WO2020100350A1 - Feuille de résine - Google Patents

Feuille de résine Download PDF

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Publication number
WO2020100350A1
WO2020100350A1 PCT/JP2019/029214 JP2019029214W WO2020100350A1 WO 2020100350 A1 WO2020100350 A1 WO 2020100350A1 JP 2019029214 W JP2019029214 W JP 2019029214W WO 2020100350 A1 WO2020100350 A1 WO 2020100350A1
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WO
WIPO (PCT)
Prior art keywords
resin sheet
inorganic filler
weight
resin
less
Prior art date
Application number
PCT/JP2019/029214
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English (en)
Japanese (ja)
Inventor
弘貴 大関
大貴 ▲高▼野
拓人 小齊
Original Assignee
積水化学工業株式会社
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
Priority claimed from JP2018243066A external-priority patent/JP2020079380A/ja
Application filed by 積水化学工業株式会社 filed Critical 積水化学工業株式会社
Priority to EP19883379.0A priority Critical patent/EP3882304B1/fr
Priority to US17/285,608 priority patent/US11970609B2/en
Priority to CN201980067691.8A priority patent/CN112867754B/zh
Publication of WO2020100350A1 publication Critical patent/WO2020100350A1/fr

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    • 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
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/10—Block- or graft-copolymers containing polysiloxane sequences

Definitions

  • the present invention relates to a resin sheet containing an aromatic polycarbonate resin.
  • thermoplastic resins such as polycarbonate resin have excellent durability, light weight, and moldability. Therefore, the thermoplastic resin is used in various fields such as the field of construction, the field of home appliances, and the field of transportation.
  • thermoplastic resins include interior materials for railway vehicles, aircraft, ships, and transportation equipment such as automobiles.
  • thermoplastic resin In the above applications, it is required that the molded product using a thermoplastic resin has excellent flame retardancy and impact resistance.
  • thermoplastic resins generally burn easily and are weak against impact, studies have been widely conducted to improve the flame retardancy and impact resistance of molded articles using the thermoplastic resin.
  • Patent Document 1 A) an aromatic polycarbonate and / or an aromatic polyester carbonate, B) a specific silicone / acrylate composite rubber, C) a specific talc, and D) a specific flameproofing agent.
  • Patent Document 2 discloses a composition containing A) an aromatic polycarbonate and / or a polyester carbonate, B) a reinforcing agent, C) a thermoplastic homopolymer and / or a copolymer, and D) a specific phosphorus compound. Is disclosed. Further, Patent Document 2 describes that a molded body can be manufactured by injection molding the above composition.
  • impact resistance may decrease when the flame retardancy of the molded product is increased. Further, in a conventional molded product containing a resin, the flame retardance may be lowered when the impact resistance of the molded product is increased.
  • the molded product obtained from the composition described in Patent Document 1 can increase flame retardancy and impact resistance to some extent, but is not sufficient, and further improvement in flame retardancy and impact resistance is required.
  • a molded body obtained by molding the composition described in Patent Document 1 by injection molding, blow molding, and thermoforming from a sheet or film formed in advance uneven distribution of talc (inorganic filler) occurs in the molded body. Easily, and as a result, flame retardancy and impact resistance are likely to decrease.
  • the molded product obtained from the composition described in Patent Document 2 does not contain an inorganic filler, it is difficult to sufficiently enhance both flame retardancy and impact resistance. Even when the composition described in Patent Document 2 is mixed with an inorganic filler, in a molded product obtained by molding the composition by injection molding or the like, uneven distribution of the inorganic filler in the molded product is likely to occur. As a result, flame retardancy and impact resistance are likely to decrease.
  • the object of the present invention is to provide a resin sheet having excellent flame retardancy and impact resistance.
  • an aromatic polycarbonate resin an inorganic filler, a phosphorus-containing compound, and a silicon-containing compound, and has a first surface on one side in the thickness direction, the first surface In the cross section of the resin sheet in the direction orthogonal to, when the area-divided area of the inorganic filler is calculated by the area-division method, the ratio of the standard deviation of the area-divided area to the average value of the area-divided area is 0.
  • a resin sheet having a size of 53 or less is provided.
  • the average of the orientation angle of the inorganic filler is 30 degrees or less.
  • the occupation area ratio of the inorganic filler per unit area is S1
  • the first surface and In the cross section of the resin sheet in the orthogonal direction when the occupation area ratio of the inorganic filler per unit area is S2, the ratio of S1 to S2 is 2.0 or more.
  • the average particle diameter of the inorganic filler is It is 1.5 ⁇ m or less.
  • the average aspect ratio of the inorganic filler is It is 2.2 or more and 5 or less.
  • the average maximum heat generation rate measured under the condition of the heater radiant heat of 50 kW / m 2 and the ignition is 140 kW / m 2 or less in accordance with ISO5660-1.
  • the inorganic filler is talc.
  • the content of the inorganic filler with respect to 100 parts by weight of the aromatic polycarbonate resin is 10 parts by weight or more and 40 parts by weight or less.
  • the phosphorus-containing compound is a phosphoric acid ester.
  • the content of the phosphorus-containing compound is 5 parts by weight or more and 25 parts by weight or less based on 100 parts by weight of the aromatic polycarbonate resin.
  • the silicon-containing compound is a core-shell particle including a core and a shell arranged on the surface of the core.
  • the content of the silicon-containing compound is 2 parts by weight or more and 20 parts by weight or less based on 100 parts by weight of the aromatic polycarbonate resin.
  • the resin sheet contains a fluorine-based resin, and the content of the fluorine-based resin is 0.5 parts by weight or more and 2 parts by weight or less based on 100 parts by weight of the aromatic polycarbonate resin.
  • the resin sheet is an extruded sheet molded product.
  • the resin sheet is an interior material for a transportation machine.
  • the resin sheet is an interior material for railway vehicles.
  • the resin sheet according to the present invention contains an aromatic polycarbonate resin, an inorganic filler, a phosphorus-containing compound, and a silicon-containing compound.
  • the resin sheet according to the present invention has the first surface on one side in the thickness direction.
  • the standard deviation of the area division area is calculated when the area division area of the inorganic filler is calculated by the area division method.
  • the ratio of the area division area to the average value is 0.53 or less. Since the resin sheet according to the present invention is provided with the above configuration, it is excellent in flame retardancy and impact resistance.
  • FIG. 1 is a perspective view schematically showing a resin sheet according to an embodiment of the present invention.
  • FIG. 2A is a cross-sectional view schematically showing the cross section of the resin sheet in the direction parallel to the first surface of the resin sheet.
  • FIG. 2B is a cross-sectional view schematically showing the cross section of the resin sheet in the direction orthogonal to the first surface.
  • FIG. 3 is a diagram for explaining the orientation angle ⁇ of the inorganic filler.
  • FIG. 4 is an electron micrograph of a cross section in a direction parallel to the first surface of the resin sheet produced in the example.
  • FIG. 5 is an electron micrograph of a cross section in a direction orthogonal to the first surface of the resin sheet produced in the example.
  • the resin sheet according to the present invention contains an aromatic polycarbonate resin, an inorganic filler, a phosphorus-containing compound, and a silicon-containing compound.
  • the resin sheet according to the present invention has the first surface on one side in the thickness direction.
