WO2006011521A1 - Feuille de mousse, et procédé et appareil pour sa fabrication - Google Patents

Feuille de mousse, et procédé et appareil pour sa fabrication Download PDF

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Publication number
WO2006011521A1
WO2006011521A1 PCT/JP2005/013750 JP2005013750W WO2006011521A1 WO 2006011521 A1 WO2006011521 A1 WO 2006011521A1 JP 2005013750 W JP2005013750 W JP 2005013750W WO 2006011521 A1 WO2006011521 A1 WO 2006011521A1
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WO
WIPO (PCT)
Prior art keywords
sheet
thermoplastic resin
foamed
gas
cylinder
Prior art date
Application number
PCT/JP2005/013750
Other languages
English (en)
Japanese (ja)
Inventor
Toshiya Nishibayashi
Original Assignee
Dueller Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dueller Corporation filed Critical Dueller Corporation
Priority to CN2005800258633A priority Critical patent/CN1993410B/zh
Publication of WO2006011521A1 publication Critical patent/WO2006011521A1/fr

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Classifications

    • 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
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/34—Auxiliary operations
    • B29C44/3442—Mixing, kneading or conveying the foamable material
    • B29C44/3446—Feeding the blowing agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/22—After-treatment of expandable particles; Forming foamed products
    • 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
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • 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
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
    • 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
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • B29C48/21—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/0079—Liquid crystals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/04—Condition, form or state of moulded material or of the material to be shaped cellular or porous
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/25—Solid
    • B29K2105/253—Preform
    • B29K2105/256—Sheets, plates, blanks or films
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0012—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular thermal properties
    • B29K2995/0015—Insulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0012—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular thermal properties
    • B29K2995/0016—Non-flammable or resistant to heat
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised by the use 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; Derivatives of such polymers
    • C08J2333/04—Characterised by the use 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; Derivatives of such polymers esters
    • C08J2333/06—Characterised by the use 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; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical

Definitions

  • the present invention relates to a foam sheet.
  • the present invention relates to a light reflector for a planar light source used in a backlight mechanism for a display device such as a liquid crystal, such as a light reflector, a separator material such as a battery, a packaging material, and a steel sheet laminate material.
  • Foam sheet that can be suitably used as a plate, its production method, apparatus suitable for use in its production, and use of this foam sheet
  • V V
  • a light reflection plate V
  • a display device
  • a cold cathode ray tube is used as an illumination light source, light is uniformly propagated and diffused from the edge of the light guide plate within the surface of the light guide plate, and further the light guide plate force
  • a reflector is provided under the light guide plate.
  • cold cathode ray tubes are provided in parallel at the lower part of the liquid crystal screen, and the cold cathode ray tubes are arranged in parallel on the reflector.
  • the reflection plate a flat plate or a cold cathode ray tube part formed into a semicircular concave shape is used.
  • the reflector serves to uniformly irradiate the entire screen of the liquid crystal display device.
  • the role is big. Reflectors that satisfy this role are required to have high reflection characteristics.
  • a film containing fine bubbles inside or a film added with a white pigment is used alone or with these films.
  • a laminate of metal and plastic plates has been used.
  • a biaxially stretched white polyester film having relatively small directivity in reflected light is often used.
  • the biaxially stretched white polyester film is formed by adding a filler to the resin and forming fine voids by stretching after forming the sheet.
  • liquid crystal display devices have been mainly used for notebook computers in the past. In recent years, however, their use has been expanded to various devices such as desktop computers, televisions, and mobile phone displays. Yes. In addition, there is a demand for brighter and clearer images. Improvements to achieve a high-brightness and high-definition liquid crystal screen are being promoted, and the required characteristics for the reflector are becoming more severe. For this reason, studies for improving the reflection characteristics of the stretched white polyester film have been intensively conducted (see Patent Documents 2 and 3).
  • the roll was held in a pressurized inert gas, the polyester resin sheet was impregnated with an inert gas, and then heated and foamed under normal pressure.
  • a polyester foam resin sheet (see Patent Document 4) is known (available from Furukawa Electric Co., Ltd. under the name MCPET (registered trademark): Emshipet). Since the polyester resin foam sheet obtained by this method uses the bubble generation mechanism when the pressure of the inert gas is released, impurities such as foaming due to stretching are removed. It does not contain or the size of bubbles is not completely aligned. As a result, the reflection characteristics can be improved as compared with the stretched white polyester film. In addition, since it is not a stretched film, it can be molded easily.
  • the above-mentioned polyester resin foam sheet compensates for the disadvantages of the stretched white polyester film.
  • the productivity is not good.
  • the surface becomes rough because bubbles are easily broken on the sheet surface.
