WO2017170793A1 - Closed-cell foam sheet, and display device - Google Patents

Closed-cell foam sheet, and display device Download PDF

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Publication number
WO2017170793A1
WO2017170793A1 PCT/JP2017/013108 JP2017013108W WO2017170793A1 WO 2017170793 A1 WO2017170793 A1 WO 2017170793A1 JP 2017013108 W JP2017013108 W JP 2017013108W WO 2017170793 A1 WO2017170793 A1 WO 2017170793A1
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WO
WIPO (PCT)
Prior art keywords
sheet
closed
recess
resin
foam sheet
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PCT/JP2017/013108
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French (fr)
Japanese (ja)
Inventor
秀明 矢野
彰人 土肥
麻美 松本
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積水化学工業株式会社
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Priority to JP2017520997A priority Critical patent/JP7020911B2/en
Publication of WO2017170793A1 publication Critical patent/WO2017170793A1/en

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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06Working-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 chemical blowing agent
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/36After-treatment
    • GPHYSICS
    • G09EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09FDISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements

Definitions

  • the present invention relates to a closed cell foam sheet and a display device.
  • the front plate composed of a glass plate, an acrylic plate or the like disposed on the front side of the display device, and the display panel are also reduced in thickness.
  • the front plate and the display panel are easily broken.
  • an impact absorbing sheet is disposed over the entire rear surface of the display panel or on the periphery in order to prevent damage and failure of the display device due to impact repeatedly applied in everyday life. It has been known.
  • the impact-absorbing sheet is required to have high flexibility in order to obtain impact-absorbing properties against repeated impacts, and foamed sheets are widely used.
  • foamed sheet for example, as described in Patent Document 1, a polyethylene-based crosslinked foamed sheet containing a large number of closed cells is known.
  • urethane foam sheets, rubber foam sheets, and the like are also used.
  • the present invention has been made in view of the above problems, and an object of the present invention is to provide a foam sheet having high impact absorption and a display device including the same.
  • this invention provides the following foam sheet and a display apparatus provided with the same.
  • a region having at least one concave portion having a depth of 1 to 99% with respect to the thickness which is any region in which the area of a region divided into 25 and a 1 cm ⁇ 1 cm square region is reduced.
  • a closed cell foam sheet having 9 or more.
  • a display device comprising the closed-cell foamed sheet according to [1] and a display panel.
  • a closed cell foam sheet having high shock absorption and a display device including the same are provided.
  • FIG. It is a conceptual diagram for demonstrating the area
  • FIG. It is a schematic diagram which shows the one aspect
  • the numerical values “above” and “below” related to the description of numerical ranges are numerical values that can be arbitrarily combined.
  • the numerical range indicated by using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively, The value and the maximum value may be arbitrarily combined.
  • the closed-cell foamed sheet of the present invention (hereinafter sometimes simply referred to as “foamed sheet”) is any region in which the area of a region divided into 25 and a square region of 1 cm ⁇ 1 cm is reduced, It has 9 or more regions having at least one recess having a depth of 1 to 99% of the thickness.
  • the 25% compressive strength is reduced to obtain high shock absorption, and excellent pooling resistance is also obtained.
  • the moderate softness relieves the stress generated during the operation of the display device, and a secondary excellent pooling resistance can be obtained.
  • pooling property means the bleeding of the liquid crystal by press.
  • the area divided into 25 is an area that is set by dividing the vertical direction and the horizontal direction of the closed cell foam sheet into 5 equal parts.
  • the closed cell foam sheet is a square having four angles of 90 °, such as a square or a rectangle
  • the vertical and horizontal sides are divided into five equal parts as shown in FIG.
  • These 25 areas are defined as 25 divided areas.
  • the sheet has a shape other than a square or a rectangle, for example, a parallelogram shown in FIG. 1-b, the vertical and horizontal sides of the circumscribed square or rectangle are divided into five equal parts and set.
  • the area is defined as a 25-divided area.
  • the circumscribed rectangle is set by dividing the vertical and horizontal sides into five equal parts as in 1-b of FIG. These 25 areas are defined as 25 divided areas.
  • a shape other than a square or a rectangle such as a parallelogram shown by 1-d in FIG. Although it exists (in the case of 1-d, two in the upper left and two in the lower right, a total of four), including these, the area is divided into 25 areas.
  • the sheet size when the sheet size is a square of 20 cm ⁇ 20 cm, when divided into 25 areas, one area becomes a square of 4 cm ⁇ 4 cm.
  • the square area since the area of a 1 cm ⁇ 1 cm square area (hereinafter sometimes simply referred to as “square area”) is smaller than the 25 divided area, the square area is defined as the area in the present invention.
  • the method for setting the square area is the same as the method for setting the 25-divided area except that the 25-divided area is divided into 1 cm by dividing the vertical and horizontal sides into five equal parts.
  • the area is selected from the 25 divided areas and the square area in which the area becomes smaller in consideration of the area where a human finger touches the touch panel when operating the touch panel. For example, even if there is at least one recess in a square area of 4 cm ⁇ 4 cm, the pooling resistance may not be reliably obtained unless there is a recess at or near the location where the finger touches. Therefore, according to the present invention, the area of the region is 1 cm 2 of 1 cm ⁇ 1 cm at the maximum, and the presence of a recess in the region can improve the pooling resistance obtained as a secondary.
  • the number of regions having recesses is preferably 10 or more, more preferably 12 or more, and still more preferably 14 or more.
  • the 25 divided region is larger than a 1 cm ⁇ 1 cm square area of 1 cm 2 , that is, the total area of the sheet is larger than 25 cm 2 , so that there are 25 or more square regions.
  • the ratio of the region having a recess having a depth of 1 to 99%, preferably 1 to 90% with respect to the thickness is preferably 40% or more, more preferably 50% or more, and 60%. The above is more preferable.
  • the ratio of the area having the recesses to the entire area is within the above range, the impact absorption and the pooling resistance are improved.
  • the recess has a depth of 1 to 99% with respect to the thickness of the foam sheet.
  • the depth of the recess is 1 to 99% with respect to the thickness of the sheet, the impact absorbability and the pooling resistance are improved.
  • the depth of the recess is preferably 5 to 95%, more preferably 10 to 90%, and still more preferably 20 to 80% with respect to the thickness of the sheet.
  • shape is not particularly limited, but is linear such as a straight line or a curve, circular, elliptical, and similar shapes. In general circles, squares, rectangles, parallelograms, trapezoids, and similar shapes, etc. A substantially polygonal shape such as a similar shape, or a combination of these can be selected as appropriate. Moreover, as a kind of shape, you may use independently and may use it in combination of multiple types.
  • a linear concave portion may exist alone, a linear concave portion and a circular concave portion may exist at the same time, or linear shapes having different shapes such as a linear concave portion and a curved concave portion. It may exist at the same time.
  • cross-sectional shape The shape of the concave sheet viewed from the cross section (hereinafter, sometimes simply referred to as “cross-sectional shape”) is not particularly limited, and is generally V-shaped, square, rectangular, trapezoidal, or the like, semicircular, semielliptical, etc. Any of the substantially semicircular shapes may be used.
  • the shape of the recess is due to the method of forming the recess.
  • a concave portion is formed by cutting with a cutter
  • the shape of the concave portion is linear, and the cross-sectional shape is V-shaped.
  • the shape of the concave portion is substantially square.
  • the shape of the concave portion is substantially circular and the cross-sectional shape is V-shaped.
  • the width of the concave portion is preferably 0.1 to 2 mm, more preferably 0.3 to 1.5 mm, and still more preferably 0.4 to 1 mm.
  • the width is within the above range, impact absorbability and pooling resistance are improved, and the recesses can be easily processed.
  • this linear recessed part exists over at least 2 area
  • the length of one side is preferably 0.1 to 4.5 mm, more preferably 0.2 to 3 mm, still more preferably 0.3 to 2 mm, and more preferably 0.5 to 1.5 mm. Particularly preferred. Further, the length of one side is preferably 2 to 90% as a ratio with respect to the length of one side of the entire sheet (the length of one side of the circumscribed rectangle when the sheet shape is not a square). A length of 60% is more preferred, and a length of 15-40% is even more preferred.
  • the shape of the concave portion is a line shape or a shape other than a substantially square shape, that is, a substantially circular shape, a substantially triangular shape, a substantially polygonal shape, or the like
  • the size is preferably inscribed in the substantially square shape.
  • the area ratio of the recesses on the entire surface of the sheet is preferably 1 to 90%.
  • the area ratio of the recess is more preferably 3 to 50%, and further preferably 5 to 30%.
  • the area ratio of the recess is more preferably 10 to 90%, further preferably 20 to 85%.
  • FIGS. 2 and 3 show an example of the embodiment of the foam sheet of the present invention.
  • the embodiment shown in FIGS. 2 and 3 is merely an example, and the foamed sheet of the present invention is not limited to the embodiment shown in FIGS.
  • Each mode shown in FIG. 2 has a 25-divided area and has various patterns of recesses.
  • the sheet 2-a has a plurality of straight concave portions. Of the 25 divided regions, there are no recesses in the five rightmost regions, but there are linear recesses in the other 20 regions. Even if it has a region where there is no recess, such as the sheet 2-a, if there are 9 or more regions having a recess, the presence of recesses in other regions Therefore, high impact absorption as a whole sheet and excellent pooling resistance can be obtained. Moreover, in one area
  • the sheet 2-b also has a plurality of linear recesses, and there are not only vertical but also vertical straight recesses and horizontal straight recesses as in 2-a. In the case of the 2-b sheet, it is shown that all the regions have recesses, and that one region may have a plurality of vertical and horizontal straight recesses.
  • the sheet 2-c has a plurality of curved concave portions, and there are no concave portions in a total of four areas, two in the upper left and two in the lower right, but the other 21 areas are curved concave It is the area which has.
  • the 2-d sheet has a plurality of rectangular recesses.
  • This sheet has a recess in the entire region, for example, there is one recess in the upper left region, two recesses in the lower region, and a recess in the right region. There are four places.
  • the sheet 2-e has a plurality of circular recesses. In this case, there are no recesses in the five regions of the bottom row, but the other 20 regions are regions having at least one circular recess. As shown in 2-e, the shape of the recess may be a shape cut off in the middle. Further, the arrangement of the recesses may be regular as in the 2-d sheet, or may be irregular as in the 2-e sheet.
  • the 2-f sheet also has a plurality of circular recesses. The number of recesses is smaller than that of 2-e sheet, and the number of regions having recesses is as small as 9. However, even in such an aspect, the structure of the present invention is provided, and high shock absorption and excellent pooling resistance are achieved. It can be a sheet having the properties.
  • the 2-g sheet has one rectangular recess in the sheet. This sheet has a recess in the entire region. As shown in the 2-g sheet, the entire surface of one region may be a recess, but from the viewpoint of improving shock absorption and pooling resistance, the number of regions where the entire surface is a recess is 12 or less. Preferably, 10 or less is more preferable, and 8 or less is still more preferable. Further, when the region is a square region, the number of the square regions is preferably 50% or less, more preferably 40% or less, and still more preferably 35% or less with respect to the total number of regions.
  • the 2-h sheet has a square opening in the sheet, and vertical and horizontal straight concave portions exist on the peripheral edge of the frame-shaped sheet.
  • This sheet has a plurality of recesses in 16 regions at the peripheral edge.
  • the foamed sheet of the present invention may have an opening.
  • the shape of the opening is not particularly limited, and examples include the shape exemplified as the shape of the recess, for example, a linear shape, a substantially circular shape, a substantially quadrangular shape, a substantially triangular shape, a substantially polygonal shape, and a combination thereof.
  • the opening may be provided at one place as shown by the 2-h sheet, or may be provided at a plurality of places.
  • the area ratio of the openings to the entire sheet surface is preferably 1 to 90%, more preferably 10 to 85%, and still more preferably 20 to 85%.
  • the area ratio of the opening is within the above range, the recess can be sufficiently formed, and the impact absorption and the pooling resistance are improved.
  • Each mode shown in FIG. 3 has a square area and has various patterns of recesses. Although only two examples are shown in FIG. 3, for example, a sheet having concave portions having the same pattern as the concave portions having various patterns shown in FIG. Can be.
  • the 3-a sheet has concave portions having the same pattern as that of the 2-a sheet. However, since the area is 1 cm 2 or more in the 25 divided areas, a square area is applied as the area.
  • This sheet has no recess in the left end, the right end, and the region of the sixth row from the left, but has a recess in the other regions.
  • the number of regions having recesses is 54, and the ratio of regions having recesses to the entire region (81) is 66.7%.
  • the 3-b sheet like the 3-a sheet, has a plurality of straight concave portions, and the regions having the concave portions are the second row from the top, the second row from the bottom, and the third row from the left.
  • the ratio of the region (35) having the recesses to the entire region (81) is 43.2%.
  • the foamed sheet of the present invention is a closed cell foamed sheet composed of closed cells.
  • the closed cell means that the closed cell rate is 70% or more. That is, the bubbles included in the foam sheet are generally closed cells. From the viewpoint of improving impact absorption and pooling resistance, the closed cell ratio is preferably 90 to 100%, more preferably 95 to 100%.
  • Open cell ratio F 1 (%) 100 ⁇ (W 2 ⁇ W 1 ) / V 2
  • Closed cell ratio F 2 (%) 100 ⁇ F 1
  • the repulsive force against the pressure is large, so that it is generally effective for the expression of pooling resistance.
  • the repulsive force is too large, the impact absorbability may decrease, and it can be said that the impact absorbability and the pooling resistance are contradictory.
  • the repulsive force indicated by 25% compressive strength or the like is reduced, and the repulsive force is small despite being a closed cell foam sheet.
  • the 25% compressive strength of the foamed sheet is preferably 40 to 200 kPa, more preferably 50 to 180 kPa, and still more preferably 60 to 170 kPa for the foamed sheet before the recess is provided.
  • the 25% compressive strength of the foamed sheet of the present invention after providing the recesses is preferably 3 to 90 kPa. Furthermore, 15 to 90 kPa is preferable, 20 to 80 kPa is more preferable, and 30 to 70 kPa is still more preferable. Further, the reduction rate of the 25% compressive strength before and after providing the recesses is preferably 15 to 80%, more preferably 30 to 75%, and still more preferably 50 to 70%.
  • the foamed sheet of the present invention is provided with the recesses, so that the compressive strength is reduced by 25% in spite of being closed cells, and the impact absorption and the pooling resistance are improved.
  • the 25% compressive strength is a value measured according to JIS K 6767.
  • the thickness of the foam sheet is preferably 0.03 to 0.6 mm, considering the thickness desired for use in a display device, the ease of obtaining shock absorption and pooling resistance, and the like, preferably 0.05 to 0 mm. 0.5 mm is more preferable, and 0.06 to 0.3 mm is even more preferable.
  • the density of foam sheet, shock absorption, in view of improving the resistance to pooling resistance preferably 60 ⁇ 600kg / m 3, preferably 60 ⁇ 400kg / m 3, more preferably 150 ⁇ 600kg / m 3, 180 ⁇ 480kg / M 3 is more preferable.
  • the average cell diameter of the bubbles in the foam sheet is preferably 25 to 300 ⁇ m, more preferably 30 to 300 ⁇ m, still more preferably 35 to 230 ⁇ m, and most preferably 50 to 180 ⁇ m in MD.
  • TD 30 to 330 ⁇ m is preferable, 50 to 300 ⁇ m is more preferable, and 60 to 250 ⁇ m is still more preferable.
  • ZD is preferably 10 to 80 ⁇ m, more preferably 15 to 75 ⁇ m, still more preferably 20 to 70 ⁇ m.
  • the foam sheet is obtained by crosslinking and foaming a resin sheet of a resin material described later.
  • the degree of crosslinking of the foamed sheet is usually about 5 to 60% by mass, preferably 10 to 40% by mass.
  • the raw material resin constituting the closed-cell foamed sheet of the present invention may be, for example, any of polyolefin resin, acrylic resin, silicone resin, urethane resin, rubber resin, and shock absorption and anti-pooling Considering the properties, it is preferable to use a polyolefin resin.
  • the polyolefin resin which is a preferable material in the present invention, will be described.
  • the polyolefin resin used to form the foamed sheet include a polyethylene resin, a polypropylene resin, or a mixture thereof.
  • polyethylene is a polyethylene resin from the viewpoint of improving impact absorption and pooling resistance. Based resins are preferred. More specifically, examples thereof include polyethylene resins, polypropylene resins, or mixtures thereof polymerized with a polymerization catalyst such as a Ziegler-Natta compound, a metallocene compound, and a chromium oxide compound. Among these, polymerization of a metallocene compound is included. A polyethylene resin polymerized with a catalyst is preferred.
  • the polyethylene resin may be an ethylene homopolymer, but by copolymerizing ethylene with a small amount (for example, 30% by mass or less of the total monomers, preferably 1 to 10% by mass) of ⁇ -olefin as necessary. Polyethylene resins obtained are preferred, and among them, linear low density polyethylene is preferred.
  • a polyethylene-based resin particularly a linear low density polyethylene, obtained by a polymerization catalyst of a metallocene compound, it becomes easy to obtain a foamed sheet having improved flexibility, mechanical strength, and pooling resistance. Moreover, as will be described later, it is easy to maintain high performance even if the foam sheet is thin.
  • ⁇ -olefin constituting the polyethylene resin examples include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, and 1-octene. . Of these, ⁇ -olefins having 4 to 10 carbon atoms are preferred.
  • the polyethylene resin an ethylene-vinyl acetate copolymer is also preferably used.
  • the ethylene-vinyl acetate copolymer is usually a copolymer containing 50% by mass or more of ethylene units.
  • the polyethylene resin, the ethylene-vinyl acetate copolymer, or a mixture thereof obtained by the polymerization catalyst of the metallocene compound is preferably contained in the foamed sheet in an amount of 50% by mass or more, more preferably 60% by mass. As described above, it is most preferably contained by 100% by mass.
  • polypropylene resin examples include a propylene homopolymer, a propylene- ⁇ -olefin copolymer containing 50% by mass or more of a propylene unit, and the like. These may be used alone or in combination of two or more.
  • Specific examples of the ⁇ -olefin constituting the propylene- ⁇ -olefin copolymer include ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1- Among these, ⁇ -olefins having 6 to 12 carbon atoms are preferable.
  • Suitable metallocene compounds include compounds such as bis (cyclopentadienyl) metal complexes having a structure in which a transition metal is sandwiched between ⁇ -electron unsaturated compounds. More specifically, tetravalent transition metals such as titanium, zirconium, nickel, palladium, hafnium, and platinum have one or more cyclopentadienyl rings or their analogs as ligands (ligands). The compound to be mentioned is mentioned. Such metallocene compounds have uniform active site properties and each active site has the same activity. A polymer synthesized using a metallocene compound has high uniformity such as molecular weight, molecular weight distribution, composition, and composition distribution.
  • Examples of the ligand include a cyclopentadienyl ring and an indenyl ring. These cyclic compounds may be substituted with a hydrocarbon group, a substituted hydrocarbon group or a hydrocarbon-substituted metalloid group.
  • Examples of the hydrocarbon group include a methyl group, an ethyl group, various propyl groups, various butyl groups, various amyl groups, various hexyl groups, 2-ethylhexyl groups, various heptyl groups, various octyl groups, various nonyl groups, and various decyl groups. , Various cetyl groups, phenyl groups and the like.
  • the “various” means various isomers including n-, sec-, tert-, and iso-. Moreover, what polymerized the cyclic compound as an oligomer may be used as a ligand. In addition to ⁇ -electron unsaturated compounds, monovalent anion ligands such as chlorine and bromine or divalent anion chelate ligands, hydrocarbons, alkoxides, arylamides, aryloxides, amides, arylamides, phosphides, aryls Phosphide or the like may be used.
  • monovalent anion ligands such as chlorine and bromine or divalent anion chelate ligands, hydrocarbons, alkoxides, arylamides, aryloxides, amides, arylamides, phosphides, aryls Phosphide or the like may be used.