  • the standard deviation of the area division area is calculated when the area division area of the inorganic filler is calculated by the area division method.
  • the ratio of the area division area to the average value is 0.53 or less.
  • the resin sheet according to the present invention is provided with the above configuration, it has excellent flame retardancy and impact resistance.
  • the resin sheet according to the present invention can improve both flame retardancy and impact resistance.
  • FIG. 1 is a perspective view schematically showing a resin sheet according to an embodiment of the present invention.
  • the inorganic filler and the like are not shown.
  • the resin sheet 1 shown in FIG. 1 has a first surface 1a on one side in the thickness direction.
  • the resin sheet 1 has the thickness direction and a direction orthogonal to the thickness direction.
  • the direction orthogonal to the thickness direction is, for example, the MD direction or the TD direction.
  • the MD direction is the flow direction of the resin sheet at the time of manufacturing the resin sheet
  • the TD direction is the direction orthogonal to the flow direction of the resin sheet.
  • the resin sheet 1 has a thickness direction, an MD direction, and a TD direction.
  • the lateral direction is the MD direction. It is preferable that the thickness direction, the MD direction, and the TD direction are orthogonal to each other.
  • the thickness direction is preferably a direction orthogonal to the first surface.
  • the direction orthogonal to the thickness direction is preferably a direction parallel to the first surface.
  • the cross section along the line X1-X1 in FIG. 1 corresponds to the cross section of the resin sheet in the direction parallel to the first surface of the resin sheet.
  • the cross section taken along line X2-X2 in FIG. 1 corresponds to the cross section of the resin sheet in the direction orthogonal to the first surface.
  • the cross section along the line X2-X2 in FIG. 1 corresponds to the cross section along the MD direction and the cross section along the thickness direction.
  • FIG. 2A is a cross-sectional view schematically showing a cross section of the resin sheet in a direction parallel to the first surface of the resin sheet.
  • FIG. 2B is a cross-sectional view schematically showing the cross section of the resin sheet in the direction orthogonal to the first surface.
  • FIG. 2 (a) shows a cross section 11A of the resin sheet in a direction parallel to the first surface of the resin sheet. In the cross section 11A, the inorganic filler 21A is observed.
  • FIG. 2B shows a cross section 11B of the resin sheet in a direction orthogonal to the first surface of the resin sheet.
  • the cross section 11B is a cross section along the MD direction of the resin sheet and a cross section along the thickness direction. In the cross section 11B, the inorganic filler 21B is observed.
  • the standard deviation of the area division area the area The ratio of the division area to the average value (standard deviation of area division area / average value of area division area) is 0.53 or less. If the above ratio (standard deviation of area-divided area / average value of area-divided area) exceeds 0.53, the distribution of the inorganic filler in the resin sheet tends to be uneven, and as a result, flame retardancy and impact resistance It may decrease.
  • the ratio of the standard deviation of the area division areas to the average value of the area division areas is preferably 0.52 or less, more preferably 0.51 or less, More preferably, it is 0.50 or less.
  • the ratio standard deviation of area-divided area / average value of area-divided area
  • the dispersed state of the inorganic filler in the resin sheet can be improved, and the flame retardancy and impact resistance can be improved. It can be further enhanced.
  • the occupation area ratio of the inorganic filler per unit area is S1 (%)
  • the occupied area ratio of the inorganic filler per unit area is S2 (%).
  • the ratio (S1 / S2) of S1 to S2 is preferably 2.0 or more, more preferably 2.1 or more, still more preferably 2.2 or more.
  • flame retardancy can be further enhanced. More specifically, when the ratio (S1 / S2) is equal to or more than the lower limit, the inorganic filler in the resin sheet can be oriented in a direction parallel to the first surface.
  • the cross section of the resin sheet in the direction parallel to the first surface is preferably the cross section at the central position in the thickness direction of the resin sheet.
  • the cross section of the resin sheet in the direction parallel to the first surface is preferably a cross section passing through the center of the resin sheet.
  • FIG. 3 is a diagram for explaining the orientation angle ⁇ of the inorganic filler.
  • FIG. 3 shows the inorganic filler 21B observed in the cross section of the resin sheet in the direction orthogonal to the first surface.
  • the inorganic filler 21B has one end 21Ba and the other end 21Bb in the cross section of the resin sheet in the direction orthogonal to the first surface, and the distance between the one end 21Ba and the other end 21Bb is in the direction orthogonal to the first surface. It is the major axis of the inorganic filler 21 in the cross section of the resin sheet.
  • FIG. 3 shows the inorganic filler 21B observed in the cross section of the resin sheet in the direction orthogonal to the first surface.
  • the inorganic filler 21B has one end 21Ba and the other end 21Bb in the cross section of the resin sheet in the direction orthogonal to the first surface, and the distance between the one end 21Ba and the other end 21Bb is in the direction orthogonal to the first
  • X is a direction orthogonal to the thickness direction of the resin sheet in the cross section of the resin sheet in the direction orthogonal to the first surface
  • Y is a cross section of the resin sheet in the direction orthogonal to the first surface.
  • It is the thickness direction of the resin sheet
  • L is the major axis direction of the inorganic filler in the cross section of the resin sheet in the direction orthogonal to the first surface, and the orientation direction.
  • the angle formed by the direction X orthogonal to the thickness direction of the resin sheet and the orientation direction L of the inorganic filler is the orientation angle ⁇ of the inorganic filler 21.
  • the direction X orthogonal to the thickness direction of the resin sheet is preferably the MD direction.
  • the orientation angle ⁇ means the smaller of the angles formed by the direction (preferably MD direction) orthogonal to the thickness direction of the resin sheet and the orientation direction of the inorganic filler. Therefore, the maximum value of the orientation angle ⁇ is 90 degrees.
  • the average value of the orientation angle ⁇ of the inorganic filler is preferably 10 degrees or more, more preferably Is 12 degrees or more, and more preferably 14 degrees or more.
  • the average value of the orientation angle ⁇ of the inorganic filler is preferably 32 degrees or less, more preferably Is 30 degrees or less, more preferably 28 degrees or less, even more preferably 25 degrees or less, and particularly preferably 22 degrees or less.
  • the gas barrier effect effectively acts on the generation of combustion gas even when the resin sheet burns, thereby burning. Since the speed can be effectively suppressed, the flame retardancy can be further enhanced. Further, when the average value of the orientation angle ⁇ of the inorganic filler is equal to or more than the above lower limit, it is possible to effectively suppress the variation in mechanical strength of the resin sheet.
  • the average particle diameter D of the inorganic filler is preferably 0.6 ⁇ m or more, more preferably 0. It is at least 0.7 ⁇ m, preferably at most 1.5 ⁇ m, more preferably at most 1.4 ⁇ m.
  • flame retardancy and impact resistance can be further enhanced.
  • the inorganic filler is present in the cross section along the MD direction. It is preferable that the average particle diameter D of 1 satisfies the above lower limit, and the average particle diameter D of the inorganic filler satisfies the above upper limit.
  • the average aspect ratio A of the inorganic filler is preferably 2 or more, more preferably 2.2. Or more, more preferably 2.4 or more, preferably 5 or less, more preferably 4.5 or less.
  • the average aspect ratio A of the inorganic filler is not less than the lower limit and not more than the upper limit, flame retardancy and impact resistance can be further enhanced.
