel to provide a hard coat layer. Further, adhesion to the hard coat layer is also required.
- a methacrylic resin excellent in adhesion with a hard coat layer made of a transparent acrylic hard coat paint is often used as transparency, weather resistance, scratch resistance, and photosensitive.
- the methacrylic resin has a high water absorption rate, and there is a problem that the front panel is likely to warp due to a change in humidity in the use environment and a humidity difference between the device side and the outside air side.
- Patent Document 1 a hard coat plate using a plastic sheet using a methyl methacrylate-styrene copolymer resin as an intermediate layer while the surface layer is made of methacrylic resin is known (Patent Document 1).
- the plastic sheet used in Patent Document 1 may be warped depending on the usage environment. Further, depending on the composition of the methyl methacrylate-styrene copolymer resin, adhesion to the methacrylic resin layer may be insufficient.
- Patent Document 2 a resin having a low water absorption rate in order to reduce warpage against humidity change while maintaining adhesion to a photosensitive curable resin.
- Patent Document 2 a technique using a plastic sheet using a resin having a high polarity and a high water absorption as a surface layer.
- Patent Document 2 emphasizes the stability of the Fresnel lens shape and the adhesion to the base material, it is different from the photosensitive curable resin in which monomers and oligomers having a small number of functional groups are used.
- Adhesion is good, but the adhesion with a hard coat layer using a photosensitive acrylic hard coat paint composed of a monomer or oligomer having a relatively large number of functional groups with emphasis on increasing the crosslinking density and imparting scratch resistance. There was a shortage.
- the surface of the plastic sheet used in Patent Document 2 may deteriorate or deteriorate after the weather resistance test, and the adhesion with the photosensitive curable resin may decrease.
- the present invention relates to a synthetic resin laminate, and in particular, is used for a transparent substrate material and a protective material, and has transparency, low warpage, interlayer adhesion, and adhesion to a hard coat layer made of a photosensitive hard coat paint.
- a synthetic resin laminate excellent in scratch resistance and weather resistance.
- (meth) acrylic acid is formed on both surfaces of a thermoplastic resin layer containing 65 to 90 mol% of styrene structural units with respect to all the structural units. It has been found that a synthetic resin laminate having these characteristics can be obtained by providing a (meth) acrylic ester-styrene copolymer resin layer obtained by copolymerizing an ester monomer and a styrene monomer with a certain composition. Reached.
- (meth) acryl shows methacryl and / or acryl. That is, the present invention provides the following synthetic resin laminate.
- thermoplastic resin (A) layer containing 65 to 90 mol% of a styrene structural unit and a thermoplastic resin (B) layer with respect to all the structural units, and has (B) layers on both sides of the (A) layer.
- a synthetic resin laminate wherein the thermoplastic resin (B) mainly comprises a (meth) acrylate structural unit (a) represented by the following general formula (1) and a styrene structural unit, and a (meth) acrylic ester
- a synthetic resin laminate which is a (meth) acrylate-styrene copolymer resin having a molar ratio of the structural unit (a) to the styrene structural unit of 70:30 to 84:16.
- thermoplastic resin (A) is 70 to 80 mol%. 3.
- the molar ratio of the (meth) acrylate structural unit (a) and the styrene structural unit contained in the thermoplastic resin (B) is 74:26 to 80:20. 4).
- the thermoplastic resin (A) is one of methyl methacrylate-styrene copolymer resin and acrylonitrile-styrene copolymer resin. 5.
- thermoplastic resin (A) is a methyl methacrylate-styrene copolymer resin having a molar ratio of methyl methacrylate structural unit to styrene structural unit of 10:90 to 35:65. 6).
- thermoplastic resin (A) is an acrylonitrile-styrene copolymer resin having a molar ratio of an acrylonitrile structural unit to a styrene structural unit of 10:90 to 35:65.
- the synthetic resin laminate of the present invention is excellent in transparency, low warpage, interlayer adhesion, adhesion to a hard coat layer using a photosensitive hard coat paint, scratch resistance, and weather resistance.
- the laminate is used as a transparent substrate material, a transparent protective material, and the like, and is particularly preferably used for a front panel of a display device.
- the synthetic resin laminate of the present invention has a thermoplastic resin (A) layer containing 65 to 90 mol% of a styrene structural unit and a thermoplastic resin (B) layer with respect to all the structural units, and the (A) layer A synthetic resin laminate having (B) layers on both sides thereof, wherein (B) includes a (meth) acrylate structural unit (a) represented by the following general formula (1) and a styrene structural unit, A synthetic resin laminate characterized in that it is a (meth) acrylate-styrene copolymer resin in which the molar ratio of the (meth) acrylate structural unit (a) to the styrene structural unit is 70:30 to 84:16. is there.
- R1 is hydrogen or a methyl group
- R2 is an alkyl group having 1 to 18 carbon atoms.
- R2 of the (meth) acrylic ester structural unit represented by the general formula (1) used in the present invention is an alkyl group having 1 to 18 carbon atoms, and includes a methyl group, an ethyl group, a butyl group, a lauryl group, and a stearyl group. Cyclohexyl group, isobornyl group, and the like. These can be used alone or in combination of two or more. Among these, a (meth) acrylic acid ester structural unit in which R2 is a methyl group and / or an ethyl group is preferable, and a methyl methacrylate structural unit in which R1 is a methyl group and R2 is a methyl group is more preferable.
- thermoplastic resin (B) layer needs to be laminated on both sides of the thermoplastic resin (A) layer.
- thermoplastic resin (B) is laminated on only one side of the thermoplastic resin (A)
- the saturated water absorption rate of the thermoplastic resin (A) and the thermoplastic resin (B) is different, so the humidity change May be warped.
- thermoplastic resin (A) used in the present invention contains 65 to 90 mol% of styrene structural units with respect to all the structural units.
- thermoplastic resin (A) methyl methacrylate-styrene copolymer resin, acrylonitrile-styrene copolymer resin, or the like can be used.
- Preferred thermoplastic resins (A) include a methyl methacrylate-styrene copolymer resin having a molar ratio of methyl methacrylate structural unit to styrene structural unit of 10:90 to 35:65, mole of acrylonitrile structural unit and styrene structural unit.
- thermoplastic resin (B) examples thereof include acrylonitrile-styrene copolymer resins having a ratio of 10:90 to 35:65, and contain 65 to 90 mol% of styrene structural units with respect to all the structural units, and interface adhesion with thermoplastic resin (B).