  • a non-foamed layer is provided on the surface, there is also a drawback that the reflection property is adversely affected only by the method in which the non-foamed sheet is bonded after foaming the polyester resin sheet.
  • a methyl methacrylate polymer and a foaming agent are melt-kneaded with an extruder to obtain a cylindrical foam, and then stretched / cooled and taken into a cut sheet to obtain a foamed sheet.
  • a manufacturing method is known (see Patent Document 5).
  • a method of forming a laminated article by extruding a fine-cell polymer material in the form of a sheet is known (see Patent Document 6).
  • these methods cannot control the size of the bubbles, the size of the bubbles increases, and a sufficient improvement in reflection characteristics cannot be expected.
  • the laminate of the foamed sheet and the non-foamed sheet is assumed to be laminated by adhesion.
  • a boundary is formed at the lamination interface, so reflection, refraction, and light absorption at the interface occur, and the total reflection characteristics are likely to be adversely affected. It is done.
  • Patent Documents 7 to 9 there is known a method of obtaining a porous or foamable film or sheet by allowing a gas to act on the resin composition in an extruder.
  • the concentration of the inert gas in the polymer is kept low, the bubbles only grow larger and cannot be used for a light reflecting plate by fine foaming.
  • gas concentration on both sides of the sheet can vary due to the release of gas after sheeting, and there is a mixture of foaming parts and parts that do not foam much. Cause non-uniformity.
  • the method disclosed in Patent Document 9 has a disadvantage that the bubble size grows large during stretching.
  • Patent Document 1 Japanese Patent Laid-Open No. 63-62104
  • Patent Document 2 JP 2003-160682 A
  • Patent Document 3 Japanese Patent Laid-Open No. 2001-305313
  • Patent Document 4 Japanese Patent No. 2713556
  • Patent Document 5 Japanese Unexamined Patent Publication No. 2000-86795
  • Patent Document 6 Special Table 2001—510749
  • Patent Document 7 Japanese Patent Laid-Open No. 2002-338726
  • Patent Document 8 Japanese Unexamined Patent Publication No. 2000-119432
  • Patent Document 9 Japanese Patent No. 2902242
  • the present invention is an unstretched foam sheet comprising a thermoplastic resin, in which 80% or more of the bubbles contained in the sheet have a cell diameter in the range of 0.1 to 20 / ⁇ ⁇ . And a porosity force S20 to 80%.
  • a step of sheeting a molten polymer of thermoplastic resin in which gas is dissolved in a non-foamed state by exposing the sheet to a vacuum at a temperature of 50 to 200 ° C.
  • the present invention relates to a method for producing a foam sheet including a step of generating bubbles.
  • the present invention relates to a method for producing a foam sheet, characterized by coextruding a thermoplastic resin in which a gas is dissolved and a thermoplastic resin in which a gas is not dissolved.
  • the screw, the cylinder, and the temperature control of the cylinder An extruder having a knot mechanism, characterized in that a nozzle for introducing a gas supplied from a high-pressure gas supply unit provided outside the cylinder is provided on an inner surface of a part of the cylinder.
  • the present invention relates to an extrusion apparatus for producing foamed sheets.
  • a vacuum chamber apparatus having a chamber and a sealing mechanism capable of reducing the pressure inside the casting roll and Z or casting roll of the sheet forming machine, and the vacuum chamber apparatus
  • the present invention relates to a foam sheet manufacturing apparatus in which an accompanying vacuum generator is disposed.
  • FIG. 1 is a schematic explanatory view showing a sheet manufacturing apparatus according to an embodiment of the present invention.
  • FIG. 2 is a schematic explanatory view showing a longitudinal section of an extrusion apparatus nozzle portion in an embodiment of the present invention.
  • FIG. 3 is a schematic explanatory view showing a cross section of the extrusion device nozzle portion shown in FIG. 2 cut at position A.
  • a non-stretched cast sheet has fine bubbles in the range of 0.1 to 20 ⁇ m and has a bubble density of a certain level or more.
  • the porosity representing the phase occupancy is in the range of 20 to 80%, the foamed sheet to be used for the light reflecting plate or the like has a beautiful surface, easy processability, and good properties that are not found in the conventional foamed sheet. We found that it was possible to obtain a high productivity.
  • the foamed sheet of the present invention is an unstretched sheet, it can be easily molded according to the application to which the foamed sheet is applied.
  • non-stretched means that uniaxial or biaxial stretching is not performed for the purpose of causing the sheet to be oriented, and stretching that occurs with casting or sheeting is allowed.
