WO2014157103A1 - Feuille de résine de polycarbonate - Google Patents

Feuille de résine de polycarbonate Download PDF

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Publication number
WO2014157103A1
WO2014157103A1 PCT/JP2014/058110 JP2014058110W WO2014157103A1 WO 2014157103 A1 WO2014157103 A1 WO 2014157103A1 JP 2014058110 W JP2014058110 W JP 2014058110W WO 2014157103 A1 WO2014157103 A1 WO 2014157103A1
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Prior art keywords
sheet
roll
polycarbonate
polycarbonate resin
thickness
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PCT/JP2014/058110
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English (en)
Japanese (ja)
Inventor
船木　章
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出光興産株式会社
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
    • B29C48/885—External treatment, e.g. by using air rings for cooling tubular films
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
    • B29C48/911—Cooling
    • B29C48/9135—Cooling of flat articles, e.g. using specially adapted supporting means
    • B29C48/914—Cooling of flat articles, e.g. using specially adapted supporting means cooling drums
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
    • B29C48/911—Cooling
    • B29C48/9135—Cooling of flat articles, e.g. using specially adapted supporting means
    • B29C48/9145—Endless cooling belts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
    • B29C48/911—Cooling
    • B29C48/9135—Cooling of flat articles, e.g. using specially adapted supporting means
    • B29C48/915—Cooling of flat articles, e.g. using specially adapted supporting means with means for improving the adhesion to the supporting means
    • B29C48/9155—Pressure rollers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92761—Mechanical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/92—Measuring, controlling or regulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/54—Yield strength; Tensile strength
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays

Definitions

  • the present invention relates to a polycarbonate resin sheet.
  • an object of the present invention is to provide a polycarbonate resin sheet having a small phase difference even if it is thick.
  • the polycarbonate resin sheet of the present invention is a polycarbonate resin sheet provided with a polycarbonate layer, and the polycarbonate layer contains 5% by mass to 100% by mass of a branched polycarbonate and 0% by mass to 95% by mass of an aromatic polycarbonate. It consists of a resin composition, the thickness of the sheet is 1 mm or more and 4 mm or less, and the retardation value Re (nm) in the sheet surface and the thickness t (mm) of the sheet satisfy the following condition (1) or (2). It is characterized by. (1) When the thickness t of the sheet is 1 mm ⁇ t ⁇ 2.5 mm, Re ⁇ 11.25t + 2.5 (2) When the thickness t of the sheet is 2.5 mm ⁇ t ⁇ 4 mm, Re ⁇ 30.625
  • the polycarbonate layer which consists of a resin composition containing 5 to 100 mass% of branched polycarbonate and 0 to 95 mass% of aromatic polycarbonate is provided.
  • a polycarbonate resin sheet thinner than about 500 ⁇ m is relatively rapidly cooled in the cooling and solidification process, and tends to be solidified while maintaining the MD orientation in the molten resin film.
  • a sheet thicker than about 500 ⁇ m, particularly a polycarbonate resin sheet having a thickness exceeding 1 mm is relatively gradually cooled during sheet manufacturing, the surface is cooled by being sandwiched between a mirror-shaped metal belt and a cooling roll.
  • the branched nucleus structure of the branched polycarbonate is a structure derived from 1,1,1-tris (4-hydroxyphenyl) -alkanes described in the following general formula (I). It is preferable.
  • R represents hydrogen or an alkyl group having 1 to 5 carbon atoms
  • R 1 to R 6 each represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 5 carbon atoms.
  • the structure derived from the 1,1,1-tris (4-hydroxyphenyl) -alkanes is derived from 1,1,1-tris (4-hydroxyphenyl) -ethane. It is preferable to have a structure.
  • the polycarbonate resin sheet of the present invention preferably includes at least one polymethyl methacrylate layer. Since polymethyl methacrylate has a surface hardness higher than that of polycarbonate, for example, when used for applications such as a front plate of a display member for which surface hardness is required, the polymethyl methacrylate layer is used as a surface layer as it is or as a hard coat layer. It can be used as an undercoat layer.
  • the polycarbonate resin sheet of the present invention includes a first cooling roll whose surface is coated with an elastic material, a metal belt having a mirror surface and wound between a second cooling roll, and the metal belt.
  • a polycarbonate resin sheet produced using a production apparatus comprising a first cooling roll disposed opposite to the first cooling roll, wherein 5% by mass to 100% by mass of branched polycarbonate and A resin composition containing 0 to 95% by weight of an aromatic polycarbonate is extruded in a molten state from a die attached to an extruder and introduced between the metal belt and the third cooling roll, A polycarbonate resin sheet is formed by cooling while being transported by the metal belt and being peeled off from the metal belt, and is peeled off from the metal belt.
  • the warp of the polycarbonate resin sheet is corrected by a warp correction drive roll while controlling the sheet tension between the metal belt and the warp correction drive roll to 0.1 MPa or more and 0.7 MPa or less, and the warp correction drive roll
  • the polycarbonate resin sheet is taken up while the sheet tension between the warp correction drive roll and the drive pinch roll is controlled to 0.5 MPa or less by the drive pinch roll disposed on the downstream side of the sheet, and the thickness of the sheet is 1 mm. It is characterized by being manufactured so that the retardation value Re (nm) in the sheet plane and the sheet thickness t (mm) satisfy the following condition (1) or (2).
  • (1) When the thickness t of the sheet is 1 mm ⁇ t ⁇ 2.5 mm, Re ⁇ 11.25t + 2.5 (2)
  • the thickness t of the sheet is 2.5 mm ⁇ t ⁇ 4 mm, Re ⁇ 30.625
  • a polycarbonate resin sheet (hereinafter sometimes abbreviated as a sheet) is a polycarbonate resin sheet provided with a polycarbonate layer, and the polycarbonate layer is 5% by mass or more and 100% by mass or less of branched polycarbonate.
  • a resin composition containing 0% by mass to 95% by mass of an aromatic polycarbonate the thickness of the sheet is 1 mm or more and 4 mm or less, and the retardation value Re (nm) in the sheet surface and the sheet thickness t (mm) Satisfies the following condition (1) or (2).
  • Polycarbonate has a large intrinsic birefringence value, and high tension control is required to produce a low retardation sheet.
  • high tension control is required to produce a low retardation sheet.
  • TD direction
  • the tension is necessary to control the tension within a specific tension range in the temperature range near the glass transition point Tg of polycarbonate.
  • the branched polycarbonate in the resin composition is less than 5% by mass, it is difficult to obtain the effect of adding the polycarbonate for branching, that is, the effect of improving the MD orientation.