- the ratio of the styrene structural unit to the total structural unit of the thermoplastic resin (A) is preferably 70 to 90 mol%, more preferably 70 to 80 mol%.
- a resin that satisfies this requirement there may be mentioned a methyl methacrylate-styrene copolymer resin having a molar ratio of methyl methacrylate structural unit to styrene structural unit of 10:90 to 25:75.
- the ratio of the styrene structural unit to the total structural unit of the thermoplastic resin (A) is less than 65 mol%, the synthetic resin laminate may be warped due to a change in humidity.
- thermoplastic resin (A) can be blended with other resins without impairing transparency and within a range in which the proportion of styrene constituent units of the blended composition does not deviate from 65 to 90 mol%.
- examples thereof include methyl methacrylate-styrene copolymer resin, polymethyl methacrylate, polystyrene, and polycarbonate.
- the thermoplastic resin (B) used in the present invention is a (meth) acrylate-styrene copolymer mainly composed of a (meth) acrylate structural unit (a) represented by the general formula (1) and a styrene structural unit.
- a total proportion of the (meth) acrylic ester structural unit (a) and the styrene structural unit is 90 to 100 mol% with respect to the total of all the structural units of the thermoplastic resin (B), Is 95 to 100 mol%.
- the molar composition ratio of the (meth) acrylic ester structural unit (a) represented by the formula (1) in the thermoplastic resin (B) to the styrene structural unit is in the range of 70:30 to 84:16.
- the thermoplastic resin (B) used in the present invention is obtained by copolymerizing a (meth) acrylic acid ester monomer and a styrene monomer.
- a known method can be used for the polymerization of the (meth) acrylic acid ester monomer and the styrene monomer, and for example, it can be produced by a bulk polymerization method or a solution polymerization method.
- a monomer composition containing a monomer, a chain transfer agent, and a polymerization initiator is continuously supplied to a complete mixing tank and is continuously polymerized at 100 to 180 ° C.
- solvent used in this case examples include hydrocarbon solvents such as toluene, xylene, cyclohexane and methylcyclohexane, ester solvents such as ethyl acetate and methyl isobutyrate, ketone solvents such as acetone and methyl ethyl ketone, tetrahydrofuran and dioxane. And ether solvents such as methanol and alcohol solvents such as methanol and isopropanol.
- thermoplastic resin (A) and the thermoplastic resin (B) in the present invention can be mixed and used for the thermoplastic resin (A) and the thermoplastic resin (B) in the present invention.
- the additive include an antioxidant, an ultraviolet absorber, an anticolorant, an antistatic agent, a release agent, a lubricant, a dye, a pigment, an inorganic filler, and a resin filler.
- the method of mixing is not particularly limited, and a method of compounding the whole amount, a method of dry blending the master batch, a method of dry blending the whole amount, and the like can be used.
- a method by coextrusion or the like can be used as a method for producing the synthetic resin laminate of the present invention.
- the method of coextrusion is not particularly limited, and a known method can be used.
- the (B) layer is laminated on both sides of the (A) layer with the feed block, extruded into a sheet shape with a T-die, and then cooled while passing through a forming roll to form a desired laminate.
- the (B) layer is laminated on both of the (A) layer in the multi-manifold die, extruded into a sheet, and then cooled by passing through a forming roll to form a desired laminate.
- molding roll is not specifically limited, The method of pinching and cooling with a some metal roll and the method of pinching and cooling with a metal roll, a nonmetal roll, or a metal belt can be illustrated.
- the thickness of the synthetic resin laminate in the present invention is preferably in the range of 0.1 to 10.0 mm. If the thickness is in the range of 0.1 mm or more, transfer failure and thickness accuracy failure due to bank omission do not occur. Further, when the thickness is in the range of 10.0 mm or less, there is no occurrence of a thickness accuracy defect or an appearance defect due to uneven cooling after molding.
- the range is more preferably 0.3 to 5.0 mm, and still more preferably 0.3 to 3.0 mm.
- the thickness (one side) of the thermoplastic resin (B) layer of the synthetic resin laminate in the present invention is preferably within 25% of the total thickness of the synthetic resin laminate, and preferably in the range of 10 to 500 ⁇ m. If the thickness (one side) of the (B) layer is within 25% of the total thickness of the synthetic resin laminate, warpage due to humidity change does not occur. Also, when the thickness is in the range of 10 ⁇ m or more, the scratch resistance and weather resistance are good, and when the thickness is in the range of 500 ⁇ m or less, no warpage occurs due to a change in humidity. More preferably, it is in the range of 15 to 150 ⁇ m.
- a hard coat treatment can be applied to one side or both sides of the synthetic resin laminate of the present invention.
- the hard coat layer is formed by using a photosensitive hard coat paint that is cured using light energy.
- a photosensitive hard coat paint to be cured using light energy a photocurable resin composition in which a photopolymerization initiator is added to a resin composition composed of monofunctional and / or polyfunctional acrylate monomers and / or oligomers. Etc.
- the method for applying the hard coat paint in the present invention is not particularly limited, and a known method can be used. Examples thereof include brush, gravure roll, dipping, flow coating, spray, ink jet, and the method described in Japanese Patent No. 4161182.
- the synthetic resin laminate of the present invention can be subjected to one or more of antireflection treatment, antifouling treatment, antistatic treatment, weather resistance treatment and antiglare treatment on one side or both sides.
- the methods of antireflection treatment, antifouling treatment, antistatic treatment, weather resistance treatment and antiglare treatment are not particularly limited, and known methods can be used. For example, a method of applying a reflection reducing coating, a method of depositing a dielectric thin film, a method of applying an antistatic coating, and the like can be mentioned.
- the total light transmittance of the synthetic resin laminate of the present invention is preferably 85% or more, more preferably 88% or more, and further preferably 90% or more.
- test pieces each having a width of 10 cm and a length of 30 cm were prepared from the synthetic resin laminate after the hard coat treatment obtained in the following examples and comparative examples.
- the test piece was pressed against a cylinder with a diameter of 80 mm so that the longitudinal direction of the test piece was the circumferential direction, and the presence or absence of peeling at the laminated interface was examined.
- the number of test pieces in which delamination occurred was less than 3, the test piece passed and 3 or more test pieces were regarded as defective.