  • metallocene compounds containing tetravalent transition metals and ligands include, for example, cyclopentadienyl titanium tris (dimethylamide), methylcyclopentadienyl titanium tris (dimethylamide), bis (cyclopentadienyl) titanium dichloride, dimethyl And silyltetramethylcyclopentadienyl-t-butylamidozirconium dichloride.
  • the metallocene compound exhibits an action as a catalyst in the polymerization of various olefins by combining with a specific cocatalyst (co-catalyst).
  • specific cocatalyst include methylaluminoxane (MAO) and boron compounds.
  • the proportion of the cocatalyst used with respect to the metallocene compound is preferably 100,000 to 1,000,000 mole times, more preferably 50 to 5,000 mole times.
  • the Ziegler-Natta compound is a triethylaluminum-titanium tetrachloride solid composite, which is obtained by reducing titanium tetrachloride with an organoaluminum compound and then treating with various electron donors and electron acceptors.
  • a method of combining a composition, an organoaluminum compound, and an aromatic carboxylic acid ester see JP-A 56-1000080, JP-A 56-120712, JP-A 58-104907), halogens Method of supported catalyst in which magnesium tetrachloride is brought into contact with magnesium tetrachloride and various electron donors (see JP-A-57-63310, JP-A-63-43915, JP-A-63-83116), etc. What was manufactured by is preferable.
  • the polyethylene resin preferably has a low density in order to increase the flexibility, mechanical strength, and recovery rate of the foam sheet.
  • the density of the polyethylene resin is preferably 0.920 g / cm 3 or less, more preferably 0.880 to 0.915 g / cm 3 , still more preferably 0.885 to 0.910 g / cm 3. It is. The density is measured according to ASTM D792.
  • polyolefin resin resin other than the above-mentioned polyolefin resin can also be used, and resin other than polyethylene resin and polypropylene resin may be used by further mixing with polyethylene resin and polypropylene resin.
  • the polyolefin resin may be mixed with various additives and other components described later, and the foamed sheet is obtained by crosslinking and foaming a polyolefin resin containing additives and other components. Is preferred.
  • other components contained in the foamed sheet include resins and rubbers other than polyolefin-based resins, and these are total and less in content than polyolefin-based resins, and are usually based on 100 parts by mass of polyolefin-based resin. It is about 50 parts by mass or less, preferably about 30 parts by mass or less.
  • the method for producing the foamed sheet of the present invention is not particularly limited, and examples thereof include a method including the following steps (1) to (5).
  • Step (1) Melting resin materials such as raw resin, additives such as pyrolytic foaming agent, and other additives added as necessary, at a temperature lower than the decomposition temperature of the pyrolytic foaming agent, Step of kneading and molding into a resin sheet by a known molding method
  • Step (2) Step of crosslinking the resin sheet obtained in step (1)
  • Step (5) Step of forming a recess in the foamed sheet obtained by stretching
  • the above steps (1) to (5) are: Although you may perform in order of this process, it does not necessarily need to perform in order of this process, for example, you may perform a process (3) after a process (4). Moreover, two processes may be performed simultaneously, for example, you may perform
  • a raw material resin, additives such as a pyrolytic foaming agent, and resin materials such as other additives are supplied to an extruder such as a single screw extruder or a twin screw extruder, etc.
  • the resin material is made into a sheet-like resin sheet by melting and kneading at a temperature lower than the decomposition temperature of the decomposable foaming agent and extruding by extrusion molding or the like.
  • examples of the additive other than the thermal decomposition type foaming agent include a decomposition temperature adjusting agent, a crosslinking aid, an antioxidant, a cell nucleating agent, a colorant, a flame retardant, an antistatic agent, a filler, and the like.
  • the raw material resin may be a polyolefin resin as described above, but may be a mixture of a polyolefin resin and a resin component other than the polyolefin resin, or may be a resin component other than the polyolefin resin.
  • thermally decomposable foaming agent for example, one having a decomposition temperature higher than the melting temperature of the raw material resin can be used.
  • an organic or inorganic chemical foaming agent having a decomposition temperature of 160 to 270 ° C. can be used.
  • organic foaming agent examples include azo compounds such as azodicarbonamide, metal salts of azodicarboxylic acid (such as barium azodicarboxylate) and azobisisobutyronitrile; nitroso compounds such as N, N′-dinitrosopentamethylenetetramine; And hydrazine derivatives such as hydrazodicarbonamide, 4,4′-oxybis (benzenesulfonylhydrazide) and toluenesulfonylhydrazide; and semicarbazide compounds such as toluenesulfonyl semicarbazide.
  • azo compounds such as azodicarbonamide, metal salts of azodicarboxylic acid (such as barium azodicarboxylate) and azobisisobutyronitrile
  • nitroso compounds such as N, N′-dinitrosopentamethylenetetramine
  • hydrazine derivatives such as hydrazodicarbonamide
  • the inorganic foaming agent examples include ammonium acid, sodium carbonate, ammonium hydrogen carbonate, sodium hydrogen carbonate, ammonium nitrite, sodium borohydride, anhydrous monosodium citrate, and the like.
  • azo compounds and nitroso compounds are preferable from the viewpoint of obtaining fine bubbles, and from the viewpoints of economy and safety, and azodicarbonamide, azobisisobutyronitrile, N, N′-dinitrosopentamethylene. Tetramine is more preferred, and azodicarbonamide is still more preferred.
  • These pyrolytic foaming agents can be used alone or in combination of two or more.
  • the amount of the pyrolytic foaming agent added is preferably 1 to 10 parts by weight, more preferably 1.5 to 5 parts by weight, and more preferably 1.5 to 3 parts by weight with respect to 100 parts by weight of the raw material resin (for example, polyolefin resin). Part is more preferred.
  • the decomposition temperature adjusting agent that can be used as another additive is blended to lower the decomposition temperature of the pyrolytic foaming agent, or to increase or adjust the decomposition rate.
  • Specific examples of the compound include zinc oxide, zinc stearate, urea and the like.
  • 0.01 to 5 parts by mass of the decomposition temperature regulator is blended with respect to 100 parts by mass of the raw material resin in order to adjust the surface state of the foam sheet.
  • crosslinking aid examples include polyfunctional monomers.
  • crosslinking aid examples include trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, trimellitic acid triallyl ester, 1,2,4-benzenetricarboxylic acid triallyl ester, triallyl isocyanurate, and the like.
  • Compounds having three functional groups in the molecule; two compounds in one molecule such as 1,6-hexanediol dimethacrylate, 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, divinylbenzene, etc.
  • the addition amount of the crosslinking aid is preferably 0.2 to 10 parts by mass, more preferably 0.3 to 5 parts by mass, and still more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the raw material resin.
  • the addition amount is 0.2 parts by mass or more, it is possible to stably obtain the desired degree of crosslinking of the foam sheet, and when it is 10 parts by mass or less, the degree of crosslinking of the foam sheet is easily controlled.
  • antioxidants examples include phenolic antioxidants such as 2,6-di-t-butyl-p-cresol.
  • step (2) the resin sheet obtained in step (1) is crosslinked.
  • Crosslinking in the step (2) is preferably performed by irradiating the resin sheet with ionizing radiation.
  • the ionizing radiation include ⁇ -rays, ⁇ -rays, ⁇ -rays, and electron beams, and electron beams are more preferable.
  • the amount of ionizing radiation applied to the resin sheet is preferably 1 to 10 Mrad, more preferably 1.5 to 8 Mrad.
  • the irradiation amount of ionizing radiation is preferably 0.3 to 8 Mrad, more preferably 0.5 to 5.5 Mrad.
  • the irradiation amount of ionizing radiation By setting the irradiation amount of ionizing radiation to the above lower limit value or more, it becomes easy to impart a shear viscosity necessary for foaming the resin sheet. Moreover, by setting it as the said upper limit or less, the shear viscosity of a resin sheet does not become high too much, but foamability becomes favorable. Therefore, it becomes easy to obtain the above-described density foam sheet, and the appearance of the foam sheet is also improved.
  • the degree of progress of crosslinking is usually influenced by the raw material resin, the type of additives, etc., the irradiation dose of ionizing radiation is usually adjusted while measuring the degree of crosslinking so that the degree of crosslinking described above is obtained. To.
  • step (3) the resin sheet is heated to a temperature equal to or higher than the decomposition temperature of the thermally decomposable foaming agent and foamed.
  • this process (3) is implemented after the said process (2).
  • the temperature at which foaming is carried out depends on the decomposition temperature of the pyrolytic foaming agent, but is usually from 140 to 300 ° C, preferably from 160 to 260 ° C.
  • the method for foaming the resin sheet is not particularly limited, and examples thereof include a method of heating with hot air, a method of heating with infrared rays, a method using a salt bath, a method using an oil bath, and the like. Good.
  • step (4) the resin sheet is stretched.
  • Stretching may be performed after foaming the resin sheet, or may be performed while foaming the resin sheet.
  • the stretching may be performed with a known apparatus such as a uniaxial stretching machine or a biaxial stretching machine.
  • stretching after making a resin sheet foam it is better to continue extending
  • crosslinking agents such as an organic peroxide
  • organic peroxides include 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, and the like.
  • the addition amount of the organic peroxide is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 3 parts by mass with respect to 100 parts by mass of the raw material resin.
  • the addition amount of the organic peroxide is within the above range, crosslinking of the resin material is likely to proceed, and the amount of decomposition residue of the organic peroxide in the foamed sheet is suppressed.
  • the resin material may be foamed by gas foaming typified by carbon dioxide gas or butane gas instead of using the foaming agent, or may be foamed by a mechanical floss method.
  • Step (5) is a step of forming a recess in the foamed sheet obtained by stretching.
  • the method of forming the recess is not particularly limited, and examples thereof include a method of forming a recess using an embossing roll, a method of forming a recess using a needle roll, and a method of forming a recess using a cutter. it can.
  • the foamed sheet of the present invention can be used as it is, but may be used by providing a pressure-sensitive adhesive layer on any one or both sides.
  • the thickness of the pressure-sensitive adhesive layer is preferably 5 to 200 ⁇ m, more preferably 7 to 150 ⁇ m.
  • an adhesive which comprises the adhesive layer provided in one side or both surfaces of a foam sheet For example, an acrylic adhesive, a urethane type adhesive, a rubber-type adhesive, etc. are mentioned.
  • a method of providing the pressure-sensitive adhesive layer on the foamed sheet for example, a method of applying the pressure-sensitive adhesive using a coating machine such as a coater on at least one surface of the foamed sheet, or using a spray on at least one surface of the foamed sheet Examples thereof include a method of spraying and applying an adhesive, and a method of applying an adhesive using a brush on one surface of a foam sheet.
  • the foamed sheet of the present invention can be used as an adhesive for bonding a front plate such as an acrylic plate or a glass plate, or a touch panel provided on the front plate and the main body of the display device.
  • the foam sheet can be used by providing an opening so as to have a frame shape, or cut into a desired shape, for example, a strip shape.
  • the foamed sheet of the present invention is used as an adhesive, since the foamed sheet is a closed cell body and the bubbles are not in communication, a gap generated between the frame and the front plate when stress is applied to the frame. It is also possible to suppress entry of dust, moisture, etc. from Moreover, the effect which suppresses the failure
  • the foam sheet of this invention can be used as an impact-absorbing material of display panels, such as a liquid crystal panel, for example.
  • the shock absorber of the display panel is disposed on the back side of the display panel, and absorbs the shock applied to the display panel to prevent the display panel from being damaged or broken. Since the foamed sheet of the present invention has a shock absorbing property and a pooling resistance, it is arranged as a shock absorbing material on the back side of the display panel, so that the occurrence of pooling caused by pressing the surface of the display panel is prevented. Can also be prevented. Note that terms such as a front plate, a touch panel, a display device, an adhesive, a frame, a display panel, and a shock absorber that constitute the display device will be described later.
  • the display device of the present invention includes the closed-cell foamed sheet of the present invention and a display panel, and the foamed sheet of the present invention is used for at least one of an impact absorbing material 13 and an adhesive 16 described later.
  • An example of the display device of the present invention will be described with reference to FIG. 4 includes a display panel 11, a front plate 12 provided on the front side of the display panel 11, an adhesive 16 for bonding the front plate 12 and the frame 15, and a back side of the display panel 11.
  • the shock absorbing material 13 and the like are provided.
  • the display panel 11 is a unit that is disposed on the shock absorber 13 and includes at least a display element such as a liquid crystal display element or an organic EL display element in which a liquid crystal layer is disposed between two glass substrates. However, in addition to the display element, a protective film, a polarizing element, a retardation film, or the like may be laminated.
  • the display panel 11 further includes a backlight unit provided on the back side of the display element when the display element is a liquid crystal display element.
  • the display panel 11 preferably includes a liquid crystal display element.
  • the front plate 12 includes a cover plate material for protecting the display panel 11 and the like.
  • plate material will not be specifically limited if it has a light transmittance, An acrylic board, a glass plate, etc. are mentioned.
  • the front plate 12 may further include a member other than the cover plate material.
  • a touch panel unit (not shown) is laminated on the lower surface side of the cover plate material. It may be.
  • the impact absorbing material 13 is provided to absorb the impact when the impact is applied to the display panel 11 and the front plate 12, and a foam sheet is usually used.
  • a foam sheet is usually used.
  • the closed cell foamed sheet of the present invention having high impact absorbability is preferably used.
  • the use of the foamed sheet as the shock absorbing material 13 can also prevent the occurrence of pooling caused by pressing the display panel 11 through the front plate 12. .
  • the front plate 12 is supported by the frame 15.
  • the frame 15 has a quadrangular frame shape and is provided with a fitting portion 15 ⁇ / b> A having a lower inner peripheral side height.
  • the front plate 12 is disposed so as to be fitted to the fitting portion 15A.
  • the front plate 12 is fixed to the frame 15 by being bonded to the fitting portion 15A by the adhesive 16 arranged in the fitting portion 15A.
  • the adhesive 16 a double-sided tape or the like in which a pressure-sensitive adhesive layer is provided on both surfaces of a base material is used.
  • the base material of the double-sided tape the foamed sheet of the present invention is suitably used.
  • the foamed sheet of the present invention is excellent in impact absorption, it is possible to reduce the impact on the front plate 12 and to prevent the front surface 12 from being damaged.
  • the foam sheet of the present invention is a closed-cell body, and bubbles are not communicated, when stress is applied to the frame during use, dust from a gap generated between the frame and the front plate, There is also an effect that it is possible to suppress intrusion of moisture and the like.
  • the display panel 11 is bonded to the back surface of the front plate 12 through the adhesive layer 17, and thereby is integrated with the front plate 12 and supported by the frame 15.
  • the adhesive layer 17 is composed of an adhesive layer having optical transparency called OCA (Optically Clear Adhesive) or an adhesive layer.
  • a plate 18 arranged with a certain distance from the display panel 11 is provided on the back side of the display panel 11.
  • the plate 18 is fixed to the frame 15.
  • a clearance may be provided between the shock absorber 13 disposed on the surface of the plate 18 and the display panel 11.
  • the display device of the present invention is suitably provided in a portable device such as a notebook personal computer, a mobile phone, a smartphone, or a tablet.
  • the display device of the present invention may be a touch panel type including a touch panel unit. Although the surface of the touch panel is repeatedly pressed at a high speed, when the foam sheet of the present invention is used as the shock absorber 13, the occurrence of pooling is suppressed, so that the display performance of the display device is improved.
  • the display device of the present invention has been described with reference to FIG. 4, the display device shown in FIG. 4 shows an example of the display device of the present invention, and various modifications can be made.
  • the display panel 11 and the front plate 12 may be supported by a member other than the frame 15, and the shock absorber 13 may be disposed on a member other than the plate 18.
  • the material used for each member is only an example, and materials made of materials usually used for these members can be used.
  • ⁇ Average bubble diameter> The foamed sheet is cut into a 50mm square, immersed in liquid nitrogen for 1 minute, then cut in the thickness direction along each of MD and TD, and a digital microscope (manufactured by Keyence Corporation, product name "VHX-900") is used. Take a 200x magnified photograph, measure the bubble diameter of MD, ZD, and the bubble diameter of TD, ZD and the bubble diameter of TD, ZD for all the bubbles present on the cut surface of 2 mm in length in each of MD and TD. Repeated times.
  • the average value of the bubble diameters of all the bubbles MD and TD is taken as the average bubble diameter of the MD and TD, and the average value of the bubble diameters of all ZDs measured by the above operation is taken as the average bubble diameter of the ZD. It was.
  • ⁇ Closed cell ratio> The closed cell ratio of the foamed sheet is measured by the method described in the specification.
  • Example 1 100 parts by mass of linear low-density polyethylene (trade name “EXACT3027” manufactured by Exxon Chemical Co., Ltd.) obtained using a metallocene compound as a polyethylene resin, 2 parts by mass of azodicarbonamide as a foaming agent, , 6-di-t-butyl-p-cresol 0.3 parts by mass and 1 part by mass of zinc oxide are supplied to an extruder and melt-kneaded at 130 ° C., and then a resin sheet having a thickness of about 0.2 mm is obtained. Extruded.
  • linear low-density polyethylene trade name “EXACT3027” manufactured by Exxon Chemical Co., Ltd.
  • the resin sheet is cross-linked by irradiating an electron beam with an acceleration voltage of 800 kV on both surfaces by 5 Mrad, and then continuously fed into a foaming furnace maintained at 250 ° C. by hot air and an infrared heater to be heated and foamed. At the same time, it was stretched at a stretch ratio of MD of 1.3 times and a stretch ratio of TD of 2.0 times while foaming to obtain a foam sheet having a thickness of 0.06 mm. The resulting foamed sheet had a degree of crosslinking of 25% and a 25% compressive strength of 118 kPa.
  • This foamed sheet is cut into a 5 cm ⁇ 5 cm square, and 8 linear recesses (width: 0) are vertically used by using an embossing roll so that a pattern shown by 2-b in FIG. 2 is obtained. 5 mm, length: 40 mm, distance between lines: 5 mm, depth: 20%, number of regions having recesses: 25, recess area ratio: 12%) to obtain a foam sheet of Example 1.
  • the thickness, density, compressive strength, average cell diameter (MD, TD, ZD), and closed cell ratio were measured by the above methods. The measured values are shown in Table 1.
  • the impact absorbability and pooling resistance were evaluated by the above methods. The results are shown in Table 1.
  • Example 2 It implemented like Example 1 except the point which adjusted the mass part of the foaming agent, the draw ratio of MD, and the draw ratio of TD so that it might become the cell diameter of density of Table 1, MD, TD, and ZD. However, in Example 6, the irradiated electron beam was further changed to 7 Mrad.
  • Comparative Examples 3 and 4 In Comparative Examples 3 and 4, the properties of SCF400 (manufactured by Nitto Denko Corporation) and Poron (manufactured by Roger Sinoac Co., Ltd.), which are commercially available foamed sheets, were measured and evaluated by the above methods.
  • Example 5 A foamed sheet was prepared in the same manner as in Example 1 except that no recess was provided in Example 1, and each property was measured and evaluated.
  • Example 6 a foamed sheet was prepared in the same manner as in Example 1 except that Poron (manufactured by Roger Sinoac Co., Ltd.), which is a commercial product, was used as the foamed sheet, and each property was measured and evaluated.
  • Poron manufactured by Roger Sinoac Co., Ltd.
  • the foamed sheet of the present invention has high impact absorbability and excellent pooling resistance.
  • the foamed sheets of Comparative Examples 1 and 2 that do not have recesses are insufficient in shock absorption and pooling resistance compared to the foamed sheets of the examples.
  • Comparative Example 5 using a foam sheet having no slag was insufficient in impact absorption and pooling resistance.
  • Comparative Examples 3 and 4 using an open-cell foam sheet both the shock absorption and the pooling resistance were insufficient to reach the foam sheet of the example, and the open-cell foam sheet was also used to provide a recess.
  • Comparative Example 6 using the foamed sheet it was confirmed that both the pooling resistance and the foamed sheet of the examples were not sufficient. Further, from the results of Comparative Example 6, even when the open-celled foam sheet is provided with a recess, the 25% compressive strength is hardly reduced, and the effect of reducing the 25% compressive strength is a phenomenon peculiar to the closed-cell foamed sheet. It was confirmed that there was.