  • the bubbles contained in the sheet since 80% or more of the bubbles contained in the sheet have a bubble diameter in the range of 0.1 to 20 / zm, good reflection characteristics can be obtained. 80% or more of the bubbles contained in the sheet preferably have a bubble diameter in the range of 0.4 ⁇ m to 8 ⁇ m. If the bubble diameter is too small, it will cause a light interference effect and so on, and sufficient reflection will not be obtained. On the other hand, if the bubble diameter is too large, it is necessary to increase the sheet thickness in order to have a certain number of interfaces. As a result, the mechanical strength of the sheet becomes weaker or thicker than the desired film thickness. In some cases, the conventional stretched sheet has a uniform bubble diameter, which reduces the reflectivity of light of a specific wavelength. In the foam sheet of the present invention, it is advantageous that the bubble diameter contained in the sheet shows a normal distribution in that good reflection characteristics can be obtained.
  • the foamed sheet according to the present invention has a porosity in the range of 20 to 80%, good reflection characteristics can be obtained.
  • the porosity corresponds to the density of bubbles contained in the foam sheet, and the gas phase of the sheet
  • the occupancy ratio is expressed, and can be determined from the density of the sheet and the resin used and the sheet volume.
  • the porosity of the sheet is preferably 50 to 70%. This is because the theoretical maximum porosity is about 70% in order to maintain the spherical shape of the bubble, and if it exceeds this, the bubble collapses and good reflection characteristics can be obtained. It is not possible. On the other hand, if the porosity is too low, the density of the bubbles will be too low, so that the desired reflection characteristics cannot be obtained.
  • the foam sheet When the foam sheet is used as a reflector used in a direct light type backlight unit, the foam sheet is generally subjected to a molding force at a molding temperature of 100 ° C or higher.
  • the foamed sheet according to the present invention has a tensile elongation at break of 100% or more measured in an atmosphere of 100 ° C., and 100
  • the tensile stress at 100 ° C. and 100% elongation is preferably 50 MPa or less.
  • the tensile stress is preferably 150% or more, and the tensile stress is preferably 0 to 30 MPa or less.
  • the main thermoplastic resin constituting the foamed sheet according to the present invention is preferably a resin having a high melt tension in order to promote fine foaming. Therefore, melt flow rate (according to ASTM D1238-98) force showing molten state fluidity 0.5 to 44 gZlO min.
  • Thermoplastic resin preferable to molten fluidity 1.4 to 30 gZlO More preferred is a thermoplastic resin in minutes.
  • the fluidity of thermoplastic resin can be determined according to the measurement conditions (temperature, load, etc.) for various polymers described in ASTM D 1238-98.
  • acrylic resin and Z or methacrylic resin are used as the main thermoplastic resin constituting the foamed sheet according to the present invention. Therefore, the transparency of the resin itself is high, and as a result, reflection at the bubble interface is also good. Furthermore, as a specific example of such acrylic resin or methacrylic resin, which is excellent in light resistance and can be obtained at a relatively low cost as raw material resin, for example, a homopolymer of acrylate ester or methacrylate ester or Copolymers of 50% by weight or more of acrylic acid ester or metatalic acid ester and one or more other vinyl monomers are listed.
  • 50% by weight or more of methacrylic acid ester Among them, 50% by weight or more of methacrylic acid ester, a copolymer with the above vinyl monomer is particularly preferred. More than 50% by weight of the methacrylic acid alkyl ester, 50% by weight or less of the acrylic acid alkyl ester, alkyl methacrylate ester and alkyl acrylate ester. Preferred is a copolymer with 49% by weight or less of at least one of the bulle monomers copolymerizable with at least one U.
  • the alkyl ester of acrylic acid contained in the copolymer is preferably 0.1% by weight to 40% by weight, more preferably 1% by weight to 15% by weight. Use the above acrylic resin or methacrylic resin alone or in a blend!
  • Examples of such an acrylate ester include methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, acrylic acid phenyl, benzyl acrylate, and 2-ethylhexyl acrylate. And 2-hydroxyethyl acrylate and the like, and methyl acrylate and ethyl acrylate are particularly preferable.
  • ester of methacrylate examples include methyl methacrylate, ethyl acetate, butyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, 2-ethylhexyl methacrylate, and methacrylic acid 2 —Hydroxyethyl and the like can be mentioned, and in particular, methyl methacrylate and ethyl acetate are preferable.
  • Examples of other copolymerizable butyl monomers include acrylic acid and methacrylic acid esters such as unsaturated acids such as acrylic acid and methacrylic acid, styrene, ⁇ -methylstyrene, talari-tolyl, Examples thereof include meta-tallow-tolyl, maleic anhydride, phenol maleimide, cyclohexyl maleimide and the like.
  • the weight average molecular weight (Mw) of the above-mentioned acrylic resin or methallyl resin is preferably 40,000 to 400,000, more preferably 60,000 to 300,000. Mw force
  • Mw force The mechanical strength of the foamed sheet may not be sufficient, and if the Mw is too large, the melt viscosity will increase and the extrusion performance may decrease.
