WO2017150646A1 - 車載用液晶表示装置の前面板 - Google Patents
車載用液晶表示装置の前面板 Download PDFInfo
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- WO2017150646A1 WO2017150646A1 PCT/JP2017/008213 JP2017008213W WO2017150646A1 WO 2017150646 A1 WO2017150646 A1 WO 2017150646A1 JP 2017008213 W JP2017008213 W JP 2017008213W WO 2017150646 A1 WO2017150646 A1 WO 2017150646A1
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- resin
- resin composition
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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
- B32B2307/732—Dimensional properties
-
- 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
- B32B2457/202—LCD, i.e. liquid crystal displays
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/133308—Support structures for LCD panels, e.g. frames or bezels
- G02F1/133331—Cover glasses
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F2201/00—Constructional arrangements not provided for in groups G02F1/00 - G02F7/00
- G02F2201/38—Anti-reflection arrangements
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F2201/00—Constructional arrangements not provided for in groups G02F1/00 - G02F7/00
- G02F2201/54—Arrangements for reducing warping-twist
Definitions
- the present invention relates to a front plate of an in-vehicle liquid crystal display device, and in particular, has excellent impact resistance, heat resistance and antiglare performance, suppresses the occurrence of glare, has high scratch resistance, and has high pencil hardness.
- the present invention relates to a front plate suitable for use in an in-vehicle liquid crystal display device that is excellent in warpage.
- a liquid crystal display device is provided with a front plate for the purpose of protecting the liquid crystal panel and the like.
- a material used for the front plate of the conventional liquid crystal display device (meth) acrylic resin represented by polymethyl methacrylate (PMMA) can be mentioned.
- a front plate provided with a sheet made of a polycarbonate resin has been used because it has high impact resistance, heat resistance, secondary workability, lightness, transparency, and the like.
- the front plate of a liquid crystal display device in which a hard coat is applied on a multilayer sheet in which an acrylic resin is laminated on the surface layer of a polycarbonate resin sheet has a surface hardness and scratch resistance comparable to conventional acrylic resins with a hard coat.
- the polycarbonate resin since the polycarbonate resin has excellent impact resistance, heat resistance, workability and transparency, it is widely used as a front plate of a liquid crystal display device (see, for example, Patent Document 1).
- the front plate of a liquid crystal display device including the polycarbonate resin sheet is generally formed by melt extrusion together with an acrylic resin.
- an optical laminate for preventing reflection is generally provided on the outermost surface.
- Such an anti-reflection optical laminated body suppresses reflection of an image or reduces reflectance by scattering or interference of light.
- an antiglare film is known in which an antiglare layer having an uneven shape is formed on the surface of a transparent substrate. This antiglare film can prevent external light from being scattered due to the uneven shape of the surface, thereby preventing a decrease in visibility due to reflection of external light or reflection of an image.
- this optical laminated body is normally installed in the outermost surface of a liquid crystal display device, it is also required to give hard coat property so that it may not be damaged at the time of handling.
- Anti-glare films are required to have anti-glare properties, exhibit good contrast when placed on the surface of a liquid crystal display, and pixels and anti-glare when placed on the surface of a liquid crystal display.
- the temperature in the interior of the automobile is severe from low to high in the environment, and the front plate is susceptible to deformation due to contraction and expansion due to thermal fluctuations. Problems such as squeaking are occurring.
- a stretched front plate with high retardation is used, so that deformation is more likely to occur.
- the resin laminate obtained by laminating the acrylic resin layer on the polycarbonate resin layer has a large amount of dimensional change after moisture absorption between the laminated resin layers, and the warp in which the acrylic resin layer becomes convex. It solves the problem that occurs.
- the resin laminate of Patent Document 2 is still insufficient in warp deformation resistance under a temperature environment exceeding 40 ° C.
- the temperature of the in-vehicle display device may rise far beyond room temperature, and the resin plate used as the protective plate of the in-vehicle display device has a high temperature environment exceeding 40 ° C, for example, a temperature of 85 ° C and a humidity of 85%.
- the front plate of the in-vehicle liquid crystal display device needs to be provided with various functions such as blackout countermeasures, anti-glare properties that do not cause glare, and prevention of scratches. There was no front plate that needed to withstand all of these requirements.
- the object of the present invention is to solve at least one of the problems in the prior art. Furthermore, the present invention provides an in-vehicle liquid crystal display that exhibits excellent impact resistance, heat resistance, and antiglare performance, suppresses the occurrence of glare, has high scratch resistance, high pencil hardness, and excellent warpage. It is an object of the present invention to provide a front plate suitable for an apparatus.
- the present inventors have found that a specific configuration is effective as a front plate of an in-vehicle liquid crystal display device, and have reached the present invention.
- the present invention is as follows. ⁇ 1> A layer containing a high-hardness resin composition (B) is provided on at least one surface of a layer containing a resin (A) containing a polycarbonate resin (a1), and the high-hardness resin composition (B). It is a front plate of the vehicle-mounted liquid crystal display device which has the hard-coat layer which has an unevenness
- the layer containing the high-hardness resin composition (B) has a thickness of 10 to 250 ⁇ m, the layer containing the resin (A) containing the polycarbonate resin (a1) and the high-hardness resin composition (B).
- the total thickness of the layers to be included is 100 to 3,000 ⁇ m
- the high-hardness resin composition (B) comprises any one of the following resin compositions (B1) to (B3), -Resin composition (B1)
- a copolymer resin comprising a (meth) acrylic acid ester structural unit (a) represented by the following general formula (1) and an aliphatic vinyl structural unit (b) represented by the following general formula (2):
- the total proportion of the methacrylic ester structural unit (a) and the aliphatic vinyl structural unit (b) is 90 to 100 mol% of the total structural units of the copolymer resin, and the (meth) acrylic ester structure Copolymer resin in which the proportion of unit (a) is 65 to 80 mol% of the total constituent units of the cop
- the retardation of the front plate is 3,000 nm or more
- the standard deviation of the second derivative of the uneven shape of the hard coat layer having the unevenness is 0.1 or more.
- ⁇ 3> The in-vehicle use according to ⁇ 1> or ⁇ 2>, wherein the amount of change in warpage after the front plate is held for 120 hours in an environment of 85 ° C. and 85% relative humidity is 1,000 ⁇ m or less. It is a front plate of a liquid crystal display device.
- ⁇ 4> Any of the above ⁇ 1> to ⁇ 3>, wherein the layer containing the high-hardness resin composition (B) is coextruded with the layer containing the resin (A) containing the polycarbonate resin (a1) It is a front board of the vehicle-mounted liquid crystal display device of a crab.
- the polycarbonate resin (a1) includes a component derived from a monohydric phenol represented by the following general formula (4): It is.
- R 1 represents an alkyl group having 8 to 36 carbon atoms or an alkenyl group having 8 to 36 carbon atoms
- R 2 to R 5 each independently have a hydrogen atom, a halogen, or a substituent.
- a front plate suitable for an in-vehicle liquid crystal display device can be provided.
- the glare obtained in Example 1 is an example of a good uneven shape. It is an example of the uneven
- the glare obtained in Example 1 is an example of twice-differentiation of a concavo-convex shape with good. It is an example of the 2nd derivative of the uneven
- the front plate of the in-vehicle liquid crystal display device of the present invention has a high hardness on at least one surface of a layer containing a resin (A) containing a polycarbonate resin (a1) (hereinafter sometimes referred to as “base material layer”).
- a layer containing the resin composition (B) (hereinafter sometimes referred to as “high hardness layer”) and a hard coat layer having irregularities are provided.
- the base material layer may be a layer made of a resin (A) containing a polycarbonate resin (a1).
- the high hardness layer may be a layer made of a high hardness resin composition (B).
- the high hardness layer exists between the base material layer and the hard coat layer, and an uneven shape is given to the outermost surface of the hard coat layer that becomes the outermost layer.
- the other side of the layer containing the resin (A) containing the polycarbonate resin (a1) is not particularly specified, but both the high-hardness resin layer and the hard coat layer, or any one layer may be provided.
- the high-hardness resin layer it is desirable to use a resin selected from the high-hardness resin composition (B), and the same high-hardness resin composition (B) is used on both sides with less warpage. It is also more desirable to do.
- the hard coat layer is not particularly specified, but a hard coat layer similar to the hard coat layer having irregularities can be used. It is more desirable to form hard coat layers on both sides because warpage can be reduced. In order to prevent scratches, the hard coat layer having irregularities has a pencil hardness of preferably H or higher, more preferably 2H or higher, and particularly preferably 3H or higher.
- the front plate of the present invention can be used alone as a front plate, but may be combined and used as a front plate, for example, by laminating with another substrate such as a touch sensor.
- the backlight light source is not particularly limited, but is preferably a white light emitting diode (white LED).
- the white LED is particularly preferably a phosphor type, that is, an element that emits white light by combining a phosphor with a light emitting diode that emits blue light or ultraviolet light using a compound semiconductor.
- the front plate of the present invention when using polarized sunglasses, etc., the retardation of the layer containing the resin (A) containing the polycarbonate resin (a1) and the coloring and color caused by the unevenness thereof. Generation of unevenness can be suppressed.
- the driving method is not particularly limited, and a TN (Twisted Nematic) method, a VA (Virtical Alignment) method, an IPS (In-Place-Switching) method, etc. can be used. It is desirable that the transmission axis and the fast axis or slow axis in the plane of the layer containing the resin (A) containing the polycarbonate resin (a1) are parallel or form an angle of 45 degrees. In this case, when polarized sunglasses or the like is used, the retardation of the layer containing the resin (A) containing the polycarbonate resin (a1) and the occurrence of interference colors due to the unevenness can be suppressed.
- TN Transmission Nematic
- VA Virtual Alignment
- IPS In-Place-Switching
- the resin (A) containing the polycarbonate resin (a1) used in the present invention is a resin mainly containing the polycarbonate resin (a1).
- the content of the polycarbonate resin (a1) in the resin (A) is 75% by weight or more. However, since the impact resistance is improved by increasing the content, the content is desirably 90% by weight or more. Is 100% by weight.
- polycarbonate resin (a1) a carbonic acid ester bond in the molecular main chain, that is, — [O—R—OCO] —unit (where R is an aliphatic group, an aromatic group, or both an aliphatic group and an aromatic group) And those having a linear structure or a branched structure) are not particularly limited, but it is particularly preferable to use a polycarbonate resin containing a structural unit of the following formula (3). By using such a polycarbonate resin, a resin laminate having excellent impact resistance can be obtained.
- an aromatic polycarbonate resin for example, trade name: Iupilon S-2000, Iupilon S-1000, Iupilon E-2000, manufactured by Mitsubishi Engineering Plastics
- Iupilon S-2000 trade name: Iupilon S-2000, Iupilon S-1000, Iupilon E-2000, manufactured by Mitsubishi Engineering Plastics
- a monohydric phenol represented by the following general formula (4) as a terminal stopper.
- R 1 represents an alkyl group having 8 to 36 carbon atoms or an alkenyl group having 8 to 36 carbon atoms
- R 2 to R 5 each independently have a hydrogen atom, a halogen, or a substituent.
- R 1 represents an alkyl group having 8 to 36 carbon atoms or an alkenyl group having 8 to 36 carbon atoms
- R 2 to R 5 each independently have a hydrogen atom, a halogen, or a substituent.
- the substituent is a halogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms. is there.
- the monohydric phenol represented by the general formula (4) is represented by the following general formula (5).
- R 1 represents an alkyl group having 8 to 36 carbon atoms or an alkenyl group having 8 to 36 carbon atoms.
- the number of carbon atoms of R 1 in the general formula (4) or the general formula (5) is more preferably within a specific numerical range.
- the upper limit value of the carbon number of R 1 is preferably 36, more preferably 22, and particularly preferably 18.
- the lower limit of the number of carbon atoms in R 1, 8 is preferred, 12 it is more preferred.
- R 1 is a monohydric phenol (terminal stopper) that is an alkyl group having 16 carbon atoms
- the solvent solubility of phenol is excellent, and it is particularly preferable as a terminal terminator used for the polycarbonate resin in the present invention.
- the weight average molecular weight of the polycarbonate resin (a1) affects the impact resistance and molding conditions of the synthetic resin laminate. That is, when the weight average molecular weight is too small, the impact resistance of the synthetic resin laminate is lowered, which is not preferable. When the weight average molecular weight is too high, an excessive heat source may be required when the layer containing the polycarbonate resin (a1) is laminated, which is not preferable. Moreover, since a high temperature is required depending on the molding method, the polycarbonate resin (a1) is exposed to a high temperature, which may adversely affect its thermal stability.
- the weight average molecular weight of the polycarbonate resin (a1) is preferably 15,000 to 75,000, and more preferably 20,000 to 70,000. More preferably, it is 25,000 to 65,000.
- a weight average molecular weight is a weight average molecular weight of standard polystyrene conversion measured by gel permeation chromatography (GPC) as described in the Example mentioned later.
- the high-hardness resin composition (B) used in the present invention is selected from any one of a resin composition (B1), a resin composition (B2), and a resin composition (B3).
- the resin composition (B1) used in the present invention is a (meth) acrylic acid ester structural unit (a) represented by the general formula (1) and an aliphatic vinyl structure represented by the general formula (2).
- R1 is a hydrogen atom or a methyl group
- R2 is an alkyl group having 1 to 18 carbon atoms.
- R3 is a hydrogen atom or a methyl group
- R4 is a cyclohexyl group optionally having a hydrocarbon group having 1 to 4 carbon atoms.
- R2 is an alkyl group having 1 to 18 carbon atoms, specifically a methyl group, an ethyl group, a butyl group, a lauryl group. , Stearyl group, cyclohexyl group, isobornyl group and the like.
- (meth) acrylic acid ester structural unit (a) preferred is a (meth) acrylic acid ester structural unit in which R2 is a methyl group or an ethyl group, and further preferred is that R1 is a methyl group; Is a methyl methacrylate structural unit in which is a methyl group.
- R3 is a hydrogen atom or a methyl group
- R4 is a cyclohexyl group or a cyclohexyl group having 1 to 4 carbon atoms.
- the thing which is is mentioned preferably.
- R3 is a hydrogen atom
- R4 is a cyclohexyl group.
- the resin composition (B1) may contain one or more of the (meth) acrylic ester structural unit (a), and one or more of the aliphatic vinyl structural unit (b). You may contain.
- the total ratio of the (meth) acrylic ester structural unit (a) and the aliphatic vinyl structural unit (b) is 90 to 100 mol% with respect to the total of all the structural units of the copolymer resin, preferably Is 95 to 100 mol%, more preferably 98 to 100 mol%. That is, the resin composition (B1) is in the range of 10 mol% or less with respect to the total of all the structural units of the copolymer resin, and the (meth) acrylic acid ester structural unit (a) and the aliphatic vinyl constituent.
- a structural unit other than the unit (b) may be contained.
- Examples of the structural unit other than the (meth) acrylic ester structural unit (a) and the aliphatic vinyl structural unit (b) include, for example, a polymer obtained by polymerizing a (meth) acrylic ester monomer and an aromatic vinyl monomer. Examples thereof include a structural unit derived from an aromatic vinyl monomer containing an aromatic double bond that is not hydrogenated in the resin composition (B1) obtained by hydrogenating an aromatic double bond derived from an aromatic vinyl monomer.