  • the inorganic filler is present in the cross section along the MD direction. It is preferable that the average aspect ratio A of 1 satisfies the above lower limit, and the average aspect ratio A of the inorganic filler satisfies the above upper limit.
  • the cross section of the resin sheet in the direction orthogonal to the first surface is preferably a cross section passing through the center of the resin sheet.
  • D the average aspect ratio A of the inorganic filler is specifically measured as follows.
  • the resin sheet is cut to prepare a measurement sample A in which the cross section A of the resin sheet in the direction parallel to the first surface is exposed. Further, the resin sheet is cut to prepare a measurement sample B in which the cross section B of the resin sheet in the direction orthogonal to the first surface is exposed.
  • the resin sheet may be cut such that the cross section is exposed without cutting the resin sheet.
  • the exposed cross sections A and B may be surface-polished.
  • the cross section B of the resin sheet in the direction orthogonal to the first surface may be the cross section along the MD direction or the cross section along the TD direction.
  • the cross section B of the resin sheet in the direction orthogonal to the first surface is preferably a cross section along the MD direction.
  • the section A and the section B are photographed using an electron microscope (preferably a scanning electron microscope). It should be noted that the following (2) to (6) are calculated for an inorganic filler having a cross-sectional area (projected area) of the observed inorganic filler of more than 0.1 ⁇ m 2 when photographed with an electron microscope.
  • the area of the Voronoi region of the inorganic filler is calculated by performing Voronoi division using the centroid points of the inorganic filler as mother points.
  • the ratio (standard deviation of the area of the Voronoi region / average value of the area of the Voronoi region) of the obtained standard deviation of the area of the Voronoi region to the average value of the area of the Voronoi region is calculated.
  • the area of the Voronoi region is obtained for 100 or more arbitrarily selected inorganic fillers.
  • the occupation area ratio (%) of the inorganic filler per unit area of the cross section B is calculated, and the occupation area ratio is S2 (%). ..
  • the above S2 is the area ratio of the region where the above-mentioned inorganic filler exists in the area (cross-sectional area) 100% in the cross section B.
  • the S2 is calculated from 100 or more inorganic fillers.
  • the above S2 can be calculated, for example, by the following formula.
  • orientation angle ⁇ of inorganic filler From the electron micrograph of the cross section B, the orientation angle ⁇ is calculated for each inorganic filler using commercially available image analysis software. An average value of orientation angles ⁇ of 100 or more arbitrarily selected inorganic fillers is obtained. The orientation angle ⁇ of the inorganic filler is preferably measured in the section B including the central position in the thickness direction of the resin sheet.
  • the average particle diameter D of the inorganic filler means the average equivalent circle diameter.
  • the equivalent circle diameter means the diameter of a circle having the same area as the projected area of the inorganic filler.
  • the particle size (equivalent circle diameter) of the inorganic filler from the electron micrograph of section B above.
  • the average value of the circle equivalent diameters of 100 or more arbitrarily selected inorganic fillers is determined and is defined as the average particle diameter D.
  • the resin sheet preferably has an average maximum heat generation rate of 140 kW / m 2 or less, and 135 kW / m 2 or less, measured under the conditions of heater radiant heat of 50 kW / m 2 and ignition. It is more preferable that the amount is 130 kW / m 2 or less.
  • the average maximum heat generation rate is equal to or lower than the upper limit, flame retardancy can be further enhanced. In order to further improve flame retardancy, the lower the average maximum heat generation rate, the better.
  • the average maximum heat release rate is measured as follows.
  • the resin sheet is cut or the like to obtain a sample for measuring the heat generation rate having a length of 100 mm ⁇ width of 100 mm ⁇ thickness of 3 mm.
  • the heat generation rate is measured in accordance with ISO5660-1 by using a corn calorimeter tester under the conditions of heater radiant heat of 50 kW / m 2 and ignition.
  • a material for the resin sheet may be used to prepare a heat generation measurement sample having a thickness of 3 mm.
  • the average maximum heat release rate is a value calculated according to EN45545-2 using the heat release rate measured according to ISO5660-1.
  • N means the number of measurement plots every 2 seconds. It is preferable that n is an integer of 3 or more.
  • the average heat release rate is calculated for each of multiple heat release rate measurement samples, and the maximum value of the obtained average heat release rates is taken as the average maximum heat release rate.
  • the average maximum heat generation rate is preferably a value calculated using three or more heat generation rate measurement samples.
  • JIS K7110 Izod impact strength is measured according to 1999 is preferably at 20 kJ / m 2 or more, more preferably 22kJ / m 2 or more, 24kJ / m 2 or more Is more preferable.
  • the Izod impact strength is at least the above lower limit, the impact resistance can be further enhanced. The higher the Izod impact strength is, the better, in order to further improve the impact resistance.
  • the thickness of the resin sheet is preferably 1 mm or more, more preferably 2 mm or more, preferably 7 mm or less, more preferably 6 mm or less.
  • flame retardancy can be further improved.
  • the thickness of the resin sheet is not more than the upper limit, the impact resistance can be further improved.
  • thermoplastic resin layer the fiber reinforced resin layer, the gas barrier layer, the metal layer, and the adhesive are provided on the first surface or the second surface opposite to the first surface.
  • Other layers such as an agent layer may be laminated.
  • the resin sheet according to the present invention can be obtained by molding a resin composition containing an aromatic polycarbonate resin, an inorganic filler, a phosphorus-containing compound, and a silicon-containing compound into a sheet shape.
  • the resin sheet according to the present invention contains an aromatic polycarbonate resin.
  • the resin composition contains an aromatic polycarbonate resin.
  • the aromatic polycarbonate resins may be used alone or in combination of two or more.
  • the aromatic polycarbonate resin is preferably an aromatic polycarbonate resin having a structural unit represented by the following formula (1).
  • R1 and R2 each represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a group in which a substituent is bonded to an alkyl group having 1 to 20 carbon atoms, or an aryl group.
  • R3 and R4 each represent a hydrogen atom or an alkyl group.
  • R3 or R4 in the above formula (1) is an alkyl group
  • the carbon number of the alkyl group is preferably 1 or more, preferably 6 or less, more preferably 3 or less, still more preferably 2 or less.
  • Preferred alkyl groups include a methyl group, an ethyl group, a propyl group, a butyl group, a tert-butyl group, a pentyl group, and a heptyl group.
  • the compound for introducing the structural unit represented by the above formula (1) when obtaining the above aromatic polycarbonate resin is 2,2-bis ( 4-hydroxyphenyl) propane (bisphenol A), 2,2-bis (4-hydroxy-3-methylphenyl) propane (bisphenol C), or 1,1-bis (4-hydroxyphenyl) cyclohexane (bisphenol Z)
  • it is 2,2-bis (4-hydroxyphenyl) propane (bisphenol A).
  • the aromatic polycarbonate resin preferably has a structural unit derived from such a preferable compound.
  • aromatic polycarbonate resins having a structural unit derived from a bisphenol A type compound include “UPILON E series” manufactured by Mitsubishi Gas Chemical Company.
  • aromatic polycarbonate resins having a structural unit derived from a bisphenol Z type compound include "Panlite series” manufactured by Teijin Chemicals Co., Ltd. and "Upilon Z series” manufactured by Mitsubishi Gas Chemical Co., Inc.