  • the acrylic resin or methacrylic resin may include a rubbery polymer.
  • a rubber-like polymer By blending a rubber-like polymer with acrylic resin or methacrylic resin, the viscosity and toughness of resin can be improved, and a foam sheet with good impact resistance can be obtained.
  • the thermoplastic resin in the present invention contains a small amount, preferably in the range of 0 to 3% by weight, of a crystallization nucleating agent, a crystallization accelerator, and bubbles within a range that does not impair the reflective properties of the foam sheet.
  • additives such as inhibitors, pigments, dyes, lubricants, and optical brighteners are blended.
  • inorganic fine particles that function as a bubbling nucleating agent are preferably those that can form pores by themselves, such as calcium carbonate, magnesium carbonate, zinc carbonate, titanium oxide (anatase type, rutile). Type), zinc oxide, barium sulfate, zinc sulfide, basic tin carbonate, titanium mica, antimony oxide, magnesium oxide, calcium phosphate, silica, alumina, My strength, talc, kaolin and the like.
  • it is particularly preferable to use calcium carbonate and barium sulfate which have low absorption in the visible light range of 400 to 70 O nm. If there is absorption in the visible light range, there may be a problem that the brightness decreases.
  • Examples of the gas dissolved in the thermoplastic resin in the extruder in order to form bubbles in the sheet include carbon dioxide, nitrogen, butane, helium, and argon. Of these, carbon dioxide and nitrogen, which have low gas permeability and are inexpensive and can be handled safely, may be used alone or in combination.
  • the foamed sheet of the present invention has a beautiful surface and particularly suitable for a light reflecting plate, having a reflectance in the visible light range of 85% or more and a total light transmittance of 10% or less. It is preferable.
  • the foam sheet according to the present invention may have an embossed pattern transferred on at least one side.
  • embossing can be performed by a method in which a pattern is transferred to a thermoplastic resin sheet on a casting roll having a fine pattern formed on the surface, or by a plain casting roll.
  • the foamed sheet that has been formed into a sheet can be once wound on a roll and then transferred to a calender apparatus having a fine pattern on the surface to transfer the pattern onto the sheet.
  • the fine pattern include a satin pattern, a Hamamatsu pattern, a hemispherical pattern, a chevron pattern, a pyramid pattern, or a composite pattern thereof for efficient light reflection.
  • the thickness of the foamed sheet according to the present invention is preferably 20 to 500 ⁇ m, more preferably 35 to 350 m. If the thickness is too small, it becomes difficult to ensure the flatness of the sheet, and unevenness in brightness tends to occur when used as a light reflecting plate. On the other hand, if the thickness is too large, the moldability may deteriorate.
  • the foamed sheet according to the present invention may be a laminated sheet of two or more layers formed by arranging at least one layer according to the purpose of use.
  • the ratio of the sub-layer part Z main layer part is preferably 1Z200 to 1Z3, more preferably 1Z50 to 1Z4.
  • Sublayer part Z main layer part In the case of a three-layer laminated sheet of Z sublayer parts or a laminated sheet of three or more layers, the ratio is expressed by the total Z main layer part of both sublayer parts.
  • at least one non-foamed layer may be disposed on the laminated sheet.
  • the foamed sheet according to the present invention is preferably disposed in the laminated sheet as the main layer part.
  • the laminated sheet according to the present invention may be formed by coextrusion, extrusion lamination, thermal lamination, coating, vapor deposition or the like.
  • a laminated sheet by coextrusion is preferable.
  • Such a laminated sheet joins the polymer from the main extruder for the foam layer and the sub-extruder for the non-foam layer in the hold section installed before entering the mold section or die. Can be formed. Since this coextruded laminated sheet does not require an adhesive layer, it is advantageous for reflection characteristics and at the same time has good productivity.
  • the influence of the interface between the main layer and the sub-layer can be reduced, for example, there is no boundary between the foamed part and the non-foamed part. Therefore, it can be particularly advantageous when used as a light reflector.
  • this co-extrusion laminated sheet is composed of only a two-layer structure of a main layer (A layer) and a sub-layer (B layer) (B layer) (A layer) (B layer).
  • B layer) A layer) (B layer) (A layer) ' ⁇ ⁇ ⁇ (B layer) (A layer) (B layer) It is also possible to have such a multilayer structure, which is very effective in that the bubble formation state in the thickness direction can be easily controlled.
  • a high-pressure gas supply unit provided on the inner surface of a part of the cylinder, outside the cylinder, the screw, the cylinder, and the extruder provided with the temperature control mechanism of the cylinder.
  • the present invention relates to an extrusion apparatus for producing foamed sheets, which is provided with a nozzle for introducing a gas supplied from the above.
  • Such an extrusion apparatus is suitable for producing the foamed sheet or the laminated sheet according to the present invention.