- the proportion of the (meth) acrylic ester structural unit (a) represented by the general formula (1) is 65 to 80 mol% with respect to the total of all the structural units in the resin composition (B1). Yes, preferably 70 to 80 mol%.
- the production method of the resin composition (B1) is not particularly limited, but after polymerizing at least one (meth) acrylic acid ester monomer and at least one aromatic vinyl monomer, the aromatics derived from the aromatic vinyl monomer are used. Those obtained by hydrogenating group double bonds are preferred.
- (meth) acrylic acid shows methacrylic acid and / or acrylic acid.
- Specific examples of the aromatic vinyl monomer used at this time include styrene, ⁇ -methylstyrene, p-hydroxystyrene, alkoxystyrene, chlorostyrene, and derivatives thereof. Of these, styrene is preferred.
- a known method can be used for the polymerization of the (meth) acrylic acid ester monomer and the aromatic vinyl monomer, and for example, it can be produced by a bulk polymerization method or a solution polymerization method.
- the bulk polymerization method is carried out by a method in which the monomer composition containing the monomer and the polymerization initiator is continuously supplied to a complete mixing tank and continuously polymerized at 100 to 180 ° C.
- the monomer composition may contain a chain transfer agent as necessary.
- the polymerization initiator is not particularly limited, but t-amylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, benzoyl peroxide, 1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-di (t-hexylperoxy) cyclohexane, 1,1-di (t-butylperoxy) cyclohexane, t-hexylpropoxyisopropyl monocarbonate, t-amylperoxynormal Organic peroxides such as octoate, t-butylperoxyisopropyl monocarbonate, di-t-butyl peroxide, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile) ), 2,2'-azobis (2,4-dimethylvaleronitrile) and
- the chain transfer agent is used as necessary, and examples thereof include ⁇ -methylstyrene dimer.
- Examples of the solvent used in the solution polymerization method 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, Examples include ether solvents such as dioxane and alcohol solvents such as methanol and isopropanol.
- 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 examples include ether solvents such as dioxane and alcohol solvents such as methanol and isopropanol.
- the solvent used in the hydrogenation reaction after polymerizing the (meth) acrylic acid ester monomer and the aromatic vinyl monomer may be the same as or different from the polymerization solvent described above.
- hydrocarbon solvents such as cyclohexane and methylcyclohexane
- ester solvents such as ethyl acetate and methyl isobutyrate
- ketone solvents such as acetone and methyl ethyl ketone
- ether solvents such as tetrahydrofuran and dioxane
- alcohol solvents such as methanol and isopropanol A solvent etc.
- the resin composition used in the present invention is obtained by polymerizing the (meth) acrylic acid ester monomer and the aromatic vinyl monomer as described above, and then hydrogenating the aromatic double bond derived from the aromatic vinyl monomer. (B1) is obtained.
- the method for hydrogenation is not particularly limited, and a known method can be used. For example, it can be carried out batchwise or continuously with a hydrogen pressure of 3 to 30 MPa and a reaction temperature of 60 to 250 ° C. By setting the temperature to 60 ° C. or higher, the reaction time does not take too long, and by setting the temperature to 250 ° C. or lower, there are few occurrences of molecular chain scission or ester site hydrogenation.
- Examples of the catalyst used in the hydrogenation reaction include metals such as nickel, palladium, platinum, cobalt, ruthenium, and rhodium or oxides or salts or complex compounds of these metals, carbon, alumina, silica, silica / alumina, diatomaceous earth. And a solid catalyst supported on a porous carrier.
- the resin composition (B1) is preferably such that 70% or more of the aromatic double bond derived from the aromatic vinyl monomer is hydrogenated. That is, the ratio of the unhydrogenated site of the aromatic double bond in the structural unit derived from the aromatic vinyl monomer is preferably 30% or less. If the content exceeds 30%, the transparency of the resin composition (B1) may be lowered.
- the proportion of unhydrogenated sites is more preferably in the range of less than 10%, and still more preferably in the range of less than 5%.
- the weight average molecular weight of the resin composition (B1) is not particularly limited, but is preferably 50,000 to 400,000, and preferably 70,000 to 300,000 from the viewpoint of strength and moldability. Is more preferable.
- the said weight average molecular weight is a weight average molecular weight of standard polystyrene conversion measured by gel permeation chromatography (GPC) as described in the Example mentioned later.
- the resin composition (B1) can be blended with other resins as long as the transparency is not impaired.
- examples include methyl methacrylate-styrene copolymer resin, polymethyl methacrylate, polystyrene, polycarbonate, cycloolefin (co) polymer resin, acrylonitrile-styrene copolymer resin, acrylonitrile-butadiene-styrene copolymer resin, and various elastomers. .
- the glass transition temperature of the resin composition (B1) is preferably in the range of 110 to 140 ° C.
- the glass transition temperature in this invention is a temperature when using a differential scanning calorimetry apparatus and measuring by 10 mg of samples and the temperature increase rate of 10 degree-C / min, and calculating by the midpoint method.
- the resin composition (B2) used in the present invention is a resin (C) containing a vinyl monomer in an amount of 55 to 10% by mass (preferably 50 to 20% by mass), and styrene-unsaturated dicarboxylic acid.
- Resin composition containing 50-80% by weight of monomer unit (d1), 10-30% by weight of unsaturated dicarboxylic anhydride monomer unit (d2), and 5-30% by weight of vinyl monomer unit (d3) It is a thing.
- the resin (C) containing a vinyl monomer and the styrene-unsaturated dicarboxylic acid copolymer (D) will be described in order.
- the resin (C) containing a vinyl monomer used in the present invention include acrylonitrile, methacrylonitrile, acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, and methacrylic acid.
- vinyl monomers such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and 2-ethylhexyl methacrylate are homopolymerized, and methyl methacrylate is particularly preferred as the monomer unit.
- a copolymer containing two or more kinds of the monomer units may be used.
- the weight average molecular weight of the resin (C) containing a vinyl monomer is preferably 10,000 to 500,000, more preferably 50,000 to 300,000.
- the styrene-unsaturated dicarboxylic acid copolymer (D) used in the present invention comprises a styrene monomer unit (d1), an unsaturated dicarboxylic acid anhydride monomer unit (d2), and a vinyl monomer. Including unit (d3).
- the styrene monomer is not particularly limited, and any known styrene monomer can be used. From the viewpoint of availability, styrene, ⁇ -methylstyrene, o-methylstyrene, m- Examples thereof include methyl styrene, p-methyl styrene, and t-butyl styrene. Among these, styrene is particularly preferable from the viewpoint of compatibility. Two or more of these styrenic monomers may be mixed.
- the unsaturated dicarboxylic acid anhydride monomer include acid anhydrides such as maleic acid, itaconic acid, citraconic acid, and aconitic acid, and maleic anhydride is preferred from the viewpoint of compatibility with vinyl monomers. . Two or more of these unsaturated dicarboxylic acid anhydride monomers may be mixed.
- vinyl monomers include acrylonitrile, methacrylonitrile, acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, and n methacrylate.
- vinyl monomers such as butyl and 2-ethylhexyl methacrylate.
- Methyl methacrylate (MMA) is preferable from the viewpoint of compatibility with the resin (C) containing a vinyl monomer. Two or more of these vinyl monomers may be mixed.
- composition ratio of styrene-unsaturated dicarboxylic acid copolymer (D) is 50 to 80% by mass (preferably 50 to 75% by mass) of the styrene monomer unit (d1), the unsaturated dicarboxylic acid anhydride unit.
- the monomer unit (d2) is 10 to 30% by mass (preferably 10 to 25% by mass)
- the vinyl monomer unit (d3) is 5 to 30% by mass (preferably 7 to 27% by mass).
- the weight average molecular weight of the styrene-unsaturated dicarboxylic acid copolymer (D) is preferably 50,000 to 200,000, more preferably 80,000 to 200,000.
- the weight average molecular weight is 50,000 to 200,000, the compatibility with the resin (C) containing a vinyl monomer is good, and the effect of improving heat resistance is excellent.
- the weight average molecular weights of the resin (C) and the copolymer (D) are standard polystyrene equivalent weight average molecular weights measured by gel permeation chromatography (GPC) as described in the examples described later.
- the resin composition (B3) used in the present invention is a resin composition containing 95 to 45% by mass of the polycarbonate resin (E) and 5 to 55% by mass of the (meth) acrylate copolymer (F).
- the (meth) acrylate copolymer (F) comprises an aromatic (meth) acrylate unit (f1) and a methacrylic acid ester monomer unit (f2) in a mass ratio (f1 / f2) of 10 to 50 / 40 to 90, the polycarbonate resin (E) has a weight average molecular weight of 37,000 to 71,000, and the (meth) acrylate copolymer (F) has a weight average molecular weight of 5,000 to 30,
- the resin composition is 000.
- the polycarbonate resin (E) has a — [O—R—OCO] — unit (R is an aliphatic group, an aromatic group, or both an aliphatic group and an aromatic group, and includes a carbonate ester bond in the molecular main chain. It is not particularly limited as long as it includes a straight chain structure or a branched structure.
- the (meth) acrylate copolymer (F) used in the present invention comprises an aromatic (meth) acrylate unit (f1) and a methacrylic acid ester monomer unit (f2).
- (meth) acrylate refers to acrylate or methacrylate.
- the aromatic (meth) acrylate constituting the aromatic (meth) acrylate unit (f1) refers to a (meth) acrylate having an aromatic group in the ester portion.
- the aromatic (meth) acrylate include phenyl (meth) acrylate and benzyl (meth) acrylate. These can be used alone or in combination of two or more. Of these, phenyl methacrylate and benzyl methacrylate are preferable, and phenyl methacrylate is more preferable.
- the monomer constituting the methacrylic acid ester monomer unit (f2) is methyl methacrylate.
- the methacrylic acid ester monomer unit (f2) has an effect of being well dispersed with the polycarbonate resin, and moves to the surface of the molded body, so that the surface hardness of the molded body can be improved.
- the (meth) acrylate copolymer (F) has an aromatic (meth) acrylate unit (f1) of 10 to 50% by mass (preferably 20 to 40% by mass), and a methacrylic acid ester monomer unit (f2) 40. To 90% by mass (preferably 50 to 80% by mass) (provided that the sum of (f1) and (f2) is 100% by mass). If the content of the aromatic (meth) acrylate unit (f1) in the (meth) acrylate copolymer (F) is 10% by mass or more, it is transparent in the high addition region of the (meth) acrylate copolymer (F). If the properties are maintained and the amount is 50% by mass or less, the compatibility with the polycarbonate is not too high, and the transferability to the surface of the molded article does not decrease, so the surface hardness does not decrease.
- the weight average molecular weight of the (meth) acrylate copolymer (F) is 5,000 to 30,000, preferably 10,000 to 25,000.
- the weight average molecular weight is 5,000 to 30,000, the compatibility with the polycarbonate is good, and the effect of improving the surface hardness is excellent.
- the composition ratio of the (meth) acrylate copolymer (F) and the polycarbonate resin (E) is such that the component (E) is 95 to 45% by mass with respect to the component (F) of 5 to 55% by mass. is there.
- the component (E) is 80 to 50% by mass with respect to the component (F) of 20 to 50% by mass. More preferably, the component (E) is 70 to 50% by mass with respect to the component (F) of 30 to 50% by mass.
- the weight average molecular weight of the polycarbonate resin (E) is determined by the ease of mixing (dispersing) with the (meth) acrylate copolymer (F). That is, if the weight average molecular weight of the polycarbonate resin (E) is too large, the difference in melt viscosity between the component (E) and the component (F) becomes too large, resulting in poor mixing (dispersion) between the two and poor transparency. Or a problem that stable melt-kneading cannot be continued.
- the weight average molecular weight of the polycarbonate resin (E) is in the range of 37,000 to 71,000, preferably in the range of 42,000 to 68,000, more preferably in the range of 48,000 to 64,000. is there.
- the weight average molecular weight of polycarbonate resin (E) and (meth) acrylate copolymer (F) is the weight of standard polystyrene conversion measured by gel permeation chromatography (GPC) as described in the Example mentioned later. Average molecular weight.
- Laminate As a method for producing a laminate having a layer containing a high-hardness resin composition (B) on at least one surface of a layer containing a resin (A) containing a polycarbonate resin (a1) of the front plate used in the present invention, There is no particular limitation.
- a method of laminating a layer containing an individually formed high-hardness resin composition (B) and a layer containing a resin (A) containing a polycarbonate resin (a1) and thermocompression bonding them together A method of laminating a layer containing a hardness resin composition (B) and a layer containing a resin (A) containing a polycarbonate resin (a1) and bonding them together with an adhesive, a high hardness resin composition (B)
- co-extrusion method is preferred.
- the method of coextrusion is not particularly limited.
- a layer containing the high-hardness resin composition (B) is laminated on one side of the layer containing the resin (A) containing the polycarbonate resin (a1) in the feed block. And after extruding into a sheet form with T die, it cools, making a formation roll pass, and forms a desired laminated body.
- a layer containing the high-hardness resin composition (B) is laminated on one side of the layer containing the resin (A) containing the polycarbonate resin (a1) in the multi-manifold die and extruded into a sheet shape. Then, it is cooled while passing through a forming roll to form a desired synthetic resin laminate.
- various additives can be mixed and used for the resin (A) containing the polycarbonate resin (a1) in this invention, and the high-hardness resin composition (B) in the range which does not impair transparency.
- the additive include an antioxidant, an anticolorant, an antistatic agent, a release agent, a lubricant, a dye, and a pigment.
- 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.
- the thickness of the layer containing the high-hardness resin composition (B) affects the surface hardness and impact resistance of the synthetic resin laminate.
- the thickness of the layer containing the high-hardness resin composition (B) is 10 to 250 ⁇ m, preferably 30 to 200 ⁇ m, more preferably 60 to 150 ⁇ m.
- the total thickness of the layer containing the resin (A) containing the polycarbonate resin (a1) and the layer containing the high-hardness resin composition (B) is warpage after leaving the front plate in a high-temperature and high-humidity environment. Affects. That is, if the total thickness is too thin, the warpage after leaving in a high-temperature and high-humidity environment becomes large, and if the total thickness is too thick, the warping after leaving in a high-temperature and high-humidity environment becomes small.
- the total thickness of the layer containing the resin (A) containing the polycarbonate resin (a1) and the layer containing the high-hardness resin composition (B) is 100 to 3,000 ⁇ m, preferably 120 to 2,500 ⁇ m. More preferably, it is 150 to 2,000 ⁇ m.
- the front plate in the present invention has a retardation of 3,000 nm or more, preferably 4,000 nm or more. More preferably, it is 5,000 nm or more, and particularly preferably 6,000 nm or more. When the retardation is lower than 3,000 nm, the effect of preventing the blackout phenomenon is not sufficient.
- the upper limit of retardation is not particularly limited, but if it is 15,000 nm or more, it is sufficient to prevent the blackout phenomenon, but the deformation in a harsh environment such as the inside of a vehicle increases, so 15,000 nm.
- retardation in the present invention means that when the main refractive index of the slow axis in the sheet surface is nx, the main refractive index of the fast axis is ny, and the thickness of the sheet is d, (nx ⁇ ny ) Xd is expressed in nm.
- the production method for setting the retardation to 3,000 nm or more is not particularly limited.