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Abstract

This closed-cell foam sheet is provided with at least nine regions each having, provided in at least one place, a recess having a depth of 1-99% of the thickness, each of said regions being divided into 25, and having an area in a 1cm ×1cm square region which decreases. Furthermore, this display device is provided with the aforementioned closed-cell foam sheet, and a display panel. According to the present invention, a foam sheet exhibiting high shock absorption, and a display device which uses said foam sheet can be provided.

Description

独立気泡発泡シート、及び表示装置Closed cell foam sheet and display device
 本発明は、独立気泡発泡シート、及び表示装置に関する。 The present invention relates to a closed cell foam sheet and a display device.
 ノート型パーソナルコンピューター、携帯電話、スマートフォン、タブレット等の携帯機器は、薄型化及び軽量化が望まれており、中でもスマートフォンの薄型化及び軽量化の要求は年々高まっている。携帯機器の薄型化及び軽量化に伴い、表示装置の前面側に配置されるガラス板、アクリル板等により構成される前面板、及び表示パネルも薄型化されている。しかし、前面板及び表示パネルが薄型化されると、前面板及び表示パネルが割れやすくなる。 Demands for thinner and lighter mobile devices such as notebook personal computers, mobile phones, smart phones, and tablets are desired. In particular, the demand for thinner and lighter smartphones is increasing year by year. Along with the reduction in thickness and weight of portable devices, the front plate composed of a glass plate, an acrylic plate or the like disposed on the front side of the display device, and the display panel are also reduced in thickness. However, when the front plate and the display panel are thinned, the front plate and the display panel are easily broken.
 従来、携帯機器において、携帯する日常において繰り返して加えられる衝撃による表示装置の破損及び故障を防止するために、表示パネルの背面側の全面に渡って、又は周縁に衝撃吸収シートが配置されることが知られている。衝撃吸収シートは、繰り返して加えられる衝撃に対する衝撃吸収性を得るため、高い柔軟性等が求められており、発泡シートが広く使用されている。発泡シートとしては、例えば、特許文献1に記載されるように、多数の独立気泡を内包したポリエチレン系架橋発泡シートが知られている。また、ウレタン系発泡シートやゴム系発泡シート等も使用されている。 2. Description of the Related Art Conventionally, in a portable device, an impact absorbing sheet is disposed over the entire rear surface of the display panel or on the periphery in order to prevent damage and failure of the display device due to impact repeatedly applied in everyday life. It has been known. The impact-absorbing sheet is required to have high flexibility in order to obtain impact-absorbing properties against repeated impacts, and foamed sheets are widely used. As a foamed sheet, for example, as described in Patent Document 1, a polyethylene-based crosslinked foamed sheet containing a large number of closed cells is known. In addition, urethane foam sheets, rubber foam sheets, and the like are also used.
特開2014-214205号公報JP 2014-214205 A
 表示パネルの背面側の全面に渡って、又は周縁に衝撃吸収シートが配置される場合、携帯機器においては、通常1mm未満の極薄のものが使用される。しかし、特許文献1に記載の発泡シートでは、そのような極薄とすると、日常生活において繰り返して加えられる衝撃に対する衝撃吸収性能が優れているとはいえない場合があり、前面板、表示パネルの割れを十分に防止できない場合があった。 When the shock absorbing sheet is disposed on the entire rear surface side of the display panel or on the periphery, a very thin one having a thickness of less than 1 mm is usually used for portable devices. However, in the foam sheet described in Patent Document 1, if such an extremely thin sheet is used, it may not be said that the shock absorbing performance against the impact repeatedly applied in daily life may be excellent. In some cases, cracking could not be sufficiently prevented.
 本発明は、以上の問題点を鑑みてなされたものであり、本発明の課題は、高い衝撃吸収性を有する発泡シート、及びこれを備える表示装置を提供することである。 The present invention has been made in view of the above problems, and an object of the present invention is to provide a foam sheet having high impact absorption and a display device including the same.
 本発明者は、前記課題を解決するために鋭意検討を重ねた結果、下記の発明により下記の発明により解決できることを見出した。すなわち、本発明は、下記の発泡シート、及びこれを備える表示装置を提供するものである。 As a result of intensive studies to solve the above problems, the present inventor has found that the following invention can be solved by the following invention. That is, this invention provides the following foam sheet and a display apparatus provided with the same.
[1]25に分割した領域と1cm×1cmの正方形の領域の面積が小さくなるいずれかの領域であって、厚みに対して1~99%の深さを有する凹部を少なくとも1箇所有する領域を9以上有する独立気泡発泡シート。
[2]上記[1]に記載の独立気泡発泡シートと、表示パネルとを備える表示装置。
[1] A region having at least one concave portion having a depth of 1 to 99% with respect to the thickness, which is any region in which the area of a region divided into 25 and a 1 cm × 1 cm square region is reduced. A closed cell foam sheet having 9 or more.
[2] A display device comprising the closed-cell foamed sheet according to [1] and a display panel.
 本発明では、高い衝撃吸収性を有する独立気泡発泡シート、及びこれを備える表示装置を提供する。 In the present invention, a closed cell foam sheet having high shock absorption and a display device including the same are provided.
25に分割した領域を説明するための概念図である。It is a conceptual diagram for demonstrating the area | region divided | segmented into 25. FIG. 本発明の独立気泡発泡シートの一態様を示す模式図である。It is a schematic diagram which shows the one aspect | mode of the closed cell foam sheet of this invention. 本発明の独立気泡発泡シートの一態様を示す模式図である。It is a schematic diagram which shows the one aspect | mode of the closed cell foam sheet of this invention. 本発明の表示装置を示す模式的な断面図である。It is typical sectional drawing which shows the display apparatus of this invention. ガラス割れ高さを測定するための積層体を示す模式的な断面図である。It is typical sectional drawing which shows the laminated body for measuring glass crack height.
 以下、本発明の独立気泡発泡シートについて説明する。なお、本明細書において、数値範囲の記載に関する「以上」「以下」の数値は任意に組み合わせできる数値である。また、本明細書において、「~」を用いて示された数値範囲は、「~」の前後に記載される数値をそれぞれ最小値及び最大値として含む範囲を示し、段階的に記載される最小値及び最大値は、任意に組み合わせてもよい。 Hereinafter, the closed cell foam sheet of the present invention will be described. In the present specification, the numerical values “above” and “below” related to the description of numerical ranges are numerical values that can be arbitrarily combined. Further, in this specification, the numerical range indicated by using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively, The value and the maximum value may be arbitrarily combined.
 [独立気泡発泡シート]
 本発明の独立気泡発泡シート(以下、単に「発泡シート」と称することがある。)は、25に分割した領域と1cm×1cmの正方形の領域の面積が小さくなるいずれかの領域であって、厚みに対して1~99%の深さを有する凹部を少なくとも1箇所有する領域を9以上有するものである。本発明においては、凹部が存在する領域を9以上有するという構成とすることで、25%圧縮強度を小さくして高い衝撃吸収性が得られるとともに、優れた耐プーリング性も得られる。より具体的には、凹部がシート上にある程度均一に存在するような構成とすることで、発泡シート自体の25%圧縮強度が低減して適度に柔らかくなり、高い衝撃吸収性が得られる。またこの適度な柔らかさにより、表示装置の操作の際に生じる応力が緩和され、副次的に優れた耐プーリング性も得られる。なお、プーリング性とは、押圧による液晶の滲みのことを意味する。
[Closed cell foam sheet]
The closed-cell foamed sheet of the present invention (hereinafter sometimes simply referred to as “foamed sheet”) is any region in which the area of a region divided into 25 and a square region of 1 cm × 1 cm is reduced, It has 9 or more regions having at least one recess having a depth of 1 to 99% of the thickness. In the present invention, by having 9 or more regions where the recesses are present, the 25% compressive strength is reduced to obtain high shock absorption, and excellent pooling resistance is also obtained. More specifically, by adopting a configuration in which the recesses are present to some extent uniformly on the sheet, the 25% compressive strength of the foamed sheet itself is reduced and becomes moderately soft, and high impact absorption is obtained. In addition, the moderate softness relieves the stress generated during the operation of the display device, and a secondary excellent pooling resistance can be obtained. In addition, pooling property means the bleeding of the liquid crystal by press.
 25に分割した領域(以下、単に「25分割領域」と称することがある。)は、独立気泡発泡シートの縦方向と横方向とをそれぞれ5等分して設定する領域である。例えば、独立気泡発泡シートが正方形又は長方形のような四つの角度が90°の四角形である場合、図1の1-aに示されるように、縦横の辺を五等分にして分割して設定する25の領域のことを、25分割領域とする。シートが正方形又は長方形以外の形状、例えば、図1の1-bに示される平行四辺形の場合は、その外接する正方形又は長方形の縦横の辺を五等分にして分割して設定する25の領域のことを、25分割領域とする。また、図1の1-cに示される楕円形のような略円形の場合も、図1の1-bと同様に、外接する四角形について、縦横の辺を五等分にして分割して設定する25の領域のことを、25分割領域とする。
 なお、正方形、長方形以外の形状で、例えば図1の1-dに示される、1-bをより寝かせた平行四辺形のような形状の場合、25の領域うち、シートが全く存在しない領域が存在するが(1-dの場合は左上に2つ、右下に2つの計4つ)、これらも含めて25分割領域とする。
The area divided into 25 (hereinafter, simply referred to as “25 divided areas”) is an area that is set by dividing the vertical direction and the horizontal direction of the closed cell foam sheet into 5 equal parts. For example, when the closed cell foam sheet is a square having four angles of 90 °, such as a square or a rectangle, the vertical and horizontal sides are divided into five equal parts as shown in FIG. These 25 areas are defined as 25 divided areas. If the sheet has a shape other than a square or a rectangle, for example, a parallelogram shown in FIG. 1-b, the vertical and horizontal sides of the circumscribed square or rectangle are divided into five equal parts and set. The area is defined as a 25-divided area. Also, in the case of a substantially circular shape such as the ellipse shown in 1-c of FIG. 1, the circumscribed rectangle is set by dividing the vertical and horizontal sides into five equal parts as in 1-b of FIG. These 25 areas are defined as 25 divided areas.
In the case of a shape other than a square or a rectangle, such as a parallelogram shown by 1-d in FIG. Although it exists (in the case of 1-d, two in the upper left and two in the lower right, a total of four), including these, the area is divided into 25 areas.
 また、例えば、図1の1-aで、シートの大きさが20cm×20cmの正方形の場合、25の領域に分割すると、一つの領域は4cm×4cmの正方形となる。このような場合は、25分割領域よりも、1cm×1cmの正方形の領域(以下、単に「正方形領域」と称することがある。)の面積の方が小さいため、正方形領域を本発明における領域とする。正方形領域の設定の方法は、上記の25分割領域の縦横の辺を五等分にして分割した点を、1cmで分割した以外は、25分割領域の設定方法と同じである。 Also, for example, in 1-a of FIG. 1, when the sheet size is a square of 20 cm × 20 cm, when divided into 25 areas, one area becomes a square of 4 cm × 4 cm. In such a case, since the area of a 1 cm × 1 cm square area (hereinafter sometimes simply referred to as “square area”) is smaller than the 25 divided area, the square area is defined as the area in the present invention. To do. The method for setting the square area is the same as the method for setting the 25-divided area except that the 25-divided area is divided into 1 cm by dividing the vertical and horizontal sides into five equal parts.
 本発明において、領域を、25分割領域、及び正方形領域のいずれか面積が小さくなる方とするのは、タッチパネルを操作する際の人の指が該タッチパネルに触れる面積を考慮したものである。例えば、4cm×4cmの正方形の領域に、凹部を少なくとも1箇所有したとしても、指が触れる箇所、又はその近傍に凹部が存在しなければ、耐プーリング性は確実に得られない場合がある。よって、本発明は、領域の面積は最大でも1cm×1cmの1cmとし、該領域中に凹部を存在させることで、副次的に得られる耐プーリング性を向上させることもできる。 In the present invention, the area is selected from the 25 divided areas and the square area in which the area becomes smaller in consideration of the area where a human finger touches the touch panel when operating the touch panel. For example, even if there is at least one recess in a square area of 4 cm × 4 cm, the pooling resistance may not be reliably obtained unless there is a recess at or near the location where the finger touches. Therefore, according to the present invention, the area of the region is 1 cm 2 of 1 cm × 1 cm at the maximum, and the presence of a recess in the region can improve the pooling resistance obtained as a secondary.
 衝撃吸収性及び耐プーリング性を向上させる観点から、凹部を有する領域の数は、10以上が好ましく、12以上がより好ましく、14以上が更に好ましい。
 また、領域が正方形領域であるとき、25分割領域は1cm×1cmの正方形の面積1cmより大きくなる、すなわち、シート全面の面積は25cmよりも大きくなるため、正方形領域が25以上存在することがある。この場合、厚みに対して1~99%、好ましくは1~90%の深さを有する凹部を有する領域の、全領域に対する割合は、40%以上が好ましく、50%以上がより好ましく、60%以上が更に好ましい。全領域に対する凹部を有する領域の割合が上記範囲内であると、衝撃吸収性及び耐プーリング性が向上する。
From the viewpoint of improving impact absorption and pooling resistance, the number of regions having recesses is preferably 10 or more, more preferably 12 or more, and still more preferably 14 or more.
In addition, when the region is a square region, the 25 divided region is larger than a 1 cm × 1 cm square area of 1 cm 2 , that is, the total area of the sheet is larger than 25 cm 2 , so that there are 25 or more square regions. There is. In this case, the ratio of the region having a recess having a depth of 1 to 99%, preferably 1 to 90% with respect to the thickness is preferably 40% or more, more preferably 50% or more, and 60%. The above is more preferable. When the ratio of the area having the recesses to the entire area is within the above range, the impact absorption and the pooling resistance are improved.
 凹部は、発泡シートの厚みに対して1~99%の深さを有する。凹部の深さが、シートの厚みに対して1~99%であると、衝撃吸収性、及び耐プーリング性が向上する。これと同様の観点、及び加工の容易性を考慮すると、凹部の深さは、シートの厚みに対して5~95%が好ましく、10~90%が好ましく、20~80%が更に好ましい。 The recess has a depth of 1 to 99% with respect to the thickness of the foam sheet. When the depth of the recess is 1 to 99% with respect to the thickness of the sheet, the impact absorbability and the pooling resistance are improved. In consideration of the same viewpoint and ease of processing, the depth of the recess is preferably 5 to 95%, more preferably 10 to 90%, and still more preferably 20 to 80% with respect to the thickness of the sheet.
 凹部の、シートの上からみた形状(以下、単に「形状」と称することがある。)は、特に制限はないが、直線、曲線等の線状、円形、楕円形、及びこれに類する形状等の略円形、正方形、長方形、平行四辺形、台形、及びこれに類する形状等の略四角形、正三角形、直角二等辺三角形、及びこれに類する形状等の略三角形、その他、五角形、六角形、及びこれに類する形状等の略多角形、及びこれらを組み合わせた形状から適宜選択して採用することができる。また、形状の種類としては単独でもよいし、複数種を組み合わせて用いてもよい。例えば、線状の凹部が単独で存在していてもよいし、線状の凹部と円形の凹部とが同時に存在していてもよいし、直線の凹部と曲線の凹部という異なる形状の線状が同時に存在していてもよい。 The shape of the concave portion as viewed from above the sheet (hereinafter sometimes simply referred to as “shape”) is not particularly limited, but is linear such as a straight line or a curve, circular, elliptical, and similar shapes. In general circles, squares, rectangles, parallelograms, trapezoids, and similar shapes, etc. A substantially polygonal shape such as a similar shape, or a combination of these can be selected as appropriate. Moreover, as a kind of shape, you may use independently and may use it in combination of multiple types. For example, a linear concave portion may exist alone, a linear concave portion and a circular concave portion may exist at the same time, or linear shapes having different shapes such as a linear concave portion and a curved concave portion. It may exist at the same time.
 凹部のシートの断面でみた形状(以下、単に「断面形状」と称することがある。)も、特に制限はなく、V字形、正方形、長方形、台形等の略四角形、半円形、半楕円形等の略半円形のいずれであってもよい。 The shape of the concave sheet viewed from the cross section (hereinafter, sometimes simply referred to as “cross-sectional shape”) is not particularly limited, and is generally V-shaped, square, rectangular, trapezoidal, or the like, semicircular, semielliptical, etc. Any of the substantially semicircular shapes may be used.
 凹部の形状は、凹部を形成する方法に起因する。例えば、カッターを用いて切り傷により凹部を形成した場合は、凹部の形状は線状を呈し、かつ断面形状はV字形となり、エンボスロールを用いて凹部を形成した場合は、凹部の形状は略四角形、又は略円形を呈し、かつ断面形状は略四角形、又は略半円形となり、針ロールを用いて凹部を形成した場合は、凹部の形状は略円形を呈し、かつ断面形状はV字形となる。
 衝撃吸収性及び耐プーリング性を向上させ、また凹部の加工が容易な点を考慮すると、カッターを用いて切り傷により凹部を形成することが好ましい。すなわち、本発明においては、線状の凹部であることが好ましい。
The shape of the recess is due to the method of forming the recess. For example, when a concave portion is formed by cutting with a cutter, the shape of the concave portion is linear, and the cross-sectional shape is V-shaped. When the concave portion is formed using an embossing roll, the shape of the concave portion is substantially square. When the concave portion is formed by using a needle roll, the shape of the concave portion is substantially circular and the cross-sectional shape is V-shaped.
In view of improving impact absorption and pooling resistance, and taking into account the ease of processing the recess, it is preferable to form the recess by cutting using a cutter. That is, in this invention, it is preferable that it is a linear recessed part.
 凹部の形状が線状を呈する場合、凹部の幅は0.1~2mmが好ましく、0.3~1.5mmがより好ましく、0.4~1mmが更に好ましい。幅が上記範囲内であると、衝撃吸収性、及び耐プーリング性が向上し、凹部の加工も容易である。
 また、凹部の形状が線状を呈する場合、該線状の凹部は、衝撃吸収性及び耐プーリング性がより向上する観点から、少なくとも2つの領域に渡って存在することが好ましい。