  • the high pressure is preferably a pressure that exceeds the critical point.
  • the critical point is a temperature of 31.1 ° C and a pressure of 7.52 MPa. It is. Therefore, the high-pressure gas supply unit is preferably a device capable of supplying various gases in a state exceeding their critical points.
  • the extrusion apparatus that can be used in the present invention includes a single-screw extruder, a twin-screw extruder, a tandem extruder that connects single-screw extruders, and a tandem extruder that combines a twin-screw extruder and a single-screw extruder. Either is acceptable.
  • the cylinder part of the extruder is equipped with a temperature control device including a heater for heating, an air cooling device for cooling, a water cooling device or an oil cooling device, which can be controlled by dividing into 5 to 10 blocks. Preferably there is.
  • the cylinder is preferably blocked in the same section as the temperature control section. Screws are usually divided into a zone that feeds mainly the raw resin, a zone that melts and compresses the resin, and a compression and kneading zone. The dimensions of the screw are optimally designed according to the grease used.
  • a nozzle for dissolving a gas in the resin melted in the extruder is installed, and preferably disposed in a melt compression zone of a screw dimension. Specifically, the nozzle is installed on the inner surface of one block portion of the cylinder located in the melt compression zone to introduce gas supplied from a high-pressure gas supply unit provided outside.
  • the shape of the nozzle is preferably a structure with fine holes on the inner surface of one block part of the cylinder, for example, a pore diameter of 30 / zm or less and a porosity of 25% or less.
  • Such ring-shaped metals sinter metal powder or metal fiber U, preferred to be composed of letting material.
  • a vacuum chamber apparatus having a chamber and a sealing mechanism capable of reducing the inside after the casting roll and Z or casting roll of the sheet forming machine, and the vacuum chamber
  • the present invention relates to a foam sheet manufacturing apparatus in which a vacuum generator attached to one apparatus is arranged.
  • a powerful manufacturing apparatus is suitable for manufacturing the foamed sheet or laminated sheet according to the present invention.
  • such a vacuum chamber apparatus is preferably capable of depressurizing the interior of the depressurizable chamber to 30 KPa or less.
  • the sheet forming machine usable in the present invention is usually an extruder for melting the resin, a flat die for forming a sheet, a cast roll for cooling the sheet, a sheet take-up device, a sheet It consists of a take-off device.
  • Flat dies include multi-hold types that are stacked inside the die, which is preferred by T dies, and those that have a feed block device that is stacked just before the die.
  • Cast rolls usually have a temperature control function, and the temperature control method may be a combination of circulating cooling water, hot water, or oil, or an induction heating method.
  • the sheet take-up device may have a roll temperature control function following the cast roll, and may also be provided with a thickness measurement device, defect detection device, antistatic device, surface treatment device such as corona treatment and frame treatment. Is possible.
  • the wrinkle removing device can also include a turret mechanism, a touch roll mechanism, a rewinding mechanism, a tension control device, and the like.
  • the chamber apparatus that can be used in the present invention has a box-like shape having a section along the curvature of the roll above the roll in the take-up device following the cast roll or cast roll and having a width matching the sheet.
  • the air inside the chamber can be exhausted and depressurized by a vacuum pump provided outside.
  • the chamber box has a sealing mechanism for holding the vacuum and is composed of multiple rooms as necessary.
  • the seal mechanism attached to the chamber apparatus usable in the present invention includes an inlet seal on the inlet side, an outlet seal on the outlet, and side seals arranged on both sides with respect to the flow direction of the sheet.
  • inlet seal and outlet seal Labyrinth seal type, contact roller type seal type, etc. can be adopted.
  • side seal a labyrinth seal type, a contact guide type, or the like can be adopted.
  • the method for producing a foam sheet according to the present invention is preferred and / or the power to explain specific examples below.
  • the present invention is not limited to these specific examples.
  • thermoplastic resin chip that is a heated and Z or dried raw material is pre-heated into a foam-extrudable main extruder (A) and a sub-extruder that does not perform foaming ( Supply to B).
  • the main extruder (A) is supplied with gas, preferably under supercritical conditions, by a gas supply device placed outside the machine. Inside the main extruder (A), the melted thermoplastic resin and gas are sufficiently mixed, and the gas is dissolved in the thermoplastic resin and extruded.
  • Main extruder (A) The polymer (a) from which force is also extruded and the polymer (b) extruded from the sub-extruder (B) are fed into the feed block (b) (a) (b) 3 After merging to form a layer, it is supplied to a T-die and discharged into a sheet. At this time, the polymer (a) adjusts the gas supply amount so that the gas is dissolved and the gas bubbles are generated, but the foam is in a non-foamed sheet state.