  • the viscosity average molecular weight (Mv) of the above aromatic polycarbonate resin is preferably 10,000 or more, more preferably 15,000 or more, preferably 50,000 or less, more preferably 40,000 or less.
  • Mv The viscosity average molecular weight
  • the viscosity average molecular weight is not less than the lower limit and not more than the upper limit, flame retardancy and impact resistance can be further enhanced.
  • the aromatic polycarbonate resin may have a branched structure or may not have a branched structure.
  • the above aromatic polycarbonate resin can be produced by a conventionally known method.
  • Examples of the method for producing the above aromatic polycarbonate resin include a melt polymerization method and a phase interface method.
  • a method for producing an aromatic polycarbonate resin by the above-mentioned melt polymerization method there is a method of reacting a diphenol compound and a diphenyl carbonate compound in a molten state by utilizing a transesterification reaction.
  • a diphenol compound and a diphenyl carbonate compound are put into a reactor equipped with a stirrer and a distilling concentrator, and the reactor is heated to a predetermined temperature under a nitrogen gas atmosphere to melt. It can be in a state.
  • a branching agent, a chain terminator and the like may be used in the method for producing an aromatic polycarbonate resin by the melt polymerization method.
  • a diphenol compound As a method for producing an aromatic polycarbonate resin by the phase interface method, a diphenol compound, a carbonic acid halide or an aromatic dicarboxylic acid dihalide, a branching agent if necessary, and a chain terminator if necessary. And a method of reacting with.
  • a carbonic acid halide may be used, an aromatic dicarboxylic acid dihalide may be used, or a carbonic acid halide and an aromatic dicarboxylic acid dihalide may be used.
  • the above diphenol compound is not particularly limited.
  • a conventionally known diphenol compound can be used.
  • the said diphenol compound only 1 type may be used and 2 or more types may be used together.
  • the above diphenyl carbonate compound is not particularly limited.
  • a conventionally known diphenyl carbonate compound can be used. Only 1 type may be used for the said diphenyl carbonate compound and 2 or more types may be used together.
  • the above carbonic acid halide is not particularly limited.
  • a conventionally known carbonic acid halide can be used as the carbonic acid halide.
  • the carbonate halide may be used alone or in combination of two or more.
  • the above carbonic acid halide is preferably phosgene.
  • the aromatic dicarboxylic acid dihalide is not particularly limited.
  • As the aromatic dicarboxylic acid dihalide a conventionally known aromatic dicarboxylic acid dihalide can be used.
  • As for the said aromatic dicarboxylic acid dihalide only 1 type may be used and 2 or more types may be used together.
  • the aromatic dicarboxylic acid dihalide is preferably benzenedicarboxylic acid dihalide.
  • branching agent is not particularly limited.
  • a conventionally known branching agent can be used.
  • the said branching agent only 1 type may be used and 2 or more types may be used together.
  • the branching agent is preferably a trifunctional phenol compound or a tetrafunctional phenol compound, more preferably triphenol, tetraphenol, or a phenol compound having at least three functional groups with low reactivity. More preferably, 1,1,1-tris- (p-hydroxyphenyl) ethane.
  • An aromatic polycarbonate resin having a branched structure can be favorably obtained by using these preferable branching agents.
  • the above branching agent may be a phenol compound having an amine functional group.
  • the branching agent is a phenol compound having an amine functional group
  • the amine functional group acts as an active functional group
  • the aromatic polycarbonate resin is branched through an amide bond.
  • the above chain terminator is not particularly limited.
  • As the chain terminator a conventionally known chain terminator can be used.
  • the above chain terminators may be used alone or in combination of two or more.
  • the above chain terminator includes phenol; p-chlorophenol; p-tert-butylphenol; 2,4,6-tribromophenol; DE-A 2,842,005.
  • Long-chain alkylphenols such as 4- (1,3-tetramethylbutyl) -phenol and monoalkylphenols having 8 to 20 carbon atoms in the alkyl substituent; or 3,5-di-tert-butylphenol
  • p- Alkylphenols such as isooctylphenol, p-tert-octylphenol, p-dodecylphenol, 2- (3,5-dimethylheptyl) -phenol, and 4- (3,5-dimethylheptyl) -phenol are preferable.
  • the content of the chain terminator is preferably 0.5 mol or more and preferably 10 mol or less with respect to 100 mol of the diphenol compound.
  • the content of the aromatic polycarbonate resin in 100% by weight of the resin sheet is preferably 50% by weight or more, more preferably 55% by weight or more, preferably 85% by weight or less, more preferably 80% by weight or less.
  • the content of the aromatic polycarbonate resin is not less than the above lower limit and not more than the above upper limit, flame retardancy and impact resistance can be further enhanced.
  • the resin sheet according to the present invention contains an inorganic filler.
  • the resin composition contains an inorganic filler.
  • flame retardancy and impact resistance can be improved.
  • the resin sheet does not contain the inorganic filler it is difficult to improve both flame retardancy and impact resistance.
  • the said inorganic filler only 1 type may be used and 2 or more types may be used together.
  • inorganic filler talc, mica, montmorillonite, silica, diatomaceous earth, alumina, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, ferrites, calcium hydroxide, magnesium hydroxide, aluminum hydroxide.
  • the inorganic filler is preferably talc, mica, or montmorillonite, and more preferably talc.
  • the above talc may be compressed talc.
  • the resin composition can be easily processed.
  • the above-mentioned inorganic filler may be surface-treated such as silanization treatment, plasma treatment, ashing treatment and the like.
  • silanization treatment a surface-treated inorganic filler such as silanization treatment
  • the compatibility with the aromatic polycarbonate resin is further improved.
  • the particle diameter and shape of the inorganic filler are such that the average particle diameter D and the average aspect ratio A calculated when observing a specific cross section of the resin sheet can be set to the preferable ranges, respectively. It is preferably shaped.
  • the volume average particle diameter (D50) of the inorganic filler is preferably 1 ⁇ m or more, and more preferably from the viewpoint of setting the average particle diameter D to the preferable range, and from the viewpoint of further improving flame retardancy and impact resistance. It is preferably 1.5 ⁇ m or more, preferably 6 ⁇ m or less, and more preferably 5 ⁇ m or less.
  • the volume average particle diameter of the above inorganic filler is an average diameter measured on a volume basis, and is a value of a median diameter (D50) of 50%.
  • the volume average particle diameter (D50) can be measured by a laser diffraction / scattering method, an image analysis method, a Coulter method, a centrifugal sedimentation method, or the like.
  • the volume average particle diameter (D50) of the inorganic filler is preferably determined by measurement by a laser diffraction / scattering method.
  • the average aspect ratio of the inorganic filler is preferably 2.2 or more, and more preferably from the viewpoint of setting the average aspect ratio A to the preferable range and further improving the flame retardancy and impact resistance. It is 2.4 or more, preferably 5 or less, more preferably 4.5 or less.
  • the above aspect ratio is the ratio of the volume average particle diameter of the inorganic filler to the average thickness of the inorganic filler (volume average particle diameter of inorganic filler / thickness of inorganic filler).
  • the aspect ratio can be measured by a water surface particle film method or the like.
  • the average aspect ratio is the average aspect ratio of a plurality of inorganic fillers.