When the shape of the concave portion is linear, the width of the concave portion is preferably 0.1 to 2 mm, more preferably 0.3 to 1.5 mm, and still more preferably 0.4 to 1 mm. When the width is within the above range, impact absorbability and pooling resistance are improved, and the recesses can be easily processed.
Moreover, when the shape of a recessed part exhibits linear form, it is preferable that this linear recessed part exists over at least 2 area | region from a viewpoint which shock absorption property and pooling resistance improve more.
 凹部の形状が略四角形の場合、一辺の長さは0.1~4.5mmが好ましく、0.2~3mmがより好ましく、0.3~2mmが更に好ましく、0.5~1.5mmが特に好ましい。また、一辺の長さはシート全面の一辺の長さ(シート形状が四角形ではない場合は、外接する四角形の一辺の長さ)に対する割合としては、2~90%の長さが好ましく、5~60%の長さがより好ましく、15~40%の長さが更に好ましい。
 また、凹部の形状が線状、略四角形以外の形状、すなわち略円形、略三角形、略多角形等の場合、上記略四角形の中に内接する大きさであることが好ましい。
When the shape of the concave portion is substantially square, the length of one side is preferably 0.1 to 4.5 mm, more preferably 0.2 to 3 mm, still more preferably 0.3 to 2 mm, and more preferably 0.5 to 1.5 mm. Particularly preferred. Further, the length of one side is preferably 2 to 90% as a ratio with respect to the length of one side of the entire sheet (the length of one side of the circumscribed rectangle when the sheet shape is not a square). A length of 60% is more preferred, and a length of 15-40% is even more preferred.
Further, when the shape of the concave portion is a line shape or a shape other than a substantially square shape, that is, a substantially circular shape, a substantially triangular shape, a substantially polygonal shape, or the like, the size is preferably inscribed in the substantially square shape.
 シート全面における凹部の面積比率は、1~90%であることが好ましい。面積比率が1~90%であれば、衝撃吸収性、耐プーリング性がより向上する。また、これと同様の観点から、凹部の形状が線状の場合の凹部の面積比率は3~50%がより好ましく、5~30%が更に好ましい。また、凹部の形状が線状以外の場合、凹部の面積比率は10~90%がより好ましく、20~85%が更に好ましい。 The area ratio of the recesses on the entire surface of the sheet is preferably 1 to 90%. When the area ratio is 1 to 90%, the impact absorption and pooling resistance are further improved. Further, from the same viewpoint, when the shape of the recess is linear, the area ratio of the recess is more preferably 3 to 50%, and further preferably 5 to 30%. When the shape of the recess is other than linear, the area ratio of the recess is more preferably 10 to 90%, further preferably 20 to 85%.
(独立気泡発泡シートの各種態様)
 より具体的に、本発明の発泡シートの態様について図面を用いて説明する。図2及び3に本発明の発泡シートの態様の一例を示す。図2及び3に示される態様はあくまで一例を示すものであり、本発明の発泡シートは図2及び3に示される態様に制限されることはない。
(Various aspects of closed cell foam sheet)
More specifically, the embodiment of the foam sheet of the present invention will be described with reference to the drawings. 2 and 3 show an example of the embodiment of the foam sheet of the present invention. The embodiment shown in FIGS. 2 and 3 is merely an example, and the foamed sheet of the present invention is not limited to the embodiment shown in FIGS.
 図2に示される各態様は、領域が25分割領域のものであり、各種パターンの凹部を有するものである。
 2-aのシートは、直線の凹部を複数本有するものである。25分割領域中、右端の5つの領域には凹部は存在しないが、それ以外の20の領域に直線の凹部が存在する。2-aのシートのように、凹部が存在しない領域を有していても、該領域における衝撃吸収性及び耐プーリング性は、凹部を有する領域が9以上あれば、他の領域の凹部の存在により補われるため、シート全体としての高い衝撃吸収性と優れた耐プーリング性とが得られる。また、1つの領域において、複数の直線の凹部を有していてもよい。
Each mode shown in FIG. 2 has a 25-divided area and has various patterns of recesses.
The sheet 2-a has a plurality of straight concave portions. Of the 25 divided regions, there are no recesses in the five rightmost regions, but there are linear recesses in the other 20 regions. Even if it has a region where there is no recess, such as the sheet 2-a, if there are 9 or more regions having a recess, the presence of recesses in other regions Therefore, high impact absorption as a whole sheet and excellent pooling resistance can be obtained. Moreover, in one area | region, you may have several linear recessed part.
 2-bのシートも、線状の凹部を複数本有するものであり、2-aのように縦だけでなく、縦の直線の凹部と横の直線の凹部とが存在している。2-bのシートの場合は、全ての領域が凹部を有するものとなっており、また1つの領域において、縦横の複数の直線の凹部を有していてもよいことが示されている。2-cのシートは、曲線の凹部を複数本有するものであり、左上の2つ及び右下の2つの計4つの領域で凹部は存在しないが、それ以外の21の領域は、曲線の凹部を有する領域となっている。 The sheet 2-b also has a plurality of linear recesses, and there are not only vertical but also vertical straight recesses and horizontal straight recesses as in 2-a. In the case of the 2-b sheet, it is shown that all the regions have recesses, and that one region may have a plurality of vertical and horizontal straight recesses. The sheet 2-c has a plurality of curved concave portions, and there are no concave portions in a total of four areas, two in the upper left and two in the lower right, but the other 21 areas are curved concave It is the area which has.
 2-dのシートは、四角形の凹部を複数個有するものである。このシートは、全領域において凹部を有しており、例えば左上の領域には凹部が一箇所存在し、1つ下の領域には凹部が二箇所存在し、その1つ右の領域には凹部が四箇所存在している。 The 2-d sheet has a plurality of rectangular recesses. This sheet has a recess in the entire region, for example, there is one recess in the upper left region, two recesses in the lower region, and a recess in the right region. There are four places.
 2-eのシートは、円形の凹部を複数個有するものである。この場合、一番下の列の5つの領域で凹部は存在しないが、それ以外の20の領域は、少なくとも1箇所の円形の凹部を有する領域となっている。2-eに示されるように、凹部の形状は途中で切れたような形状であってもよい。また、凹部の配列は2-dのシートのように規則性を有していてもよいし、2-eのシートのように不規則であってもよい。
 2-fのシートも、円形の凹部を複数個有するものである。2-eのシートに比べて凹部の数は少なく、また凹部を有する領域も9と少ないが、このような態様でも、本発明の構成を有しており、高い衝撃吸収性と優れた耐プーリング性とを有するシートとなり得る。
The sheet 2-e has a plurality of circular recesses. In this case, there are no recesses in the five regions of the bottom row, but the other 20 regions are regions having at least one circular recess. As shown in 2-e, the shape of the recess may be a shape cut off in the middle. Further, the arrangement of the recesses may be regular as in the 2-d sheet, or may be irregular as in the 2-e sheet.
The 2-f sheet also has a plurality of circular recesses. The number of recesses is smaller than that of 2-e sheet, and the number of regions having recesses is as small as 9. However, even in such an aspect, the structure of the present invention is provided, and high shock absorption and excellent pooling resistance are achieved. It can be a sheet having the properties.
 2-gのシートは、シート内に四角形の凹部を1つ有するものである。このシートは、全領域において凹部を有している。2-gのシートに示されるように、一つの領域の全面が凹部であってもよいが、衝撃吸収性と耐プーリング性を向上させる観点から、全面が凹部である領域の数は12以下が好ましく、10以下がより好ましく、8以下が更に好ましい。また、領域が正方形領域であるときは、該正方形領域の数は、全領域数に対して50%以下が好ましく、40%以下がより好ましく、35%以下が更に好ましい。
 なお、25分割領域の場合、全面が凹部である領域の数が25のときは、全面が凹部になってしまう、すなわちシート全面にわたって結果として凹部が存在しないシートとなってしまうため、本発明の効果が得られないのは言うまでもない。これは、正方形領域の場合、その全ての正方形領域の全面が凹部であるときも、同様である。
The 2-g sheet has one rectangular recess in the sheet. This sheet has a recess in the entire region. As shown in the 2-g sheet, the entire surface of one region may be a recess, but from the viewpoint of improving shock absorption and pooling resistance, the number of regions where the entire surface is a recess is 12 or less. Preferably, 10 or less is more preferable, and 8 or less is still more preferable. Further, when the region is a square region, the number of the square regions is preferably 50% or less, more preferably 40% or less, and still more preferably 35% or less with respect to the total number of regions.
In the case of 25 divided regions, when the number of regions whose entire surface is a recess is 25, the entire surface becomes a recess, that is, the sheet does not have a recess as a result over the entire surface of the sheet. Needless to say, no effect can be obtained. In the case of a square region, the same applies when the entire surface of all the square regions is a recess.
 2-hのシートは、シート内に正方形の開口部を有しており、額縁状となったシートの周縁部に、縦横の直線の凹部が存在するものである。このシートは、周縁部の16の領域において複数の凹部を有している。
 2-hのシートで示されるように、本発明の発泡シートは、開口部を有していてもよい。この場合、開口部の形状は特に制限はなく、凹部の形状として例示した形状、例えば、線状、略円形、略四角形、略三角形、略多角形、及びこれらを組み合わせた形状が挙げられる。また、開口部は2-hのシートで示されるように1箇所であってもよいし、複数箇所あってもよい。
The 2-h sheet has a square opening in the sheet, and vertical and horizontal straight concave portions exist on the peripheral edge of the frame-shaped sheet. This sheet has a plurality of recesses in 16 regions at the peripheral edge.
As shown by the 2-h sheet, the foamed sheet of the present invention may have an opening. In this case, the shape of the opening is not particularly limited, and examples include the shape exemplified as the shape of the recess, for example, a linear shape, a substantially circular shape, a substantially quadrangular shape, a substantially triangular shape, a substantially polygonal shape, and a combination thereof. Further, the opening may be provided at one place as shown by the 2-h sheet, or may be provided at a plurality of places.
 開口部を有する場合、シート全面に対する開口部の面積比率は、1~90%が好ましく、10~85%がより好ましく、20~85%が更に好ましい。開口部の面積比率が上記範囲内であると、凹部を十分に形成することができ、衝撃吸収性及び耐プーリング性が向上する。 In the case of having openings, the area ratio of the openings to the entire sheet surface is preferably 1 to 90%, more preferably 10 to 85%, and still more preferably 20 to 85%. When the area ratio of the opening is within the above range, the recess can be sufficiently formed, and the impact absorption and the pooling resistance are improved.
 図3に示される各態様は、領域が正方形領域のものであり、各種パターンの凹部を有するものである。図3には二例しか示されていないが、例えば、図2に示される各種パターンの凹部と同じパターンの凹部を有するものであって、領域が正方形領域となるシートも、本発明の発泡シートとなり得る。
 3-aのシートは、上記2-aのシートと同じパターンの凹部を有するものであるが、25分割領域では1cm以上の面積となるため、領域として正方形領域が適用されるシートである。このシートは、左端、右端、及び左から6番目の列の領域で凹部が存在しないが、他の領域では凹部を有している。凹部を有する領域の数は54であり、全領域(81)に対する、凹部を有する領域の割合は、66.7%である。
Each mode shown in FIG. 3 has a square area and has various patterns of recesses. Although only two examples are shown in FIG. 3, for example, a sheet having concave portions having the same pattern as the concave portions having various patterns shown in FIG. Can be.
The 3-a sheet has concave portions having the same pattern as that of the 2-a sheet. However, since the area is 1 cm 2 or more in the 25 divided areas, a square area is applied as the area. This sheet has no recess in the left end, the right end, and the region of the sixth row from the left, but has a recess in the other regions. The number of regions having recesses is 54, and the ratio of regions having recesses to the entire region (81) is 66.7%.
 3-bのシートは、3-aのシートと同じように、直線の凹部を複数本有しており、凹部を有する領域は上から二列目、下から二列目、左から三列目、及び右から三列目の領域で囲まれた、合計35の領域に凹部が存在している。全領域(81)に対する凹部を有する領域(35)の割合は、43.2%である。領域が正方形領域の場合、凹部を有する領域が9以上あれば、高い衝撃吸収性及び優れた耐プーリング性は得られるが、上記の通り40%以上の領域が凹部を有すると、衝撃吸収性及び耐プーリング性は向上する。 The 3-b sheet, like the 3-a sheet, has a plurality of straight concave portions, and the regions having the concave portions are the second row from the top, the second row from the bottom, and the third row from the left. In addition, there are recesses in a total of 35 regions surrounded by the region in the third row from the right. The ratio of the region (35) having the recesses to the entire region (81) is 43.2%. When the region is a square region, if there are 9 or more regions having recesses, high shock absorption and excellent pooling resistance can be obtained, but if 40% or more regions have recesses as described above, impact absorption and Pooling resistance is improved.
(独立気泡発泡シートの性能)
 本発明の発泡シートは独立気泡体で構成される独立気泡発泡シートである。独立気泡体とは、独立気泡率が70%以上であることを意味する。すなわち、発泡シートの内部に包含された気泡は概ね独立気泡となっている。衝撃吸収性及び耐プーリング性を向上させる観点から、独立気泡率は、好ましくは90~100%、より好ましくは95~100%である。
(Performance of closed cell foam sheet)
The foamed sheet of the present invention is a closed cell foamed sheet composed of closed cells. The closed cell means that the closed cell rate is 70% or more. That is, the bubbles included in the foam sheet are generally closed cells. From the viewpoint of improving impact absorption and pooling resistance, the closed cell ratio is preferably 90 to 100%, more preferably 95 to 100%.
 独立気泡率は、下記の要領で測定できる。
 まず、発泡シートから一辺が5cmの平面正方形状の試験片を切り出す。そして、試験片の厚みを測定して試験片の見掛け体積Vを算出すると共に、試験片の質量Wを測定する。次に、気泡の占める体積Vを下記式に基づいて算出する。なお、試験片を構成している樹脂材料の密度はρ(g/cm)とする。
  気泡の占める体積V=V-W/ρ
 続いて、試験片を23℃の蒸留水中に水面から100mmの深さに沈めて、試験片に15kPaの圧力を3分間にわたり加える。その後、水中で加圧から解放し、1分間静置した後、試験片を水中から取り出して試験片の表面に付着した水分を除去して試験片の質量Wを測定し、下記式に基づいて連続気泡率F及び独立気泡率Fを算出する。
  連続気泡率F(%)=100×(W-W)/V
  独立気泡率F(%)=100-F
The closed cell ratio can be measured as follows.
First, a flat square test piece having a side of 5 cm is cut out from the foam sheet. Then, by measuring the thickness of the test piece to calculate the apparent volume V 1 of the test piece, measuring the mass W 1 of the specimen. Next, the volume V 2 occupied by the bubbles is calculated based on the following formula. The density of the resin material constituting the test piece is ρ (g / cm 3 ).
Volume occupied by bubbles V 2 = V 1 −W 1 / ρ
Subsequently, the test piece is immersed in distilled water at 23 ° C. to a depth of 100 mm from the water surface, and a pressure of 15 kPa is applied to the test piece for 3 minutes. Then, after releasing from pressurization in water and allowing to stand for 1 minute, the test piece was taken out of water, the water adhering to the surface of the test piece was removed, and the mass W 2 of the test piece was measured. Te to calculate the open cell ratio F 1 and the closed cell ratio F 2.
Open cell ratio F 1 (%) = 100 × (W 2 −W 1 ) / V 2
Closed cell ratio F 2 (%) = 100−F 1
 発泡シート中の気泡が独立気泡であると、押圧に対する反発力が大きいため、一般的に耐プーリング性の発現に有効である。一方、反発力が大きすぎると、衝撃吸収性が低下する場合があり、衝撃吸収性と耐プーリング性とは相反する性能といえる。本発明においては、この独立気泡発泡シートに凹部を設けることにより、25%圧縮強度等により指標される反発力を低減させることを見出し、独立気泡発泡シートであるにも関わらず、反発力が小さいものとすることで、衝撃吸収性、及び耐プーリング性の向上を可能とした。 If the bubbles in the foam sheet are closed cells, the repulsive force against the pressure is large, so that it is generally effective for the expression of pooling resistance. On the other hand, if the repulsive force is too large, the impact absorbability may decrease, and it can be said that the impact absorbability and the pooling resistance are contradictory. In the present invention, it has been found that by providing a recess in this closed cell foam sheet, the repulsive force indicated by 25% compressive strength or the like is reduced, and the repulsive force is small despite being a closed cell foam sheet. By making it possible, it was possible to improve impact absorption and pooling resistance.
 発泡シートの25%圧縮強度は、凹部を設ける前の発泡シートについては、40~200kPaが好ましく、50~180kPaがより好ましく、60~170kPaが更に好ましい。凹部を設けた後の、本発明の発泡シートの25%圧縮強度は、3~90kPaが好ましい。更に、15~90kPaが好ましく、20~80kPaがより好ましく、30~70kPaが更に好ましい。また、凹部を設ける前と後とにおける25%圧縮強度の低減率は、好ましくは15~80%、より好ましくは30~75%、更に好ましくは50~70%の範囲となる。
 このように、本発明の発泡シートは、凹部を設けることで、独立気泡であるにも関わらず25%圧縮強度が低減し、衝撃吸収性、及び耐プーリング性が向上する。本明細書において、25%圧縮強度は、JIS K 6767に準拠して測定される値である。また、25%圧縮強度の低減率は、下記の式で表される数値である。
   fΔ=(f-f)/f×100
   fΔ:25%圧縮強度の低減率(%)
   f:凹部を設ける前の発泡シートの25%圧縮強度(kPa)
   f:凹部を設けた後の発泡シートの25%圧縮強度(kPa)
The 25% compressive strength of the foamed sheet is preferably 40 to 200 kPa, more preferably 50 to 180 kPa, and still more preferably 60 to 170 kPa for the foamed sheet before the recess is provided. The 25% compressive strength of the foamed sheet of the present invention after providing the recesses is preferably 3 to 90 kPa. Furthermore, 15 to 90 kPa is preferable, 20 to 80 kPa is more preferable, and 30 to 70 kPa is still more preferable. Further, the reduction rate of the 25% compressive strength before and after providing the recesses is preferably 15 to 80%, more preferably 30 to 75%, and still more preferably 50 to 70%.
As described above, the foamed sheet of the present invention is provided with the recesses, so that the compressive strength is reduced by 25% in spite of being closed cells, and the impact absorption and the pooling resistance are improved. In this specification, the 25% compressive strength is a value measured according to JIS K 6767. The reduction rate of 25% compressive strength is a numerical value represented by the following formula.
f Δ = (f 0 −f 1 ) / f 0 × 100
: Reduction rate of 25% compression strength (%)
f 0 : 25% compressive strength (kPa) of the foamed sheet before providing the recesses