  • the branched polycarbonate is preferably contained in an amount of 8 to 50% by mass, more preferably 10 to 30% by mass.
  • the aromatic polycarbonate is contained in an amount of 0% by mass to 95% by mass. That is, the resin composition may be composed only of a branched polycarbonate.
  • the branched polycarbonate tends to have a high raw material price, and from the viewpoint of economic rationality, the aromatic polycarbonate is preferably contained in an amount of 50% by mass to 92% by mass, and more preferably 70% by mass to 90% by mass. More preferred.
  • the thickness of the sheet is preferably 1 mm or more and 4 mm or less. If the thickness is within this range, a sheet having a low retardation can be obtained by controlling the tension of the sheet due to the effect of adding the branched polycarbonate. When the thickness is smaller than 1 mm, the effect of adding the branched polycarbonate is strong, the MD orientation becomes too high, and the tension control of the sheet may be difficult. On the other hand, if the thickness exceeds 4 mm, the film formation itself becomes difficult, and it becomes too slow to cause the effect of adding the branched polycarbonate to be hardly exhibited.
  • the thickness of the sheet is preferably 1 mm or more and 4 mm or less because the effect of adding the branched polycarbonate can be obtained more greatly.
  • the retardation value Re (nm) in the sheet surface and the sheet thickness t (mm) satisfy the above condition (1) or (2).
  • the retardation value Re (nm) in the sheet surface is obtained by storing the formed sheet in an environment at 23 ° C. for 24 hours, and then rotating the retardation value at a pitch of 50 mm in the sheet width direction (TD) at 23 ° C. It is a value obtained by measuring by the method and calculating the average value.
  • FIG. 1 shows a sheet (A) having a polycarbonate layer made of a resin composition containing a branched polycarbonate, and a sheet having a polycarbonate layer made of a resin composition containing an aromatic polycarbonate and not containing a branched polycarbonate.
  • (B) is manufactured at various thicknesses, the retardation value of the sheet is calculated by the method described above, and the relationship between the thickness and the retardation Re is shown.
  • a straight line connecting the points (C) can be derived, and when the thickness t of the sheet is 1 mm ⁇ t ⁇ 2.5 mm, the condition ( Re ⁇ 11.25t + 2.5 in 1) is derived.
  • 30.625 in the condition (2) is a value derived from the retardation value when the sheet thickness in the condition (1) is 2.5 mm.
  • the retardation value Re satisfies the above formula (1) or (2)
  • the sheet has a low phase difference, and can be suitably used as an optical sheet used for, for example, a liquid crystal display element.
  • R is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
  • alkyl group having 1 to 5 carbon atoms include methyl group, ethyl group, n-propyl group, n-butyl group, and n-pentyl group.
  • R 1 to R 6 are a hydrogen atom, a halogen atom or an alkyl group having 1 to 5 carbon atoms, and they may be the same or different.
  • the halogen atom include chlorine, bromine, fluorine, and iodine.
  • alkyl group having 1 to 5 carbon atoms examples include methyl group, ethyl group, n-propyl group, n-butyl group, and n-pentyl group.
  • R is preferably a methyl group
  • R 1 to R 6 are each preferably a hydrogen atom.
  • 1,1,1-tris (4-hydroxyphenyl) -alkanes are preferred, and in particular, 1,1,1-tris where R is a methyl group and R 1 to R 6 are each a hydrogen atom.
  • (4-Hydroxyphenyl) -ethane is preferred.
  • branching agents include, for example, phloroglucin; melittic acid; trimellitic acid; trimellitic acid chloride; trimellitic anhydride; gallic acid; gallic acid n-propyl; protocatechuic acid; pyromellitic acid; Resorcinic acid; ⁇ -resorcinic acid; resorcinaldehyde; trimethyl chloride; trimethyl trichloride; 4-chloroformyl phthalic anhydride; benzophenone tetracarboxylic acid; 2,4,4'-trihydroxybenzophenone;2,4'-tetrahydroxybenzophenone;2,4,4'-trihydroxyphenylether; 2,2 ', 4,4'-tetrahydroxyphenyl ether; 2,4,4'-trihydroxydiphenyl-2-propane; , 2'-bis (2,4-dihydroxy) propane; 2,2 ', 4 4'-tetrahydroxydiphenylmethane;2,4,4'-trihydroxy
  • the branched polycarbonate preferably has a viscosity average molecular weight of 15,000 to 40,000. If the viscosity average molecular weight is less than 15,000, impact resistance may be lowered. On the other hand, if it exceeds 40,000, moldability may be deteriorated.
  • the branched polycarbonate preferably has an acetone-soluble content of 3.5% by weight or less. If the acetone-soluble content exceeds 3.5% by weight, impact resistance may decrease.
  • the acetone-soluble component means a component that is Soxhlet extracted from a target branched polycarbonate using acetone as a solvent.