- ⁇ Weather resistance evaluation> The weather resistance test using a QUV tester (ATLAS-UVCON: manufactured by Toyo Seiki Seisakusho Co., Ltd.) for the synthetic resin laminates after hard coat treatment or the synthetic resin plates after hard coat treatment obtained in the following examples and comparative examples Implemented. The test was conducted for 360 hours by irradiating from a UVA-340 light source at 50 ° C. with an irradiation intensity of 25 W / m 2 for 4 hours from the hard coat layer side and at 60 ° C. for 4 hours of wetness as one cycle.
- a QUV tester ATLAS-UVCON: manufactured by Toyo Seiki Seisakusho Co., Ltd.
- test piece after the test was cut in an orthogonal notch reaching the synthetic resin laminate or the synthetic resin plate through the hard coat layer, and performing a peel test to perform the hard test after the weather resistance test. Evaluation of adhesion to the coat layer. Those without peeling were regarded as acceptable.
- a test piece having a length of 20 cm and a width of 20 cm was cut from the synthetic resin laminate after the hard coat treatment or the synthetic resin plate after the hard coat treatment obtained from the following examples and comparative examples, and the temperature was 23 ° C. and the relative humidity was 50.
- the test piece having a thickness of 1.5 mm was held for 24 hours in a state where only a portion having a thickness of 0.3 mm from the hard coat layer side was immersed in water.
- the test piece before and after the test is projected downward and left on the horizontal plane, and the amount of change in the gap length between the four corners of the test piece and the horizontal plane is measured. The total value of the amount of change does not exceed 5.0 mm. Passed.
- Example 1 Synthetic resin using a multilayer extruder having a single screw extruder with a shaft diameter of 32 mm, a single screw extruder with a shaft diameter of 65 mm, a feed block connected to the full extruder, and a T die connected to the feed block A laminate was formed.
- a methyl methacrylate-styrene (78:22) copolymer resin [manufactured by Nippon Steel Chemical Co., Ltd., trade name: Estyrene MS750] (resin B1) was continuously introduced into a single screw extruder having a shaft diameter of 32 mm, and a cylinder temperature of 250 Extrusion was performed under the conditions of ° C and a discharge rate of 8 kg / h.
- methyl methacrylate-styrene (20:80) copolymer resin [manufactured by Nippon Steel Chemical Co., Ltd., trade name: Estyrene MS200] (resin A1) was continuously introduced into a single screw extruder having a shaft diameter of 65 mm, and the cylinder temperature was Extrusion was performed at 260 ° C. and a discharge speed of 50 kg / h.
- the feed block connected to the entire extruder was provided with two types and three layers of distribution pins, and the layers (B1) were introduced and laminated on both sides of the (A1) layer at a temperature of 260 ° C. Extruded into a sheet shape with a T-die with a temperature of 270 ° C.
- the photosensitive hard coat paint (C) obtained in Synthesis Example 1 is applied onto the resin B1 layer of the obtained synthetic resin laminate using a bar coater so that the coating thickness after curing is 3 to 8 ⁇ m.
- Example 2 Example 1 except that instead of the resin A1 used in Example 1, an acrylonitrile-styrene (20:80) copolymer resin [manufactured by Asahi Kasei Chemicals Corporation, trade name: Stylac AST8701] (resin A2) was used. Similarly, a synthetic resin laminate in which the resin B1 is laminated on both surfaces of the resin A2 and a synthetic resin laminate after the hard coat treatment provided with a hard coat layer on the resin B1 layer of the obtained synthetic resin laminate are obtained. It was. The thickness of the obtained synthetic resin laminate was 1.5 mm, and the thickness (one side) of the resin B1 layer was 90 ⁇ m near the center. The evaluation results are shown in Table 1. The results of transparency evaluation, scratch resistance evaluation, interlayer adhesion evaluation, adhesion evaluation with the hard coat layer, weather resistance evaluation, and low warpage evaluation were good, and the overall judgment was acceptable.
- an acrylonitrile-styrene (20:80) copolymer resin [manufactured
- Example 3 Example 1 except that a methyl methacrylate-styrene (30:70) copolymer resin [manufactured by Nippon Steel Chemical Co., Ltd., trade name: Estyrene MS300] (resin A3) was used instead of the resin A1 used in Example 1.
- a synthetic resin laminate in which the resin B1 is laminated on both surfaces of the resin A3, and a synthetic resin laminate after the hard coat treatment provided with a hard coat layer on the resin B1 layer of the obtained synthetic resin laminate Obtained.
- the thickness of the obtained synthetic resin laminate was 1.5 mm, and the thickness (one side) of the resin B1 layer was 90 ⁇ m near the center.
- the evaluation results are shown in Table 1. The results of transparency evaluation, scratch resistance evaluation, interlayer adhesion evaluation, adhesion evaluation with the hard coat layer, weather resistance evaluation, and low warpage evaluation were good, and the overall judgment was acceptable.
- Example 4 A methyl methacrylate-styrene (80:20) copolymer resin [manufactured by Denki Kagaku Kogyo Co., Ltd., trade name: Acristar KT-80SG] (resin B2) was used in place of the resin B1 used in Example 1.
- resin B2 was used in place of the resin B1 used in Example 1.
- the thickness of the resulting synthetic resin laminate was 1.5 mm, and the thickness (one side) of the resin B2 layer was 90 ⁇ m near the center.
- the evaluation results are shown in Table 1. The results of transparency evaluation, scratch resistance evaluation, interlayer adhesion evaluation, adhesion evaluation with the hard coat layer, weather resistance evaluation, and low warpage evaluation were good, and the
- Example 5 Example 1 except that methyl methacrylate-styrene (74:26) copolymer resin [manufactured by Nippon Steel Chemical Co., Ltd., trade name: Estyrene MS750LF] (resin B3) was used instead of resin B1 used in Example 1.
- a synthetic resin laminate in which resin B3 is laminated on both surfaces of resin A1, and a synthetic resin laminate after a hard coat treatment provided with a hard coat layer on resin B3 layer of the obtained synthetic resin laminate Obtained.
- the thickness of the resulting synthetic resin laminate was 1.5 mm, and the thickness (one side) of the resin B3 layer was 90 ⁇ m near the center.
- the evaluation results are shown in Table 1. The results of transparency evaluation, scratch resistance evaluation, interlayer adhesion evaluation, adhesion evaluation with the hard coat layer, weather resistance evaluation, and low warpage evaluation were good, and the overall judgment was acceptable.