  • the content of the inorganic filler in 100% by weight of the resin sheet is preferably 8% by weight or more, more preferably 12% by weight or more, preferably 25% by weight or less, and more preferably 20% by weight or less.
  • the content of the inorganic filler is at least the above lower limit, flame retardancy can be further enhanced.
  • the content of the inorganic filler is not more than the above upper limit, the impact resistance can be further enhanced.
  • the content of the inorganic filler with respect to 100 parts by weight of the aromatic polycarbonate resin is preferably 10 parts by weight or more, more preferably 15 parts by weight or more, preferably 40 parts by weight or less, and more preferably 30 parts by weight or less.
  • the content of the inorganic filler is at least the above lower limit, flame retardancy can be further enhanced.
  • the content of the inorganic filler is not more than the above upper limit, the impact resistance can be further enhanced.
  • the resin sheet according to the present invention contains a phosphorus-containing compound.
  • the resin composition contains a phosphorus-containing compound.
  • the phosphorus-containing compound is preferably a phosphorus-based flame retardant.
  • flame retardancy can be enhanced. If the resin sheet does not contain the phosphorus-containing compound, the flame retardancy may be poor.
  • the said phosphorus containing compound only 1 type may be used and 2 or more types may be used together.
  • the phosphorus-containing compound may be a phosphorus-containing compound having a halogen atom, or may be a phosphorus-containing compound having no halogen atom, a phosphorus-containing compound having no halogen atom and a phosphorus-containing compound having a halogen atom. It may be a mixture with a compound.
  • the above-mentioned phosphorus-containing compound may be a compound containing a phosphorus atom, and may be a compound derived from resorcinol, hydroquinone, bisphenol A, diphenylphenol and the like.
  • Examples of the phosphorus-containing compound include a phosphoric acid monomer, a phosphoric acid oligomer, a phosphonate ester, an organophosphite, a phosphonate, a phosphonate amine, a phosphate, a phosphazene, and a phosphate ester.
  • the above phosphorus-containing compound is preferably a phosphoric acid ester.
  • the phosphate ester is a compound having a phosphate ester structure.
  • the phosphoric acid ester may be a phosphoric acid monoester, a phosphoric acid diester, or a phosphoric acid triester.
  • Examples of the phosphoric acid ester include tributyl phosphate, triphenyl phosphate, tricresyl phosphate, diphenyl cresyl phosphate, diphenyl octyl phosphate, diphenyl-2-ethyl cresyl phosphate, tri- (isopropylphenyl) phosphate, resorcinol crosslinked diphosphate, And bisphenol A crosslinked diphosphate and the like.
  • the phosphoric acid ester is preferably an oligomeric phosphoric acid ester derived from bisphenol A.
  • the content of the phosphorus-containing compound in 100% by weight of the resin sheet is preferably 2% by weight or more, more preferably 4% by weight or more, preferably 18% by weight or less, more preferably 15% by weight or less.
  • the content of the phosphorus-containing compound is at least the above lower limit, flame retardancy can be further enhanced.
  • the content of the phosphorus-containing compound is not more than the upper limit, the impact resistance can be further enhanced.
  • the content of the phosphorus-containing compound relative to 100 parts by weight of the aromatic polycarbonate resin is preferably 3 parts by weight or more, more preferably 5 parts by weight or more, further preferably 7 parts by weight or more, preferably 25 parts by weight or less, more preferably Is 20 parts by weight or less.
  • the content of the phosphorus-containing compound is at least the above lower limit, flame retardancy can be further enhanced.
  • the content of the phosphorus-containing compound is not more than the upper limit, the impact resistance can be further enhanced.
  • the resin sheet according to the present invention contains a silicon-containing compound.
  • the silicon-containing compound is preferably a silicone-based flame retardant.
  • flame retardancy can be enhanced.
  • flame retardancy may be poor.
  • the said silicon-containing compound only 1 type may be used and 2 or more types may be used together.
  • the above silicon-containing compound may be a compound containing a silicon atom.
  • the silicon-containing compound is preferably polyorganosiloxane.
  • the above polyorganosiloxane preferably has an aromatic skeleton.
  • the polyorganosiloxane having an aromatic skeleton include polydiphenylsiloxane, polymethylphenylsiloxane, polydimethyldiphenylsiloxane, and cyclic siloxane having a phenyl group.
  • the above polyorganosiloxane may have functional groups such as silanol groups, epoxy groups, silanol groups, epoxy groups, alkoxy groups, hydrosilyl groups, and vinyl groups.
  • functional groups such as silanol groups, epoxy groups, silanol groups, epoxy groups, alkoxy groups, hydrosilyl groups, and vinyl groups.
  • the content of the silanol group in 100% by weight of the polyorganosiloxane is preferably 1% by weight or more, more preferably 2% by weight or more, and further preferably 3% by weight. % Or more, particularly preferably 5% by weight or more.
  • the content of the silanol group in 100% by weight of the polyorganosiloxane is preferably 10% by weight or less, more preferably 9% by weight or less, and further preferably 8% by weight. % Or less, particularly preferably 7.5% by weight or less.
  • the content of the silanol group is equal to or higher than the lower limit and equal to or lower than the upper limit, flame retardancy can be further enhanced.
  • the content of the silanol group exceeds 10% by weight, the thermal stability and wet heat stability of the resin composition may decrease as compared with the case where the content is 10% by weight or less.
  • the content of the alkoxy group is preferably 10% by weight or less in 100% by weight of the polyorganosiloxane.
  • the flame retardancy can be further enhanced.
  • the content of the alkoxy group exceeds 10% by weight, the resin composition may gelate more easily than when the content is 10% by weight or less.
  • the molecular weight of the silicon-containing compound and the polyorganosiloxane is preferably 450 or more, more preferably 1000 or more, still more preferably 1500 or more, particularly preferably 1700 or more, preferably 300,000 or less, more preferably 100,000 or less, It is more preferably 20,000 or less, particularly preferably 15,000 or less.
  • the molecular weights of the silicon-containing compound and the polyorganosiloxane are not less than the lower limit, the heat resistance of the silicon-containing compound and the polyorganosiloxane can be increased.
  • the stability of the resin composition can be increased, and the silicon-containing compound and the polyorganosiloxane are dispersed in the resin sheet.
  • the flame retardancy can be improved.
  • the molecular weights of the silicon-containing compound and the polyorganosiloxane can be specified. , Means the molecular weight that can be calculated from the structural formula. Further, when the silicon-containing compound and the polyorganosiloxane are polymers, the molecular weights of the silicon-containing compound and the polyorganosiloxane are in terms of polystyrene measured by gel permeation chromatography (GPC). The weight average molecular weight is shown.
  • the silicon-containing compound may be silicon-containing particles.
  • the silicon-containing particles are particles containing silicon.
  • the silicon-containing compound is preferably core-shell particles having a core and a shell arranged on the surface of the core. That is, the resin sheet preferably includes core-shell particles including a core and a shell arranged on the surface of the core. It is also preferable that the silicon-containing compound is contained in the resin sheet as the core-shell particles.
  • the core-shell particle may have a silicon atom in the core, or may have a silicon atom in the shell.
  • the core-shell particles have a silicon atom in the core
  • the core-shell particles have a silicon atom in the shell
  • the core-shell particles The whole can be regarded as a silicon-containing compound.