f 1 : 25% compressive strength (kPa) of the foamed sheet after providing the recesses
 発泡シートの厚みは、表示装置に用いる場合に所望される厚み、及び衝撃吸収性、耐プーリング性の得られやすさ等を考慮すると、0.03~0.6mmが好ましく、0.05~0.5mmがより好ましく、0.06~0.3mmが更に好ましい。 The thickness of the foam sheet is preferably 0.03 to 0.6 mm, considering the thickness desired for use in a display device, the ease of obtaining shock absorption and pooling resistance, and the like, preferably 0.05 to 0 mm. 0.5 mm is more preferable, and 0.06 to 0.3 mm is even more preferable.
 発泡シートの密度は、衝撃吸収性、耐プーリング性を向上させる観点から、60~600kg/mが好ましく、60~400kg/mが好ましく、150~600kg/mがより好ましく、180~480kg/mが更に好ましい。 The density of foam sheet, shock absorption, in view of improving the resistance to pooling resistance, preferably 60 ~ 600kg / m 3, preferably 60 ~ 400kg / m 3, more preferably 150 ~ 600kg / m 3, 180 ~ 480kg / M 3 is more preferable.
 発泡シートにおける気泡の平均気泡径は、MDにおいて25~300μmが好ましく、30~300μmがより好ましく、35~230μmが更に好ましく、50~180μmが最も好ましい。TDにおいては、30~330μmが好ましく、50~300μmがより好ましく、60~250μmが更に好ましい。また、ZDにおいて10~80μmが好ましく、15~75μmがより好ましく、20~70μmが更に好ましい。気泡の平均気泡径が上記範囲内であると、衝撃吸収性、耐プーリング性を向上させることができる。 The average cell diameter of the bubbles in the foam sheet is preferably 25 to 300 μm, more preferably 30 to 300 μm, still more preferably 35 to 230 μm, and most preferably 50 to 180 μm in MD. In TD, 30 to 330 μm is preferable, 50 to 300 μm is more preferable, and 60 to 250 μm is still more preferable. Further, ZD is preferably 10 to 80 μm, more preferably 15 to 75 μm, still more preferably 20 to 70 μm. When the average bubble diameter of the bubbles is within the above range, impact absorbability and pooling resistance can be improved.
 発泡シートは、後述する樹脂材料の樹脂シート等を架橋、発泡することで得られるものである。発泡シートの架橋度は、通常、5~60質量%程度となるものであるが、好ましくは10~40質量%である。
 架橋度は、以下の測定方法で測定されるものである。発泡シートから100mgの試験片を採取し、試験片の質量A(mg)を精秤する。次に、この試験片を120℃のキシレン30cm3中に浸漬して24時間放置した後、200メッシュの金網で濾過して金網上の不溶解分を採取、真空乾燥し、不溶解分の質量B(mg)を精秤する。得られた値から、下記式により架橋度(質量%)を算出する。
      架橋度(質量%)=100×(B/A)
The foam sheet is obtained by crosslinking and foaming a resin sheet of a resin material described later. The degree of crosslinking of the foamed sheet is usually about 5 to 60% by mass, preferably 10 to 40% by mass.
The degree of crosslinking is measured by the following measuring method. A 100 mg test piece is collected from the foamed sheet, and the mass A (mg) of the test piece is precisely weighed. Next, this test piece was immersed in 30 cm 3 of xylene at 120 ° C. and allowed to stand for 24 hours, and then filtered through a 200-mesh wire mesh to collect the insoluble matter on the wire mesh, vacuum dried, and the mass of the insoluble matter. Weigh B (mg) precisely. From the obtained value, the degree of crosslinking (mass%) is calculated by the following formula.
Crosslinking degree (% by mass) = 100 × (B / A)
(原料樹脂)
 本発明の独立気泡発泡シートを構成する原料樹脂としては、例えば、ポリオレフィン系樹脂、アクリル系樹脂、シリコーン系樹脂、ウレタン系樹脂、ゴム系樹脂のいずれであってもよく、衝撃吸収性及び耐プーリング性を考慮すると、ポリオレフィン系樹脂を用いることが好ましい。
(Raw resin)
The raw material resin constituting the closed-cell foamed sheet of the present invention may be, for example, any of polyolefin resin, acrylic resin, silicone resin, urethane resin, rubber resin, and shock absorption and anti-pooling Considering the properties, it is preferable to use a polyolefin resin.
 本発明において好ましい材料である、ポリオレフィン系樹脂について説明する。
 発泡シートを形成するために使用されるポリオレフィン系樹脂としては、ポリエチレン系樹脂、ポリプロピレン系樹脂、またはこれらの混合物が挙げられ、衝撃吸収性及び耐プーリング性を向上させる観点から、これらの中ではポリエチレン系樹脂が好ましい。より具体的には、チーグラー・ナッタ化合物、メタロセン化合物、酸化クロム化合物等の重合触媒で重合されたポリエチレン系樹脂、ポリプロピレン系樹脂、又はこれらの混合物が挙げられ、これらの中では、メタロセン化合物の重合触媒で重合されたポリエチレン系樹脂が好ましい。
The polyolefin resin, which is a preferable material in the present invention, will be described.
Examples of the polyolefin resin used to form the foamed sheet include a polyethylene resin, a polypropylene resin, or a mixture thereof. Among these, polyethylene is a polyethylene resin from the viewpoint of improving impact absorption and pooling resistance. Based resins are preferred. More specifically, examples thereof include polyethylene resins, polypropylene resins, or mixtures thereof polymerized with a polymerization catalyst such as a Ziegler-Natta compound, a metallocene compound, and a chromium oxide compound. Among these, polymerization of a metallocene compound is included. A polyethylene resin polymerized with a catalyst is preferred.
 ポリエチレン系樹脂は、エチレン単独重合体でもよいが、エチレンと必要に応じて少量(例えば、全モノマーの30質量%以下、好ましくは1~10質量%)のα-オレフィンとを共重合することにより得られるポリエチレン系樹脂が好ましく、その中でも、直鎖状低密度ポリエチレンが好ましい。 The polyethylene resin may be an ethylene homopolymer, but by copolymerizing ethylene with a small amount (for example, 30% by mass or less of the total monomers, preferably 1 to 10% by mass) of α-olefin as necessary. Polyethylene resins obtained are preferred, and among them, linear low density polyethylene is preferred.
 メタロセン化合物の重合触媒により得られた、ポリエチレン系樹脂、特に直鎖状低密度ポリエチレンを用いることにより、柔軟性、機械強度、耐プーリング性を向上させた発泡シートを得やすくなる。また、後述するように、発泡シートを薄厚にしても高い性能を維持しやすくなる。 By using a polyethylene-based resin, particularly a linear low density polyethylene, obtained by a polymerization catalyst of a metallocene compound, it becomes easy to obtain a foamed sheet having improved flexibility, mechanical strength, and pooling resistance. Moreover, as will be described later, it is easy to maintain high performance even if the foam sheet is thin.
 ポリエチレン系樹脂を構成するα-オレフィンとして、具体的には、プロピレン、1-ブテン、1-ペンテン、4-メチル-1-ペンテン、1-ヘキセン、1-ヘプテン、及び1-オクテン等が挙げられる。なかでも、炭素数4~10のα-オレフィンが好ましい。
 また、ポリエチレン系樹脂としては、エチレン-酢酸ビニル共重合体も好ましく用いられる。エチレン-酢酸ビニル共重合体は、通常、エチレン単位を50質量%以上含有する共重合体である。
Specific examples of the α-olefin constituting the polyethylene resin include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, and 1-octene. . Of these, α-olefins having 4 to 10 carbon atoms are preferred.
As the polyethylene resin, an ethylene-vinyl acetate copolymer is also preferably used. The ethylene-vinyl acetate copolymer is usually a copolymer containing 50% by mass or more of ethylene units.
 メタロセン化合物の重合触媒により得られたポリエチレン系樹脂、エチレン-酢酸ビニル共重合体、又はこれらの混合物は、発泡シートにおいて樹脂全量に対して好ましくは50質量%以上含有され、さらに好ましくは60質量%以上、最も好ましくは100質量%含有される。 The polyethylene resin, the ethylene-vinyl acetate copolymer, or a mixture thereof obtained by the polymerization catalyst of the metallocene compound is preferably contained in the foamed sheet in an amount of 50% by mass or more, more preferably 60% by mass. As described above, it is most preferably contained by 100% by mass.
 また、ポリプロピレン系樹脂としては、例えば、プロピレン単独重合体、プロピレン単位を50質量%以上含有するプロピレン-α-オレフィン共重合体等が挙げられる。これらは1種を単独で、又は複数種を併用してもよい。
 プロピレン-α-オレフィン共重合体を構成するα-オレフィンとしては、具体的には、エチレン、1-ブテン、1-ペンテン、4-メチル-1-ペンテン、1-ヘキセン、1-ヘプテン、1-オクテン等が挙げられ、これらの中では、炭素数6~12のα-オレフィンが好ましい。
Examples of the polypropylene resin include a propylene homopolymer, a propylene-α-olefin copolymer containing 50% by mass or more of a propylene unit, and the like. These may be used alone or in combination of two or more.
Specific examples of the α-olefin constituting the propylene-α-olefin copolymer include ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1- Among these, α-olefins having 6 to 12 carbon atoms are preferable.
 好適なメタロセン化合物としては、遷移金属をπ電子系の不飽和化合物で挟んだ構造を有するビス(シクロペンタジエニル)金属錯体等の化合物が挙げられる。より具体的には、チタン、ジルコニウム、ニッケル、パラジウム、ハフニウム、及び白金等の四価の遷移金属に、1又は2以上のシクロペンタジエニル環又はその類縁体がリガンド(配位子)として存在する化合物が挙げられる。
 このようなメタロセン化合物は、活性点の性質が均一であり各活性点が同じ活性度を備えている。メタロセン化合物を用いて合成した重合体は、分子量、分子量分布、組成、組成分布等の均一性が高くなるため、メタロセン化合物を用いて合成した重合体を含むシートを架橋した場合には、架橋が均一に進行する。均一に架橋されたシートは、均一に延伸しやすくなるため、架橋ポリオレフィン樹脂発泡シートの厚みを均一にしやすくなり、薄厚にしても高い性能を維持しやすくなる。
Suitable metallocene compounds include compounds such as bis (cyclopentadienyl) metal complexes having a structure in which a transition metal is sandwiched between π-electron unsaturated compounds. More specifically, tetravalent transition metals such as titanium, zirconium, nickel, palladium, hafnium, and platinum have one or more cyclopentadienyl rings or their analogs as ligands (ligands). The compound to be mentioned is mentioned.
Such metallocene compounds have uniform active site properties and each active site has the same activity. A polymer synthesized using a metallocene compound has high uniformity such as molecular weight, molecular weight distribution, composition, and composition distribution. Therefore, when a sheet containing a polymer synthesized using a metallocene compound is crosslinked, crosslinking occurs. Progress evenly. Since the uniformly crosslinked sheet is easily stretched uniformly, the thickness of the crosslinked polyolefin resin foamed sheet is easily uniformed, and high performance is easily maintained even when the sheet is thin.
 リガンドとしては、例えば、シクロペンタジエニル環、インデニル環等が挙げられる。これらの環式化合物は、炭化水素基、置換炭化水素基又は炭化水素-置換メタロイド基により置換されていてもよい。炭化水素基としては、例えば、メチル基、エチル基、各種プロピル基、各種ブチル基、各種アミル基、各種ヘキシル基、2-エチルヘキシル基、各種ヘプチル基、各種オクチル基、各種ノニル基、各種デシル基、各種セチル基、フェニル基等が挙げられる。なお、「各種」とは、n-、sec-、tert-、iso-を含む各種異性体を意味する。
 また、環式化合物をオリゴマーとして重合したものをリガンドとして用いてもよい。
 更に、π電子系の不飽和化合物以外にも、塩素や臭素等の一価のアニオンリガンド又は二価のアニオンキレートリガンド、炭化水素、アルコキシド、アリールアミド、アリールオキシド、アミド、アリールアミド、ホスフィド、アリールホスフィド等を用いてもよい。
Examples of the ligand include a cyclopentadienyl ring and an indenyl ring. These cyclic compounds may be substituted with a hydrocarbon group, a substituted hydrocarbon group or a hydrocarbon-substituted metalloid group. Examples of the hydrocarbon group include a methyl group, an ethyl group, various propyl groups, various butyl groups, various amyl groups, various hexyl groups, 2-ethylhexyl groups, various heptyl groups, various octyl groups, various nonyl groups, and various decyl groups. , Various cetyl groups, phenyl groups and the like. The “various” means various isomers including n-, sec-, tert-, and iso-.
Moreover, what polymerized the cyclic compound as an oligomer may be used as a ligand.
In addition to π-electron unsaturated compounds, monovalent anion ligands such as chlorine and bromine or divalent anion chelate ligands, hydrocarbons, alkoxides, arylamides, aryloxides, amides, arylamides, phosphides, aryls Phosphide or the like may be used.
 四価の遷移金属やリガンドを含むメタロセン化合物としては、例えば、シクロペンタジエニルチタニウムトリス(ジメチルアミド)、メチルシクロペンタジエニルチタニウムトリス(ジメチルアミド)、ビス(シクロペンタジエニル)チタニウムジクロリド、ジメチルシリルテトラメチルシクロペンタジエニル-t-ブチルアミドジルコニウムジクロリド等が挙げられる。
 メタロセン化合物は、特定の共触媒(助触媒)と組み合わせることにより、各種オレフィンの重合の際に触媒としての作用を発揮する。具体的な共触媒としては、メチルアルミノキサン(MAO)、ホウ素系化合物等が挙げられる。なお、メタロセン化合物に対する共触媒の使用割合は、10~100万モル倍が好ましく、50~5,000モル倍がより好ましい。
Examples of metallocene compounds containing tetravalent transition metals and ligands include, for example, cyclopentadienyl titanium tris (dimethylamide), methylcyclopentadienyl titanium tris (dimethylamide), bis (cyclopentadienyl) titanium dichloride, dimethyl And silyltetramethylcyclopentadienyl-t-butylamidozirconium dichloride.
The metallocene compound exhibits an action as a catalyst in the polymerization of various olefins by combining with a specific cocatalyst (co-catalyst). Specific examples of the cocatalyst include methylaluminoxane (MAO) and boron compounds. The proportion of the cocatalyst used with respect to the metallocene compound is preferably 100,000 to 1,000,000 mole times, more preferably 50 to 5,000 mole times.
 チーグラー・ナッタ化合物は、トリエチルアルミニウム-四塩化チタン固体複合物であって、四塩化チタンを有機アルミニウム化合物で還元し、更に各種の電子供与体及び電子受容体で処理して得られた三塩化チタン組成物と、有機アルミニウム化合物と、芳香族カルボン酸エステルとを組み合わせる方法(特開昭56-100806号、特開昭56-120712号、特開昭58-104907号の各公報参照)、及びハロゲン化マグネシウムに四塩化チタンと各種の電子供与体を接触させる担持型触媒の方法(特開昭57-63310号、特開昭63-43915号、特開昭63-83116号の各公報参照)等で製造されたものが好ましい。 The Ziegler-Natta compound is a triethylaluminum-titanium tetrachloride solid composite, which is obtained by reducing titanium tetrachloride with an organoaluminum compound and then treating with various electron donors and electron acceptors. A method of combining a composition, an organoaluminum compound, and an aromatic carboxylic acid ester (see JP-A 56-1000080, JP-A 56-120712, JP-A 58-104907), halogens Method of supported catalyst in which magnesium tetrachloride is brought into contact with magnesium tetrachloride and various electron donors (see JP-A-57-63310, JP-A-63-43915, JP-A-63-83116), etc. What was manufactured by is preferable.
 上記ポリエチレン系樹脂としては、発泡シートの柔軟性、機械強度、及び回復速度を高めるために、低密度であることが好ましい。上記ポリエチレン系樹脂の密度は、具体的には、0.920g/cm以下が好ましく、より好ましくは0.880~0.915g/cm、更に好ましくは0.885~0.910g/cmである。なお、密度はASTM D792に準拠して測定したものである。 The polyethylene resin preferably has a low density in order to increase the flexibility, mechanical strength, and recovery rate of the foam sheet. Specifically, the density of the polyethylene resin is preferably 0.920 g / cm 3 or less, more preferably 0.880 to 0.915 g / cm 3 , still more preferably 0.885 to 0.910 g / cm 3. It is. The density is measured according to ASTM D792.
 なお、ポリオレフィン系樹脂としては、上記したポリオレフィン系樹脂以外の樹脂も使用可能であり、ポリエチレン系樹脂およびポリプロピレン系樹脂以外の樹脂を、ポリエチレン系樹脂、ポリプロピレン系樹脂にさらに混合して使用してもよい。
 さらに、ポリオレフィン系樹脂には、後述する各種添加剤やその他の成分を混合してもよく、発泡シートは、添加剤、その他の成分等を含むポリオレフィン系樹脂を架橋、発泡されたものであることが好ましい。
 発泡シートに含有されるその他の成分としては、ポリオレフィン系樹脂以外の樹脂、ゴムが挙げられ、これらは合計で、ポリオレフィン系樹脂よりも含有量が少なく、ポリオレフィン系樹脂100質量部に対して、通常50質量部以下、好ましくは30質量部以下程度である。
In addition, as polyolefin resin, resin other than the above-mentioned polyolefin resin can also be used, and resin other than polyethylene resin and polypropylene resin may be used by further mixing with polyethylene resin and polypropylene resin. Good.
Furthermore, the polyolefin resin may be mixed with various additives and other components described later, and the foamed sheet is obtained by crosslinking and foaming a polyolefin resin containing additives and other components. Is preferred.
Examples of other components contained in the foamed sheet include resins and rubbers other than polyolefin-based resins, and these are total and less in content than polyolefin-based resins, and are usually based on 100 parts by mass of polyolefin-based resin. It is about 50 parts by mass or less, preferably about 30 parts by mass or less.
(発泡シートの製造方法)
 本発明の発泡シートの製造方法は、特に限定されないが、例えば以下の工程(1)~(5)を含む方法が挙げられる。
 工程(1):原料樹脂、熱分解型発泡剤等の添加剤、及び必要に応じて添加される他の添加剤等の樹脂材料を、熱分解型発泡剤の分解温度未満の温度で溶融、混練して公知の成形方法により樹脂シートに成形する工程
 工程(2):工程(1)で得られた樹脂シートを架橋する工程
 工程(3):樹脂シートを、熱分解型発泡剤の分解温度以上に加熱して発泡させる工程
 工程(4):樹脂シートを、延伸する工程
 工程(5):延伸して得た発泡シートに凹部を形成する工程
 以上の工程(1)~(5)は、この工程順に行ってもよいが、必ずしもこの工程順に行う必要はなく、例えば工程(4)の後に工程(3)を行ってもよい。また、2つの工程を同時に行ってもよく、例えば、工程(3)と(4)を同時に行ってもよい。
(Method for producing foam sheet)
The method for producing the foamed sheet of the present invention is not particularly limited, and examples thereof include a method including the following steps (1) to (5).
Step (1): Melting resin materials such as raw resin, additives such as pyrolytic foaming agent, and other additives added as necessary, at a temperature lower than the decomposition temperature of the pyrolytic foaming agent, Step of kneading and molding into a resin sheet by a known molding method Step (2): Step of crosslinking the resin sheet obtained in step (1) Step (3): Decomposition temperature of the thermally decomposable foaming agent Step of heating and foaming Step (4): Step of stretching the resin sheet Step (5): Step of forming a recess in the foamed sheet obtained by stretching The above steps (1) to (5) are: Although you may perform in order of this process, it does not necessarily need to perform in order of this process, for example, you may perform a process (3) after a process (4). Moreover, two processes may be performed simultaneously, for example, you may perform process (3) and (4) simultaneously.
(工程(1))
 工程(1)では、原料樹脂、熱分解型発泡剤等の添加剤、及び他の添加剤等の樹脂材料を、単軸押出機、二軸押出機等の押出機等に供給して、熱分解型発泡剤の分解温度未満の温度で溶融、混練して、押出成形等により押し出して、樹脂材料をシート状の樹脂シートとする。
 ここで、熱分解型発泡剤以外の他の添加剤としては、分解温度調節剤、架橋助剤、酸化防止剤、気泡核剤、着色剤、難燃剤、帯電防止剤、充填材等が挙げられる。また、原料樹脂は、上記したようにポリオレフィン系樹脂が挙げられるが、ポリオレフィン系樹脂とポリオレフィン系樹脂以外の樹脂成分との混合物でもよいし、ポリオレフィン系樹脂以外の樹脂成分であってもよい。
(Process (1))