- Example 1 except that a methyl methacrylate-styrene (60:40) copolymer resin [manufactured by Nippon Steel Chemical Co., Ltd., trade name: Estyrene MS600] (resin D1) was used instead of the resin A1 used in Example 1.
- a synthetic resin laminate in which resin B1 is laminated on both surfaces of resin D1, and a synthetic resin laminate after a hard coat treatment provided with a hard coat layer on resin B1 layer of the obtained synthetic resin laminate Obtained.
- the thickness of the obtained synthetic resin laminate was 1.5 mm, and the thickness (one side) of the resin B1 layer was 90 ⁇ m near the center.
- the evaluation results are shown in Table 1. The results of transparency evaluation, scratch resistance evaluation, interlayer adhesion evaluation, adhesion evaluation with the hard coat layer, and weather resistance evaluation were good, respectively, but the results of the low warpage evaluation were poor. It was a failure.
- Resin D1 was used instead of resin A1 used in Example 1, and methyl methacrylate-styrene (90:10) copolymer resin [manufactured by Denki Kagaku Kogyo Co., Ltd., trade name: Acristar KT, instead of resin B1 ⁇ 80D]
- a synthetic resin laminate after a hard coat treatment provided with a coat layer was obtained.
- the thickness of the resultant synthetic resin laminate was 1.5 mm, and the thickness (one side) of the resin D2 layer was 90 ⁇ m near the center.
- the evaluation results are shown in Table 1. Although the results of transparency evaluation, scratch resistance evaluation, interlayer adhesion evaluation, adhesion evaluation with the hard coat layer, and weather resistance evaluation were good, the results of the low warpage evaluation were poor and failed in the comprehensive judgment. Met.
- Comparative Example 3 A synthetic resin laminate in which the resin D1 is laminated on both surfaces of the resin A1 in the same manner as in Example 1 except that the resin D1 is used instead of the resin B1 used in Example 1, and the obtained synthetic resin laminate
- the synthetic resin laminated body after the hard-coat process which provided the hard-coat layer on the resin D1 layer was obtained.
- the thickness of the obtained synthetic resin laminate was 1.5 mm, and the thickness (one side) of the resin D1 layer was 90 ⁇ m near the center.
- the evaluation results are shown in Table 1. The results of transparency evaluation, interlayer adhesion evaluation, and low warpage evaluation were good, respectively, but the results of scratch resistance evaluation, adhesion evaluation with the hard coat layer, and weather resistance evaluation were poor. It was a failure.
- Comparative Example 4 A synthetic resin laminate in which the resin D2 is laminated on both surfaces of the resin A1 in the same manner as in Example 1 except that the resin D2 is used instead of the resin B1 used in Example 1, and the obtained synthetic resin laminate
- the synthetic resin laminated body after the hard-coat process which provided the hard-coat layer on resin D2 layer was obtained.
- the thickness of the resultant synthetic resin laminate was 1.5 mm, and the thickness (one side) of the resin D2 layer was 90 ⁇ m near the center.
- the evaluation results are shown in Table 1. Although the results of transparency evaluation, scratch resistance evaluation, adhesion evaluation with the hard coat layer, and weather resistance evaluation were good, the results of interlayer adhesion evaluation and low warpage evaluation were poor, and were not evaluated in the comprehensive judgment. It was a pass.
- Comparative Example 5 Resin on both sides of resin A1 in the same manner as in Example 1 except that methacrylic resin [trade name: Delpet 80NE manufactured by Asahi Kasei Chemicals Corporation] (resin D3) was used instead of resin B1 used in Example 1.
- methacrylic resin trade name: Delpet 80NE manufactured by Asahi Kasei Chemicals Corporation
- resin D3 methacrylic resin
- a synthetic resin laminate in which D3 was laminated, and a synthetic resin laminate after a hard coat treatment in which a hard coat layer was provided on the resin D3 layer of the obtained synthetic resin laminate were obtained.
- the thickness of the obtained synthetic resin laminate was 1.5 mm, and the thickness (one side) of the resin D3 layer was 90 ⁇ m near the center.
- the evaluation results are shown in Table 1. The results of transparency evaluation, scratch resistance evaluation, adhesion evaluation with the hard coat layer, and weather resistance evaluation were good respectively, but the results of interlayer adhesion evaluation and low warpage evaluation were poor, respectively, and comprehensive judgment It was a
- Comparative Example 6 Synthetic resin using a multilayer extruder having a single screw extruder with a shaft diameter of 32 mm, a single screw extruder with a shaft diameter of 65 mm, a feed block connected to the full extruder, and a T die connected to the feed block A laminate was formed.
- Resin B1 was continuously introduced into a single screw extruder having a shaft diameter of 32 mm and extruded under conditions of a cylinder temperature of 250 ° C. and a discharge speed of 4 kg / h.
- Resin A1 was continuously introduced into a single screw extruder having a shaft diameter of 65 mm and extruded at a cylinder temperature of 260 ° C. and a discharge speed of 50 kg / h.
- the feed block connected to the whole extruder was provided with two types and two layers of distribution pins, and the layer (B1) was introduced and laminated on one side of the (A1) layer at a temperature of 260 ° C.
- the set temperature of the roll was 80 ° C., 80 ° C., and 90 ° C. in order from the upstream side.
- the thickness of the obtained synthetic resin laminate was 1.5 mm, and the thickness of the resin B1 layer was 90 ⁇ m near the center.
- the photosensitive hard coat paint (C) obtained in Synthesis Example 1 is applied onto the resin B1 layer of the obtained synthetic resin laminate using a bar coater so that the coating thickness after curing is 3 to 8 ⁇ m. Covered with film and pressure bonded, cured with UV irradiation at a line speed of 1.5 m / min on a conveyor equipped with a high pressure mercury lamp with a light source distance of 12 cm and an output of 80 W / cm 2 to peel off the PET film, The synthetic resin laminated body after the hard coat process provided was obtained. The evaluation results are shown in Table 1. Although the results of transparency evaluation, scratch resistance evaluation, interlayer adhesion evaluation, adhesion evaluation with the hard coat layer, and weather resistance evaluation were good, the results of the low warpage evaluation were poor, and the overall judgment was Failed
- Comparative Example 7 A synthetic resin plate was formed using a single-layer extrusion apparatus having a single-screw extruder having a shaft diameter of 65 mm and a T-die. Resin B1 was continuously introduced into a single-screw extruder having a shaft diameter of 65 mm and extruded at a cylinder temperature of 260 ° C. and a discharge speed of 50 kg / h. It was extruded in a sheet form with a T-die having a temperature of 270 ° C. connected to the tip, and cooled while transferring the mirror surface with three mirror finish rolls to obtain a synthetic resin plate of resin B1.