  • the branched polycarbonate can be produced by various methods. For example, a method disclosed in JP-A-3-182524, that is, (1) a polycarbonate oligomer derived from an aromatic dihydric phenol, a branching agent represented by the general formula (I) and phosgene, (2) Aromatic dihydric phenols and (3) end terminator are reacted while stirring so that the reaction mixture containing them becomes a turbulent flow, and when the viscosity of the reaction mixture increases, an alkaline aqueous solution is added. It can manufacture efficiently by the method of making a reaction liquid mixture react as a laminar flow.
  • the aromatic polycarbonate (PC) may be anything other than the above-mentioned branched polycarbonate, that is, any non-branched polycarbonate, and there are various types.
  • a polymer having a structural unit represented by the general formula (II) is preferable.
  • X is a hydrogen atom, a halogen atom or an alkyl group having 1 to 8 carbon atoms, and m and n are integers of 1 to 4 respectively. Several X may be the same and may differ.
  • Y is a single bond, an alkylene group having 1 to 8 carbon atoms or an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, or —S—, — An SO—, —SO 2 —, —O—, —CO— bond or a bond represented by the formula (III-1) or (III-2) is shown. ]
  • X is preferably a hydrogen atom
  • Y is preferably an ethylene group or a propylene group.
  • This aromatic polycarbonate can be easily produced by reacting a dihydric phenol represented by the following general formula (IV) with a phosgene or a carbonic acid diester compound. That is, for example, in the presence of a known acid acceptor or molecular weight regulator in a solvent such as methylene chloride, by reaction of a dihydric phenol with a carbonate precursor such as phosgene, or like dihydric phenol and diphenyl carbonate. Produced by transesterification with a carbonate precursor.
  • dihydroxydiarylcycloalkanes examples include 1,1-bis (4-hydroxyphenyl) cyclohexane; 1,1-bis (3,5-dichloro-4-hydroxyphenyl) cyclohexane; 1,1-bis (4- Hydroxyphenyl) cyclodecane.
  • dihydroxydiaryl sulfones examples include bis (4-hydroxyphenyl) sulfone; bis (3,5-dimethyl-4-hydroxyphenyl) sulfone; bis (3-chloro-4-hydroxyphenyl) sulfone.
  • dihydroxydiaryl ethers examples include bis (4-hydroxyphenyl) ether; bis (3,5-dimethyl-4-hydroxyphenyl) ether.
  • R 7 , R 8 and R 9 are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a phenyl group, and may be the same or different. Further, s and t are each 0 or an integer of 1 or more. ]
  • Examples of the alkyl group having 1 to 6 carbon atoms in the general formula (VI) include a methyl group, an ethyl group, a propyl group, an n-butyl group, an isobutyl group, an amyl group, an isoamyl group, and a hexyl group.
  • aromatic polycarbonates it is preferable to use an aromatic polycarbonate having a relatively low molecular weight from the viewpoint of only low retardation. This is because when the molecular weight is low, the glass transition point of the sheet is relatively low, and even when the sheet is peeled off from the belt / mirror roll, the slow axis is TD even at the same sheet temperature and the same sheet tension. This is because it is easy to reduce the birefringence of the refractive index ellipsoid facing the surface.
  • a relatively high molecular weight aromatic polycarbonate for example, from the viewpoint of impact resistance required for applications such as the front plate of the display member. Therefore, the viscosity average molecular weight is from 19,000 to 25,000. It is more preferable to use the aromatic polycarbonate.
  • the resin composition of the present embodiment contains, for example, various additives or other synthetic resins, elastomers, etc., as long as the purpose of the present invention is not impaired. can do.
  • the various additives include antioxidants such as hindered phenols, phosphites, phosphates, and amines, UV absorbers such as benzotriazoles and benzophenones, and light such as hindered amines.
  • Stabilizers aliphatic carboxylic acid ester-based and paraffin-based external lubricants, internal lubricants such as silicone oil and polyethylene wax, mold release agents, antistatic agents, colorants and the like.
  • hindered phenol antioxidant examples include BHT (2,6-ditert-butyl-p-cresol), “Irganox 1076” (trade name) and “Irganox 1010” (product) manufactured by BASF Japan Ltd. Name), “Ethyl 330” (trade name) manufactured by Ethyl Co., Ltd., “Sumilyzer GM” (trade name) manufactured by Sumitomo Chemical Co., Ltd., etc. are preferably used.
  • polyester polyethylene terephthalate, holyethylene terephthalate, etc.
  • polyamide polyethylene, polypropylene, polystyrene, acrylonitrile / styrene copolymer (AS resin), acrylonitrile / butadiene / styrene copolymer (AS).
  • ABS resin polymethyl methacrylate and the like.
  • the sheet of the present embodiment may have a single layer structure or a multilayer structure.
  • the manufacturing apparatus 1 is made of a metal wound around a die 10 of an extruder, a first cooling roll 11, a second cooling roll 12, and a fourth cooling roll 14.
  • a belt 15 (hereinafter, abbreviated as “belt 15”), and a third cooling roll 13 disposed to face the first cooling roll 11 with the sheet 30 and the belt 15 interposed therebetween are provided.
  • a fourth cooling roll 14 is disposed below the first cooling roll 11, and a second cooling roll 12 is disposed at substantially the same height as the fourth cooling roll 14.
  • the third cooling roll 13 is disposed opposite to the first cooling roll 11 at substantially the same height position.