In the step (1), a raw material resin, additives such as a pyrolytic foaming agent, and resin materials such as other additives are supplied to an extruder such as a single screw extruder or a twin screw extruder, etc. The resin material is made into a sheet-like resin sheet by melting and kneading at a temperature lower than the decomposition temperature of the decomposable foaming agent and extruding by extrusion molding or the like.
Here, examples of the additive other than the thermal decomposition type foaming agent include a decomposition temperature adjusting agent, a crosslinking aid, an antioxidant, a cell nucleating agent, a colorant, a flame retardant, an antistatic agent, a filler, and the like. . The raw material resin may be a polyolefin resin as described above, but may be a mixture of a polyolefin resin and a resin component other than the polyolefin resin, or may be a resin component other than the polyolefin resin.
 熱分解型発泡剤としては、例えば、原料樹脂の溶融温度より高い分解温度を有するものを使用することができる。例えば、分解温度が160~270℃の有機系又は無機系の化学発泡剤を用いることができる。 As the thermally decomposable foaming agent, for example, one having a decomposition temperature higher than the melting temperature of the raw material resin can be used. For example, an organic or inorganic chemical foaming agent having a decomposition temperature of 160 to 270 ° C. can be used.
 有機系発泡剤としては、アゾジカルボンアミド、アゾジカルボン酸金属塩(アゾジカルボン酸バリウム等)、アゾビスイソブチロニトリル等のアゾ化合物;N,N’-ジニトロソペンタメチレンテトラミン等のニトロソ化合物;ヒドラゾジカルボンアミド、4,4'-オキシビス(ベンゼンスルホニルヒドラジド)、トルエンスルホニルヒドラジド等のヒドラジン誘導体;トルエンスルホニルセミカルバジド等のセミカルバジド化合物等、が挙げられる。
 無機系発泡剤としては、酸アンモニウム、炭酸ナトリウム、炭酸水素アンモニウム、炭酸水素ナトリウム、亜硝酸アンモニウム、水素化ホウ素ナトリウム、無水クエン酸モノソーダ等が挙げられる。
 これらの中では、微細な気泡を得る観点、及び経済性、安全面の観点から、アゾ化合物、ニトロソ化合物が好ましく、アゾジカルボンアミド、アゾビスイソブチロニトリル、N,N’-ジニトロソペンタメチレンテトラミンがより好ましく、アゾジカルボンアミドが更に好ましい。これらの熱分解型発泡剤は、単独で又は複数種を組み合わせて使用することができる。
Examples of the organic foaming agent include azo compounds such as azodicarbonamide, metal salts of azodicarboxylic acid (such as barium azodicarboxylate) and azobisisobutyronitrile; nitroso compounds such as N, N′-dinitrosopentamethylenetetramine; And hydrazine derivatives such as hydrazodicarbonamide, 4,4′-oxybis (benzenesulfonylhydrazide) and toluenesulfonylhydrazide; and semicarbazide compounds such as toluenesulfonyl semicarbazide.
Examples of the inorganic foaming agent include ammonium acid, sodium carbonate, ammonium hydrogen carbonate, sodium hydrogen carbonate, ammonium nitrite, sodium borohydride, anhydrous monosodium citrate, and the like.
Among these, azo compounds and nitroso compounds are preferable from the viewpoint of obtaining fine bubbles, and from the viewpoints of economy and safety, and azodicarbonamide, azobisisobutyronitrile, N, N′-dinitrosopentamethylene. Tetramine is more preferred, and azodicarbonamide is still more preferred. These pyrolytic foaming agents can be used alone or in combination of two or more.
 熱分解型発泡剤の添加量は、原料樹脂(例えば、ポリオレフィン系樹脂)100質量部に対して1~10質量部が好ましく、1.5~5質量部がより好ましく、1.5~3質量部が更に好ましい。 The amount of the pyrolytic foaming agent added is preferably 1 to 10 parts by weight, more preferably 1.5 to 5 parts by weight, and more preferably 1.5 to 3 parts by weight with respect to 100 parts by weight of the raw material resin (for example, polyolefin resin). Part is more preferred.
 他の添加剤として用い得る分解温度調節剤は、熱分解型発泡剤の分解温度を低くしたり、分解速度を速めたり調節するものとして配合されるものである。具体的な化合物としては、酸化亜鉛、ステアリン酸亜鉛、尿素等が挙げられる。分解温度調節剤は、発泡シートの表面状態等を調整するために、例えば原料樹脂100質量部に対して0.01~5質量部配合する。 The decomposition temperature adjusting agent that can be used as another additive is blended to lower the decomposition temperature of the pyrolytic foaming agent, or to increase or adjust the decomposition rate. Specific examples of the compound include zinc oxide, zinc stearate, urea and the like. For example, 0.01 to 5 parts by mass of the decomposition temperature regulator is blended with respect to 100 parts by mass of the raw material resin in order to adjust the surface state of the foam sheet.
 架橋助剤としては、多官能モノマー等が挙げられる。架橋助剤をポリオレフィン系樹脂に添加することによって、後述する工程(2)において照射する電離性放射線量を低減して、電離性放射線の照射に伴う樹脂分子の切断、劣化を防止する。 Examples of the crosslinking aid include polyfunctional monomers. By adding a crosslinking aid to the polyolefin-based resin, the ionizing radiation dose irradiated in the step (2) described later is reduced, and the resin molecules are prevented from being cut and deteriorated due to the irradiation of the ionizing radiation.
 架橋助剤としては、具体的には、トリメチロールプロパントリメタクリレート、トリメチロールプロパントリアクリレート、トリメリット酸トリアリルエステル、1,2,4-ベンゼントリカルボン酸トリアリルエステル、トリアリルイソシアヌレート等の1分子中に3個の官能基を持つ化合物;1,6-ヘキサンジオールジメタクリレート、1,9-ノナンジオールジメタクリレート、1,10-デカンジオールジメタクリレート、ジビニルベンゼン等の1分子中に2個の官能基を持つ化合物;フタル酸ジアリル、テレフタル酸ジアリル、イソフタル酸ジアリル、エチルビニルベンゼン、ネオペンチルグリコールジメタクリレート、ラウリルメタクリレート、ステアリルメタクリレート等、が挙げられる。これらの架橋助剤は、単独で又は2以上を組み合わせて使用する。 Specific examples of the crosslinking aid include trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, trimellitic acid triallyl ester, 1,2,4-benzenetricarboxylic acid triallyl ester, triallyl isocyanurate, and the like. Compounds having three functional groups in the molecule; two compounds in one molecule such as 1,6-hexanediol dimethacrylate, 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, divinylbenzene, etc. Compounds having a functional group; diallyl phthalate, diallyl terephthalate, diallyl isophthalate, ethyl vinyl benzene, neopentyl glycol dimethacrylate, lauryl methacrylate, stearyl methacrylate and the like. These crosslinking aids are used alone or in combination of two or more.
 架橋助剤の添加量は、原料樹脂100質量部に対して0.2~10質量部が好ましく、0.3~5質量部がより好ましく、0.5~5質量部が更に好ましい。該添加量が0.2質量部以上であると発泡シートが所望する架橋度を安定して得ることが可能となり、10質量部以下であると発泡シートの架橋度の制御が容易となる。 The addition amount of the crosslinking aid is preferably 0.2 to 10 parts by mass, more preferably 0.3 to 5 parts by mass, and still more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the raw material resin. When the addition amount is 0.2 parts by mass or more, it is possible to stably obtain the desired degree of crosslinking of the foam sheet, and when it is 10 parts by mass or less, the degree of crosslinking of the foam sheet is easily controlled.
 また、酸化防止剤としては、2,6-ジ-t-ブチル-p-クレゾール等のフェノール系酸化防止剤等が挙げられる。 Examples of the antioxidant include phenolic antioxidants such as 2,6-di-t-butyl-p-cresol.
(工程(2))
 工程(2)では、工程(1)で得た樹脂シートを架橋する。工程(2)における架橋は、電離性放射線を樹脂シートに照射して行うことが好ましい。電離性放射線としては、α線、β線、γ線、電子線等が挙げられるが、電子線がより好ましい。樹脂シートに対する電離性放射線の照射量は、1~10Mradが好ましく、1.5~8Mradがより好ましい。また、架橋助剤を用いる場合の電離性放射線の照射量は0.3~8Mradが好ましく、0.5~5.5Mradがより好ましい。
 電離性放射線の照射量は、上記下限値以上とすることで、樹脂シートの発泡に必要な剪断粘度を付与しやすくなる。また、上記上限値以下とすることで樹脂シートの剪断粘度が高くなりすぎず発泡性が良好になる。そのため、上記した密度の発泡シートを得やすくなり、さらには発泡シートの外観も良好となる。
 ただし、架橋の進行度は、通常、原料樹脂、添加剤の種類等により影響されるため、電離性放射線の照射量は、通常は架橋度を測定しながら調整し、上記した架橋度となるようにする。
(Process (2))
In step (2), the resin sheet obtained in step (1) is crosslinked. Crosslinking in the step (2) is preferably performed by irradiating the resin sheet with ionizing radiation. Examples of the ionizing radiation include α-rays, β-rays, γ-rays, and electron beams, and electron beams are more preferable. The amount of ionizing radiation applied to the resin sheet is preferably 1 to 10 Mrad, more preferably 1.5 to 8 Mrad. In the case of using a crosslinking aid, the irradiation amount of ionizing radiation is preferably 0.3 to 8 Mrad, more preferably 0.5 to 5.5 Mrad.
By setting the irradiation amount of ionizing radiation to the above lower limit value or more, it becomes easy to impart a shear viscosity necessary for foaming the resin sheet. Moreover, by setting it as the said upper limit or less, the shear viscosity of a resin sheet does not become high too much, but foamability becomes favorable. Therefore, it becomes easy to obtain the above-described density foam sheet, and the appearance of the foam sheet is also improved.
However, since the degree of progress of crosslinking is usually influenced by the raw material resin, the type of additives, etc., the irradiation dose of ionizing radiation is usually adjusted while measuring the degree of crosslinking so that the degree of crosslinking described above is obtained. To.
(工程(3))
 工程(3)では、樹脂シートを、熱分解型発泡剤の分解温度以上に加熱して発泡する。通常、本工程(3)は、上記工程(2)の後に実施する。
 加熱発泡させる温度は、熱分解型発泡剤の分解温度によるが、通常140~300℃、好ましくは160~260℃である。また、樹脂シートを発泡させる方法としては、特に制限はなく、例えば、熱風により加熱する方法、赤外線により加熱する方法、塩浴による方法、オイルバスによる方法等が挙げられ、これらは併用してもよい。
(Process (3))
In step (3), the resin sheet is heated to a temperature equal to or higher than the decomposition temperature of the thermally decomposable foaming agent and foamed. Usually, this process (3) is implemented after the said process (2).
The temperature at which foaming is carried out depends on the decomposition temperature of the pyrolytic foaming agent, but is usually from 140 to 300 ° C, preferably from 160 to 260 ° C. The method for foaming the resin sheet is not particularly limited, and examples thereof include a method of heating with hot air, a method of heating with infrared rays, a method using a salt bath, a method using an oil bath, and the like. Good.
(工程(4))
 工程(4)では、樹脂シートを、延伸する。延伸により、得られる発泡シートの気泡の平均気泡径、気泡数、発泡シートの厚み等を調整することができる。延伸は、樹脂シートを発泡させた後に行ってもよいし、樹脂シートを発泡させつつ行ってもよい。延伸は、例えば一軸延伸機、二軸延伸機等の公知の装置で行うとよい。
 なお、樹脂シートを発泡させた後に延伸を行う場合には、樹脂シートを冷却することなく発泡時の溶融状態を維持したまま続けて延伸したほうがよいが、樹脂シートを冷却した後、再度、加熱して溶融又は軟化状態とした上で延伸してもよい。
(Process (4))
In step (4), the resin sheet is stretched. By stretching, the average cell diameter, the number of cells, the thickness of the foam sheet, and the like of the foam sheet can be adjusted. Stretching may be performed after foaming the resin sheet, or may be performed while foaming the resin sheet. The stretching may be performed with a known apparatus such as a uniaxial stretching machine or a biaxial stretching machine.
In addition, when extending | stretching after making a resin sheet foam, it is better to continue extending | stretching, maintaining the molten state at the time of foaming, without cooling a resin sheet, but after cooling a resin sheet, it heats again. Then, it may be stretched after being in a molten or softened state.
 また、上記では架橋を電離性放射線を使用して行う例を説明したが、ポリオレフィン系樹脂に、添加剤として有機過酸化物等の架橋剤を配合しておき、ポリオレフィン系樹脂を加熱して有機過酸化物を分解させる方法等で行ってもよい。そのような有機過酸化物としては、例えば、1,1-ビス(t-ブチルパーオキシ)3,3,5-トリメチルシクロヘキサン、1,1-ビス(t-ブチルパーオキシ)シクロヘキサン等が挙げられる。 Moreover, although the example which performs bridge | crosslinking using ionizing radiation was demonstrated above, crosslinking agents, such as an organic peroxide, are mix | blended with polyolefin resin as an additive, polyolefin resin is heated, and organic You may carry out by the method of decomposing | disassembling a peroxide. Examples of such organic peroxides include 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, and the like. .
 有機過酸化物の添加量は、原料樹脂100質量部に対し、0.01~5質量部が好ましく、0.1~3質量部がより好ましい。有機過酸化物の添加量が上記範囲内であると、樹脂材料の架橋が進行しやすく、また、発泡シート中における有機過酸化物の分解残渣の量を抑制する。
 また、樹脂材料は、上記発泡剤を使用する代わりに、炭酸ガスやブタンガスに代表されるガス発泡により発泡させてもよいし、メカニカルフロス法により発泡させてもよい。
The addition amount of the organic peroxide is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 3 parts by mass with respect to 100 parts by mass of the raw material resin. When the addition amount of the organic peroxide is within the above range, crosslinking of the resin material is likely to proceed, and the amount of decomposition residue of the organic peroxide in the foamed sheet is suppressed.
Further, the resin material may be foamed by gas foaming typified by carbon dioxide gas or butane gas instead of using the foaming agent, or may be foamed by a mechanical floss method.
 (工程(5))
 工程(5)は、延伸して得られた発泡シートに凹部を形成する工程である。凹部を形成する方法は特に限定されず、例えば、エンボスロールを用いて凹部を形成する方法、針ロールを用いて凹部を形成する方法、カッターを用いて凹部を形成する方法などを例示することができる。
(Process (5))
Step (5) is a step of forming a recess in the foamed sheet obtained by stretching. The method of forming the recess is not particularly limited, and examples thereof include a method of forming a recess using an embossing roll, a method of forming a recess using a needle roll, and a method of forming a recess using a cutter. it can.
(発泡シートの使用形態及び用途)
 本発明の発泡シートは、そのままで用いることもできるが、いずれか一方の面又は両面に粘着剤層を設けて用いてもよい。粘着剤層の厚みは、好ましくは5~200μmであり、より好ましくは7~150μmである。
 発泡シートの一方の面又は両面に設けられる粘着剤層を構成する粘着剤としては、特に制限はなく、例えば、アクリル系粘着剤、ウレタン系粘着剤、ゴム系粘着剤等が挙げられる。
(Usage and use of foam sheet)
The foamed sheet of the present invention can be used as it is, but may be used by providing a pressure-sensitive adhesive layer on any one or both sides. The thickness of the pressure-sensitive adhesive layer is preferably 5 to 200 μm, more preferably 7 to 150 μm.
There is no restriction | limiting in particular as an adhesive which comprises the adhesive layer provided in one side or both surfaces of a foam sheet, For example, an acrylic adhesive, a urethane type adhesive, a rubber-type adhesive, etc. are mentioned.
 発泡シートに粘着剤層を設ける方法としては、例えば、発泡シートの少なくとも一方の面にコーター等の塗工機を用いて粘着剤を塗布する方法、発泡シートの少なくとも一方の面にスプレーを用いて粘着剤を噴霧、塗布する方法、発泡シートの一方の面に刷毛を用いて粘着剤を塗布する方法等が挙げられる。 As a method of providing the pressure-sensitive adhesive layer on the foamed sheet, for example, a method of applying the pressure-sensitive adhesive using a coating machine such as a coater on at least one surface of the foamed sheet, or using a spray on at least one surface of the foamed sheet Examples thereof include a method of spraying and applying an adhesive, and a method of applying an adhesive using a brush on one surface of a foam sheet.
 本発明の発泡シートは、アクリル板、ガラス板等の前面板、又は該前面板に設けられるタッチパネルと表示装置の本体とを接着するための接着材として用いることができる。この場合、発泡シートは額縁状となるように開口部を設けて用いる、又は所望の形状、例えば短冊型にカットして用いることができる。本発明の発泡シートを接着材として用いる場合、発泡シートが独立気泡体であり、気泡が連通していないことから、フレームに応力が加わった際に、該フレームと前面板との間に生じるギャップからの埃、水分等の浸入を抑制することも可能となる。また、衝撃吸収性により、前面板の破損を抑制する効果も得られる。 The foamed sheet of the present invention can be used as an adhesive for bonding a front plate such as an acrylic plate or a glass plate, or a touch panel provided on the front plate and the main body of the display device. In this case, the foam sheet can be used by providing an opening so as to have a frame shape, or cut into a desired shape, for example, a strip shape. When the foamed sheet of the present invention is used as an adhesive, since the foamed sheet is a closed cell body and the bubbles are not in communication, a gap generated between the frame and the front plate when stress is applied to the frame. It is also possible to suppress entry of dust, moisture, etc. from Moreover, the effect which suppresses the failure | damage of a front plate is also acquired by shock absorption.
 また、本発明の発泡シートは、例えば、液晶パネル等の表示パネルの衝撃吸収材として使用することができる。表示パネルの衝撃吸収材は、表示パネルの背面側に配置され、表示パネルに作用される衝撃を吸収して、表示パネルの破損、故障を防止するというものである。本発明の発泡シートは、衝撃吸収性とともに、耐プーリング性も有するため、表示パネルの背面側に衝撃吸収材として配置されることで、表示パネルの表面が押圧されることで生じるプーリングの発生をも防止し得る。
 なお、上記の表示装置を構成する前面板、タッチパネル、表示装置、接着材、フレーム、表示パネル、衝撃吸収材等の用語については、後述する。
Moreover, the foam sheet of this invention can be used as an impact-absorbing material of display panels, such as a liquid crystal panel, for example. The shock absorber of the display panel is disposed on the back side of the display panel, and absorbs the shock applied to the display panel to prevent the display panel from being damaged or broken. Since the foamed sheet of the present invention has a shock absorbing property and a pooling resistance, it is arranged as a shock absorbing material on the back side of the display panel, so that the occurrence of pooling caused by pressing the surface of the display panel is prevented. Can also be prevented.
Note that terms such as a front plate, a touch panel, a display device, an adhesive, a frame, a display panel, and a shock absorber that constitute the display device will be described later.
[表示装置]
 本発明の表示装置は、本発明の独立気泡発泡シートと、表示パネルとを備えるものであり、本発明の発泡シートは、後述する衝撃吸収材13、接着材16の少なくともいずれか一方に用いられる。本発明の表示装置の一例を、図4を用いて説明する。