- the temperature of the roll was set to 80 ° C., 80 ° C., and 90 ° C. from the upstream side.
- the thickness of the obtained synthetic resin plate was 1.5 mm.
- the photosensitive hard coat paint (C) obtained in Synthesis Example 4 was applied on the resin B1 layer of the obtained synthetic resin plate using a bar coater so that the coating thickness after curing was 3 to 8 ⁇ m. Covered with pressure, and cured by irradiation with UV light on a conveyor equipped with a high pressure mercury lamp with a light source distance of 12 cm and an output of 80 W / cm 2, with a line speed of 1.5 m / min. A synthetic resin plate after the hard coat treatment was obtained.
- the evaluation results are shown in Table 1. Although the results of transparency evaluation, scratch resistance evaluation, interlayer adhesion evaluation, adhesion evaluation with the hard coat layer, and weather resistance evaluation were good, the results of the low warpage evaluation were poor, and the overall judgment was not good. It was a pass.
- Comparative Example 8 A synthetic resin plate of resin A1 and a hard coat layer on the resin A1 layer of the obtained synthetic resin plate are provided in the same manner as in comparative example 7 except that resin A1 is used instead of resin B1 used in comparative example 7. A synthetic resin plate after the hard coat treatment was obtained. The thickness of the obtained synthetic resin plate was 1.5 mm. The evaluation results are shown in Table 1. The results of the transparency evaluation and the low warpage evaluation were good, respectively, but the results of the scratch resistance evaluation, the adhesion evaluation with the hard coat layer, and the weather resistance evaluation were poor, respectively. It was.
- Comparative Example 9 A synthetic resin plate of resin A2 and a hard coat layer on the resin A2 layer of the obtained synthetic resin plate are provided in the same manner as in comparative example 7 except that resin A2 is used instead of resin B1 used in comparative example 7. A synthetic resin plate after the hard coat treatment was obtained. The thickness of the obtained synthetic resin plate was 1.5 mm. The evaluation results are shown in Table 1. The results of transparency evaluation, adhesion evaluation with the hard coat layer, and low warpage evaluation were good, respectively, but the results of scratch resistance evaluation and weather resistance evaluation were poor, respectively. It was.
- thermoplastic resin laminate of the present invention is characterized by excellent transparency, low warpage, interlayer adhesion, adhesion with a hard coat layer using a photosensitive hard coat paint, scratch resistance, and weather resistance.
- the synthetic resin laminate is used as a transparent substrate material, a transparent protective material, and the like, and particularly suitably used for a front panel of a display device.
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Abstract
Description
すなわち、本発明は、以下の合成樹脂積層体を提供するものである。