  • the sheet discharged from the T-die is landed on a casting roll and cooled. At this time, the sheet is usually a transparent uniform sheet. After cooling to a predetermined temperature on the casting roll, the sheet is introduced into the take-up roll following the casting roll. Next, the sheet is exposed to a vacuum state by a vacuum chamber provided on the take-up roll. Then, a sheet
  • the foamed sheet or laminated sheet according to the present invention can be produced by a method including a step of foaming by extruding a thermoplastic resin in which a gas is dissolved.
  • a non-foamed or foamed sheet that is foamed without using a vacuum chamber device may be passed through the vacuum chamber device!
  • the present invention provides a process in which a molten polymer of thermoplastic resin dissolved in gas is sheeted in a non-foamed state, and bubbles are generated by exposing the sheet to a vacuum at a temperature of 50 to 200 ° C.
  • the present invention relates to a method for producing a foam sheet including a process. Such manufacturing method The method is suitable for the production of the foamed sheet or laminated sheet according to the present invention, and the above steps are preferably continuous.
  • the temperature condition is preferably 70 to 120 ° C.
  • sheeting in a non-foamed state means that gas is dissolved in the molten resin polymer, but sheeting is performed in a state where no foaming occurs when the molten resin is discharged at the die portion. This can be done by reducing the amount of gas to be dissolved and controlling the Z or discharge conditions. Since the non-foamed sheet has a gas dissolved in the polymer, it can be easily foamed by applying a stimulus such as reduced pressure to the sheet.
  • the bubble generation state can be easily controlled by adjusting the conditions such as the temperature of the sheet and the pressure reduction, so that the bubble size and the number of bubbles can be easily optimized. Better ,.
  • the foam sheet can be produced by co-extrusion of a thermoplastic resin in which a gas is dissolved and a thermoplastic resin in which a gas is not dissolved.
  • a production method is suitable for producing the foamed sheet or laminated sheet according to the present invention.
  • the foamed sheet of the present invention can be obtained by using a sheeting device and a vacuum chamber device following gas supply extrusion. Therefore, it is possible to produce a sheet excellent in reflection characteristics, workability, and surface smoothness in-line with high productivity.
  • the foamed sheet or laminated sheet according to the present invention can be suitably used as a light reflecting plate.
  • a light reflecting plate may be obtained by molding the foamed sheet or the laminated sheet.
  • the molding process in the present invention means that a molded body is obtained by performing vacuum molding, pressure molding, press molding, calendering or the like using a temperature-controlled mold.
  • the reflectivity is measured with a spectrophotometer U-3410 (manufactured by Hitachi, Ltd.), a ⁇ 60 integrating sphere 130-06-06 (manufactured by Hitachi, Ltd.) and a 10 ° C inclined spacer.
  • the reflectance in the visible light range (380 to 780 nm) was determined on both sides of the foamed sheet or laminated sheet, and the higher value was taken as the reflectance.
  • the porosity is the ratio of the volume of bubbles to the volume of the resin sheet, the sheet thickness and area, the volume of the sample was determined, the weight was measured, and the porosity was determined using the following formula.
  • 10 measurement points are provided at equal intervals in the width direction of the foamed sheet or laminated sheet, and the thickness of the measurement points is measured using a thickness gauge (teclock thickness gauge). After that, the average of the measured values at each point was taken as the thickness of the foam sheet
  • the total light transmittance was evaluated for foamed sheets and laminated sheets according to JIS K7105: 1981.
  • Tensile stress is measured when a sheet of 1 Omm width and 100 mm length is held at 100 ° C for 5 minutes using a Tensilon UCT-100 tensile tester manufactured by Orientec Co., Ltd. and then stretched at 300 mmZ. This is the average value of the stress values at the time of 100% elongation in the sheet longitudinal direction and transverse direction.
  • Optical acrylic resin (Sumitomo Chemical Co., Ltd. Sumipex MGSS) preheated at 120 ° C for 4 hours as a raw material, this is the first stage 35mm, LZD 34 single screw extruder, The second stage is a 50mm, LZD 28 single-screw extruder tandem extruder, and a high-pressure gas supply unit installed outside the extruder is 38 ° C, 15 MPa, which exceeds supercritical conditions. Then, carbon dioxide gas was supplied to the nozzle provided in the cylinder part of the melt compression part of the first stage extruder and dissolved and kneaded in the resin. At this time, the amount of carbon dioxide supplied was 0.38 kgZh with respect to the discharge amount of the extruder 14.7 kgZh. The extrusion temperature at this time was 240 ° C for the first stage and 200 ° C for the second stage.
  • This sheet was cut with a microtome without crushing the film cross section, and the cut cross section was observed with a scanning electron microscope S-2100A type (manufactured by Hitachi, Ltd.) at a magnification of 500 times. Had a bubble diameter in the range of 14 ⁇ m in the center and more than 80% of the bubbles in the range of 20 ⁇ m or less. The void ratio due to the bubbles was 76% by calculating the density force.