- the polycarbonate resin (a1) can be obtained by increasing the draw rate and increasing the draw ratio in the flow direction of the polycarbonate resin.
- the retardation of the layer containing the resin (A) to be contained can be increased, and the retardation of the front plate can be 3,000 nm or more.
- a hard coat layer is formed on the layer containing the high-hardness resin composition (B) so as not to be damaged during handling.
- the hard coat layer is formed by a hard coat process using a hard coat paint that is cured using thermal energy and / or light energy.
- thermal energy examples include polyorganosiloxane-based and cross-linked acrylic-based thermosetting resin compositions.
- the hard coat paint to be cured using light energy examples include, for example, tris (acryloxyethyl) isocyanurate (a21) 40 to 80% by weight and bifunctional and / or trifunctional copolymerizable with (a21).
- a photocurable resin composition in which 1 to 10 parts by weight of a photopolymerization initiator (a23) is added to 100 parts by weight of a resin composition comprising 20 to 40% by weight of the (meth) acrylate compound (a22). It is done.
- a functional (meth) acrylate monomer and a bifunctional or higher polyfunctional urethane (meth) acrylate oligomer and / or a bifunctional or higher polyfunctional polyester (meth) acrylate oligomer and / or a bifunctional or higher polyfunctional epoxy (meth) acrylate oligomer examples thereof include a photocurable resin composition in which 1 to 10 parts by mass of a photopolymerization initiator is added to 100 parts by mass of a resin composition comprising 40 to 80% by mass of the compound.
- the film thickness of the hard coat layer is preferably 1 ⁇ m or more and 40 ⁇ m or less, and more preferably 2 ⁇ m or more and 10 ⁇ m or less.
- the film thickness of the hard coat layer can be measured by observing the cross section with a microscope or the like and actually measuring from the coating film interface to the surface.
- pretreatment of the coated surface may be performed before the hard coat.
- treatment include known methods such as sandblasting, solvent treatment, corona discharge treatment, chromic acid treatment, flame treatment, hot air treatment, ozone treatment, ultraviolet treatment, and primer treatment with a resin composition.
- the surface of the hard coat layer has an uneven shape in order to impart antiglare properties.
- the uneven shape in the present invention means that the center line average roughness (Ra) defined by JIS-B-0601 is 0.01 or more. In order to obtain high antiglare properties, the center line average roughness (Ra) is preferably 0.05 or more.
- the standard deviation of the second derivative of the concavo-convex shape of the hard coat layer is 0.10 or more, and more preferably 0.125 or more. More preferably, it is 0.13 or more, Most preferably, it is 0.15 or more. When the standard deviation is smaller than 0.10, there is a problem that glare is likely to occur.
- the calculation method of the standard deviation of the second derivative of the uneven shape of the hard coat layer in the present invention is as follows. The uneven shape can be measured by a confocal microscope (for example, OLYMPUS scanning confocal laser microscope LEXT OLS3100).
- the observation magnification is 500 times, the step in the Z direction is 0.01 ⁇ m, the three-dimensional shape measurement is performed, and the line profile in the X direction at an arbitrary position is formed into an uneven shape.
- data is acquired in steps of 0.25 ⁇ m, and the standard deviation of the second derivative is calculated by Excel.
- Excel's SLOPE function is used, and the slope of 7 consecutive points calculated by the SLOPE function is used as a differential once.
- the C column shows an input example of the SLOPE function when the A column is the X coordinate (unit is ⁇ m) and the B column is the Z coordinate (unit is ⁇ m).
- the second differentiation is performed by repeating the first differentiation twice.
- FIGS. 3 and 4 are the results of calculating the second derivative by the method described above, respectively.
- the result of calculating the standard deviation using the value differentiated twice is the standard deviation of the concave / convex shape twice, and in the present invention, the average of the standard deviations calculated at four locations for one sample is calculated. We will use it.
- the method for applying the hard coat paint in the present invention is not particularly limited, and a known method can be used. Examples include spin coating, dipping, spraying, slide coating, bar coating, roll coating, gravure coating, meniscus coating, flexographic printing, screen printing, beat coating, and blurring. . Examples of the method for forming the unevenness include molding by a mold and formation of a coating film by coating. Molding by a mold can be produced by a method of curing with ultraviolet rays in a state where a mold having a shape complementary to the concavo-convex surface is produced and a transparent substrate coated with an ultraviolet curable resin is adhered.
- the coating film is formed by coating by applying a coating solution for forming a concavo-convex layer containing a resin component and translucent particles onto a transparent substrate by a known coating method such as gravure coating or bar coating. It can be formed by drying and curing.
- ⁇ Weight average molecular weight> A standard polystyrene was dissolved in chloroform in advance and measured by GPC in the same manner with reference to a calibration curve measured by gel permeation chromatography (GPC). The weight average molecular weight of each was calculated by comparing the two.
- the apparatus configuration of GPC is as follows. Device: Weights 2690 Column: Shodex GPC KF-805L 8 ⁇ ⁇ 300 mm 2-linked developing solvent: chloroform flow rate: 1 ml / min Temperature: 30 ° C
- the test piece was cut into a 10 ⁇ 6 cm square.
- the cut test piece was set in a two-point support holder, placed in an environmental test machine set at a temperature of 23 ° C. and a relative humidity of 50% for 24 hours or more, and after adjusting the state, the warpage was measured (before treatment).
- the test piece was set in a holder, put into an environmental test machine set at a temperature of 85 ° C. and a relative humidity of 85%, and kept in that state for 120 hours. Further, the holder was moved into an environmental testing machine set at a temperature of 23 ° C. and a relative humidity of 50%, and the warpage was measured again after being held for 4 hours in this state (after treatment).
- a three-dimensional shape measuring machine equipped with an electric stage (KS-1100 manufactured by KEYENCE Inc.) was used, and the taken specimen was left horizontally in a convex state and scanned at intervals of 1 mm. The bulge in the center was measured as a warp.
- the absolute value of the difference in warpage before and after processing, that is, was evaluated as shape stability. Note that the measurement limit of the measuring instrument was 2,000 ⁇ m, and anything that warped more than that was impossible to measure.
- ⁇ Glitter> The entire screen of the liquid crystal display device was displayed in green, and a front plate was placed on the display element and observed visually to check for glare.
- ⁇ Standard deviation of twice-differentiation of uneven shape of hard coat layer having unevenness> The surface shape of the hard coat with the handle was measured with a confocal microscope (OLYMPUS scanning confocal laser microscope LEXT OLS3100). The observation magnification was 500 times, the step in the Z direction was 0.01 ⁇ m, three-dimensional shape measurement was performed, and the line profile (length 255.75 ⁇ m) in the X direction at an arbitrary position was formed into an uneven shape. In the X direction, data was acquired in steps of 0.25 ⁇ m, and the standard deviation of the second derivative was calculated by Excel.
- a 1000 mL autoclave apparatus was charged with 500 parts by weight of a 10% by weight methyl isobutyrate solution of (B1-1 ′) and 1 part by weight of 10% by weight Pd / C (manufactured by NE Chemcat), at a hydrogen pressure of 9 MPa and 200 ° C. for 15 hours.
- the aromatic double bond site of the vinyl copolymer resin (B1-1 ′) was hydrogenated.
- the catalyst was removed by a filter and introduced into a solvent removal apparatus to obtain a pellet-like vinyl copolymer resin (B1-1).
- the proportion of the methyl methacrylate structural unit in the vinyl copolymer resin (B1-1) is 75 mol%, and the result of the absorbance measurement at a wavelength of 260 nm shows the hydrogenation of the aromatic double bond site.
- the reaction rate was 99%.
- the weight average molecular weight (standard polystyrene conversion) measured by gel permeation chromatography was 125,000.
- This composition was mixed for 20 minutes with a blender, melt-kneaded at a cylinder temperature of 240 ° C. using a twin screw extruder with a screw diameter of 26 mm, extruded into a strand, pelletized with a pelletizer, and the resin composition (B2-1 )
- the pellets could be manufactured stably.
- R-200 is 60% by mass as the styrene-unsaturated dicarboxylic acid copolymer (D), and methyl methacrylate resin parapet HR-L is 40% by mass as the resin (C) containing a vinyl monomer.
- R-200 is 70% by mass as the styrene-unsaturated dicarboxylic acid copolymer (D), and methyl methacrylate resin parapet HR-L is 30% by mass as the resin (C) containing a vinyl monomer.
- This composition was mixed for 20 minutes with a blender, melt-kneaded at a cylinder temperature of 240 ° C. using a twin-screw extruder with a screw diameter of 26 mm, extruded into a strand, pelletized with a pelletizer, and the resin composition (B2-4 )
- the pellets could be manufactured stably.
- R-100 is 75% by mass as the styrene-unsaturated dicarboxylic acid copolymer (D), and methyl methacrylate resin parapet HR-L is 25% by mass as the resin (C) containing a vinyl monomer.
- Production Example 7 [Production of Resin Composition (B2)] Except for R-100 as 85% by mass as styrene-unsaturated dicarboxylic acid copolymer (D) and 15% by mass of methyl methacrylate resin parapet HR-L as resin (C) containing vinyl monomer. Gave a resin composition (B2-6) in the same manner as in Production Example 5. The pellets could be manufactured stably.
- This composition was mixed for 20 minutes with a blender, melt-kneaded at a cylinder temperature of 240 ° C. using a twin screw extruder with a screw diameter of 26 mm, extruded into a strand, pelletized with a pelletizer, and the resin composition (B2-7 )
- the pellets could be manufactured stably.
- This composition was mixed for 20 minutes with a blender, melt-kneaded at a cylinder temperature of 240 ° C. using a twin screw extruder with a screw diameter of 26 mm, extruded into a strand, pelletized with a pelletizer, and the resin composition (B2-8 )
- the pellets could be manufactured stably.
- This composition was mixed with a blender for 20 minutes, melt-kneaded at a cylinder temperature of 240 ° C. using a twin screw extruder with a screw diameter of 26 mm, extruded into a strand, pelletized with a pelletizer, and the resin composition (B2-9 )
- the pellets could be manufactured stably.
- Production Example 12 [Production of Resin Composition (B3)] A resin composition (B3-2) was obtained by pelletizing in the same manner as in Production Example 11 except that the charging ratio of the (meth) acrylate copolymer (F) to the polycarbonate resin (E) was 50:50. Pelletization could be produced stably.
- Production Example 13 [Production of Resin Composition (B3)] Except that the charging ratio of (meth) acrylate copolymer (F) and polycarbonate resin (E) was 20:80, pelletization was performed in the same manner as in Production Example 11 to obtain a resin composition (B3-3). Pelletization could be produced stably.
- Comparative Production Example 1 [Production of Comparative Example of Resin Composition (B3)] Pelletization was performed in the same manner as in Production Example 11 except that the charging ratio of the (meth) acrylate copolymer (F) and the polycarbonate resin (E) was 60:40. The pelletization was unstable and the resin composition (B3-4) could not be produced.
- Production Example 15 [Production of photocurable resin composition (X1) coated on high hardness layer]
- a mixing vessel equipped with a stirring blade 60 parts by mass of tris (2-acryloxyethyl) isocyanurate (manufactured by Aldrich) and 40 parts by mass of neopentyl glycol oligoacrylate (manufactured by Osaka Organic Chemical Industry, trade name: 215D) 1 part by mass of 2,4,6-trimethylbenzoyldiphenylphosphine oxide (manufactured by Ciba Japan, trade name: DAROCUR TPO), 0.3 part by mass of 1-hydroxycyclohexyl phenyl ketone (manufactured by Aldrich), A composition comprising 1 part by mass of 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol (manufactured by Ciba Japan, trade name: TINUVIN234) It was introduced and stir
- Production Example 16 [Production of photocurable resin composition (X2) coated on polycarbonate substrate layer]
- a mixing tank equipped with a stirring blade 40 parts by mass of 1,9-nonanediol diacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name: Biscote # 260) and a hexafunctional urethane acrylate oligomer (manufactured by Shin-Nakamura Chemical Co., Ltd., (Trade name: U-6HA) 40 parts by mass, 20 parts by mass of a condensate having a succinic acid / trimethylolethane / acrylic acid molar ratio of 1/2/4, and 2,4,6-trimethylbenzoyldiphenylphosphine 2.8 parts by mass of oxide (manufactured by Ciba Japan, trade name: DAROCUR TPO), 1 part by mass of benzophenone (manufactured by Aldrich), 2- (2H-benzotriazol-2-y
- PET film (Y1) with handle 50 parts by mass of MEK, 50 parts by mass of acrylic UV curable resin (100% solid content, trade name: Light Acrylate DPE-6A, manufactured by Kyoeisha Chemical Co., Ltd.), silica fine particles (octylsilane-treated fumed silica, average primary particle size 12 nm) 0.5 parts by mass, manufactured by Nippon Aerosil Co., Ltd., 1 part by mass of acrylsilane-treated silica (average particle size: 1.9 ⁇ m, trade name: SE6050-SYB, manufactured by Admatex Co., Ltd.), and 3 parts by weight of photoinitiator (trade name) Irgacure 184 (manufactured by Ciba Specialty Chemicals Co., Ltd.) was mixed and stirred to prepare a coating liquid (i).
- acrylic UV curable resin 100% solid content, trade name: Light Acrylate DPE-6A, manufactured by Kyoeisha Chemical Co., Ltd.
- the coating liquid (i) is applied to a PET (polyethylene terephthalate) film so as to have a dry film thickness of 2.5 ⁇ m, dried at 80 ° C. for 2 minutes, and equipped with a high pressure mercury lamp with a light source distance of 12 cm and an output of 80 W / cm.
- a patterned PET film (Y1) was produced by irradiating with an ultraviolet ray at a line speed of 1.5 m / min.
- Production Example 18 [Production of patterned PET film (Y2)] A patterned PET film (Y2) was produced in the same manner as in Production Example 17 except that the dry film thickness of the coating liquid (i) was 3.5 ⁇ m.
- the coating liquid (ii) is applied to a PET (polyethylene terephthalate) film so as to have a dry film thickness of 1.5 ⁇ m, dried at 80 ° C. for 2 minutes, and equipped with a high pressure mercury lamp with a light source distance of 12 cm and an output of 80 W / cm.
- a patterned PET film (Y3) was prepared by irradiating with an ultraviolet ray on a conveyor at a line speed of 1.5 m / min and curing.
- the polymerization solution was separated into an aqueous phase and an organic phase, the organic phase was neutralized with phosphoric acid, and washing with pure water was repeated until the pH of the washing solution became neutral.
- the polycarbonate resin powder was obtained by evaporating the organic solvent from the purified polycarbonate resin solution.
- the obtained polycarbonate resin powder was melt kneaded at a cylinder temperature of 260 ° C. using a twin screw extruder with a screw diameter of 35 mm, extruded into a strand shape, and pelletized with a pelletizer.
- the weight average molecular weight of the obtained polycarbonate resin (A1) was 47,000.
- Example 1 Synthetic resin using a multi-layer extrusion apparatus having a single-screw extruder with a shaft diameter of 35 mm, a single-screw extruder with a shaft diameter of 65 mm, a feed block connected to all the extruders, and a T-die connected to the feed block A laminate was formed.
- the vinyl copolymer resin (B1-1) obtained in Production Example 1 was continuously introduced into a single-screw extruder having a shaft diameter of 35 mm and extruded under the conditions of a cylinder temperature of 240 ° C. and a discharge speed of 2.6 kg / h.