2.熱可塑性樹脂(A)に含有されるスチレン構成単位が70~80モル%である1に記載の合成樹脂積層体。
3.熱可塑性樹脂(B)に含有される(メタ)アクリル酸エステル構成単位(a)とスチレン構成単位のモル比が74:26~80:20である1に記載の合成樹脂積層体。
4.熱可塑性樹脂(A)がメタクリル酸メチル-スチレン共重合樹脂、アクリロニトリル-スチレン共重合樹脂のいずれかである1に記載の合成樹脂積層体。
5.熱可塑性樹脂(A)がメタクリル酸メチル構成単位とスチレン構成単位のモル比が10:90~35:65であるメタクリル酸メチル-スチレン共重合樹脂である1に記載の合成樹脂積層体。
6.熱可塑性樹脂(A)がアクリロニトリル構成単位とスチレン構成単位のモル比が10:90~35:65であるアクリロニトリル-スチレン共重合樹脂である1に記載の合成樹脂積層体。
7.片面または両面にハードコート処理を施したものである1~6のいずれかに記載の合成樹脂積層体。
8.片面または両面に反射防止処理、防汚処理、帯電防止処理、耐候性処理および防眩処理から選択されるいずれか一つ以上の処理を施したものである1~6のいずれかに記載の合成樹脂積層体。
9.上記1~6のいずれかの合成樹脂積層体からなる透明性基板材料。
10.上記1~6のいずれかの合成樹脂積層体からなる透明性保護材料。
熱可塑性樹脂(A)の全構成単位に対するスチレン構成単位の割合は70~90モル%が好ましく、70~80モル%がより好ましい。これを満足する樹脂としてメタクリル酸メチル構成単位とスチレン構成単位のモル比が10:90~25:75のメタクリル酸メチル-スチレン共重合樹脂が挙げられる。
熱可塑性樹脂(A)の全構成単位に対するスチレン構成単位の割合が65モル%未満となると、湿度の変化により合成樹脂積層体に反りが発生することがある。反りの観点からは熱可塑性樹脂(A)の全構成単位に対するスチレン構成単位の割合が高いほど好ましいが、メタクリル酸メチル-スチレン共重合樹脂あるいはアクリロニトリル-スチレン共重合樹脂の全構成単位に対するスチレン構成単位の割合が90モル%を超えると、熱可塑性樹脂(B)との界面密着性が実用上不十分となる場合があり適さない。
熱可塑性樹脂(B)における式(1)で表される(メタ)アクリル酸エステル構成単位(a)と、スチレン構成単位とのモル構成比は70:30~84:16の範囲であり、70:30~80:20であるとより好ましく、74:26~80:20であるとさらに好ましく、74:26~78:22の範囲であると特に好ましい。
(メタ)アクリル酸エステル構成単位(a)とスチレン構成単位との合計に対する(メタ)アクリル酸エステル構成単位(a)のモル構成比が70%未満であると、感光性ハードコート塗料からなるハードコート層との密着性が低くなったり、耐擦傷性が低くなったり、耐候性試験後に表面が劣化、変質したりすることがあるので実用的ではない。また84%を超える範囲であると湿度変化による反りが大きくなったり、熱可塑性樹脂(A)層との密着性が不十分となったりする場合がある。
溶液重合法では、モノマー、連鎖移動剤、および重合開始剤を含むモノマー組成物を完全混合槽に連続的に供給し、100~180℃で連続重合する方法などにより行われる。
共押出の方法は特に限定されず、公知の方法を用いることが出来る。例えば、フィードブロック方式では、フィードブロックで(A)層の両面に(B)層を積層し、Tダイでシート状に押し出した後、成形ロールを通過させながら冷却し所望の積層体を形成する。また、マルチマニホールド方式では、マルチマニホールドダイ内で(A)層の両方に(B)層を積層し、シート状に押し出した後、成形ロールを通過させ挟圧しながら冷却し所望の積層体を形成する。
この成形ロールは特に限定されないが、複数の金属ロールで挟圧して冷却する方法や、金属ロールと非金属ロールまたは金属ベルトで挟圧して冷却する方法を例示することができる。
実施例および比較例で得られた合成樹脂積層体の評価は以下のように行った。
以下の実施例、比較例にて得られたハードコート処理後の合成樹脂積層体またはハードコート処理後の合成樹脂板について全光線透過率(JIS K 7105)を、色差計(日本電色工業(株)製:COH―400)にて測定した。全光線透過率85%以上のものを合格とした。
以下の実施例、比較例にて得られたハードコート処理後の合成樹脂積層体またはハードコート処理後の合成樹脂板について、JIS K 5600-5-4に準拠し、ハードコート層側の表面に対して角度45度、荷重750gで次第に硬度を増して鉛筆を押し付け、きず跡を生じなかった最も硬い鉛筆硬度から耐擦傷性の評価を行った。鉛筆硬度3H以上のものを合格とした。
以下の実施例、比較例にて得られたハードコート処理後の合成樹脂積層体から幅10cm×長さ30cmの試験片を10枚作製した。1枚の試験片の長手方向が円周方向となるように直径80mmの円筒に押し付けて、積層した界面における剥離の有無を調べた。層間の剥離が生じた試験片の枚数が3枚未満のものを合格、3枚以上のものを不良とした。
以下の実施例、比較例にて得られたハードコート処理後の合成樹脂積層体またはハードコート処理後の合成樹脂板についてJIS K 5600-5-6に準拠し、ハードコート層を貫通し合成樹脂積層体または合成樹脂板に達する直交した切り込みを入れ、剥離試験を行いハードコート層の密着性の評価を実施。剥離のないものを合格とした。
以下の実施例、比較例にて得られたハードコート処理後の合成樹脂積層体またはハードコート処理後の合成樹脂板についてQUV試験機(ATLAS-UVCON:東洋精機製作所製)を用いて耐候性試験を実施。条件は、50℃でUVA-340の光源から25W/m2の照射強度でハードコート層側から4時間照射、60℃で4時間湿潤を1サイクルとして、360時間試験した。試験後の試験片に対しJIS K 5600-5-6に準拠し、ハードコート層を貫通し合成樹脂積層体または合成樹脂板に達する直交した切り込みを入れ、剥離試験を行い耐候性試験後のハードコート層との密着性を評価。剥離のないものを合格とした。
以下の実施例および比較例より得られたハードコート処理後の合成樹脂積層体またはハードコート処理後の合成樹脂板から長さ20cm×幅20cmの試験片を切削し、温度23℃、相対湿度50%の環境にて状態調整をした後、厚さ1.5mmの試験片に対しハードコート層側から0.3mmの厚みの部分のみが水中に浸漬している状態で24時間保持した。試験前後の試験片を下に凸として水平面に静置し、試験片の4隅と水平面との隙間長さの変化量を測定し、その変化量の合算値が5.0mmを超えないものを合格とした。
前記透明性評価、耐擦傷性評価、層間密着性評価、ハードコート層との密着性評価、耐候性評価、低反り性評価の結果の全ての評価で合格のものを総合判定で合格、一つでも不合格の評価があれば不合格とした。