 図4に示される表示装置10は、表示パネル11、表示パネル11の前面側に設けられる前面板12、該前面板12とフレーム15とを接着する接着材16、表示パネル11の背面側に配置される衝撃吸収材13等を備えている。
[Display device]
The display device of the present invention includes the closed-cell foamed sheet of the present invention and a display panel, and the foamed sheet of the present invention is used for at least one of an impact absorbing material 13 and an adhesive 16 described later. . An example of the display device of the present invention will be described with reference to FIG.
4 includes a display panel 11, a front plate 12 provided on the front side of the display panel 11, an adhesive 16 for bonding the front plate 12 and the frame 15, and a back side of the display panel 11. The shock absorbing material 13 and the like are provided.
 表示パネル11は、衝撃吸収材13の上に配置されており、2枚のガラス基材間に、液晶層等を配置した液晶表示素子、有機EL表示素子等の表示素子を少なくとも含むユニットであるが、表示素子以外にも、保護フィルム、偏光素子、位相差フィルム等が積層されたものであってもよい。また、表示パネル11は、表示素子が液晶表示素子である場合等には、表示素子の背面側に設けられたバックライトユニットをさらに備える。なお、表示パネル11は、液晶表示素子を含むことが好ましい。 The display panel 11 is a unit that is disposed on the shock absorber 13 and includes at least a display element such as a liquid crystal display element or an organic EL display element in which a liquid crystal layer is disposed between two glass substrates. However, in addition to the display element, a protective film, a polarizing element, a retardation film, or the like may be laminated. The display panel 11 further includes a backlight unit provided on the back side of the display element when the display element is a liquid crystal display element. The display panel 11 preferably includes a liquid crystal display element.
 前面板12は、表示パネル11等を保護するためのカバー板材を含む。カバー板材は、光透過性を有していれば特に限定されないが、アクリル板、ガラス板等が挙げられる。前面板12は、カバー板材以外の部材をさらに含んでいてもよく、例えば、表示装置10がタッチパネル式のものである場合には、カバー板材の下面側にタッチパネルユニット(図示せず)が積層されていてもよい。 The front plate 12 includes a cover plate material for protecting the display panel 11 and the like. Although a cover board | plate material will not be specifically limited if it has a light transmittance, An acrylic board, a glass plate, etc. are mentioned. The front plate 12 may further include a member other than the cover plate material. For example, when the display device 10 is a touch panel type, a touch panel unit (not shown) is laminated on the lower surface side of the cover plate material. It may be.
 衝撃吸収材13は、表示パネル11及び前面板12に衝撃が加わったときに、その衝撃を吸収するために設けられるものであり、通常発泡シートが用いられる。この発泡シートとしては、高い衝撃吸収性を有する本発明の独立気泡発泡シートが好適に用いられる。また、本発明の発泡シートは耐プーリング性に優れることから、衝撃吸収材13に該発泡シートを用いると、前面板12を通じて表示パネル11が押圧されることで生じるプーリングの発生をも防止し得る。 The impact absorbing material 13 is provided to absorb the impact when the impact is applied to the display panel 11 and the front plate 12, and a foam sheet is usually used. As this foamed sheet, the closed cell foamed sheet of the present invention having high impact absorbability is preferably used. In addition, since the foamed sheet of the present invention is excellent in pooling resistance, the use of the foamed sheet as the shock absorbing material 13 can also prevent the occurrence of pooling caused by pressing the display panel 11 through the front plate 12. .
 前面板12は、フレーム15によって支持される。フレーム15は、四角枠状を呈するとともに、内周側の高さが低くなって嵌合部15Aが設けられている。前面板12は、嵌合部15Aに嵌合されるように配置される。なお、前面板12は、嵌合部15Aに配置された接着材16により嵌合部15Aに接着されることでフレーム15に固定される。接着材16には、基材の両面に粘着剤層が設けられた両面テープ等が用いられる。この両面テープの基材としては、本発明の発泡シートが好適に用いられる。本発明の発泡シートは衝撃吸収性に優れるため、前面板12への衝撃を緩和し、該前面12の破損を抑制することができる。なお、本発明の発泡シートは独立気泡体であり、気泡が連通していないことから、使用中にフレームに応力が加わった場合に、該フレームと前面板との間に生じるギャップからの埃、水分等の浸入を抑制することも可能となるという効果も得られる。 The front plate 12 is supported by the frame 15. The frame 15 has a quadrangular frame shape and is provided with a fitting portion 15 </ b> A having a lower inner peripheral side height. The front plate 12 is disposed so as to be fitted to the fitting portion 15A. The front plate 12 is fixed to the frame 15 by being bonded to the fitting portion 15A by the adhesive 16 arranged in the fitting portion 15A. As the adhesive 16, a double-sided tape or the like in which a pressure-sensitive adhesive layer is provided on both surfaces of a base material is used. As the base material of the double-sided tape, the foamed sheet of the present invention is suitably used. Since the foamed sheet of the present invention is excellent in impact absorption, it is possible to reduce the impact on the front plate 12 and to prevent the front surface 12 from being damaged. In addition, since the foam sheet of the present invention is a closed-cell body, and bubbles are not communicated, when stress is applied to the frame during use, dust from a gap generated between the frame and the front plate, There is also an effect that it is possible to suppress intrusion of moisture and the like.
 表示パネル11は、接着層17を介して前面板12の背面に接着され、それにより、前面板12と一体となりフレーム15により支持される。なお、接着層17は、OCA(Optically Clear Adhesive)と呼ばれる光透過性を有する接着剤層、又は粘着剤層により構成される。 The display panel 11 is bonded to the back surface of the front plate 12 through the adhesive layer 17, and thereby is integrated with the front plate 12 and supported by the frame 15. The adhesive layer 17 is composed of an adhesive layer having optical transparency called OCA (Optically Clear Adhesive) or an adhesive layer.
 また、表示パネル11の背面側には、表示パネル11と一定の間隔を置いて配置されるプレート18が設けられる。プレート18は、フレーム15に固定されている。プレート18の表面上に配置される衝撃吸収材13と表示パネル11との間には、クリアランスが設けられていてもよい。 Further, on the back side of the display panel 11, a plate 18 arranged with a certain distance from the display panel 11 is provided. The plate 18 is fixed to the frame 15. A clearance may be provided between the shock absorber 13 disposed on the surface of the plate 18 and the display panel 11.
 本発明の表示装置は、ノート型パーソナルコンピューター、携帯電話、スマートフォン、タブレット等の携帯機器に好適に設けられる。
 また、本発明の表示装置は、タッチパネルユニットを備える、タッチパネル式のものであってもよい。タッチパネルの表面は、高速で繰り返し押圧されるが、衝撃吸収材13として本発明の発泡シートを用いた場合、プーリングの発生を抑制するので、表示装置の表示性能が改善される。
The display device of the present invention is suitably provided in a portable device such as a notebook personal computer, a mobile phone, a smartphone, or a tablet.
The display device of the present invention may be a touch panel type including a touch panel unit. Although the surface of the touch panel is repeatedly pressed at a high speed, when the foam sheet of the present invention is used as the shock absorber 13, the occurrence of pooling is suppressed, so that the display performance of the display device is improved.
 なお、本発明の表示装置について、図4を用いて説明してきたが、図4に示される表示装置は、本発明の表示装置の一例を示すものであって、種々の改変が可能である。例えば、表示パネル11及び前面板12は、フレーム15以外の部材によって支持されていてもよいし、衝撃吸収材13は、プレート18以外の部材の上に配置されていてもよい。また、各部材に用いられる材料も、一例を記載したにすぎず、これらの部材に通常用いられる材料からなるものを用いることができる。 Although the display device of the present invention has been described with reference to FIG. 4, the display device shown in FIG. 4 shows an example of the display device of the present invention, and various modifications can be made. For example, the display panel 11 and the front plate 12 may be supported by a member other than the frame 15, and the shock absorber 13 may be disposed on a member other than the plate 18. Moreover, the material used for each member is only an example, and materials made of materials usually used for these members can be used.
 本発明を実施例により更に詳細に説明するが、本発明はこれらの例によってなんら限定されるものではない。
 なお、本明細書における各種物性、評価方法は、以下のとおりである。
<厚み>
 JIS K6767の方法に従って測定した。
<密度>
 JIS K6767の方法に従って測定した。
<25%圧縮強度>
 発泡シートの25%圧縮強度は、JIS K6767の方法に従い、具体的には、測定装置(ORIENTEC社製、製品名「TENSILON RTG-1250」)を用いて、3回繰り返して測定し、その平均値を25%圧縮強度とした。
Examples The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
Various physical properties and evaluation methods in this specification are as follows.
<Thickness>
It measured according to the method of JIS K6767.
<Density>
It measured according to the method of JIS K6767.
<25% compressive strength>
The 25% compressive strength of the foamed sheet was measured three times repeatedly according to the method of JIS K6767, specifically, using a measuring device (manufactured by ORIENTEC, product name “TENSILON RTG-1250”). Was 25% compressive strength.
<平均気泡径>
 発泡シートを50mm四方にカットし、液体窒素に1分間浸した後にMD及びTDそれぞれに沿って厚み方向に切断して、デジタルマイクロスコープ(株式会社キーエンス製、製品名「VHX-900」)を用いて200倍の拡大写真を撮り、MD、TDそれぞれにおける長さ2mm分の切断面に存在する全ての気泡についてMD、ZDの気泡径、及びTD、ZDの気泡径を測定し、その操作を5回繰り返した。そして、全ての気泡のMD、TDそれぞれの気泡径の平均値をMD、TDの平均気泡径とするとともに、以上の操作によって測定された全てのZDの気泡径の平均値をZDの平均気泡径とした。
<Average bubble diameter>
The foamed sheet is cut into a 50mm square, immersed in liquid nitrogen for 1 minute, then cut in the thickness direction along each of MD and TD, and a digital microscope (manufactured by Keyence Corporation, product name "VHX-900") is used. Take a 200x magnified photograph, measure the bubble diameter of MD, ZD, and the bubble diameter of TD, ZD and the bubble diameter of TD, ZD for all the bubbles present on the cut surface of 2 mm in length in each of MD and TD. Repeated times. The average value of the bubble diameters of all the bubbles MD and TD is taken as the average bubble diameter of the MD and TD, and the average value of the bubble diameters of all ZDs measured by the above operation is taken as the average bubble diameter of the ZD. It was.
<独立気泡率>
 発泡シートの独立気泡率は、明細書記載の方法で測定したものである。
<Closed cell ratio>
The closed cell ratio of the foamed sheet is measured by the method described in the specification.
[衝撃吸収性評価(ガラス割れ高さ)]
 図5に示すように、ガラス板(100mm×100mmの正方形、厚み:0.55mm、コーニング社製、商品名「ゴリラガラス3」)の上に、その両面に両面PETテープ(世紀水化学工業株式会社製、商品名「LCD部材固定用両面テープ 3801X」を貼りつけた発泡シート(100mm×100mm)をガラス板の両端に貼付け、発泡シートを介してアクリル板(厚み10mm:、三菱レイヨン株式会社製、商品名「アクリライト」)を積層した積層体を作製した。この積層体を、ガラス面を下にして落下させる。10cmの高さから10回落下させて割れなければ、更に10cm上(20cmの高さ)から10回落下させていき、割れたときの高さをガラス割れ高さとし、衝撃吸収性の指標とした。ガラス割れ高さが高いほど、繰り返し加えられる衝撃に対する衝撃吸収性に優れることを意味する。
[Evaluation of shock absorption (glass crack height)]
As shown in FIG. 5, on a glass plate (100 mm × 100 mm square, thickness: 0.55 mm, manufactured by Corning, trade name “Gorilla Glass 3”), double-sided PET tape (Stock of Century Water Chemicals Co., Ltd.) A foam sheet (100 mm x 100 mm) with a product name "Double-sided tape 3801X for fixing LCD members" affixed to both ends of a glass plate and an acrylic plate (thickness 10 mm: manufactured by Mitsubishi Rayon Co., Ltd.) through the foam sheet , Product name “Acrylite”) was produced, and the laminate was dropped with the glass surface down.If it was dropped 10 times from a height of 10 cm and not broken, it was further 10 cm above (20 cm). The glass break height is taken as the glass break height, and it was used as an index of shock absorption. The better the impact absorption against an impact applied returned.
[耐プーリング性評価]
 50mm×70mmの発泡シートの上に4.7インチの液晶パネルを配置させ、液晶パネルの表面に押し棒を用いて荷重をかけて、以下の基準で評価した。ここで、押し棒はφ15mmであり、その先端にはゴム(硬度:30)を設け、人間の指で押すことを想定した押し棒とした。
 A:荷重6N以上で、プーリングは発生しなかった。
 B:荷重3N以上5N未満で、わずかにプーリングが発生した。
 C:荷重3N未満でプーリングが発生した。
[Pooling resistance evaluation]
A 4.7-inch liquid crystal panel was placed on a 50 mm × 70 mm foam sheet, a load was applied to the surface of the liquid crystal panel using a push rod, and evaluation was performed according to the following criteria. Here, the push bar has a diameter of 15 mm, rubber (hardness: 30) is provided at the tip, and the push bar is assumed to be pushed by a human finger.
A: When the load was 6N or more, pooling did not occur.
B: Slight pooling occurred at a load of 3N or more and less than 5N.
C: Pooling occurred when the load was less than 3N.
[実施例1]
 ポリエチレン系樹脂としてのメタロセン化合物を用いて得られた直鎖状低密度ポリエチレン(エクソン・ケミカル社製、商品名「EXACT3027」)100質量部と、発泡剤としてのアゾジカルボンアミド2質量部と、2,6-ジ-t-ブチル-p-クレゾール0.3質量部と、酸化亜鉛1質量部とを押出機に供給して130℃で溶融混練し、その後、厚み約0.2mmの樹脂シートとして押出した。
 次に、樹脂シートを、その両面に加速電圧800kVの電子線を5Mrad照射して架橋した後、熱風及び赤外線ヒーターにより250℃に保持された発泡炉内に連続的に送り込んで加熱して発泡させるとともに、発泡させながらMDの延伸倍率1.3倍、TDの延伸倍率2.0倍で延伸させて、厚み0.06mmの発泡シートを得た。得られた発泡シートの架橋度は25%であり、25%圧縮強度は118kPaだった。この発泡シートを5cm×5cmの正方形にカットし、図2の2-bで示されるパターンとなるよう、エンボスロールを用いて縦に8本、横に8本の線状の凹部(幅:0.5mm、長さ:40mm、線間距離:5mm、深さ:20%、凹部を有する領域数:25、凹部面積比率:12%)を設けて、実施例1の発泡シートとした。実施例1の発泡シートについて、上記の方法により、厚み、密度、圧縮強度、平均気泡径(MD、TD、ZD)、独立気泡率を測定した。測定値を表1に示す。また、上記の方法により、衝撃吸収性、耐プーリング性を評価した。その結果を表1に示す。
[Example 1]
100 parts by mass of linear low-density polyethylene (trade name “EXACT3027” manufactured by Exxon Chemical Co., Ltd.) obtained using a metallocene compound as a polyethylene resin, 2 parts by mass of azodicarbonamide as a foaming agent, , 6-di-t-butyl-p-cresol 0.3 parts by mass and 1 part by mass of zinc oxide are supplied to an extruder and melt-kneaded at 130 ° C., and then a resin sheet having a thickness of about 0.2 mm is obtained. Extruded.
Next, the resin sheet is cross-linked by irradiating an electron beam with an acceleration voltage of 800 kV on both surfaces by 5 Mrad, and then continuously fed into a foaming furnace maintained at 250 ° C. by hot air and an infrared heater to be heated and foamed. At the same time, it was stretched at a stretch ratio of MD of 1.3 times and a stretch ratio of TD of 2.0 times while foaming to obtain a foam sheet having a thickness of 0.06 mm. The resulting foamed sheet had a degree of crosslinking of 25% and a 25% compressive strength of 118 kPa. This foamed sheet is cut into a 5 cm × 5 cm square, and 8 linear recesses (width: 0) are vertically used by using an embossing roll so that a pattern shown by 2-b in FIG. 2 is obtained. 5 mm, length: 40 mm, distance between lines: 5 mm, depth: 20%, number of regions having recesses: 25, recess area ratio: 12%) to obtain a foam sheet of Example 1. For the foamed sheet of Example 1, the thickness, density, compressive strength, average cell diameter (MD, TD, ZD), and closed cell ratio were measured by the above methods. The measured values are shown in Table 1. Moreover, the impact absorbability and pooling resistance were evaluated by the above methods. The results are shown in Table 1.
[実施例2~6]
 表1の密度、MD、TD、ZDの気泡径となるように、発泡剤の質量部、MDの延伸倍率及びTDの延伸倍率を調整した点以外は、実施例1と同様に実施した。ただし、実施例6においては、さらに、照射される電子線を7Mradに変更した。
[Examples 2 to 6]
It implemented like Example 1 except the point which adjusted the mass part of the foaming agent, the draw ratio of MD, and the draw ratio of TD so that it might become the cell diameter of density of Table 1, MD, TD, and ZD. However, in Example 6, the irradiated electron beam was further changed to 7 Mrad.
[比較例1、2]
 表1の密度、MD、TD、ZDの気泡径となるように、発泡剤の質量部、MDの延伸倍率及びTDの延伸倍率を調整した点、及び凹部を設けなかった点以外は、実施例1と同様に発泡シートを作製し、上記の方法により、各性状を測定し、衝撃吸収性、耐プーリングの評価をした。
[Comparative Examples 1 and 2]
Except for the point of adjusting the mass part of the foaming agent, the draw ratio of MD and the draw ratio of TD, and the point of not providing the recess so as to obtain the density, MD, TD, and ZD cell diameter in Table 1. A foamed sheet was prepared in the same manner as in No. 1, and each property was measured by the above method to evaluate impact absorption and anti-pooling.
[比較例3、4]
 比較例3、4では、発泡シートとして市販品であるSCF400(日東電工社製)、Poron(株式会社ロジャースイノアック社製)について、上記の方法により、各性状を測定し、また評価した。
[Comparative Examples 3 and 4]
In Comparative Examples 3 and 4, the properties of SCF400 (manufactured by Nitto Denko Corporation) and Poron (manufactured by Roger Sinoac Co., Ltd.), which are commercially available foamed sheets, were measured and evaluated by the above methods.
[比較例5]
 実施例1で、凹部を設けなかった点以外は、実施例1と同様に発泡シートを作製し、各性状を測定し、評価した。
[Comparative Example 5]
A foamed sheet was prepared in the same manner as in Example 1 except that no recess was provided in Example 1, and each property was measured and evaluated.
[比較例6]
 実施例1で、発泡シートとして市販品であるPoron(株式会社ロジャースイノアック社製)を用いた以外は、実施例1と同様に発泡シートを作製し、各性状を測定し、評価した。
[Comparative Example 6]
In Example 1, a foamed sheet was prepared in the same manner as in Example 1 except that Poron (manufactured by Roger Sinoac Co., Ltd.), which is a commercial product, was used as the foamed sheet, and each property was measured and evaluated.
Figure JPOXMLDOC01-appb-T000001
 