  • the third cooling roll 13 is provided so as to come into contact with the first cooling roll 11 via the sheet 30 and the belt 15 and to hold the sheet 30 pressed to the third cooling roll 13 side by the belt 15. Yes. That is, the belt 15 and the sheet 30 in contact with the belt 15 meander so as to be wound around a part of the peripheral surface 131 of the third cooling roll 13.
  • the belt temperature controller 16 has a cooling surface 161 that is disposed between the first and second cooling rolls 11 and 12 and substantially faces the peripheral surface 131 with the belt 15 interposed therebetween.
  • the cooling surface 161 cools the belt 15 from a position where the belt 15 and the first cooling roll 11 are separated from a position where the sheet 30 and the belt 15 are separated.
  • the roll temperature control means and the belt temperature control means preferably control the temperature of the peripheral surface 131 and the temperature of the belt 15 to (Tg ⁇ 60 ° C.) or more and (Tg + 30 ° C.) or less.
  • Tg is the glass transition point of the polycarbonate resin. If the temperature of the peripheral surface 131 and the temperature of the belt 15 are less than (Tg ⁇ 60 ° C.), a large phase difference tends to occur when the sheet 30 is rapidly cooled and pinched. On the other hand, when the temperature of the peripheral surface 131 and the temperature of the belt 15 exceed (Tg + 30 ° C.), the retardation unevenness and the thickness unevenness tend to occur due to the tension at the time of peeling.
  • the die 10 has an extrusion port 101 through which the sheet 30 is extruded.
  • the distance from the extrusion port 101 until the resin is introduced between the belt 15 and the third cooling roll 13 (air gap) is preferably 200 mm or less, and more preferably 180 mm or less. If the air gap exceeds 200 mm, the sheet 30 may flutter and uneven thickness may occur, and the molten sheet 30 is cooled before being nipped (nip), and a phase difference tends to occur. It is in.
  • the first detector-equipped guide roll 17 is disposed between the belt 15 and the warp correction drive roll 18.
  • the first load detector 171 provided on the first detector-equipped guide roll 17 can measure the load applied to the sheet 30 between the belt 15 and the warp correction drive roll 18.
  • the sheet tension can be calculated from the detected value of the load.
  • this 1st load detector 171 and the curvature correction roll speed control means of the curvature correction drive roll 18 are electrically connected via the sequencer, and speed control can be performed based on the information of this detected value. .
  • the distance between the first detector-equipped guide roll 17 and the belt 15 disposed upstream is 500 mm or less, and the distance between the guide roll 19 or the warp correction driving roll 18 disposed downstream is 500 mm or less. It is preferable to install in. If the distance exceeds the upper limit, it tends to be difficult to keep the sheet tension constant in the sheet width direction, and as a result, it tends to be difficult to make the retardation value low in the sheet width direction uniform.
  • the warp correction drive roll 18 includes a warp correction roll speed control means (not shown) for controlling the speed of the warp correction drive roll 18.
  • the warp correction roll speed control means include those capable of controlling the speed with high accuracy by a vector inverter motor or the like.
  • seat 30 can be sent, controlling the speed
  • the sheet tension between the belt 15 and the warp correction drive roll 18 can be controlled to 0.1 MPa or more and 0.7 MPa or less. As a result, the variation in phase difference can be reduced over the entire sheet surface while reducing the sheet warpage of the sheet 30.
  • a resin composition containing 5% by mass or more and 100% by mass or less of a branched polycarbonate and 0% by mass or more and 95% by mass or less of an aromatic polycarbonate is blended in advance and supplied to a hopper of an extruder. Then, the molten polycarbonate is extruded from the extrusion port 101 of the die 10 attached to the extruder and introduced between the belt 15 and the third cooling roll 13. At this time, the linear pressure applied between the third cooling roll 13 and the belt 15 is controlled to 300 N / cm or less by the nip pressure control means.
  • the sheet 30 peeled from the belt 15 is sent to the warp correction drive roll 18 via the first detector-equipped guide roll 17 and the guide roll 19.
  • the first load detector 171 provided on the first detector-equipped guide roll 17 measures the load applied to the seat 30.
  • the sheet tension is controlled to 0.1 MPa or more and 0.7 MPa or less by controlling the speed of the warp correction driving roll 18 based on the detected value.
  • the temperature of the peripheral surface 181 of the warp correction driving roll 18 is controlled to (Tg ⁇ 20 ° C.) or more and (Tg + 30 ° C.) or less by the sheet temperature control means 22 on the warp correction driving roll 18. In this way, the warp of the sheet 30 is corrected by the warp correction drive roll 18.