  • the above-mentioned silicon-containing compound is a core-shell particle, not only flame retardancy can be enhanced, but also impact resistance can be enhanced.
  • the organic compound forming the core and the organic compound forming the shell are chemically bonded.
  • the chemical bond is preferably a graft bond.
  • core-shell particles examples include silicone-based core-shell type rubbery polymers such as silicone-acrylate-methylmethacrylate copolymer and silicone-acrylate-acrylonitrile-styrene copolymer.
  • the core-shell particles preferably have a core-shell rubber structure.
  • the volume average particle diameter (D50) of the core-shell particles is preferably 100 nm or more, more preferably 250 nm or more, preferably 800 nm or less. is there.
  • the core-shell particles having a volume average particle diameter (D50) of not less than the above lower limit and not more than the above upper limit can be produced by an emulsion polymerization method.
  • the volume average particle diameter of the core-shell particles is an average diameter measured on a volume basis, and is a value of a median diameter (D50) of 50%.
  • the volume average particle diameter (D50) can be measured by a laser diffraction / scattering method, an image analysis method, a Coulter method, a centrifugal sedimentation method, or the like.
  • the volume average particle diameter (D50) of the core-shell particles is preferably obtained by measurement by a laser diffraction / scattering method.
  • the content of the silicon-containing compound in 100% by weight of the resin sheet is preferably 1% by weight or more, more preferably 2% by weight or more, preferably 15% by weight or less, and more preferably 12% by weight or less.
  • the content of the silicon-containing compound is at least the above lower limit, flame retardancy can be further enhanced.
  • the content of the silicon-containing compound is at most the above upper limit, the impact resistance can be further enhanced.
  • the content of the core-shell particles in 100% by weight of the resin sheet is preferably 1% by weight or more, more preferably 2% by weight or more. , Preferably 15% by weight or less, more preferably 12% by weight or less.
  • flame retardancy can be further enhanced.
  • the content of the core-shell particles is less than or equal to the upper limit, the impact resistance can be further enhanced.
  • the content of the silicon-containing compound with respect to 100 parts by weight of the aromatic polycarbonate resin is preferably 2 parts by weight or more, more preferably 4 parts by weight or more, preferably 20 parts by weight or less, and more preferably 15 parts by weight or less.
  • the content of the silicon-containing compound is at least the above lower limit, flame retardancy can be further enhanced.
  • the content of the silicon-containing compound is at most the above upper limit, the impact resistance can be further enhanced.
  • the content of the core-shell particles relative to 100 parts by weight of the aromatic polycarbonate resin is preferably 2 parts by weight or more, more preferably 4 parts by weight.
  • the above is preferably 20 parts by weight or less, more preferably 15 parts by weight or less.
  • flame retardancy can be further enhanced.
  • the content of the core-shell particles is less than or equal to the upper limit, the impact resistance can be further enhanced.
  • the resin sheet according to the present invention preferably contains a fluororesin.
  • the resin composition preferably contains a fluororesin.
  • the flame retardancy can be further enhanced. Only one type of the above-mentioned fluororesin may be used, or two or more types may be used in combination.
  • Examples of the above-mentioned fluorine-based resin include homopolymers having a fluorinated alpha-olefin monomer as a structural unit and copolymers having a fluorinated alpha-olefin monomer as a structural unit.
  • the fluorinated alpha-olefin monomer is an alpha-olefin monomer containing a substituent having at least one fluorine atom.
  • fluorinated alpha-olefin monomer examples include tetrafluoroethylene (CF 2 ⁇ CF 2 ), CHF ⁇ CF 2 , vinylidene fluoride (CH 2 ⁇ CF 2 ), CH 2 ⁇ CHF, chlorotrifluoroethylene (CClF ⁇ CF).
  • CCl 2 CF 2
  • CClF CClF
  • CHF CCl 2
  • CH 2 CClF
  • CCl 2 CClF
  • CF 3 CF CHF
  • CF 3 CH CF 2
  • CF 3 CH CH 2
  • CF 3 CF CHF
  • CHF 2 CH CHF
  • CF 3 CH CH 2
  • fluorine-based resin examples include poly (tetrafluoroethylene) homopolymer (PTFE), poly (hexafluoroethylene), poly (tetrafluoroethylene-hexafluoroethylene), and poly (tetrafluoroethylene-ethylene-propylene). Can be mentioned.
  • the poly (tetrafluoroethylene) homopolymer (PTFE) may be fiber-forming or non-fiber-forming.
  • the content of the fluororesin in 100% by weight of the resin sheet is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, preferably 1.5% by weight or less, more preferably 1% by weight. % Or less.
  • the content of the fluororesin is at least the above lower limit, flame retardancy can be further enhanced.
  • the content of the fluororesin is not more than the above upper limit, the impact resistance can be further enhanced.
  • the content of the fluorine-based resin with respect to 100 parts by weight of the aromatic polycarbonate resin is preferably 0.3 parts by weight or more, more preferably 0.5 parts by weight or more, preferably 2 parts by weight or less, and more preferably 1.5 parts by weight. It is less than or equal to parts by weight.
  • the content of the fluororesin is at least the above lower limit, flame retardancy can be further enhanced.
  • the content of the fluororesin is not more than the above upper limit, the impact resistance can be further enhanced.
  • the resin sheet may contain other components as long as the object of the present invention is not impaired.
  • the above resin composition may contain other components as long as the object of the present invention is not impaired.
  • Other components include anti-drip agent, antioxidant, heat stabilizer, light stabilizer, UV absorber, colorant, plasticizer, lubricant, release agent, and reinforcing agent. Only 1 type may be used for each of the said other components, and 2 or more types may be used together.
  • the content of the other component is not particularly limited, but for example, the content of the other component with respect to 100 parts by weight of the aromatic polycarbonate resin is preferably 0.01.
  • the amount is at least parts by weight, more preferably at least 0.1 parts by weight, even more preferably at least 0.5 parts by weight, preferably at most 10 parts by weight, more preferably at most 5 parts by weight.
  • antioxidants examples include alkylated monophenols; alkylated polyphenols; alkylated reaction products of polyphenols such as tetrakis [methylene (3,5-di-tert-butyl-4-hydroxyhydrocinnamate)] methane with dienes.
  • the content of the antioxidant with respect to 100 parts by weight of the aromatic polycarbonate resin is preferably 0.01 part by weight or more, and preferably 0.1 part by weight or less.
  • the light stabilizer examples include benzotriazole such as 2- (2-hydroxy-5-methylphenyl) benzotriazole and 2- (2-hydroxy-5-tert-octylphenyl) -benzotriazole; and 2-hydroxy- 4-n-octoxybenzophenone and the like can be mentioned.
  • the content of the light stabilizer with respect to 100 parts by weight of the aromatic polycarbonate resin is preferably 0.01 part by weight or more, and preferably 5 parts by weight or less.
  • UV absorber examples include hydroxybenzophenone; hydroxybenzotriazole; hydroxybenzotriazine; cyanoacrylate; oxanilide; benzoxazinone; 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3 -Tetramethylbutyl) -phenol; 2-hydroxy-4-n-octyloxybenzophenone; 2- [4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl]- 5- (octyloxy) -phenol; 2,2 '-(1,4-phenylene) bis (4H-3,1-benzoxazin-4-one); 1,3-bis [(2-cyano-3, 3-diphenylacryloyl) oxy] -2,2-bis [[(2-cyano-3,3-diphenylacryloyl) oxy] methyl] propane; 2,2 ′-(1,4-phenylene) bis (4H-3 , 1-benz
  • the content of the UV absorber with respect to 100 parts by weight of the aromatic polycarbonate resin is preferably 0.01 part by weight or more, and preferably 5 parts by weight or less.