  • the reflectance of this sheet in the visible light range was measured to be 85% and the total light transmittance was 6%.
  • Example 2 Except that the discharge rate of the extruder was 14.3 kgZh and carbon dioxide gas was supplied at a rate of 0.03 kgZh, sheeting was performed in the same manner as in Example 1 to obtain a transparent smooth sheet. It was. When this sheet was heated to 90 ° C. and placed in a desiccator (vacuum vessel) and depressurized to 28 kPa, it foamed and became cloudy.
  • a desiccator vacuum vessel
  • the bubble diameter was 10 ⁇ m at the center and more than 85% of the bubbles were in the range of 20 ⁇ m or less. Had a diameter.
  • the porosity was 56%.
  • This sheet had a reflectance in the visible light range of 88% and a total light transmittance of 7%. The surface condition was somewhat rough, but the reflectivity was low It did not reach below.
  • the tensile breaking elongation at 100 ° C was 195%, and the tensile stress at 100 ° C and 100% elongation was 12.5 MPa.
  • a transparent sheet obtained by the same method as in Example 2 was placed in a desiccator while being heated to 50 ° C., and the pressure was reduced to 28 kPa.
  • the obtained foam sheet had a small bubble size, the bubble diameter was 7 m at the center, and 100% of the bubbles had a bubble diameter in the range of 20 ⁇ m or less.
  • the porosity was 32%.
  • This sheet had a reflectance in the visible light range of 89% and a total light transmittance of 10%.
  • the surface condition was a problem force.
  • the transparent sheet obtained in the same manner as in Example 2 was placed in a desiccator while being heated to 140 ° C., and the pressure was reduced to 28 kPa.
  • the resulting foam sheet increased in bubble size and variation.
  • the bubble diameter was 18 ⁇ m at the center and 80% of the bubbles had a bubble diameter in the range of 20 ⁇ m or less.
  • the porosity was 61%.
  • This sheet had a reflectance in the visible light range of 86% and a total light transmittance of 9%. There were traces of broken bubbles on the surface.
  • the obtained white laminated sheet (average thickness: 245 m) had a very smooth surface.
  • the bubble diameter was 8 m at the center and 90% of the bubbles had a bubble diameter in the range of 20 ⁇ m or less.
  • the porosity was 50%.
  • This sheet had a reflectance in the visible light range of 89% and a total light transmittance of 9%.
  • the tensile breaking elongation at 100 ° C was 163%, and the tensile stress at 100 ° C and 100% elongation was 13.3 MPa.
  • Sheeting was performed in the same manner as in Example 1 except that the amount of carbon dioxide gas was increased to 0.6 kg / h, and a white foam sheet was obtained. However, there were frequent bubbles immediately after the die and explosions occurred. In addition, a wavy phenomenon was observed on the sheet surface, and the porosity increased to 85%.
  • Example 2 When a sheet was formed in the same manner as in Example 1 except that the amount of carbon dioxide gas was reduced to 0.1 kgZh, a translucent sheet was obtained.
  • the bubble diameter was distributed in the range of 20-: LOO m, and large bubbles of 50 ⁇ m or more accounted for 50% or more.
  • Sheeting was performed in the same manner as in Example 1 except that the carbon dioxide gas was further reduced to 0.05 kgZh. As a result, a substantially transparent sheet was obtained. However, in some places, bubbles larger than 2 mm appeared irregularly.
  • Sheeting was performed in the same manner as in Example 1 except that carbon dioxide gas was not supplied, and a transparent sheet was obtained.
  • the sheet was depressurized with a desiccator in the same manner as in Example 2. However, the generation of bubbles was not observed.
  • Example 2 The transparent unfoamed sheet obtained in Example 2 was put into a desiccator while being heated to 40 ° C. and depressurized. Generation of bubbles was not observed.
  • Example 2 When the transparent unfoamed sheet obtained in Example 2 was put into a desiccator while being heated to 210 ° C. and depressurized, the surface foamed like a balloon in some places.
  • the transparent unfoamed sheet obtained in Example 2 was put in a desiccator while being heated to 90 ° C. in the same manner as in Example 2, and the pressure was reduced.
  • the obtained sheet had larger bubbles growing than the sheet obtained in Example 2, and the bubble diameter was 30 m at the center and the bubbles were 60% of the particles had a bubble diameter in the range of 20 ⁇ m or less.
  • This sheet had a reflectance in the visible light range of 75% and a total light transmittance of 6%.
  • the foamed sheet of the present invention can be applied to reflectors, packaging materials, steel sheet laminating materials, separator materials, etc. due to its whiteness, weather resistance, heat retention, insulation, fine bubble content, etc.