- a polycarbonate resin (A2) (manufactured by Mitsubishi Engineering Plastics, trade name: Iupilon S-1000, weight average molecular weight: 59,000) was continuously introduced into a single-screw extruder having a shaft diameter of 65 mm, and a cylinder temperature of 280 Extrusion was performed at a temperature of 5 ° C. and a discharge speed of 50.0 kg / h.
- the feed block connected to the entire extruder was provided with two types and two layers of distribution pins, and was laminated at a temperature of 270 ° C. by introducing vinyl copolymer resin (B1-1) and polycarbonate resin (A2).
- a laminate of a high hardness layer containing a vinyl copolymer resin (B1-1) having a retardation of 4500 nm and a base material layer containing a polycarbonate resin (A2) was obtained.
- the thickness of the obtained laminate was 1,200 ⁇ m, and the thickness of the high hardness layer containing the vinyl copolymer resin (B1-1) was 60 ⁇ m near the center.
- the coating thickness after curing the photocurable resin composition (X1) obtained in Production Example 15 is 3 to 8 ⁇ m. It apply
- a bar coater is used so that the coating thickness after curing the photocurable resin composition (X2) obtained in Production Example 16 on the base material layer containing the polycarbonate resin (A2) is 3 to 8 ⁇ m. It was applied, covered with a PET film and pressure-bonded.
- UV light is irradiated and cured 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, and the patterned PET film and PET film are peeled off and vinyl copolymerized.
- a front plate provided with a hard coat layer made of a photocurable resin composition (X1) and (X2) on a high hardness layer containing resin (B1-1) and a base material layer containing polycarbonate resin (A2), respectively. Obtained.
- Example 2 Each extruder in a multi-layer 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 all the extruders, and a T die connected to the feed block A synthetic resin laminate was molded using a multi-layer extrusion apparatus having connected multi-manifold dies.
- the resin composition (B2-1) obtained in Production Example 2 was continuously introduced into a single screw extruder having a shaft diameter of 32 mm and extruded under the conditions of a cylinder temperature of 240 ° C. and a discharge rate of 2.1 kg / h.
- a polycarbonate resin (A2) (manufactured by Mitsubishi Engineering Plastics, trade name: Iupilon S-1000, weight average molecular weight: 59,000) was continuously introduced into a single screw extruder having a shaft diameter of 65 mm, and the cylinder temperature was 270. Extrusion was performed at 3 ° C. and a discharge rate of 30.0 kg / h.
- the feed block connected to the entire extruder was provided with two types and two layers of distribution pins, and the temperature was set to 270 ° C., and the resin composition (B2-1) and the polycarbonate resin (A2) were introduced and laminated.
- Example 3 A high-hardness layer containing a resin composition (B2-2) and a polycarbonate resin (B2-2) were produced in the same manner as in Example 2 except that the high-hardness layer was produced using the resin composition (B2-2) obtained in Production Example 3.
- the photocurable resin composition (X1) was formed to obtain a front plate.
- Example 4 A high-hardness layer containing a resin composition (B2-3) and a polycarbonate resin (B2-3) were produced in the same manner as in Example 2 except that the high-hardness layer was produced using the resin composition (B2-3) obtained in Production Example 4.
- the photocurable resin composition (X1) was formed to obtain a front plate.
- Example 5 A high-hardness layer containing a resin composition (B2-4) and a polycarbonate resin (B2-4) were produced in the same manner as in Example 2 except that the high-hardness layer was produced using the resin composition (B2-4) obtained in Production Example 5.
- the photocurable resin composition (X1) was formed to obtain a front plate.
- Example 6 A high-hardness layer containing a resin composition (B2-5) and a polycarbonate resin (B2-5) were produced in the same manner as in Example 2 except that the high-hardness layer was produced using the resin composition (B2-5) obtained in Production Example 6.
- the total thickness of the obtained laminate was 1,000 ⁇ m, and the thickness of the high hardness layer containing the resin composition (B2-5) was 60 ⁇ m near the center.
- the retardation was 3700 nm.
- the photocurable resin composition (X1) was formed to obtain a front plate.
- Example 7 A high-hardness layer containing a resin composition (B2-6) and a polycarbonate resin (B2-6) were prepared in the same manner as in Example 2 except that the high-hardness layer was produced using the resin composition (B2-6) obtained in Production Example 7.
- a high-hardness layer and a polycarbonate resin (B2-6) containing the laminate resin composition (B2-6) were used in the same manner as in Example 1 except that the patterned PET film (Y1) was changed to a patterned PET film (Y2).
- a hard coat layer composed of the photocurable resin compositions (X1) and (X2) was formed, respectively, to obtain a front plate.
- Example 8 Each extruder in a multi-layer 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 all the extruders, and a T die connected to the feed block A synthetic resin laminate was molded using a multi-layer extrusion apparatus having connected multi-manifold dies.
- the resin composition (B2-7) obtained in Production Example 8 was continuously introduced into a single screw extruder having a shaft diameter of 32 mm and extruded under the conditions of a cylinder temperature of 240 ° C. and a discharge rate of 2.1 kg / h.
- a polycarbonate resin (A2) (manufactured by Mitsubishi Engineering Plastics, trade name: Iupilon S-1000, weight average molecular weight: 59,000) was continuously introduced into a single screw extruder having a shaft diameter of 65 mm, and the cylinder temperature was 270. Extrusion was performed at 3 ° C. and a discharge rate of 30.0 kg / h.
- the feed block connected to the whole extruder was provided with two types and two layers of distribution pins, and the temperature was set to 270 ° C., and the resin composition (B2-7) and the polycarbonate resin (A2) were introduced and laminated.
- the photocurable resin composition (X1) was respectively formed on the high hardness layer containing the resin composition (B2-7) of the laminate and the base material layer containing the polycarbonate resin (A2). And a hard coat layer made of (X2) was formed to obtain a front plate.
- Example 9 A high hardness layer containing the resin composition (B2-8) and a polycarbonate resin (A2) in the same manner as in Example 8, except that the resin composition (B2-8) was used instead of the resin composition (B2-7). ) was obtained.
- the total thickness of the obtained laminate was 1,000 ⁇ m, and the thickness of the high hardness layer containing the resin composition (B2-8) was 60 ⁇ m near the center.
- the retardation was 4700 nm.
- the photocurable resin composition (X1) was formed to obtain a front plate.
- Example 10 A high-hardness layer containing a resin composition (B2-9) and a polycarbonate resin (A2) in the same manner as in Example 8, except that the resin composition (B2-9) was used instead of the resin composition (B2-7). ) was obtained.
- the total thickness of the obtained laminate was 1,000 ⁇ m, and the thickness of the high hardness layer containing the resin composition (B2-9) was 60 ⁇ m near the center. The retardation was 5200 nm.
- the photocurable resin composition (X1) was formed to obtain a front plate.
- Example 11 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.
- the resin composition (B3-1) obtained in Production Example 11 was continuously introduced into a single screw extruder having a shaft diameter of 32 mm and extruded under the conditions of a cylinder temperature of 240 ° C. and a discharge speed of 2.1 kg / h.
- a polycarbonate resin (A3) (manufactured by Mitsubishi Engineering Plastics, trade name: Iupilon S-3000, mass average molecular weight: 47,000) was continuously introduced into a single screw extruder having a shaft diameter of 65 mm, and a cylinder temperature of 270 Extrusion was performed at 0 ° C. and a discharge speed of 30.0 kg / h.
- the feed block connected to the entire extruder was provided with two types and two layers of distribution pins, and the resin composition (B3-1) and the polycarbonate resin (A3) were introduced and laminated at a temperature of 270 ° C.
- Example 12 A resin composition (B3) was prepared in the same manner as in Example 1 except that the resin composition (B3-2) obtained in Production Example 12 was used instead of the resin composition (B3-1) used in Example 11.
- the thickness of the obtained laminate was 1,000 ⁇ m, and the thickness of the high hardness layer containing the resin composition (B3-2) was 60 ⁇ m near the center. The retardation was 6200 nm.
- the photocurable resin composition (X1) was formed to obtain a front plate.
- Example 13 Instead of the resin composition (B3-1) used in Example 11, the resin composition (B3-3) obtained in Production Example 13 was used, and the discharge speed was set to 7.0 kg / h.
- the thickness of the obtained laminate was 1,000 ⁇ m, and the thickness of the high hardness layer containing the resin composition (B3-3) was 200 ⁇ m near the center.
- the retardation was 4700 nm.
- Example 14 A resin composition (B3) was prepared in the same manner as in Example 11 except that the resin composition (B3-5) obtained in Production Example 14 was used instead of the resin composition (B3-1) used in Example 11.
- the thickness of the obtained laminate was 1,000 ⁇ m, and the thickness of the high hardness layer containing the resin composition (B3-5) was 60 ⁇ m near the center.
- the retardation was 4500 nm.
- Example 15 A laminate was prepared and a hard coat was formed in the same manner as in Example 1 except that the polycarbonate resin (A2) produced in Production Example 20 was used as the polycarbonate resin (A2) to obtain a front plate.
- Example 16 A laminate was prepared and a hard coat was formed in the same manner as in Example 2 except that the polycarbonate resin (A1) produced in Production Example 20 was used as the polycarbonate resin (A2) to obtain a front plate.
- Example 17 A laminate was produced and a hard coat was formed in the same manner as in Example 3 except that the polycarbonate resin (A1) produced in Production Example 20 was used as the polycarbonate resin (A2) to obtain a front plate.
- Example 18 A laminate was produced and a hard coat was formed in the same manner as in Example 4 except that the polycarbonate resin (A1) produced in Production Example 20 was used as the polycarbonate resin (A2) to obtain a front plate.
- Example 19 A laminate was prepared and a hard coat was formed in the same manner as in Example 5 except that the polycarbonate resin (A1) produced in Production Example 20 was used as the polycarbonate resin (A2) to obtain a front plate.
- Example 20 A laminate was produced and a hard coat was formed in the same manner as in Example 6 except that the polycarbonate resin (A2) was changed to the polycarbonate resin (A1) produced in Production Example 20, and a front plate was obtained.
- Example 21 A laminate was produced and a hard coat was formed in the same manner as in Example 7 except that the polycarbonate resin (A2) produced in Production Example 20 was used as the polycarbonate resin (A2) to obtain a front plate.
- Example 22 A laminate was prepared and a hard coat was formed in the same manner as in Example 8 except that the polycarbonate resin (A2) produced in Production Example 20 was used as the polycarbonate resin (A2) to obtain a front plate.
- Example 23 A laminate was produced and a hard coat was formed in the same manner as in Example 9 except that the polycarbonate resin (A2) produced in Production Example 20 was used as the polycarbonate resin (A2) to obtain a front plate.
- Example 24 A laminate was produced and a hard coat was formed in the same manner as in Example 10 except that the polycarbonate resin (A2) produced in Production Example 20 was used as the polycarbonate resin (A2) to obtain a front plate.
- Example 25 A laminate was prepared and a hard coat was formed in the same manner as in Example 11 except that the polycarbonate resin (A3) was changed to the polycarbonate resin (A1) produced in Production Example 20, and a front plate was obtained.
- Example 26 A laminate was prepared and a hard coat was formed in the same manner as in Example 12 except that the polycarbonate resin (A3) was changed to the polycarbonate resin (A1) produced in Production Example 20, and a front plate was obtained.
- Example 27 A laminate was produced and a hard coat was formed in the same manner as in Example 13 except that the polycarbonate resin (A3) was changed to the polycarbonate resin (A1) produced in Production Example 20, and a front plate was obtained.
- Example 28 A laminate was produced and a hard coat was formed in the same manner as in Example 14 except that the polycarbonate resin (A3) was changed to the polycarbonate resin (A1) produced in Production Example 20, and a front plate was obtained.
- Comparative Example 3 On the base material layer containing the high hardness layer containing the methyl methacrylate resin and the polycarbonate resin (A2) of the laminate in the same manner as in Comparative Example 1 except that the patterned PET film (Y1) was changed to the patterned PET film (Y3). A hard coat layer composed of the photocurable resin composition (X1) and (X2), respectively, was formed to obtain a front plate.
- Comparative Example 4 On the base material layer containing the high hardness layer containing the methyl methacrylate resin and the polycarbonate resin (A1) of the laminate in the same manner as in Comparative Example 2, except that the patterned PET film (Y1) was changed to the patterned PET film (Y3). A hard coat layer composed of the photocurable resin composition (X1) and (X2), respectively, was formed to obtain a front plate.
- Example 6 A laminated body and a hard coat were formed in the same manner as in Example 2 except that the take-up speed was adjusted so that the retardation was 2000 nm, and a front plate was obtained.
- the front plate obtained in each example and comparative example was evaluated for shape stability, pencil hardness, glaring, blackout, standard deviation of roughness of the uneven shape of the hard coat layer having unevenness, and roughness. .
- the evaluation results, layer thicknesses, and retardation values are summarized in the following table. As can be seen from the table below, when the configuration in the present invention is used, it is excellent in shape stability, pencil hardness, no glare, and measures against blackout are possible. It can be used suitably.
- Comparative Examples 1 to 4 using methyl methacrylate resin as the high-hardness resin composition (B) are inferior in shape stability, and the standard deviation of the second derivative of the uneven shape of the hard coat layer having unevenness is less than 0.1. In Comparative Examples 3 to 5, glare was generated, and in Comparative Example 6 in which the retardation of the front plate was less than 3,000 nm, the blackout result was not good.
- a front plate of an in-vehicle liquid crystal display device can be provided.