攪拌翼を備えた混合層に、トリス(2-アクロキシエチル)イソシアヌレート(Aldrich社製)60部と、ネオペンチルグリコールオリゴアクリレート(大阪有機化学工業社製、商品名:ビスコート#215D)40部と、2,4,6-トリメチルベンゾイルジフェニルフォスフィンオキサイド(チバ・ジャパン社製、商品名:DAROCUR TPO)2.8部と、ベンゾフェノン(Aldrich社製)1部からなる組成物を導入し、40℃に保持しながら1時間攪拌して感光性ハードコート塗料(C)を得た。
軸径32mmの単軸押出機と、軸径65mmの単軸押出機と、全押出機に連結されたフィードブロックと、フィードブロックに連結されたTダイとを有する多層押出装置を用いて合成樹脂積層板を成形した。軸径32mmの単軸押出機にメタクリル酸メチル-スチレン(78:22)共重合樹脂〔新日鉄化学(株)製、商品名:エスチレンMS750〕(樹脂B1)を連続的に導入し、シリンダ温度250℃、吐出速度8kg/hの条件で押し出した。また軸径65mmの単軸押出機にメタクリル酸メチル-スチレン(20:80)共重合樹脂〔新日鉄化学(株)製、商品名:エスチレンMS200〕(樹脂A1)を連続的に導入し、シリンダ温度260℃、吐出速度50kg/hで押し出した。全押出機に連結されたフィードブロックは2種3層の分配ピンを備え、温度260℃として(A1)層の両面に(B1)層を導入し積層した。その先に連結された温度270℃のTダイでシート状に押し出し、3本の鏡面仕上げロールで鏡面を転写しながら冷却し、樹脂A1の両面に樹脂B1が積層された合成樹脂積層体を得た。このときロールの設定温度は上流側から順に80℃、80℃、90℃とした。得られた合成樹脂積層体の厚みは1.5mm、樹脂B1層の厚み(片側)は中央付近で90μmであった。
得られた合成樹脂積層体の樹脂B1層上に合成例1で取得した感光性ハードコート塗料(C)を硬化後の塗膜厚さが3~8μmとなるようバーコーターを用いて塗布しPETフィルムで覆って圧着し、光源距離12cm、出力80W/cm2の高圧水銀灯を備えたコンベアでラインスピード1.5m/分の条件で紫外線を照射し硬化させてPETフィルムを剥離し、ハードコート層を備えたハードコート処理後の合成樹脂積層体を得た。評価結果を表1に示す。透明性評価、耐擦傷性評価、層間密着性評価、ハードコート層との密着性評価、耐候性評価、低反り性評価の結果はそれぞれ良好であり、総合判定は合格であった。
実施例1で使用した樹脂A1の代わりにアクリロニトリル-スチレン(20:80)共重合樹脂〔旭化成ケミカルズ(株)製、商品名:スタイラックAST8701〕(樹脂A2)を使用した以外は実施例1と同様にして樹脂A2の両面に樹脂B1が積層された合成樹脂積層体ならびに、得られた合成樹脂積層体の樹脂B1層上にハードコート層を備えたハードコート処理後の合成樹脂積層体を得た。得られた合成樹脂積層体の厚みは1.5mm、樹脂B1層の厚み(片側)は中央付近で90μmであった。評価結果を表1に示す。透明性評価、耐擦傷性評価、層間密着性評価、ハードコート層との密着性評価、耐候性評価、低反り性評価の結果はそれぞれ良好であり、総合判定は合格であった
実施例1で使用した樹脂A1の代わりにメタクリル酸メチル-スチレン(30:70)共重合樹脂〔新日鉄化学(株)製、商品名:エスチレンMS300〕(樹脂A3)を使用した以外は実施例1と同様にして樹脂A3の両面に樹脂B1が積層された合成樹脂積層体ならびに、得られた合成樹脂積層体の樹脂B1層上にハードコート層を備えたハードコート処理後の合成樹脂積層体を得た。得られた合成樹脂積層体の厚みは1.5mm、樹脂B1層の厚み(片側)は中央付近で90μmであった。評価結果を表1に示す。透明性評価、耐擦傷性評価、層間密着性評価、ハードコート層との密着性評価、耐候性評価、低反り性評価の結果はそれぞれ良好であり、総合判定は合格であった
実施例1で使用した樹脂B1の代わりにメタクリル酸メチル-スチレン(80:20)共重合樹脂〔電気化学工業(株)製、商品名:アクリスターKT-80SG〕(樹脂B2)を使用した以外は実施例1と同様にして樹脂A1の両面に樹脂B2が積層された合成樹脂積層体ならびに、得られた合成樹脂積層体の樹脂B2層上にハードコート層を備えたハードコート処理後の合成樹脂積層体を得た。得られた合成樹脂積層体の厚みは1.5mm、樹脂B2層の厚み(片側)は中央付近で90μmであった。評価結果を表1に示す。透明性評価、耐擦傷性評価、層間密着性評価、ハードコート層との密着性評価、耐候性評価、低反り性評価の結果はそれぞれ良好であり、総合判定は合格であった
実施例1で使用した樹脂B1の代わりにメタクリル酸メチル-スチレン(74:26)共重合樹脂〔新日鉄化学(株)製、商品名:エスチレンMS750LF〕(樹脂B3)を使用した以外は実施例1と同様にして樹脂A1の両面に樹脂B3が積層された合成樹脂積層体ならびに、得られた合成樹脂積層体の樹脂B3層上にハードコート層を備えたハードコート処理後の合成樹脂積層体を得た。得られた合成樹脂積層体の厚みは1.5mm、樹脂B3層の厚み(片側)は中央付近で90μmであった。評価結果を表1に示す。透明性評価、耐擦傷性評価、層間密着性評価、ハードコート層との密着性評価、耐候性評価、低反り性評価の結果はそれぞれ良好であり、総合判定は合格であった
実施例1で使用した樹脂A1の代わりにメタクリル酸メチル-スチレン(60:40)共重合樹脂〔新日鉄化学(株)製、商品名:エスチレンMS600〕(樹脂D1)を使用した以外は実施例1と同様にして樹脂D1の両面に樹脂B1が積層された合成樹脂積層体ならびに、得られた合成樹脂積層体の樹脂B1層上にハードコート層を備えたハードコート処理後の合成樹脂積層体を得た。得られた合成樹脂積層体の厚みは1.5mm、樹脂B1層の厚み(片側)は中央付近で90μmであった。評価結果を表1に示す。透明性評価、耐擦傷性評価、層間密着性評価、ハードコート層との密着性評価、耐候性評価の結果はそれぞれ良好であったが、低反り性評価の結果は不良であり、総合判定では不合格であった。
実施例1で使用した樹脂A1の代わりに樹脂D1を使用し、樹脂B1の代わりにメタクリル酸メチル-スチレン(90:10)共重合樹脂〔電気化学工業(株)製、商品名:アクリスターKT-80D〕(樹脂D2)を使用した以外は実施例1と同様にして樹脂D1の両面に樹脂D2が積層された合成樹脂積層体ならびに、得られた合成樹脂積層体の樹脂D2層上にハードコート層を備えたハードコート処理後の合成樹脂積層体を得た。得られた合成樹脂積層体の厚みは1.5mm、樹脂D2層の厚み(片側)は中央付近で90μmであった。評価結果を表1に示す。透明性評価、耐擦傷性評価、層間密着性評価、ハードコート層との密着性評価、耐候性評価の結果は良好であったものの、低反り性評価の結果は不良であり総合判定では不合格であった。
実施例1で使用した樹脂B1の代わりに樹脂D1を使用した以外は実施例1と同様にして樹脂A1の両面に樹脂D1が積層された合成樹脂積層体ならびに、得られた合成樹脂積層体の樹脂D1層上にハードコート層を備えたハードコート処理後の合成樹脂積層体を得た。得られた合成樹脂積層体の厚みは1.5mm、樹脂D1層の厚み(片側)は中央付近で90μmであった。評価結果を表1に示す。透明性評価、層間密着性評価、低反り性評価の結果はそれぞれ良好であったが、耐擦傷性評価、ハードコート層との密着性評価、耐候性評価の結果はそれぞれ不良であり、総合判定では不合格であった。