  • the scope of application is not limited to these.
  • the foam sheet of the present invention can be particularly suitably used as a light reflecting plate for a planar light source used in a backlight mechanism of a liquid crystal display device.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Optical Elements Other Than Lenses (AREA)
  • Liquid Crystal (AREA)
  • Laminated Bodies (AREA)
  • Molding Of Porous Articles (AREA)

Abstract

La présente invention concerne une feuille de mousse non étirée contenant une résine thermoplastique. Le diamètre d’au moins 80 % des bulles d'air contenues dans la feuille mesure de 0,1 à 20 µm et la porosité de la feuille de mousse est de 20 à 80 %. L’invention décrit en outre un procédé de fabrication d'une telle feuille de mousse et un appareil convenant pour la fabrication d’une telle feuille de mousse. La présente invention décrit également une plaque réfléchissant la lumière utilisant une telle feuille de mousse et un affichage.
PCT/JP2005/013750 2004-07-30 2005-07-27 Feuille de mousse, et procédé et appareil pour sa fabrication WO2006011521A1 (fr)

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WO2008136255A1 (fr) * 2007-04-26 2008-11-13 Nitto Denko Corporation Elément réfléchissant la lumière contenant une mousse en résine de polyoléfine, et procédé de production de celui-ci
WO2017216110A1 (fr) * 2016-06-16 2017-12-21 Tarkett Gdl Procédé de production d'un film de piézoélectret
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JP4782617B2 (ja) * 2006-06-08 2011-09-28 帝人デュポンフィルム株式会社 ポリエステル積層フィルムのロール
JP5211508B2 (ja) * 2007-02-28 2013-06-12 東レ株式会社 液晶反射用白色積層ポリエステルフイルム
JP4999073B2 (ja) * 2007-03-22 2012-08-15 古河電気工業株式会社 樹脂発泡構造体、光反射板および樹脂発泡構造体の製造方法
JP2009086430A (ja) * 2007-10-01 2009-04-23 Furukawa Electric Co Ltd:The 光反射用成型体
KR101079004B1 (ko) * 2007-12-31 2011-11-01 주식회사 삼양사 섬유 보강 고분자 스트립, 그 제조방법 및 이를 이용한지오그리드
JP5089436B2 (ja) * 2008-02-29 2012-12-05 古河電気工業株式会社 光反射シートおよびその製造方法
JP5259719B2 (ja) * 2008-08-04 2013-08-07 丸尾カルシウム株式会社 多孔質ポリオレフィン樹脂発泡シート及びその製造方法
US8779017B2 (en) 2008-11-14 2014-07-15 Mitsui Chemicals, Inc. Foam and production method of the same
JP5555525B2 (ja) * 2010-03-31 2014-07-23 積水化成品工業株式会社 樹脂発泡シートの製造方法及び反射シート
CN102085689A (zh) * 2010-11-26 2011-06-08 卢文成 无机发泡板的生产方法
JP2012189661A (ja) * 2011-03-09 2012-10-04 Mitsubishi Plastics Inc オレフィン系樹脂反射材
CN104114365B (zh) * 2012-06-18 2016-01-20 古河电气工业株式会社 发泡片
CN104165329B (zh) * 2014-08-13 2016-08-17 福建省锐驰电子科技有限公司 一种可吸塑反射片
KR102353732B1 (ko) * 2015-02-16 2022-01-21 삼성디스플레이 주식회사 보호 필름 및 이의 제조 방법
FR3080997B1 (fr) * 2018-05-14 2020-05-08 Compagnie Generale Des Etablissements Michelin Installation d'extrusion pour des profiles complexes en melanges elastomeriques
CN112300436B (zh) * 2019-07-24 2022-12-13 中国科学院宁波材料技术与工程研究所 聚合物发泡材料及其制备方法
KR102119789B1 (ko) * 2020-02-03 2020-06-05 김하무 차량 디스플레이용 확산판 제조방법
KR102458420B1 (ko) * 2022-01-10 2022-10-25 안종호 실리콘시트 성형 장치
CN117801353B (zh) * 2023-10-20 2024-07-05 广东瑞捷新材料股份有限公司 一种pei发泡扩散板及其制备方法

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US11292163B2 (en) 2012-03-30 2022-04-05 Mucell Extrusion, Llc Method of forming polymeric foam and related foam articles
WO2017216110A1 (fr) * 2016-06-16 2017-12-21 Tarkett Gdl Procédé de production d'un film de piézoélectret
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KR20070039106A (ko) 2007-04-11
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JP4093419B2 (ja) 2008-06-04
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KR100842524B1 (ko) 2008-07-01
TW200615317A (en) 2006-05-16
TWI347334B (en) 2011-08-21

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