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Abstract
Description
液晶表示装置においては、一般に最表面には反射防止のための光学積層体が設けられている。このような反射防止用の光学積層体は、光の散乱や干渉によって、像の映り込みを抑制したり反射率を低減したりするものである。
反射防止用光学積層体の1つとして、透明性基材の表面に凹凸形状を有する防眩層を形成した防眩性フィルムが知られている。この防眩性フィルムは、表面の凹凸形状によって外光を散乱させて外光の反射や像の映り込みによる視認性の低下を防止することができる。また、この光学積層体は、通常、液晶表示装置の最表面に設置されるものであるため、取り扱い時に傷がつかないように、ハードコート性を付与することも要求される。
このような液晶表示装置をカーナビゲーション等の車載用途で使用する場合、自動車室内は環境下で低温から高温まで温度変化が激しく、前面板は熱変動による収縮膨張のため変形を生じやすく、変形による軋み音の発生等問題が起きている。特に、近年では、偏光サングラスによるブラックアウト対策として、延伸された高レターデーションの前面板が用いられているため、さらに変形が生じやすくなっている。
以上のように、車載用液晶表示装置の前面板では、ブラックアウト対策、ギラツキの発生しない防眩性、傷つき防止といった様々な機能を付与する必要があり、さらに、自動車室内という過酷な環境下に耐える必要があるが、これらすべてを満足するような前面板はなかった。
<1> ポリカーボネート樹脂(a1)を含む樹脂(A)を含む層の少なくとも一方の面に、高硬度樹脂組成物(B)を含む層を有し、更に、該高硬度樹脂組成物(B)を含む層上に、凹凸を有するハードコート層を有し、下記条件(i)から(iv)を満たすことを特徴とする車載用液晶表示装置の前面板である。
(i)前記高硬度樹脂組成物(B)を含む層の厚みが10~250μmであり、前記ポリカーボネート樹脂(a1)を含む樹脂(A)を含む層と前記高硬度樹脂組成物(B)を含む層との合計厚みが100~3,000μmであり、
(ii)前記高硬度樹脂組成物(B)が以下の樹脂組成物(B1)から(B3)のいずれか1つからなり、
・樹脂組成物(B1)
下記一般式(1)で表される(メタ)アクリル酸エステル構成単位(a)と、下記一般式(2)で表される脂肪族ビニル構成単位(b)とを含む共重合樹脂であって、前記メタクリル酸エステル構成単位(a)と前記脂肪族ビニル構成単位(b)との合計割合が前記共重合樹脂の全構成単位の90~100モル%であり、前記(メタ)アクリル酸エステル構成単位(a)の割合が前記共重合樹脂の全構成単位の65~80モル%である共重合樹脂:
・樹脂組成物(B2)
ビニル系単量体を含有する樹脂(C)を55~10質量%、およびスチレン-不飽和ジカルボン酸系共重合体(D)を45~90質量%含む樹脂組成物であって、前記スチレン-不飽和ジカルボン酸系共重合体(D)が、スチレン系単量体単位(d1)50~80質量%、不飽和ジカルボン酸無水物単量体単位(d2)10~30質量%、およびビニル系単量体単位(d3)5~30質量%を含む樹脂組成物:
・樹脂組成物(B3)
ポリカーボネート樹脂(E)を95~45質量%、および(メタ)アクリレート共重合体(F)を5~55質量%含む樹脂組成物であって、前記(メタ)アクリレート共重合体(F)が、芳香族(メタ)アクリレート単位(f1)とメタクリル酸エステル単量体単位(f2)とを質量比(f1/f2)で10~50/40~90含み、かつ、前記ポリカーボネート樹脂(E)の重量平均分子量が37,000~71,000であり、前記(メタ)アクリレート共重合体(F)の重量平均分子量が5,000~30,000である樹脂組成物:
(iii)前記前面板のレターデーションが3,000nm以上であり、
(iv)前記凹凸を有するハードコート層の凹凸形状の2回微分の標準偏差が0.1以上である。
<2> 前記前面板が、前記凹凸を有するハードコート層とは反対の面にもハードコート層を有する上記<1>に記載の車載用液晶表示装置の前面板である。
<3> 前記前面板が、温度85℃で相対湿度85%の環境下に120時間保持した後の反りの変化量が1,000μm以下である上記<1>または<2>に記載の車載用液晶表示装置の前面板である。
<4> 前記高硬度樹脂組成物(B)を含む層が、前記ポリカーボネート樹脂(a1)を含む樹脂(A)を含む層と共に共押出されたものである上記<1>から<3>のいずれかに記載の車載用液晶表示装置の前面板である。
<5> 前記ポリカーボネート樹脂(a1)が、下記一般式(4)で表わされる1価フェノール由来の成分を含む上記<1>から<4>のいずれかに記載の車載用液晶表示装置の前面板である。
本発明の車載用液晶表示装置の前面板は、ポリカーボネート樹脂(a1)を含む樹脂(A)を含む層(以下、「基材層」と呼ぶことがある)の少なくとも一方の面に、高硬度樹脂組成物(B)を含む層(以下、「高硬度層」と呼ぶことがある)および凹凸を有するハードコート層が設けられている。前記基材層は、ポリカーボネート樹脂(a1)を含む樹脂(A)からなる層であってもよい。また、前記高硬度層は、高硬度樹脂組成物(B)からなる層であってもよい。積層の順番としては、高硬度層は基材層とハードコート層の間に存在し、最表層となるハードコート層の最表面に凹凸形状が付与されている。ポリカーボネート樹脂(a1)を含む樹脂(A)を含む層の他方の面は特に指定はないが、高硬度樹脂層およびハードコート層の両方、あるいはいずれか1つの層を設けてもよい。この場合、高硬度樹脂層としては、高硬度樹脂組成物(B)から選択される樹脂を用いることが望ましく、また、両面で同一の高硬度樹脂組成物(B)を用いることが反りを少なくするためにもより望ましい。ハードコート層としては、特に指定はないが、凹凸を有するハードコート層と同様のハードコート層を用いることができる。両面にハードコート層を形成すると、反りを少なくすることが可能となることから、より望ましい。凹凸を有するハードコート層は、傷つき防止のためにも、鉛筆硬度としてはH以上が望ましく、2H以上がより望ましく、3H以上とすることが特に望ましい。
なお、本発明の前面板は、単独で前面板として使用できるが、例えばタッチセンサーなどの別の基板とラミネートするなど、複合して前面板として使用してもよい。
液晶表示装置において、駆動方式は特に限定されず、TN(Twisted Nematic)方式、VA(Virtical Alignment)方式、IPS(In-Place-Switching)方式などを用いることができるが、液晶パネル前面の偏光板の透過軸と、ポリカーボネート樹脂(a1)を含む樹脂(A)を含む層の面内の進相軸又は遅相軸とが、平行あるいは45度の角度を成す構成となるのが望ましい。この場合、偏光サングラスなどを使用したときでの、ポリカーボネート樹脂(a1)を含む樹脂(A)を含む層のレターデーション及びそのムラに起因した干渉色の発生を抑制できる。
(ポリカーボネート樹脂(a1)を含む樹脂(A))
本発明に使用されるポリカーボネート樹脂(a1)を含む樹脂(A)とは、主としてポリカーボネート樹脂(a1)を含む樹脂である。樹脂(A)中のポリカーボネート樹脂(a1)の含有量としては75重量%以上であるが、含有量を増やすことで耐衝撃性が向上することから、望ましくは90重量%以上であり、より望ましくは100重量%である。
ポリカーボネート樹脂(a1)としては、分子主鎖中に炭酸エステル結合、即ち、-[O-R-OCO]-単位(Rが脂肪族基、芳香族基、又は脂肪族基と芳香族基の双方を含むもの、さらに直鎖構造あるいは分岐構造を有するもの)を含むものであれば特に限定されるものではないが、特に下記式(3)の構造単位を含むポリカーボネート樹脂を使用することが好ましい。このようなポリカーボネート樹脂を使用することで、耐衝撃性に優れた樹脂積層体を得ることができる。
より好ましくは、一般式(4)で表わされる1価フェノールは、下記一般式(5)で表わされる。
具体的には、R1の炭素数の上限値として36が好ましく、22がより好ましく、18が特に好ましい。また、R1の炭素数の下限値として、8が好ましく、12がより好ましい。
一例として、R1の炭素数が36以下であれば、ポリカーボネート樹脂を製造するにあたって生産性が高く、経済性も良い。R1の炭素数が22以下であれば、1価フェノールは、特に有機溶剤溶解性に優れており、ポリカーボネート樹脂を製造するにあたって生産性を非常に高くすることができ、経済性も向上する。
一般式(4)又は一般式(5)におけるR1の炭素数が小さすぎると、ポリカーボネート樹脂のガラス転移温度が十分に低い値とはならず、熱成形性が低下することがある。
本発明に使用される高硬度樹脂組成物(B)としては、樹脂組成物(B1)、樹脂組成物(B2)、および樹脂組成物(B3)のいずれか1つから選択される。
本発明に使用される樹脂組成物(B1)とは、一般式(1)で表される(メタ)アクリル酸エステル構成単位(a)と、一般式(2)で表される脂肪族ビニル構成単位(b)とを含む共重合樹脂であって、前記メタクリル酸エステル構成単位(a)と前記脂肪族ビニル構成単位(b)との合計割合が前記共重合樹脂の全構成単位の90~100モル%であり、前記メタクリル酸エステル構成単位(a)の割合が前記共重合樹脂の全構成単位の65~80モル%である共重合樹脂である。
一般式(1)で表される(メタ)アクリル酸エステル構成単位(a)において、R2は炭素数1~18のアルキル基であり、具体的にはメチル基、エチル基、ブチル基、ラウリル基、ステアリル基、シクロヘキシル基、イソボルニル基などが挙げられる。
前記(メタ)アクリル酸エステル構成単位(a)のうち、好ましいのはR2がメチル基又はエチル基である(メタ)アクリル酸エステル構成単位であり、更に好ましいのはR1がメチル基であり、R2がメチル基であるメタクリル酸メチル構成単位である。
前記脂肪族ビニル構成単位(b)のうち、より好ましいのはR3が水素原子であり、R4がシクロヘキシル基である脂肪族ビニル構成単位である。
前記(メタ)アクリル酸エステル構成単位(a)と前記脂肪族ビニル構成単位(b)との合計割合は、前記共重合樹脂の全構成単位の合計に対して90~100モル%であり、好ましくは95~100モル%であり、より好ましくは98~100モル%である。
すなわち、前記樹脂組成物(B1)は、前記共重合樹脂の全構成単位の合計に対して10モル%以下の範囲で、前記(メタ)アクリル酸エステル構成単位(a)及び前記脂肪族ビニル構成単位(b)以外の構成単位を含有していてもよい。
また、前記一般式(1)で表される(メタ)アクリル酸エステル構成単位(a)の割合は、前記樹脂組成物(B1)中の全構成単位の合計に対して65~80モル%であり、好ましくは70~80モル%である。 樹脂組成物(B1)中の全構成単位の合計に対する(メタ)アクリル酸エステル構成単位(a)の割合が65モル%未満であると、ポリカーボネート樹脂(a1)を含む樹脂(A)との密着性や表面硬度が低下し、実用的でない場合がある。また80モル%を超えると、積層体の吸水による反りが発生し、実用的でない場合がある。
この際に使用される芳香族ビニルモノマーとしては、具体的にはスチレン、α-メチルスチレン、p-ヒドロキシスチレン、アルコキシスチレン、クロロスチレン、及びそれらの誘導体などが挙げられる。これらの中で好ましいのはスチレンである。
塊状重合法は、上記モノマー、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。上記モノマー組成物は、必要に応じて連鎖移動剤を含んでもよい。
水素化の方法は特に限定されず、公知の方法を用いることができる。例えば、水素圧力3~30MPa、反応温度60~250℃でバッチ式あるいは連続流通式で行うことができる。温度を60℃以上とすることにより反応時間がかかり過ぎることがなく、また250℃以下とすることにより分子鎖の切断やエステル部位の水素化を起こすことが少ない。
上記重量平均分子量は、後述する実施例に記載のとおり、ゲル浸透クロマトグラフィー(GPC)により測定される、標準ポリスチレン換算の重量平均分子量である。
本発明に使用される樹脂組成物(B2)とは、ビニル系単量体を含有する樹脂(C)を55~10質量%(好ましくは、50~20質量%)、およびスチレン-不飽和ジカルボン酸系共重合体(D)を45~90質量%(好ましくは、50~80質量%)含む樹脂組成物であって、前記スチレン-不飽和ジカルボン酸系共重合体(D)が、スチレン系単量体単位(d1)50~80質量%、不飽和ジカルボン酸無水物単量体単位(d2)10~30質量%、およびビニル系単量体単位(d3)5~30質量%含む樹脂組成物である。
以下に、ビニル系単量体を含有する樹脂(C)とスチレン-不飽和ジカルボン酸系共重合体(D)について順次説明する。
本発明で用いられるビニル系単量体を含有する樹脂(C)としては、例えばアクリロニトリル、メタアクリロニトリル、アクリル酸、アクリル酸メチル、アクリル酸エチル、アクリル酸n―ブチル、アクリル酸2エチルヘキシル、メタクリル酸、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸n-ブチル、メタクリル酸2エチルヘキシル等のビニル系単量体を単独重合したものが挙げられ、特に単量体単位として、メタクリル酸メチルが好ましい。また、前記単量体単位を2種類以上含んだ共重合体でも良い。
ビニル系単量体を含有する樹脂(C)の重量平均分子量は、10,000~500,000が好ましく、より好ましくは50,000~300,000である。
本発明で用いられるスチレン-不飽和ジカルボン酸系共重合体(D)は、スチレン系単量体単位(d1)、不飽和ジカルボン酸無水物単量体単位(d2)、およびビニル系単量体単位(d3)を含む。
スチレン系単量体とは、特に限定せず、任意の公知のスチレン系単量体を用いることが出来るが、入手の容易性の観点からスチレン、α-メチルスチレン、o-メチルスチレン、m-メチルスチレン、p-メチルスチレン、t-ブチルスチレン等が挙げられる。これらの中でも、相溶性の観点からスチレンが特に好ましい。これらのスチレン系単量体は2種以上を混合しても良い。
不飽和ジカルボン酸無水物単量体としては、例えばマレイン酸、イタコン酸、シトラコン酸、アコニット酸等の酸無水物が挙げられ、ビニル系単量体との相溶性の観点から無水マレイン酸が好ましい。これらの不飽和ジカルボン酸無水物単量体は2種以上を混合しても良い。
ビニル系単量体とは、例えばアクリロニトリル、メタアクリロニトリル、アクリル酸、アクリル酸メチル、アクリル酸エチル、アクリル酸n-ブチル、アクリル酸2エチルヘキシル、メタクリル酸、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸n-ブチル、メタクリル酸2エチルヘキシル等のビニル系単量体が挙げられる。ビニル系単量体を含有する樹脂(C)との相溶性の観点からメタクリル酸メチル(MMA)が好ましい。これらのビニル系単量体は2種以上を混合しても良い。
スチレン-不飽和ジカルボン酸系共重合体(D)の組成比率は、スチレン系単量体単位(d1)50~80質量%(好ましくは、50~75質量%)、不飽和ジカルボン酸無水物単量体単位(d2)10~30質量%(好ましくは、10~25質量%)、ビニル系単量体単位(d3)5~30質量%(好ましくは、7~27質量%)である。
本発明に使用される樹脂組成物(B3)とは、ポリカーボネート樹脂(E)を95~45質量%、および(メタ)アクリレート共重合体(F)を5~55質量%含む樹脂組成物であって、前記(メタ)アクリレート共重合体(F)が、芳香族(メタ)アクリレート単位(f1)とメタクリル酸エステル単量体単位(f2)とを質量比(f1/f2)で10~50/40~90含み、かつ、前記ポリカーボネート樹脂(E)の重量平均分子量が37,000~71,000であり、前記(メタ)アクリレート共重合体(F)の重量平均分子量が5,000~30,000である樹脂組成物である。
ポリカーボネート樹脂(E)は、分子主鎖中に炭酸エステル結合を含む、-[O-R-OCO]-単位(Rが脂肪族基、芳香族基、又は脂肪族基と芳香族基の双方を含むもの、さらに直鎖構造あるいは分岐構造を持つもの)を含むものであれば特に限定されるものではない。