実施例1で使用した樹脂B1の代わりに樹脂D2を使用した以外は実施例1と同様にして樹脂A1の両面に樹脂D2が積層された合成樹脂積層体ならびに、得られた合成樹脂積層体の樹脂D2層上にハードコート層を備えたハードコート処理後の合成樹脂積層体を得た。得られた合成樹脂積層体の厚みは1.5mm、樹脂D2層の厚み(片側)は中央付近で90μmであった。評価結果を表1に示す。透明性評価、耐擦傷性評価、ハードコート層との密着性評価、耐候性評価の結果は良好であったものの、層間密着性評価、低反り性評価の結果はそれぞれ不良であり総合判定では不合格であった。
実施例1で使用した樹脂B1の代わりにメタクリル樹脂〔旭化成ケミカルズ(株)製、商品名:デルペット80NE〕(樹脂D3)を使用した以外は実施例1と同様にして樹脂A1の両面に樹脂D3が積層された合成樹脂積層体ならびに、得られた合成樹脂積層体の樹脂D3層上にハードコート層を備えたハードコート処理後の合成樹脂積層体を得た。得られた合成樹脂積層体の厚みは1.5mm、樹脂D3層の厚み(片側)は中央付近で90μmであった。評価結果を表1に示す。透明性評価、耐擦傷性評価、ハードコート層との密着性評価、耐候性評価の結果はそれぞれ良好であったが、層間密着性評価、低反り性評価の結果はそれぞれ不良であり、総合判定では不合格であった。
軸径32mmの単軸押出機と、軸径65mmの単軸押出機と、全押出機に連結されたフィードブロックと、フィードブロックに連結されたTダイとを有する多層押出装置を用いて合成樹脂積層板を成形した。軸径32mmの単軸押出機に樹脂B1を連続的に導入し、シリンダ温度250℃、吐出速度4kg/hの条件で押し出した。また軸径65mmの単軸押出機に樹脂A1を連続的に導入し、シリンダ温度260℃、吐出速度50kg/hで押し出した。全押出機に連結されたフィードブロックは2種2層の分配ピンを備え、温度260℃として(A1)層の片面に(B1)層を導入し積層した。その先に連結された温度270℃のTダイでシート状に押し出し、3本の鏡面仕上げロールで鏡面を転写しながら冷却し、樹脂A1の片面に樹脂B1が積層された合成樹脂積層体を得た。このときロールの設定温度は上流側から順に80℃、80℃、90℃とした。得られた合成樹脂積層体の厚みは1.5mm、樹脂B1層の厚みは中央付近で90μmであった。
得られた合成樹脂積層体の樹脂B1層上に合成例1で取得した感光性ハードコート塗料(C)を硬化後の塗膜厚さが3~8μmとなるようバーコーターを用いて塗布しPETフィルムで覆って圧着し、光源距離12cm、出力80W/cm2の高圧水銀灯を備えたコンベアでラインスピード1.5m/分の条件で紫外線を照射し硬化させてPETフィルムを剥離し、ハードコート層を備えたハードコート処理後の合成樹脂積層体を得た。評価結果を表1に示す。透明性評価、耐擦傷性評価、層間密着性評価、ハードコート層との密着性評価、耐候性評価の結果はそれぞれ良好であったものの、低反り性評価の結果は不良であり、総合判定は不合格であった
軸径65mmの単軸押出機とTダイとを有する単層押出装置を用いて合成樹脂板を成形した。軸径65mmの単軸押出機に樹脂B1を連続的に導入し、シリンダ温度260℃、吐出速度50kg/hで押し出した。その先に連結された温度270℃のTダイでシート状に押し出し、3本の鏡面仕上げロールで鏡面を転写しながら冷却し、樹脂B1の合成樹脂板を得た。このときロールは上流側から温度80℃、80℃、90℃とした。得られた合成樹脂板の厚みは1.5mmであった。
得られた合成樹脂板の樹脂B1層上に合成例4で取得した感光性ハードコート塗料(C)を硬化後の塗膜厚さが3~8μmとなるようバーコーターを用いて塗布しPETフィルムで覆って圧着し、光源距離12cm、出力80W/cm2の高圧水銀灯を備えたコンベアでラインスピード1.5m/分の条件で紫外線を照射し硬化させてPETフィルムを剥離し、ハードコート層を備えたハードコート処理後の合成樹脂板を得た。評価結果を表1に示す。透明性評価、耐擦傷性評価、層間密着性評価、ハードコート層との密着性評価、耐候性評価の結果は良好であったものの、低反り性評価の結果は不良であり、総合判定では不合格であった。
比較例7で使用した樹脂B1の代わりに樹脂A1を使用した以外は比較例7と同様にして樹脂A1の合成樹脂板ならびに、得られた合成樹脂板の樹脂A1層上にハードコート層を備えたハードコート処理後の合成樹脂板を得た。得られた合成樹脂板の厚みは1.5mmであった。評価結果を表1に示す。透明性評価、低反り性評価の結果はそれぞれ良好であったが、耐擦傷性評価、ハードコート層との密着性評価、耐候性評価の結果はそれぞれ不良であり、総合判定では不合格であった。
比較例7で使用した樹脂B1の代わりに樹脂A2を使用した以外は比較例7と同様にして樹脂A2の合成樹脂板ならびに、得られた合成樹脂板の樹脂A2層上にハードコート層を備えたハードコート処理後の合成樹脂板を得た。得られた合成樹脂板の厚みは1.5mmであった。評価結果を表1に示す。透明性評価、ハードコート層との密着性評価、低反り性評価の結果はそれぞれ良好であったが、耐擦傷性評価、耐候性評価の結果はそれぞれ不良であり、総合判定では不合格であった。
Claims (10)
- 熱可塑性樹脂(A)に含有されるスチレン構成単位が70~80モル%である請求項1に記載の合成樹脂積層体。
- 熱可塑性樹脂(B)に含有される(メタ)アクリル酸エステル構成単位(a)とスチレン構成単位のモル比が74:26~80:20である請求項1に記載の合成樹脂積層体。
- 熱可塑性樹脂(A)がメタクリル酸メチル-スチレン共重合樹脂、アクリロニトリル-スチレン共重合樹脂のいずれかである請求項1に記載の合成樹脂積層体。
- 熱可塑性樹脂(A)がメタクリル酸メチル構成単位とスチレン構成単位のモル比が10:90~35:65であるメタクリル酸メチル-スチレン共重合樹脂である請求項1に記載の合成樹脂積層体。
- 熱可塑性樹脂(A)がアクリロニトリル構成単位とスチレン構成単位のモル比が10:90~35:65であるアクリロニトリル-スチレン共重合樹脂である請求項1に記載の合成樹脂積層体。
- 片面または両面にハードコート処理を施したものである請求項1~6のいずれかに記載の合成樹脂積層体。
- 片面または両面に反射防止処理、防汚処理、帯電防止処理、耐候性処理および防眩処理から選択されるいずれか一つ以上の処理を施したものである請求項1~6のいずれかに記載の合成樹脂積層体。
- 請求項1~6のいずれかに記載の合成樹脂積層体からなる透明性基板材料。
- 請求項1~6のいずれかに記載の合成樹脂積層体からなる透明性保護材料。
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