  • the corrected sheet 30 is taken up by the drive pinch roll 21 via the second detector-equipped guide roll 20.
  • the second load detector 201 provided on the second detector-equipped guide roll 20 measures the load applied to the sheet 30.
  • the sheet tension is controlled to 0.5 MPa or less by controlling the speed of the drive pinch roll 21 based on the detected value.
  • the sheet 30 can be manufactured as described above. In addition, when manufacturing a sheet
  • the second embodiment is the same as the first embodiment described above except that the sheet has a multilayer structure in which at least one polymethyl methacrylate layer is provided. It is a configuration. Therefore, only the polymethyl methacrylate layer will be described, and description of other parts having the same configuration as in the first embodiment will be omitted.
  • Examples of the other monomer that can be copolymerized with methyl methacrylate include methacrylic acid esters and acrylic acid esters other than methyl methacrylate.
  • Examples of methacrylic esters other than methyl methacrylate include ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, 2-ethylhexyl methacrylate, and 2-hydroxyethyl methacrylate.
  • unsaturated acids such as methacrylic acid and acrylic acid, acrylonitrile, methacrylonitrile, maleic anhydride, phenylmaleimide, cyclohexylmaleimide and the like can also be mentioned.
  • unsaturated acids such as methacrylic acid and acrylic acid, acrylonitrile, methacrylonitrile, maleic anhydride, phenylmaleimide, cyclohexylmaleimide and the like can also be mentioned.
  • These other monomers that can be copolymerized with methyl methacrylate may be used alone or in combination of two or more.
  • the acrylic multilayer structure polymer should have an elastomer layer of about 20 to 60% by weight, preferably a hard layer as the outermost layer, and further have a hard layer as the innermost layer. It may be a thing.
  • the elastomer layer is preferably an acrylic polymer layer having a glass transition point (Tg) of less than 25 ° C.
  • Tg glass transition point
  • a polymer layer obtained by crosslinking a monomer with a polyfunctional monomer such as allyl methacrylate is preferable.
  • the monofunctional monomer is used as a main component to form a copolymer
  • other monofunctional monomers such as styrene and substituted styrene may be copolymerized as a copolymerization component.
  • the hard layer is preferably an acrylic polymer layer having a Tg of 25 ° C. or more.
  • an alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms is polymerized alone or as a main component. It is good to be.
  • the alkyl group having 1 to 4 carbon atoms include linear or branched alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, and t-butyl.
  • a copolymer having an alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms as a main component is used as a copolymer component, other alkyl methacrylate, alkyl acrylate, styrene, substituted styrene, acrylonitrile, methacrylonitrile, etc.
  • a monofunctional monomer may be used, or a polyfunctional monomer such as allyl methacrylate may be added to form a crosslinked polymer.
  • alkyl group in the alkyl methacrylate and the like include, for example, the same linear or branched alkyl group having 1 to 6 carbon atoms as exemplified for the lower alkyl group described above.
  • Example 1 An extruder, extrusion process conditions, a belt machine, first to fourth cooling rolls and a warp correction driving roll are shown below.
  • the polycarbonate resin is extruded by the following vent type single screw extruder.
  • Polymer filter Leaf disk type, 16 sheets of 8 inches, nominal filtration accuracy 20 ⁇ m.
  • Coat hanger die 1000 mm width, lip opening 3.5 mm.
  • First cooling roll roll ( ⁇ 650 mm) coated with nitrile rubber (NBR) having a thickness of 10 mm and JIS-A 60 °.
  • Second cooling roll double pipe spiral metal roll ( ⁇ 650 mm).
  • Fourth cooling roll double pipe spiral metal roll ( ⁇ 650 mm).
  • Warpage correction driving roll A non-adhesive coating film (hard, non-adhesive coding NFX-5131, manufactured by Nippon Fluoro Kogyo Co., Ltd.) is provided on the surface.
  • the physical properties of the coating film are as follows. Tape peeling force 0.5N, pencil hardness 9H or more, surface roughness Rz 0.6 ⁇ m, heat resistance 250 ° C., film thickness 2 ⁇ m.
  • Coat hanger die 1000mm width, lip opening 3.5mm
  • Extruder 2 Cylinder part; C1 / C2 / C3 / C4 / C5 / C6 220/220/225/225/205/205 ° C.
  • the PC resin was supplied to the hopper of the extruder 1 and the PMMA resin was supplied to the hopper of the extruder 2, and the laminated resin film in a molten state was extruded from the extrusion port (die lip).
  • the extruded molten resin film is introduced between a belt at 160 ° C. with an air gap of 125 mm and a third cooling roll (95 ° C.) disposed opposite to the first (8) cooling roll via this belt. Clamping was performed at a linear pressure of 250 N / cm. Then, it was cooled and peeled from the belt while being conveyed by the belt.
  • the polycarbonate resin sheet of the present invention can be used as a resin front plate of a display member.
  • an alkali-reinforced glass front plate can be used in place of a thermoplastic resin sheet front plate.