ポリカーボネート樹脂(E)の重量平均分子量は、37,000~71,000の範囲であり、好ましくは42,000~68,000の範囲であり、より好ましくは48,000~64,000の範囲である。なお、ポリカーボネート樹脂(E)および(メタ)アクリレート共重合体(F)の重量平均分子量は、後述する実施例に記載のとおり、ゲル浸透クロマトグラフィー(GPC)により測定される、標準ポリスチレン換算の重量平均分子量である。
本発明に用いられる前面板の、ポリカーボネート樹脂(a1)を含む樹脂(A)を含む層の少なくとも一方の面に高硬度樹脂組成物(B)を含む層を有する積層体の製造方法としては、特に限定されない。例えば、個別に形成した高硬度樹脂組成物(B)を含む層と、ポリカーボネート樹脂(a1)を含む樹脂(A)を含む層とを積層して両者を加熱圧着する方法、個別に形成した高硬度樹脂組成物(B)を含む層と、ポリカーボネート樹脂(a1)を含む樹脂(A)を含む層とを積層して、両者を接着剤によって接着する方法、高硬度樹脂組成物(B)を含む層と、ポリカーボネート樹脂(a1)を含む樹脂(A)とを共押出成形する方法、予め形成しておいた高硬度樹脂組成物(B)を含む層に、ポリカーボネート樹脂(a1)を含む樹脂(A)をインモールド成形して一体化する方法、などの各種方法があるが、製造コストや生産性の観点からは、共押出成形する方法が好ましい。
共押出の方法は特に限定されず、例えば、フィードブロック方式では、フィードブロックでポリカーボネート樹脂(a1)を含む樹脂(A)を含む層の片面に高硬度樹脂組成物(B)を含む層を積層し、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ポリカーボネート樹脂(a1)を含む樹脂(A)を含む層の片面に高硬度樹脂組成物(B)を含む層を積層し、シート状に押し出した後、成形ロールを通過させながら冷却し所望の合成樹脂積層体を形成する。
高硬度樹脂組成物(B)を含む層の厚さは、合成樹脂積層体の表面硬度や耐衝撃性に影響する。つまり、厚さが薄すぎると表面硬度が低くなり、好ましくない。厚さが大きすぎると耐衝撃性が悪くなり好ましくない。高硬度樹脂組成物(B)を含む層の厚みは10~250μmであり、30~200μmが好ましく、60~150μmがより好ましい。
本発明における前面板は、ブラックアウト現象を防止するためにも、レターデーションが3,000nm以上であり、4,000nm以上が好ましい。より好ましくは5,000nm以上であり、特に好ましくは6,000nm以上である。レターデーションが3,000nmよりも低くなると、ブラックアウト現象の防止効果が十分でない。レターデーションの上限は特にないが、15,000nm以上になるとブラックアウト現象の防止には十分である一方で、車内のような過酷な環境下での変形が大きくなっていくことから、15,000nm以下にすることが望ましく、より好ましくは14,000nm以下であり、特に好ましくは12,000nm以下である。
ここで、本発明における「レターデーション」とは、シート面内の遅相軸の主屈折率をnx、進相軸の主屈折率をny、シートの厚みをdとしたとき、(nx-ny)×dを、nm単位で表現したものをいう。
レターデーションを3,000nm以上とするための製造方法としては、特に限定はされないが、例えば、引き取り速度を高くして、ポリカーボネート樹脂の流れ方向の延伸倍率を高めることによって、ポリカーボネート樹脂(a1)を含む樹脂(A)を含む層のレターデーションを高めることができ、前面板のレターデーションを3,000nm以上にすることができる。
本発明における前面板は、取り扱い時に傷がつかないように、高硬度樹脂組成物(B)を含む層の上にハードコート層を形成する。例えば、熱エネルギーおよび/または光エネルギーを用いて硬化させるハードコート塗料を用いるハードコート処理によりハードコート層を形成する。熱エネルギーを用いて硬化させるハードコート塗料としては、例えば、ポリオルガノシロキサン系、架橋型アクリル系などの熱硬化性樹脂組成物が挙げられる。また、光エネルギーを用いて硬化させるハードコート塗料としては、例えば、トリス(アクリロキシエチル)イソシアヌレート(a21)40~80重量%と、(a21)と共重合可能な2官能および/または3官能の(メタ)アクリレート化合物(a22)20~40重量%とからなる樹脂組成物の100重量部に光重合開始剤(a23)が1~10重量部添加された光硬化性樹脂組成物などが挙げられる。
ハードコート層の膜厚としては、1μm以上40μm以下が望ましく、2μm以上10μm以下がより望ましい。膜厚が1μm未満であると、鉛筆硬度が低くなり、膜厚が40μmを超えると、反りが大きくなってしまう。なお、ハードコート層の膜厚は、断面を顕微鏡等で観察し、塗膜界面から表面までを実測することにより測定可能である。
ハードコート層の表面は、防眩性を付与するために凹凸形状を有している。本発明における凹凸形状とは、JIS-B-0601で規定される中心線平均粗さ(Ra)が0.01以上を意味するものとする。高い防眩性を得るためには、中心線平均粗さ(Ra)としては、0.05以上が望ましい。
凹凸形状は共焦点顕微鏡(例えば、OLYMPUS走査型共焦点レーザ顕微鏡LEXT OLS3100)により測定することができる。観察倍率は500倍とし、Z方向のステップは0.01μmで3次元の形状測定を行い、任意の位置におけるX方向のラインプロファイルを凹凸形状とする。X方向には0.25μmステップでデータを取得し、2回微分の標準偏差はエクセルによって計算する。微分はエクセルのSLOPE関数を用い、SLOPE関数で計算した連続する7点の傾きをもって1回微分とする。下記に、A列がX座標(単位はμm)、B列がZ座標(単位はμm)のときのSLOPE関数の入力例をC列に示した。2回微分は1回微分を2回繰り返すことで行う。図1および図2は、それぞれ実施例1および比較例1で得られた凹凸形状の例で、図3および図4は、それぞれ上述した方法で2回微分を計算した結果である。2回微分された値を母集団とし、標準偏差を算出した結果が、凹凸形状の2回微分の標準偏差であり、本発明では、1試料に対して4ヶ所で算出した標準偏差の平均を用いることとする。
凹凸の形成方法としては、例えば、型による成型、コーティングによる塗膜の形成等が挙げられる。型による成型は、凹凸面と相補的な形状からなる型を作製し、紫外線硬化型樹脂を塗工した透明基材を密着させた状態で、紫外線硬化する方法などにより製造することができる。
コーティングによる塗膜の形成は、樹脂成分及び透光性粒子を含有してなる凹凸層形成塗布液を、グラビアコーティング、バーコーティング等の公知の塗布方法により透明基材上に塗布し、必要に応じて乾燥、硬化することにより形成することができる。
あらかじめ標準ポリスチレンをクロロホルムに溶かしてゲルパーミエーションクロマトグラフィ(GPC)で測定した検量線を基準にして、同様にGPCで測定した。両者の比較により、それぞれの重量平均分子量を算出した。GPCの装置構成は以下の通りである。
装置:Wates 2690
カラム:Shodex GPC KF-805L 8φ×300mm 2連結
展開溶媒:クロロホルム
流速:1ml/min
温度:30℃
試験片を10×6cm四方に切り出した。切り出した試験片を2点支持型のホルダーにセットして温度23℃、相対湿度50%に設定した環境試験機に24時間以上投入して状態調整した後、反りを測定した(処理前)。次に試験片をホルダーにセットして温度85℃、相対湿度85%に設定した環境試験機の中に投入し、その状態で120時間保持した。さらに温度23℃、相対湿度50%に設定した環境試験機の中にホルダーごと移動し、その状態で4時間保持後に再度反りを測定した(処理後)。反りの測定は、電動ステージ具備の3次元形状測定機(KEYENCE社製KS-1100)を使用し、取り出した試験片を上に凸の状態で水平に静置し、1ミリ間隔でスキャンし、中央部の盛り上がりを反りとして計測した。処理前後の反り量の差の絶対値、すなわち
JIS K 5600-5-4に準拠し、表面に対して角度45度、荷重750gで凹凸を有するハードコート層の表面に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の硬度を鉛筆硬度として評価した。
液晶表示装置の画面を全面グリーン表示にして、表示素子上に前面板を載置して目視で観察を行い、ギラツキの有無を確認した。
液晶表示装置の画面を全面白表示にして、表示素子上に前面板を載置して、偏光サングラスを通して画面を観察した。そのときに、液晶表示装置の視認側の偏光板の吸収軸と偏光サングラスの吸収軸が直交するようにして観察を行った(前面板を載置しない場合に真っ黒に見える状態)。観察の結果、視認性が良好な場合を良とし、視認性が悪い場合を不可として評価した。
柄を付けたハードコートの表面形状を共焦点顕微鏡(OLYMPUS走査型共焦点レーザ顕微鏡LEXT OLS3100)により測定した。観察倍率は500倍とし、Z方向のステップは0.01μmで3次元の形状測定を行い、任意の位置におけるX方向のラインプロファイル(長さ255.75μm)を凹凸形状とした。X方向は0.25μmステップでデータを取得し、2回微分の標準偏差はエクセルによって計算した。微分はエクセルのSLOPE関数を用い、SLOPE関数で計算した連続する7点の傾きをもって1回微分とし、1回微分を2回繰り返すことで、2回微分の計算を行った。2回微分された値を母集団とし、標準偏差を算出し、1試料に対して4ヶ所で算出した標準偏差の平均を計算した。4ヶ所の平均値により凹凸形状の2回微分の標準偏差とした。
東京精密社製表面粗さ測定機「SURFCOM 480A」を用い、JIS-B-0601-1994に定める方法により中心線平均粗さ(Ra)を算出した。
精製したメタクリル酸メチル(三菱ガス化学社製)77.000モル%と、芳香族ビニルモノマーとして精製したスチレン(和光純薬工業社製)22.998モル%と、重合開始剤としてt-アミルパーオキシ-2-エチルヘキサノエート(アルケマ吉富社製、商品名:ルペロックス575)0.002モル%とからなるモノマー組成物を、ヘリカルリボン翼付き10L完全混合槽に1kg/hで連続的に供給し、平均滞留時間2.5時間、重合温度150℃で連続重合を行った。重合槽の液面が一定となるよう底部から連続的に抜き出し、脱溶剤装置に導入してペレット状のビニル共重合樹脂(B1-1’)を得た。
得られたビニル共重合樹脂(B1-1’)をイソ酪酸メチル(関東化学社製)に溶解し、10質量%イソ酪酸メチル溶液を調製した。1000mLオートクレーブ装置に(B1-1’)の10質量%イソ酪酸メチル溶液を500質量部、10質量%Pd/C(NEケムキャット社製)を1質量部仕込み、水素圧9MPa、200℃で15時間保持して、ビニル共重合樹脂(B1-1’)の芳香族二重結合部位を水素化した。フィルターにより触媒を除去し、脱溶剤装置に導入してペレット状のビニル共重合樹脂(B1-1)を得た。1H-NMRによる測定の結果、ビニル共重合樹脂(B1-1)におけるメタクリル酸メチル構成単位の割合は75モル%であり、また波長260nmにおける吸光度測定の結果、芳香族二重結合部位の水素化反応率は99%であった。ゲル浸透クロマトグラフィーにより測定した重量平均分子量(標準ポリスチレン換算)は125,000であった。
スチレン-不飽和ジカルボン酸系共重合体(D)としてR-200(電気化学工業製、重量平均分子量:185,000、d1:d2:d3=55:20:25)50質量%とビニル系単量体を含有する樹脂(C)としてメチルメタクリレート樹脂パラペットHR-L(クラレ製、重量平均分子量:90,000)50質量%とリン系添加剤PEP36(ADEKA製)500ppmとステアリン酸モノグリセリド(製品名:H-100、理研ビタミン製)0.2%とを仕込んだ。この組成物をブレンダーで20分混合後、スクリュー径26mmの2軸押出機を用い、シリンダー温度240℃で溶融混錬して、ストランド状に押出してペレタイザーでペレット化し、樹脂組成物(B2-1)を得た。ペレットは安定して製造できた。
スチレン-不飽和ジカルボン酸系共重合体(D)としてR-200を60質量%とし、ビニル系単量体を含有する樹脂(C)としてメチルメタクリレート樹脂パラペットHR-Lを40質量%とした以外は、製造例2と同様にして樹脂組成物(B2-2)を得た。ペレットは安定して製造できた。
スチレン-不飽和ジカルボン酸系共重合体(D)としてR-200を70質量%とし、ビニル系単量体を含有する樹脂(C)としてメチルメタクリレート樹脂パラペットHR-Lを30質量%とした以外は、製造例2と同様にして樹脂組成物(B2-3)を得た。ペレットは安定して製造できた。
スチレン-不飽和ジカルボン酸系共重合体(D)としてR-100(電気化学工業製、重量平均分子量:170,000、d1:d2:d3=65:15:20)65質量%とビニル系単量体を含有する樹脂(C)としてメチルメタクリレート樹脂パラペットHR-L(クラレ製、重量平均分子量:90,000)35質量%とリン系添加剤PEP36(ADEKA製)500ppmとステアリン酸モノグリセリド(製品名:H-100、理研ビタミン製)0.2%とを仕込んだ。この組成物をブレンダーで20分混合後、スクリュー径26mmの2軸押出機を用い、シリンダー温度240℃で溶融混錬して、ストランド状に押出してペレタイザーでペレット化し、樹脂組成物(B2-4)を得た。ペレットは安定して製造できた。
スチレン-不飽和ジカルボン酸系共重合体(D)としてR-100を75質量%とし、ビニル系単量体を含有する樹脂(C)としてメチルメタクリレート樹脂パラペットHR-Lを25質量%とした以外は、製造例5と同様にして樹脂組成物(B2-5)を得た。ペレットは安定して製造できた。
スチレン-不飽和ジカルボン酸系共重合体(D)としてR-100を85質量%とし、ビニル系単量体を含有する樹脂(C)としてメチルメタクリレート樹脂パラペットHR-Lを15質量%とした以外は、製造例5と同様にして樹脂組成物(B2-6)を得た。ペレットは安定して製造できた。
スチレン-不飽和ジカルボン酸系共重合体(D)としてKX-406(電気化学工業製、重量平均分子量:155,000、d1:d2:d3=69:22:9)50質量%とビニル系単量体を含有する樹脂(C)としてメチルメタクリレート樹脂パラペットHR-L(クラレ製、重量平均分子量:90,000)50質量%とリン系添加剤PEP36(ADEKA製)500ppmとステアリン酸モノグリセリド(製品名:H-100、理研ビタミン製)0.2%とを仕込んだ。この組成物をブレンダーで20分混合後、スクリュー径26mmの2軸押出機を用い、シリンダー温度240℃で溶融混錬して、ストランド状に押出してペレタイザーでペレット化し、樹脂組成物(B2-7)を得た。ペレットは安定して製造できた。
スチレン-不飽和ジカルボン酸系共重合体(D)としてKX-407(電気化学工業製、重量平均分子量:165,000、d1:d2:d3=57:23:20)75質量%とビニル系単量体を含有する樹脂(C)としてメチルメタクリレート樹脂パラペットHR-L(クラレ製、重量平均分子量:90,000)25質量%とリン系添加剤PEP36(ADEKA製)500ppmとステアリン酸モノグリセリド(製品名:H-100、理研ビタミン製)0.2%とを仕込んだ。この組成物をブレンダーで20分混合後、スクリュー径26mmの2軸押出機を用い、シリンダー温度240℃で溶融混錬して、ストランド状に押出してペレタイザーでペレット化し、樹脂組成物(B2-8)を得た。ペレットは安定して製造できた。
スチレン-不飽和ジカルボン酸系共重合体(D)としてKX-422(電気化学工業製、重量平均分子量:119,000、d1:d2:d3=57:23:20)50質量%とビニル系単量体を含有する樹脂(C)としてメチルメタクリレート樹脂パラペットHR-L(クラレ製、重量平均分子量:90,000)50質量%とリン系添加剤PEP36(ADEKA製)500ppmとステアリン酸モノグリセリド(製品名:H-100、理研ビタミン製)0.2%とを仕込んだ。この組成物をブレンダーで20分混合後、スクリュー径26mmの2軸押出機を用い、シリンダー温度240℃で溶融混錬して、ストランド状に押出してペレタイザーでペレット化し、樹脂組成物(B2-9)を得た。ペレットは安定して製造できた。