  • Examples of the colorant include titanium dioxide, carbon black, and organic dyes.
  • the plasticizer, the lubricant, or the release agent may be used alone or in combination of two or more. Many of the compounds used as plasticizers also have the properties of lubricants and template agents, and many of the compounds used as lubricants also have the properties of template agents and plasticizers. Many of these compounds also have the properties of plasticizers and lubricants.
  • plasticizer examples include phthalic acid esters such as dioctyl-4,5-epoxy-hexahydrophthalate; tris- (octoxycarbonylethyl) isocyanurate; tristearin; poly-alpha-olefin Epoxidized soybean oil; ester; fatty acid ester such as alkyl stearyl ester; stearate such as methyl stearate, stearyl stearate, pentaerythritol tetrastearate; polyethylene glycol polymer, polypropylene glycol polymer, poly (ethylene glycol-co-propylene) Glycols) copolymers such as hydrophilic and hydrophobic nonionic surfactants with methyl stearate; mixtures of methyl stearate with polyethylene-polypropylene glycol copolymers; and waxes such as beeswax, montan wax, paraffin wax, etc. Etc.
  • phthalic acid esters such as di
  • the content of each of the plasticizer, the lubricant, and the release agent is preferably 100 parts by weight of the aromatic polycarbonate resin. Is 0.1 part by weight or more, preferably 1 part by weight or less.
  • a fibrous reinforcing agent such as glass fiber may, for example, be mentioned.
  • the content of the reinforcing agent relative to 100 parts by weight of the aromatic polycarbonate resin is preferably 1 part by weight or more, more preferably 10 parts by weight or more, preferably 25 parts by weight or less, It is more preferably 20 parts by weight or less.
  • the relative amount of each component in the above other components has an important effect on the mechanical properties such as low smoke concentration property, low smoke toxicity, and ductility of the resin sheet. Even if a large amount of a certain component is added in order to improve a certain property of the resin sheet, other properties may be deteriorated.
  • the resin sheet according to the present invention is excellent in flame retardancy and impact resistance, and is therefore preferably an interior material for transportation equipment.
  • Examples of the transport aircraft include railcars, aircraft, ships, and automobiles.
  • the resin sheet according to the present invention is preferably an interior material for a railroad vehicle, preferably an interior material for an aircraft, an interior material for a ship, and preferably an interior material for an automobile.
  • the resin sheet according to the present invention is more preferably an extruded sheet molded product.
  • the resin sheet according to the present invention can be obtained by molding the resin composition into a sheet shape.
  • the method for producing the resin sheet preferably includes a step of molding the resin composition into a sheet by an extruder to obtain a resin sheet. In the step of obtaining the resin sheet, it is preferable that the ratio of the take-up speed in the take-up machine to the roll speed is 0.9 or more and 1.2 or less.
  • the method for producing the resin sheet preferably includes the following steps (a) to (c). By including the steps (a) to (c), the ratio (standard deviation of the area division area / average value of the area division area), the ratio (S1 / S2), and the average value of the orientation angle ⁇ of the inorganic filler. It is possible to favorably manufacture a resin sheet in which the average particle diameter D of the inorganic filler and the average aspect ratio A of the inorganic filler satisfy the above-described preferable ranges.
  • the ratio of the take-up speed to the roll speed (take-off speed / roll speed) in the take-up machine is 0.8 or more and 1.2.
  • the process of obtaining a resin sheet is as follows.
  • the respective contents of the aromatic polycarbonate resin, the inorganic filler, the phosphorus-containing compound and the silicon-containing compound are appropriately adjusted so as to satisfy the above-mentioned preferable range.
  • the cylinder temperature of the twin-screw extruder is preferably 260 ° C or higher, more preferably 270 ° C or higher, preferably 300 ° C or lower, and more preferably 290 ° C or lower.
  • the cylinder temperature of the twin-screw extruder is not less than the above lower limit and not more than the above upper limit, the dispersed state of the inorganic filler in the resin sheet can be improved, and flame retardancy and impact resistance can be further enhanced. ..
  • the mold temperature of the twin-screw extruder is preferably 240 ° C. or higher, more preferably 250 ° C. or higher, preferably 280 ° C. or lower, more preferably 270 ° C. or lower.
  • the mold temperature of the twin-screw extruder is not less than the above lower limit and not more than the above upper limit, the dispersed state of the inorganic filler in the resin sheet can be improved, and the flame retardancy and impact resistance can be further enhanced. it can.
  • the screw rotation speed of the twin-screw extruder is preferably 300 rpm or more, more preferably 350 rpm or more, preferably 500 rpm, more preferably 450 rpm or less.
  • the screw rotation speed of the twin-screw extruder is not less than the above lower limit and not more than the above upper limit, the dispersed state of the inorganic filler in the resin sheet can be improved, and flame retardancy and impact resistance can be further enhanced. it can.
  • step (b) it is preferable that the strand-shaped resin composition extruded in the step (a) is cooled in a water tank and then the strand-shaped resin composition is cut.
  • the average particle diameter of the pellet-shaped resin composition is preferably 0.6 mm or more, more preferably 0.7 mm or more, preferably 0.9 mm or less, more preferably 1.0 mm or less. ..
  • the cylinder temperature of the single-screw extruder is preferably 250 ° C. or higher, more preferably 260 ° C. or higher, preferably 290 ° C. or lower, more preferably 280 ° C. or lower.
  • the cylinder temperature of the single-screw extruder is equal to or higher than the lower limit and equal to or lower than the upper limit, the dispersed state of the inorganic filler in the resin sheet can be improved, and flame retardancy and impact resistance can be further enhanced. .
  • the mold temperature of the single screw extruder is preferably 270 ° C. or higher, more preferably 280 ° C. or higher, preferably 310 ° C. or lower, more preferably 300 ° C. or lower.
  • the mold temperature of the single-screw extruder is not less than the above lower limit and not more than the above upper limit, the dispersed state of the inorganic filler in the resin sheet can be improved, and flame retardancy and impact resistance can be further enhanced. it can.
  • step (c) it is preferable to make the thickness uniform by sandwiching the molten resin composition with three-stage rolls.
  • the ratio of the take-up speed to the roll speed in the take-up machine is preferably 0.9 or more, more preferably 1.00 or more, and further preferably Is 1.02 or more, particularly preferably 1.04 or more, preferably 1.07 or less, more preferably 1.10 or less.
  • the ratio (take-off speed / roll speed) is not less than the above lower limit and not more than the above upper limit, the dispersed state of the inorganic filler in the resin sheet can be improved, and flame retardancy and impact resistance are further enhanced. be able to.
  • Aromatic polycarbonate resin Aromatic polycarbonate resin (Aromatic polycarbonate resin having a structural unit derived from bisphenol A type compound, "Upilon E series” manufactured by Mitsubishi Gas Chemical Co., Inc., viscosity average molecular weight 20000)
  • Phosphorus-containing compound Phosphate ester 1 ("Fyrol Flex Sol DP” manufactured by ICL Japan)
  • Phosphate ester 2 PX-202 manufactured by Daihachi Chemical Industry Co., Ltd.