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  • Mechanical Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Polarising Elements (AREA)

Abstract

Cette feuille de résine de polycarbonate est dotée d'une couche de polycarbonate. La feuille de résine de polycarbonate est caractérisée en ce que la couche de polycarbonate comprend une composition de résine contenant 5-100 % en masse d'un polycarbonate ramifié et 0-95 % en masse d'un polycarbonate aromatique, en ce que l'épaisseur de feuille est 1-4 mm et en ce que la valeur de retard dans le plan (Re(nm)) de la feuille et de l'épaisseur de feuille (t(mm)) satisfait la condition (1) ou (2). (1) Lorsque l'épaisseur de feuille (t) est 1 mm ≤ t < 2,5 mm, Re ≤ 11,25 t + 2,5. (2) Lorsque l'épaisseur de feuille (t) est de 2,5 mm ≤ t ≤ 4 mm, Re ≤ 30,625.
PCT/JP2014/058110 2013-03-26 2014-03-24 Feuille de résine de polycarbonate WO2014157103A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2013-064972 2013-03-26
JP2013064972A JP2014188761A (ja) 2013-03-26 2013-03-26 ポリカーボネート樹脂シート

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WO2014157103A1 true WO2014157103A1 (fr) 2014-10-02

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6659378B2 (ja) * 2016-01-26 2020-03-04 マツダ株式会社 自動車用内外装部材

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09290427A (ja) * 1996-04-26 1997-11-11 Sekisui Chem Co Ltd 光学フィルムの製造方法
JP2006103169A (ja) * 2004-10-06 2006-04-20 Mitsubishi Gas Chem Co Inc 液晶ディスプレーカバー用ポリカーボネート樹脂積層体
JP2010105188A (ja) * 2008-10-28 2010-05-13 Idemitsu Unitech Co Ltd 熱可塑性樹脂シートの製造装置、製造方法及びそれにより得られた熱可塑性樹脂シート
JP2012132947A (ja) * 2010-12-17 2012-07-12 Sumika Styron Polycarbonate Ltd 液晶テレビ用前面板
WO2014027660A1 (fr) * 2012-08-14 2014-02-20 出光興産株式会社 Dispositif et procédé de production d'une feuille de résine thermoplastique et feuille de résine thermoplastique obtenue par lesdits dispositif et procédé

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09290427A (ja) * 1996-04-26 1997-11-11 Sekisui Chem Co Ltd 光学フィルムの製造方法
JP2006103169A (ja) * 2004-10-06 2006-04-20 Mitsubishi Gas Chem Co Inc 液晶ディスプレーカバー用ポリカーボネート樹脂積層体
JP2010105188A (ja) * 2008-10-28 2010-05-13 Idemitsu Unitech Co Ltd 熱可塑性樹脂シートの製造装置、製造方法及びそれにより得られた熱可塑性樹脂シート
JP2012132947A (ja) * 2010-12-17 2012-07-12 Sumika Styron Polycarbonate Ltd 液晶テレビ用前面板
WO2014027660A1 (fr) * 2012-08-14 2014-02-20 出光興産株式会社 Dispositif et procédé de production d'une feuille de résine thermoplastique et feuille de résine thermoplastique obtenue par lesdits dispositif et procédé

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JP2014188761A (ja) 2014-10-06

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