(メタ)アクリレート共重合体(F)としてメタブレンH-880(三菱レイヨン社製、重量平均分子量:14,000、f1/f2=33/66)30質量%と、ポリカーボネート樹脂(E)としてユーピロンE-2000(三菱エンジニアリングプラスチック社製、重量平均分子量:61,000)70質量%とを仕込んだ。この組成物をブレンダーで30分混合後、スクリュー径26mmの2軸押出機(東芝機械製、TEM-26SS、L/D≒40)を用い、シリンダー温度240℃で溶融混錬して、ストランド状に押出してペレタイザーでペレット化し、樹脂組成物(B3-1)を得た。ペレット化は安定して製造できた。
(メタ)アクリレート共重合体(F)とポリカーボネート樹脂(E)との仕込み比率を50:50にした以外は、製造例11と同様にペレット化し、樹脂組成物(B3-2)を得た。ペレット化は安定して製造できた。
(メタ)アクリレート共重合体(F)とポリカーボネート樹脂(E)との仕込み比率を20:80にした以外は、製造例11と同様にペレット化し、樹脂組成物(B3-3)を得た。ペレット化は安定して製造できた。
(メタ)アクリレート共重合体(F)とポリカーボネート樹脂(E)との仕込み比率を60:40にした以外は、製造例11と同様にペレット化を行った。ペレット化は不安定で樹脂組成物(B3-4)は製造不可能であった。
(メタ)アクリレート共重合体(F)としてメタブレンH-880(三菱レイヨン社製、重量平均分子量:14,000)30質量%と、ポリカーボネート樹脂(E)としてユーピロンS-3000(三菱エンジニアリングプラスチック社製、重量平均分子量:47,000)70質量%とを仕込んだ。この組成物をブレンダーで30分混合後、スクリュー径26mmの2軸押出機(東芝機械製、TEM-26SS、L/D≒40)を用い、シリンダー温度240℃で溶融混錬して、ストランド状に押出してペレタイザーでペレット化し、樹脂組成物(B3-5)を得た。ペレット化は安定して行われた。
撹拌翼を備えた混合槽に、トリス(2-アクロキシエチル)イソシアヌレート(Aldrich社製)60質量部と、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:215D)40質量部と、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)1質量部と、1-ヒドロキシシクロヘキシルフェニルケトン(Aldrich社製)0.3質量部と、2-(2H-ベンゾトリアゾール-2-イル)-4,6-ビス(1-メチル-1-フェニルエチル)フェノール(チバ・ジャパン社製、商品名:TINUVIN234)1質量部とからなる組成物を導入し、40℃に保持しながら1時間撹拌して光硬化性樹脂組成物(X1)を得た。
撹拌翼を備えた混合槽に、1,9-ノナンジオールジアクリレート(大阪有機化学工業社製、商品名:ビスコート#260)40質量部と、6官能ウレタンアクリレートオリゴマー(新中村化学工業社製、商品名:U-6HA)40質量部と、コハク酸/トリメチロールエタン/アクリル酸のモル比が1/2/4である縮合物20質量部と、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質量部と、ベンゾフェノン(Aldrich社製)1質量部と、2-(2H-ベンゾトリアゾール-2-イル)-4,6-ビス(1-メチル-1-フェニルエチル)フェノール(チバ・ジャパン社製、商品名:TINUVIN234)1質量部とからなる組成物を導入し、40℃に保持しながら1時間撹拌して光硬化性樹脂組成物(X2)を得た。
MEK50質量部に対し、アクリル系紫外線硬化型樹脂50質量部(固形分100% 商品名:ライトアクリレートDPE-6A 共栄社化学株式会社製)、シリカ微粒子(オクチルシラン処理フュームドシリカ、平均一次粒子径12nm、日本アエロジル社製)0.5質量部、アクリルシラン処理シリカ1質量部(平均粒子径1.9μm、商品名:SE6050-SYB アドマテックス株式会社製)、及び光開始剤3質量部(商品名 イルガキュア184 チバスペシャリティーケミカルズ株式会社製)を混合し攪拌することでコーティング液(i)を作製した。次に、コーティング液(i)をPET(ポリエチレンテレフタレート)フィルムにドライ膜厚2.5μmとなるように塗布し、80℃で2分乾燥後、光源距離12cm、出力80W/cm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ることで、柄目付きPETフィルム(Y1)を作製した。
コーティング液(i)のドライ膜厚を3.5μmにした以外は、製造例17と同様にして柄目付きPETフィルム(Y2)を作製した。
MEK50質量部に対し、アクリル系紫外線硬化型樹脂50質量部(固形分100% 商品名:ライトアクリレートDPE-6A 共栄社化学株式会社製)、アクリルシラン処理シリカ1.5 質量部(平均粒子径1.9μm、商品名:SE6050-SYB アドマテックス株式会社製)、及び光開始剤3質量部(商品名 イルガキュア184 チバスペシャリティーケミカルズ株式会社製)を混合し攪拌することでコーティング液(ii)を作製した。次に、コーティング液(ii)をPET(ポリエチレンテレフタレート)フィルムにドライ膜厚1.5μmとなるように塗布し、80℃で2分乾燥後、光源距離12cm、出力80W/cm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ることで、柄目付きPETフィルム(Y3)を作製した。
有機化学ハンドブック第3版(技報堂出版、1981年)P143~150に基づき、東京化成工業(株)製4-ヒドロキシ安息香酸と東京化成工業(株)製1-ヘキサデカノールを用いて脱水反応によるエステル化を行い、パラヒドロキシ安息香酸ヘキサデシルエステル(CEPB)を得た。
9w/w%の水酸化ナトリウム水溶液57.2kgに、新日鐵住友化学(株)製のビスフェノールA(以下、「BPA」という)7.1kg(31.14mol)とハイドロサルファイト30gとを加えて溶解した。これにジクロロメタン40kgを加え、撹拌しながら、溶液温度を15℃~25℃の範囲に保ちつつ、ホスゲン4.33kgを30分かけて吹き込んだ。
ホスゲンの吹き込み終了後、9w/w%の水酸化ナトリウム水溶液6kg、ジクロロメタン11kg、及び末端停止剤として製造例19で合成したパラヒドロキシ安息香酸ヘキサデシルエステル(CEPB)551g(1.52mol)をメチレンクロライド10kgに溶解させた溶液を加え、激しく撹拌して乳化させた。さらにその後、重合触媒として10mlのトリエチルアミンを溶液に加え、約40分間重合させた。
重合液を水相と有機相に分離し、有機相をリン酸で中和し、洗液のpHが中性になるまで純水で水洗を繰り返した。この精製されたポリカーボネート樹脂溶液から有機溶媒を蒸発留去することによりポリカーボネート樹脂粉末を得た。
得られたポリカーボネート樹脂粉末を、スクリュー径35mm の2軸押出機を用い、シリンダー温度260℃で溶融混練して、ストランド状に押出してペレタイザーでペレット化した。得られたポリカーボネート樹脂(A1)の重量平均分子量は47000であった。
軸径35mm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体を成形した。軸径35mmの単軸押出機に製造例1で得たビニル共重合樹脂(B1-1)を連続的に導入し、シリンダ温度240℃、吐出速度2.6kg/hの条件で押し出した。また、軸径65mmの単軸押出機にポリカーボネート樹脂(A2)(三菱エンジニアリングプラスチックス社製、商品名:ユーピロンS-1000、重量平均分子量:59,000)を連続的に導入し、シリンダ温度280℃、吐出速度50.0kg/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270℃としてビニル共重合樹脂(B1-1)とポリカーボネート樹脂(A2)とを導入し積層した。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、上流側から温度120℃、130℃、190℃とした3本の鏡面仕上げロールで鏡面を転写しながら冷却し、引き取り速度を調整してレターデーションが4500nmであるビニル共重合樹脂(B1-1)を含む高硬度層とポリカーボネート樹脂(A2)を含む基材層との積層体を得た。得られた積層体の厚みは1,200μm、ビニル共重合樹脂(B1-1)を含む高硬度層の厚みは中央付近で60μmであった。
積層体のビニル共重合樹脂(B1-1)を含む高硬度層上に、製造例15で得た光硬化性樹脂組成物(X1)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、製造例17で作製した柄目付きPETフィルム(Y1)の柄面が塗布液と接触するように覆って圧着した。次に、ポリカーボネート樹脂(A2)を含む基材層上に製造例16で得た光硬化性樹脂組成物(X2)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た。その後、光源距離12cm、出力80W/cm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、柄目付きPETフィルムおよびPETフィルムを剥離し、ビニル共重合樹脂(B1-1)を含む高硬度層およびポリカーボネート樹脂(A2)を含む基材層上に、それぞれ光硬化性樹脂組成物(X1)および(X2)から成るハードコート層を備えた前面板を得た。
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機に各押出機と連結したマルチマニホールドダイとを有する多層押出装置を用いて合成樹脂積層体を成形した。軸径32mmの単軸押出機に製造例2で得た樹脂組成物(B2-1)を連続的に導入し、シリンダー温度240℃、吐出量を2.1kg/hの条件で押し出した。また、軸径65mmの単軸押出機にポリカーボネート樹脂(A2)(三菱エンジニアリングプラスチックス社製、商品名:ユーピロンS-1000、重量平均分子量:59,000)を連続的に導入し、シリンダー温度270℃、吐出量を30.0kg/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270℃にして樹脂組成物(B2-1)とポリカーボネート樹脂(A2)とを導入し積層した。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、上流側から温度130℃、140℃、180℃とした3本の鏡面仕上げロールで鏡面を転写しながら冷却し、引き取り速度を調整してレターデーションが3500nmである樹脂組成物(B2-1)を含む高硬度層とポリカーボネート樹脂(A2)を含む基材層との積層体を得た。得られた積層体の全体厚みは1,000μm、樹脂組成物(B2-1)を含む高硬度層の厚みは中央付近で60μmであった。
続いて、実施例1と同様にして積層体の樹脂組成物(B2-1)を含む高硬度層およびポリカーボネート樹脂(A2)を含む基材層上に、それぞれ光硬化性樹脂組成物(X1)および(X2)から成るハードコート層を形成し、前面板を得た。
高硬度層を製造例3で得た樹脂組成物(B2-2)を用いて製造した以外は、実施例2と同様にして樹脂組成物(B2-2)を含む高硬度層とポリカーボネート樹脂(A2)を含む基材層との積層体を得た。得られた積層体の全体厚みは1,000μm、樹脂組成物(B2-2)を含む高硬度層の厚みは中央付近で60μmであった。レターデーションは6000nmであった。
続いて、実施例1と同様にして積層体の樹脂組成物(B2-2)を含む高硬度層およびポリカーボネート樹脂(A2)を含む基材層上に、それぞれ光硬化性樹脂組成物(X1)および(X2)から成るハードコート層を形成し、前面板を得た。
高硬度層を製造例4で得た樹脂組成物(B2-3)を用いて製造した以外は、実施例2と同様にして樹脂組成物(B2-3)を含む高硬度層とポリカーボネート樹脂(A2)を含む基材層との積層体を得た。得られた積層体の全体厚みは1,000μm、樹脂組成物(B2-3)を含む高硬度層の厚みは中央付近で60μmであった。レターデーションは4000nmであった。
続いて、実施例1と同様にして積層体の樹脂組成物(B2-3)を含む高硬度層およびポリカーボネート樹脂(A2)を含む基材層上に、それぞれ光硬化性樹脂組成物(X1)および(X2)から成るハードコート層を形成し、前面板を得た。
高硬度層を製造例5で得た樹脂組成物(B2-4)を用いて製造した以外は、実施例2と同様にして樹脂組成物(B2-4)を含む高硬度層とポリカーボネート樹脂(A2)を含む基材層との積層体を得た。得られた積層体の全体厚みは1,000μm、樹脂組成物(B2-4)を含む高硬度層の厚みは中央付近で60μmであった。レターデーションは4500nmであった。
続いて、実施例1と同様にして積層体の樹脂組成物(B2-4)を含む高硬度層およびポリカーボネート樹脂(A2)を含む基材層上に、それぞれ光硬化性樹脂組成物(X1)および(X2)から成るハードコート層を形成し、前面板を得た。
高硬度層を製造例6で得た樹脂組成物(B2-5)を用いて製造した以外は、実施例2と同様にして樹脂組成物(B2-5)を含む高硬度層とポリカーボネート樹脂(A2)を含む基材層との積層体を得た。得られた積層体の全体厚みは1,000μm、樹脂組成物(B2-5)を含む高硬度層の厚みは中央付近で60μmであった。レターデーションは3700nmであった。
続いて、実施例1と同様にして積層体の樹脂組成物(B2-5)を含む高硬度層およびポリカーボネート樹脂(A2)を含む基材層上に、それぞれ光硬化性樹脂組成物(X1)および(X2)から成るハードコート層を形成し、前面板を得た。
高硬度層を製造例7で得た樹脂組成物(B2-6)を用いて製造した以外は、実施例2と同様にして樹脂組成物(B2-6)を含む高硬度層とポリカーボネート樹脂(A2)を含む基材層との積層体を得た。得られた積層体の全体厚みは1,000μm、樹脂組成物(B2-6)を含む高硬度層の厚みは中央付近で60μmであった。レターデーションは6500nmであった。
続いて、柄目付きPETフィルム(Y1)を柄目付きPETフィルム(Y2)にした以外は、実施例1と同様にして積層体の樹脂組成物(B2-6)を含む高硬度層およびポリカーボネート樹脂(A2)を含む基材層上に、それぞれ光硬化性樹脂組成物(X1)および(X2)から成るハードコート層を形成し、前面板を得た。
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機に各押出機と連結したマルチマニホールドダイとを有する多層押出装置を用いて合成樹脂積層体を成形した。軸径32mmの単軸押出機に製造例8で得た樹脂組成物(B2-7)を連続的に導入し、シリンダー温度240℃、吐出量を2.1kg/hの条件で押し出した。また、軸径65mmの単軸押出機にポリカーボネート樹脂(A2)(三菱エンジニアリングプラスチックス社製、商品名:ユーピロンS-1000、重量平均分子量:59,000)を連続的に導入し、シリンダー温度270℃、吐出量を30.0kg/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270℃にして樹脂組成物(B2-7)とポリカーボネート樹脂(A2)とを導入し積層した。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、上流側から温度130℃、140℃、180℃とした3本の鏡面仕上げロールで鏡面を転写しながら冷却し、引き取り速度を調整してレターデーションが6000nmである樹脂組成物(B2-7)を含む高硬度層とポリカーボネート樹脂(A2)を含む基材層との積層体を得た。
得られた積層体の全体厚みは1,000μm、樹脂組成物(B2-7)を含む高硬度層の厚みは中央付近で60μmであった。