Figure JPOXMLDOC01-appb-T000001
 
 以上の実施例1~6から明らかなように、本発明の発泡シートは、高い衝撃吸収性を有すること、また優れた耐プーリング性を有することが確認された。一方、凹部を有しない比較例1及び2の発泡シートは、実施例の発泡シートに比べて、衝撃吸収性、耐プーリング性が不足しており、実施例1で用いた発泡シートであって凹部を有しない発泡シートを用いた比較例5についても、衝撃吸収性、耐プーリング性が不足していることが確認された。連続気泡の発泡シートを用いた比較例3及び4では、衝撃吸収性、耐プーリング性ともに実施例の発泡シートには至らず不足しており、同じく連続気泡の発泡シートを用い、凹部を設けた発泡シートを用いた比較例6でも、耐プーリング性ともに実施例の発泡シートには至らず不足していることが確認された。また、比較例6の結果から、連続気泡の発泡シートに凹部を設けても、25%圧縮強度はほとんど低減せず、25%圧縮強度の低減効果は、独立気泡の発泡シートに特有の現象であることが確認された。 As is clear from Examples 1 to 6 above, it was confirmed that the foamed sheet of the present invention has high impact absorbability and excellent pooling resistance. On the other hand, the foamed sheets of Comparative Examples 1 and 2 that do not have recesses are insufficient in shock absorption and pooling resistance compared to the foamed sheets of the examples. It was confirmed that Comparative Example 5 using a foam sheet having no slag was insufficient in impact absorption and pooling resistance. In Comparative Examples 3 and 4 using an open-cell foam sheet, both the shock absorption and the pooling resistance were insufficient to reach the foam sheet of the example, and the open-cell foam sheet was also used to provide a recess. Also in Comparative Example 6 using the foamed sheet, it was confirmed that both the pooling resistance and the foamed sheet of the examples were not sufficient. Further, from the results of Comparative Example 6, even when the open-celled foam sheet is provided with a recess, the 25% compressive strength is hardly reduced, and the effect of reducing the 25% compressive strength is a phenomenon peculiar to the closed-cell foamed sheet. It was confirmed that there was.
 10 表示装置
 11 表示パネル
 12 前面板
 13 衝撃吸収材
 15 フレーム
 16 接着材
 17 接着層
 18 プレート
DESCRIPTION OF SYMBOLS 10 Display apparatus 11 Display panel 12 Front plate 13 Shock absorber 15 Frame 16 Adhesive material 17 Adhesive layer 18 Plate

Claims (11)

  1.  25に分割した領域と1cm×1cmの正方形の領域の面積が小さくなるいずれかの領域であって、厚みに対して1~99%の深さを有する凹部を少なくとも1箇所有する領域を9以上有する独立気泡発泡シート。 There are 9 or more regions having at least one recess having a depth of 1 to 99% of the thickness, which is any region in which the area of the region divided into 25 and a square region of 1 cm × 1 cm is reduced. Closed cell foam sheet.
  2.  シート全面に対する前記凹部の面積比率が、1~90%である請求項1に記載の独立気泡発泡シート。 The closed-cell foamed sheet according to claim 1, wherein the area ratio of the recess to the entire sheet is 1 to 90%.
  3.  前記凹部が、線状である請求項1又は2に記載の独立気泡発泡シート。 The closed-cell foamed sheet according to claim 1 or 2, wherein the recess is linear.
  4.  前記凹部の幅が、0.1~2mmである請求項3に記載の独立気泡発泡シート。 The closed-cell foamed sheet according to claim 3, wherein the width of the recess is 0.1 to 2 mm.
  5.  前記凹部が、少なくとも2つの領域に渡って存在する請求項1~4のいずれか1項に記載の独立気泡発泡シート。 The closed-cell foamed sheet according to any one of claims 1 to 4, wherein the concave portion exists over at least two regions.
  6.  MDにおける平均気泡径が25~300μmであり、TDにおける平均気泡径が30~330μmである気泡を有する請求項1~5のいずれか1項に記載の独立気泡発泡シート。 6. The closed-cell foamed sheet according to any one of claims 1 to 5, which has bubbles having an average cell diameter in MD of 25 to 300 μm and an average cell diameter in TD of 30 to 330 μm.
  7.  密度が、60~600kg/mである請求項1~6のいずれか1項に記載の独立気泡発泡シート。 The closed-cell foamed sheet according to any one of claims 1 to 6, wherein the density is 60 to 600 kg / m 3 .
  8.  独立気泡率が、90~100%である請求項1~7のいずれか1項に記載の独立気泡発泡シート。 The closed cell foam sheet according to any one of claims 1 to 7, wherein the closed cell ratio is 90 to 100%.
  9.  25%圧縮強度が、3~90kPaである請求項1~8のいずれか1項に記載の独立気泡発泡シート。 The closed-cell foamed sheet according to any one of claims 1 to 8, wherein the 25% compressive strength is 3 to 90 kPa.
  10.  請求項1~9のいずれか1項に記載の独立気泡発泡シートと、表示パネルとを備える表示装置。 A display device comprising the closed cell foam sheet according to any one of claims 1 to 9 and a display panel.
  11.  前記表示パネルが、前記独立気泡発泡シートの上に配置される請求項10に記載の表示装置。 The display device according to claim 10, wherein the display panel is disposed on the closed cell foam sheet.
PCT/JP2017/013108 2016-03-29 2017-03-29 Closed-cell foam sheet, and display device WO2017170793A1 (en)

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JP2005350571A (en) * 2004-06-10 2005-12-22 Sekisui Chem Co Ltd Thermoplastic resin foam sheet and method for producing thermoplastic resin foam sheet
JP2007136966A (en) * 2005-11-21 2007-06-07 Asahi Fiber Glass Co Ltd Method for manufacturing polyolefin resin foamed body
JP2012025916A (en) * 2010-07-27 2012-02-09 Daicel Novafoam Ltd Foam, method of manufacturing the same, and application thereof
JP2012227977A (en) * 2009-12-28 2012-11-15 Sekisui Polymatech Co Ltd Binding and shock absorbing adhesive sheet for wiring harness
JP2015196234A (en) * 2014-04-03 2015-11-09 東レ株式会社 Abrasive pad

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JP6358825B2 (en) 2013-04-10 2018-07-18 日東電工株式会社 Resin foam composite

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Publication number Priority date Publication date Assignee Title
JP2002265661A (en) * 2001-03-08 2002-09-18 Sekisui Chem Co Ltd Method for producing open-cell foam
JP2005350571A (en) * 2004-06-10 2005-12-22 Sekisui Chem Co Ltd Thermoplastic resin foam sheet and method for producing thermoplastic resin foam sheet
JP2007136966A (en) * 2005-11-21 2007-06-07 Asahi Fiber Glass Co Ltd Method for manufacturing polyolefin resin foamed body
JP2012227977A (en) * 2009-12-28 2012-11-15 Sekisui Polymatech Co Ltd Binding and shock absorbing adhesive sheet for wiring harness
JP2012025916A (en) * 2010-07-27 2012-02-09 Daicel Novafoam Ltd Foam, method of manufacturing the same, and application thereof
JP2015196234A (en) * 2014-04-03 2015-11-09 東レ株式会社 Abrasive pad

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