  • Example 1 The composition components shown in Table 1 below were compounded in the compounding amounts (parts by weight) shown in Table 1 below to obtain a resin sheet. Specifically, a resin sheet was obtained by the following method.
  • Step of obtaining a resin composition Using a twin-screw extruder (“TEX30a” manufactured by Japan Steel Works, Ltd.), the mixture blended in the blending amounts shown in Table 1 was used at a cylinder temperature of 280 ° C., a mold temperature of 260 ° C., and a pressure of 0.7 bar (vacuum). After melt kneading under the conditions of a screw diameter of 30 mm, a rotation speed of 400 rpm, and an extrusion rate of 15 kg / hour, melt extrusion was performed.
  • TEX30a manufactured by Japan Steel Works, Ltd.
  • Step of obtaining a pellet-shaped resin composition The resin composition obtained by melt extrusion was cooled with a water-cooling system, cut into pellets using a pelletizer, and then dried at about 120 ° C. for about 5 hours to obtain a pelletized resin composition.
  • Step of obtaining a resin sheet After melting the pelletized resin composition under the conditions of a cylinder temperature of 270 ° C., a mold temperature of 290 ° C., and an extrusion rate of 20 kg / hour using a single-screw extruder (“GT50” manufactured by Plastic Engineering Laboratory Co., Ltd.), It was formed into a sheet. Next, the ratio of the take-up speed to the roll speed (take-off speed / roll speed) in the take-up machine was set to 1.05, and the take-up was performed to obtain a resin sheet having a thickness of 3 mm.
  • GT50 single-screw extruder
  • Example 2 A resin sheet having a thickness of 3 mm was produced in the same manner as in Example 1 except that the composition of the resin composition (and the resin sheet) was set as shown in Tables 1 and 2 below.
  • Example 14 to 26 The composition of the resin composition (and the resin sheet) was set as shown in Tables 3 and 4 below, and (c) in the step of obtaining the resin sheet, the ratio of the take-up speed to the roll speed in the take-off machine (take-off) A resin sheet having a thickness of 3 mm was produced in the same manner as in Example 1 except that the speed / roll speed) was set to 1.00.
  • the obtained resin sheet has a first surface on one side in the thickness direction.
  • the resin sheet was cut to prepare a measurement sample A (5 mm in length ⁇ 5 mm in width ⁇ 3 mm in thickness) in which a cross section A of the resin sheet in a direction parallel to the first surface was exposed. Further, the resin sheet was cut to prepare a measurement sample B (5 mm in length ⁇ 5 mm in width ⁇ 3 mm in thickness) in which the cross section B of the resin sheet in the direction orthogonal to the first surface was exposed. In the measurement sample B, as the cross section B, the cross section of the resin sheet along the MD direction was exposed.
  • the cross section A is a cross section at the center position in the thickness direction of the resin sheet.
  • the surface of the exposed cross-sections A and B of the measurement samples A and B was polished using "Ultramicrotome-Leica-REICHART-NISSEI ULTRACUT S" manufactured by Leica Microsystems.
  • FIG. 4 is an electron micrograph of a cross section of the resin sheet manufactured in the example in a direction parallel to the first surface. Specifically, FIG. 4 is an electron micrograph (magnification: 2000 times) of the cross section A in the measurement sample A manufactured in Example 1. The occupied area ratio S1 obtained from the electron micrograph of FIG. 4 was 10.64%.
  • FIG. 5 is an electron micrograph of a cross section of the resin sheet manufactured in the example in a direction orthogonal to the first surface. Specifically, FIG. 5 is an electron micrograph (magnification: 2000 times) of the cross section B of the measurement sample B manufactured in Example 1.
  • the occupied area ratio S2 obtained from the electron micrograph of FIG. 5 was 4.63%. From the obtained S1 and S2, the ratio of S1 to S2 (S1 / S2) was calculated to be 2.30.
  • Ratio standard deviation of area division area / average value of area division area
  • the area division area of the inorganic filler was calculated by the area division method using image analysis software (“WinROOF2015” manufactured by Mitani Corporation). More specifically, performing the Voronoi division using each centroid of the inorganic filler as each generating point, calculating the area of the Voronoi region of the inorganic filler, and the standard deviation of the area of the obtained Voronoi region, the Voronoi region. The ratio of the area to the average value (standard deviation of the area of the Voronoi region / average value of the area of the Voronoi region) was calculated. The area of the Voronoi region was calculated for 100 or more arbitrarily selected inorganic fillers.
  • S1 (%) total projected area of inorganic filler / area of observation field of cross section A ⁇ 100
  • S2 (%) total projected area of inorganic filler / area of observation field of section B ⁇ 100
  • Average particle diameter D of inorganic filler From the electron micrograph of the cross section B, the particle size (equivalent circle diameter) of the inorganic filler was calculated using image analysis software (“WinROOF2015” manufactured by Mitani Corporation), and the average value of the calculated equivalent circle diameters was calculated. The average particle diameter D was obtained. The average particle diameter D was calculated from 100 or more inorganic fillers.
  • the obtained resin sheet was cut into a length of 100 mm x width of 100 mm x thickness of 3 mm to obtain a heat generation rate measurement sample.
  • the obtained sample for heat generation rate measurement was measured in accordance with ISO5660-1 by using a cone calorimeter tester under the conditions of heater radiant heat of 50 kW / m 2 , measurement time of 20 minutes, and ignition, to generate heat. The speed was measured.
  • n in the above equation of the average heat generation rate was set to 600.
  • the obtained resin sheet was cut into a length of 80 mm, a width of 10 mm, and a thickness of 3 mm, and a V notch of 2 mm was formed therein.
  • the Izod impact strength was measured according to JIS K7110: 1999.
  • the resin sheets obtained in Examples 1 to 26 were excellent in flame retardancy and impact resistance. It is considered that this is because the dispersed state of the inorganic filler in the resin sheet is good.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
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Abstract

La présente invention concerne une feuille de résine qui a une excellente capacité ignifuge et une excellente résistance aux chocs.　Une feuille de résine selon la présente invention contient une résine de polycarbonate aromatique, une charge inorganique, un composé contenant du phosphore et un composé contenant du silicium, tout en ayant une première surface sur un côté dans la direction de l'épaisseur. Par rapport à cette feuille de résine, si des zones de segmentation respectives de la charge inorganique sont calculées au moyen d'un procédé de segmentation dans une section transversale de cette feuille de résine dans une direction perpendiculaire à la première surface, le rapport de l'écart-type des zones de segmentation à la moyenne des zones de segmentation est inférieur ou égal à 0,53.
PCT/JP2019/029214 2018-11-12 2019-07-25 Feuille de résine WO2020100350A1 (fr)

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EP19883379.0A EP3882304B1 (fr) 2018-11-12 2019-07-25 Feuille de résine
US17/285,608 US11970609B2 (en) 2018-11-12 2019-07-25 Resin sheet
CN201980067691.8A CN112867754B (zh) 2018-11-12 2019-07-25 树脂片

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JP2018243066A JP2020079380A (ja) 2018-11-12 2018-12-26 樹脂シート

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