続いて、実施例7と同様にして積層体の樹脂組成物(B2-7)を含む高硬度層およびポリカーボネート樹脂(A2)を含む基材層上に、それぞれ光硬化性樹脂組成物(X1)および(X2)から成るハードコート層を形成し、前面板を得た。
樹脂組成物(B2-7)の代わりに樹脂組成物(B2-8)を使用した以外は、実施例8と同様にして樹脂組成物(B2-8)を含む高硬度層とポリカーボネート樹脂(A2)を含む基材層との積層体を得た。得られた積層体の全体厚みは1,000μm、樹脂組成物(B2-8)を含む高硬度層の厚みは中央付近で60μmであった。レターデーションは4700nmであった。
続いて、実施例7と同様にして積層体の樹脂組成物(B2-8)を含む高硬度層およびポリカーボネート樹脂(A2)を含む基材層上に、それぞれ光硬化性樹脂組成物(X1)および(X2)から成るハードコート層を形成し、前面板を得た。
樹脂組成物(B2-7)の代わりに樹脂組成物(B2-9)を使用した以外は、実施例8と同様にして樹脂組成物(B2-9)を含む高硬度層とポリカーボネート樹脂(A2)を含む基材層との積層体を得た。得られた積層体の全体厚みは1,000μm、樹脂組成物(B2-9)を含む高硬度層の厚みは中央付近で60μmであった。レターデーションは5200nmであった。
続いて、実施例7と同様にして積層体の樹脂組成物(B2-9)を含む高硬度層およびポリカーボネート樹脂(A2)を含む基材層上に、それぞれ光硬化性樹脂組成物(X1)および(X2)から成るハードコート層を形成し、前面板を得た。
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体を成形した。軸径32mmの単軸押出機に製造例11で得た樹脂組成物(B3-1)を連続的に導入し、シリンダ温度240℃、吐出速度2.1kg/hの条件で押し出した。また、軸径65mmの単軸押出機にポリカーボネート樹脂(A3)(三菱エンジニアリングプラスチックス社製、商品名:ユーピロンS-3000、質量平均分子量:47,000)を連続的に導入し、シリンダ温度270℃、吐出速度30.0kg/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270℃として樹脂組成物(B3-1)とポリカーボネート樹脂(A3)とを導入し積層した。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、上流側から温度130℃、140℃、180℃とした3本の鏡面仕上げロールで鏡面を転写しながら冷却し、引き取り速度を調整してレターデーションが4400nmである樹脂組成物(B3-1)を含む高硬度層とポリカーボネート樹脂(A3)を含む基材層との積層体を得た。得られた積層体の厚みは1,000μm、樹脂組成物(B3-1)を含む高硬度層の厚みは中央付近で60μmであった。
続いて、実施例1と同様にして積層体の樹脂組成物(B3-1)を含む高硬度層およびポリカーボネート樹脂(A3)を含む基材層上に、それぞれ光硬化性樹脂組成物(X1)および(X2)から成るハードコート層を形成し、前面板を得た。
実施例11で使用した樹脂組成物(B3-1)の代わりに、製造例12で得た樹脂組成物(B3-2)を使用した以外は、実施例1と同様にして樹脂組成物(B3-2)を含む高硬度層とポリカーボネート樹脂(A3)を含む基材層との積層体を得た。得られた積層体の厚みは1,000μm、樹脂組成物(B3-2)を含む高硬度層の厚みは中央付近で60μmであった。レターデーションは6200nmであった。
続いて、実施例1と同様にして積層体の樹脂組成物(B3-2)を含む高硬度層およびポリカーボネート樹脂(A3)を含む基材層上に、それぞれ光硬化性樹脂組成物(X1)および(X2)から成るハードコート層を形成し、前面板を得た。
実施例11で使用した樹脂組成物(B3-1)の代わりに、製造例13で得た樹脂組成物(B3-3)を使用して、その吐出速度を7.0kg/hとし、ポリカーボネート樹脂(A3)の吐出速度を25kg/hとした以外は、実施例11と同様にして樹脂組成物(B3-1)を含む高硬度層とポリカーボネート樹脂(A3)を含む基材層との積層体を得た。得られた積層体の厚みは1,000μm、樹脂組成物(B3-3)を含む高硬度層の厚みは中央付近で200μmであった。レターデーションは4700nmであった。
続いて、実施例7と同様にして積層体の樹脂組成物(B3-3)を含む高硬度層およびポリカーボネート樹脂(A3)を含む基材層上に、それぞれ光硬化性樹脂組成物(X1)および(X2)から成るハードコート層を形成し、前面板を得た。
実施例11で使用した樹脂組成物(B3-1)の代わりに、製造例14で得た樹脂組成物(B3-5)を使用した以外は、実施例11と同様にして樹脂組成物(B3-5)を含む高硬度層とポリカーボネート樹脂(A3)を含む基材層との積層体を得た。得られた積層体の厚みは1,000μm、樹脂組成物(B3-5)を含む高硬度層の厚みは中央付近で60μmであった。レターデーションは4500nmであった。
続いて、実施例7と同様にして積層体の樹脂組成物(B3-5)を含む高硬度層およびポリカーボネート樹脂(A3)を含む基材層上に、それぞれ光硬化性樹脂組成物(X1)および(X2)から成るハードコート層を形成し、前面板を得た。
ポリカーボネート樹脂(A2)を製造例20で製造されたポリカーボネート樹脂(A1)にした以外は実施例1と同様にして、積層体の作製およびハードコートの形成を行い、前面板を得た。
ポリカーボネート樹脂(A2)を製造例20で製造されたポリカーボネート樹脂(A1)にした以外は実施例2と同様にして、積層体の作製およびハードコートの形成を行い、前面板を得た。
ポリカーボネート樹脂(A2)を製造例20で製造されたポリカーボネート樹脂(A1)にした以外は実施例3と同様にして、積層体の作製およびハードコートの形成を行い、前面板を得た。
ポリカーボネート樹脂(A2)を製造例20で製造されたポリカーボネート樹脂(A1)にした以外は実施例4と同様にして、積層体の作製およびハードコートの形成を行い、前面板を得た。
ポリカーボネート樹脂(A2)を製造例20で製造されたポリカーボネート樹脂(A1)にした以外は実施例5と同様にして、積層体の作製およびハードコートの形成を行い、前面板を得た。
ポリカーボネート樹脂(A2)を製造例20で製造されたポリカーボネート樹脂(A1)にした以外は実施例6と同様にして、積層体の作製およびハードコートの形成を行い、前面板を得た。
ポリカーボネート樹脂(A2)を製造例20で製造されたポリカーボネート樹脂(A1)にした以外は実施例7と同様にして、積層体の作製およびハードコートの形成を行い、前面板を得た。
ポリカーボネート樹脂(A2)を製造例20で製造されたポリカーボネート樹脂(A1)にした以外は実施例8と同様にして、積層体の作製およびハードコートの形成を行い、前面板を得た。
ポリカーボネート樹脂(A2)を製造例20で製造されたポリカーボネート樹脂(A1)にした以外は実施例9と同様にして、積層体の作製およびハードコートの形成を行い、前面板を得た。
ポリカーボネート樹脂(A2)を製造例20で製造されたポリカーボネート樹脂(A1)にした以外は実施例10と同様にして、積層体の作製およびハードコートの形成を行い、前面板を得た。
ポリカーボネート樹脂(A3)を製造例20で製造されたポリカーボネート樹脂(A1)にした以外は実施例11と同様にして、積層体の作製およびハードコートの形成を行い、前面板を得た。
ポリカーボネート樹脂(A3)を製造例20で製造されたポリカーボネート樹脂(A1)にした以外は実施例12と同様にして、積層体の作製およびハードコートの形成を行い、前面板を得た。
ポリカーボネート樹脂(A3)を製造例20で製造されたポリカーボネート樹脂(A1)にした以外は実施例13と同様にして、積層体の作製およびハードコートの形成を行い、前面板を得た。
ポリカーボネート樹脂(A3)を製造例20で製造されたポリカーボネート樹脂(A1)にした以外は実施例14と同様にして、積層体の作製およびハードコートの形成を行い、前面板を得た。
樹脂組成物(B2-1)の代わりにメチルメタクリレート樹脂パラペットHR-L(クラレ製、重量平均分子量:90,000)を使用した以外は実施例2と同様にして、積層体の作製およびハードコートの形成を行い、前面板を得た。
ポリカーボネート樹脂(A2)を製造例20で製造されたポリカーボネート樹脂(A1)にし、樹脂組成物(B2-1)の代わりにメチルメタクリレート樹脂パラペットHR-L(クラレ製、重量平均分子量:90,000)を使用した以外は実施例2と同様にして、積層体の作製およびハードコートの形成を行い、前面板を得た。
柄目付きPETフィルム(Y1)を柄目付きPETフィルム(Y3)にした以外は、比較例1と同様にして積層体のメチルメタクリレート樹脂を含む高硬度層およびポリカーボネート樹脂(A2)を含む基材層上に、それぞれ光硬化性樹脂組成物(X1)および(X2)から成るハードコート層を形成し、前面板を得た。
柄目付きPETフィルム(Y1)を柄目付きPETフィルム(Y3)にした以外は、比較例2と同様にして積層体のメチルメタクリレート樹脂を含む高硬度層およびポリカーボネート樹脂(A1)を含む基材層上に、それぞれ光硬化性樹脂組成物(X1)および(X2)から成るハードコート層を形成し、前面板を得た。
柄目付きPETフィルム(Y1)を柄目付きPETフィルム(Y3)にした以外は、実施例2と同様にして、積層体の樹脂組成物(B2-1)を含む高硬度層およびポリカーボネート樹脂(A2)を含む基材層上に、それぞれ光硬化性樹脂組成物(X1)および(X2)から成るハードコート層を形成し、前面板を得た。
引き取り速度を調整してレターデーションが2000nmとなるようにした以外は実施例2と同様にして、積層体の作製およびハードコートの形成を行い、前面板を得た。
下記表を見るとわかるとおり、本発明における構成を用いた場合、形状安定性、鉛筆硬度に優れ、ギラツキもなく、ブラックアウトの対策も可能であることから、車載用液晶表示装置の前面板として好適に用いることができる。一方、高硬度樹脂組成物(B)としてメチルメタクリレート樹脂を用いた比較例1~4は形状安定性に劣り、凹凸を有するハードコート層の凹凸形状の2回微分の標準偏差が0.1未満である比較例3~5はギラツキが発生し、前面板のレターデーションが3,000nm未満である比較例6はブラックアウトの結果が良くなかった。
Claims (5)
- ポリカーボネート樹脂(a1)を含む樹脂(A)を含む層の少なくとも一方の面に、高硬度樹脂組成物(B)を含む層を有し、更に、該高硬度樹脂組成物(B)を含む層上に、凹凸を有するハードコート層を有し、下記条件(i)から(iv)を満たすことを特徴とする車載用液晶表示装置の前面板。
(i)前記高硬度樹脂組成物(B)を含む層の厚みが10~250μmであり、前記ポリカーボネート樹脂(a1)を含む樹脂(A)を含む層と前記高硬度樹脂組成物(B)を含む層との合計厚みが100~3,000μmであり、
(ii)前記高硬度樹脂組成物(B)が以下の樹脂組成物(B1)から(B3)のいずれか1つからなり、
・樹脂組成物(B1)
下記一般式(1)で表される(メタ)アクリル酸エステル構成単位(a)と、下記一般式(2)で表される脂肪族ビニル構成単位(b)とを含む共重合樹脂であって、前記メタクリル酸エステル構成単位(a)と前記脂肪族ビニル構成単位(b)との合計割合が前記共重合樹脂の全構成単位の90~100モル%であり、前記(メタ)アクリル酸エステル構成単位(a)の割合が前記共重合樹脂の全構成単位の65~80モル%である共重合樹脂:
・樹脂組成物(B2)
ビニル系単量体を含有する樹脂(C)を55~10質量%、およびスチレン-不飽和ジカルボン酸系共重合体(D)を45~90質量%含む樹脂組成物であって、前記スチレン-不飽和ジカルボン酸系共重合体(D)が、スチレン系単量体単位(d1)50~80質量%、不飽和ジカルボン酸無水物単量体単位(d2)10~30質量%、およびビニル系単量体単位(d3)5~30質量%を含む樹脂組成物:
・樹脂組成物(B3)
ポリカーボネート樹脂(E)を95~45質量%、および(メタ)アクリレート共重合体(F)を5~55質量%含む樹脂組成物であって、前記(メタ)アクリレート共重合体(F)が、芳香族(メタ)アクリレート単位(f1)とメタクリル酸エステル単量体単位(f2)とを質量比(f1/f2)で10~50/40~90含み、かつ、前記ポリカーボネート樹脂(E)の重量平均分子量が37,000~71,000であり、前記(メタ)アクリレート共重合体(F)の重量平均分子量が5,000~30,000である樹脂組成物:
(iii)前記前面板のレターデーションが3,000nm以上であり、
(iv)前記凹凸を有するハードコート層の凹凸形状の2回微分の標準偏差が0.1以上である。 - 前記前面板が、前記凹凸を有するハードコート層とは反対の面にもハードコート層を有する請求項1に記載の車載用液晶表示装置の前面板。
- 前記前面板が、温度85℃で相対湿度85%の環境下に120時間保持した後の反りの変化量が1,000μm以下である請求項1または2に記載の車載用液晶表示装置の前面板。
- 前記高硬度樹脂組成物(B)を含む層が、前記ポリカーボネート樹脂(a1)を含む樹脂(A)を含む層と共に共押出されたものである請求項1から3のいずれかに記載の車載用液晶表示装置の前面板。
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CN201780014879.7A CN108700764B (zh) | 2016-03-04 | 2017-03-02 | 车载用液晶显示装置的前面板 |
KR1020187028285A KR102333266B1 (ko) | 2016-03-04 | 2017-03-02 | 차재용 액정 표시 장치의 전면판 |
EP17760110.1A EP3425448B1 (en) | 2016-03-04 | 2017-03-02 | Front plate for onboard lcd device |
JP2018503390A JP6908588B2 (ja) | 2016-03-04 | 2017-03-02 | 車載用液晶表示装置の前面板 |
US16/080,783 US10710291B2 (en) | 2016-03-04 | 2017-03-02 | Front plate for onboard LCD device |
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JP7470597B2 (ja) | 2020-08-05 | 2024-04-18 | 三菱瓦斯化学株式会社 | 透明樹脂積層体並びにそれを用いた透明基板材料及び透明保護材料 |
WO2024181290A1 (ja) * | 2023-02-27 | 2024-09-06 | 三菱瓦斯化学株式会社 | 防眩性積層体及びその製造方法 |
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US11390007B2 (en) | 2022-07-19 |
KR20180121572A (ko) | 2018-11-07 |
TW201801934A (zh) | 2018-01-16 |
EP3425448A4 (en) | 2019-09-18 |
US20210016485A1 (en) | 2021-01-21 |
US10710291B2 (en) | 2020-07-14 |
TWI773661B (zh) | 2022-08-11 |
JPWO2017150646A1 (ja) | 2018-12-27 |
CN108700764B (zh) | 2021-09-14 |
JP6908588B2 (ja) | 2021-07-28 |
CN108700764A (zh) | 2018-10-23 |
KR102333266B1 (ko) | 2021-12-01 |
EP3425448B1 (en) | 2020-07-08 |
US20190054674A1 (en) | 2019-02-21 |
EP3425448A1 (en) | 2019-01-09 |
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