EP2957672B1 - Feuille rigide et procédé pour sa fabrication - Google Patents

Feuille rigide et procédé pour sa fabrication Download PDF

Info

Publication number
EP2957672B1
EP2957672B1 EP14752242.9A EP14752242A EP2957672B1 EP 2957672 B1 EP2957672 B1 EP 2957672B1 EP 14752242 A EP14752242 A EP 14752242A EP 2957672 B1 EP2957672 B1 EP 2957672B1
Authority
EP
European Patent Office
Prior art keywords
hard sheet
elastic polymer
fiber
hardness
sheet
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Not-in-force
Application number
EP14752242.9A
Other languages
German (de)
English (en)
Other versions
EP2957672A4 (fr
EP2957672A1 (fr
Inventor
Masasi Meguro
Rei Nagayama
Nobuo Takaoka
Koichi Hayashi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kuraray Co Ltd
Original Assignee
Kuraray Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kuraray Co Ltd filed Critical Kuraray Co Ltd
Publication of EP2957672A1 publication Critical patent/EP2957672A1/fr
Publication of EP2957672A4 publication Critical patent/EP2957672A4/fr
Application granted granted Critical
Publication of EP2957672B1 publication Critical patent/EP2957672B1/fr
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B24—GRINDING; POLISHING
    • B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
    • B24B37/00—Lapping machines or devices; Accessories
    • B24B37/11—Lapping tools
    • B24B37/20—Lapping pads for working plane surfaces
    • B24B37/22—Lapping pads for working plane surfaces characterised by a multi-layered structure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B24—GRINDING; POLISHING
    • B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
    • B24B37/00—Lapping machines or devices; Accessories
    • B24B37/11—Lapping tools
    • B24B37/20—Lapping pads for working plane surfaces
    • B24B37/24—Lapping pads for working plane surfaces characterised by the composition or properties of the pad materials
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
    • D04H1/43825—Composite fibres
    • D04H1/4383—Composite fibres sea-island
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
    • D04H1/43838—Ultrafine fibres, e.g. microfibres
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
    • D06N3/0004—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using ultra-fine two-component fibres, e.g. island/sea, or ultra-fine one component fibres (< 1 denier)
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
    • D06N3/0011—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using non-woven fabrics
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/35—Abrasion, pilling or fibrillation resistance
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2211/00—Specially adapted uses
    • D06N2211/08—Cleaning articles

Definitions

  • the present invention relates to a hard sheet favorably used as a polishing pad, specifically, as a polishing layer of a polishing pad for polishing semiconductor wafers, semiconductor devices, silicon wafers, hard disks, glass substrates, optical products, various metals.
  • Integrated circuits formed on semiconductor wafers are highly integrated and have multilayer wiring. Such semiconductor wafers require a high degree of planarity.
  • CMP Chemical mechanical polishing
  • Patent Literatures 1 to 4 listed below each disclose a polishing pad formed of a polymeric foam having a closed cell structure, which is for use in CMP.
  • a polymeric foam is made by foam casting a curable-type two-component liquid polyurethane.
  • a polishing pad made of a polymeric foam has greater rigidity compared to a polishing pad of a non-woven fabric type that will be described later; and is therefore preferably used for polishing semiconductor wafers which require a high degree of planarity.
  • a polishing pad made of a polymeric foam has high rigidity. Therefore, load is selectively applied to the protrusions on the member to be polished. As a result, a relatively high polishing rate is obtained.
  • load is also selectively applied to the aggregate of abrasive grains. Therefore, scratches tend to occur easily on the surface to be polished.
  • a member having copper wiring or a low-dielectric material having weak adherence at the interface scratches or boundary separation tend to occur easily (e.g., see Non-Patent Literature 1).
  • the elastic polymer tends to foam unevenly easily; therefore, for the member to be polished, the planarity and the polishing rate during polishing tend to become uneven easily. Furthermore, since abrasive grains and polishing dust gradually clog the separate pores in the polymeric foam, the polishing rate gradually decreases.
  • Patent Literatures 5 to 14 listed below each disclose a non-woven-fabric-type polishing pad obtained by impregnating a non-woven fabric with porous polyurethane that has undergone wet coagulation.
  • a non-woven-fabric-type polishing pad has excellent flexibility and tends to deform easily. Therefore, since load is unlikely to be selectively applied to the abrasive grains that are aggregated on the surface to be polished, scratches are unlikely to occur.
  • the polishing rate is low.
  • a non-woven-fabric-type polishing pad deforms in conformity with the surface shape of the member to be polished; therefore planarization performance, i.e., the ability to planarize the member to be polished, is low.
  • Patent Literatures 15 to 18 listed below each disclose a polishing pad comprising a non-woven fabric of ultrafine fibers that is capable of high planarization performance.
  • Patent Literature 15 discloses a polishing pad as a sheet-like product comprising: a non-woven fabric formed by entanglement of ultrafine polyester fiber bundles with an average fineness of 0.0001 to 0.01 dtex; and an elastic polymer mainly composed of polyurethane included in the non-woven fabric via impregnation. This reference discloses that such polishing pad achieves a polishing work with higher precision than in the past.
  • Patent Literature 19 discloses a polishing pad comprising: an entangled fiber body formed of a fiber bundle of individual ultrafine fibers; and an elastic polymer, wherein one part of the elastic polymer is present in the fiber bundle to bundle together the individual ultrafine fibers, and the volume percent of the part excluding the pores falls within the range of 55 to 95%.
  • Patent Literature 20 discloses a polishing pad having a polishing layer and a base layer, wherein an intermediate layer with a water absorption of 1 % or less is interposed between the polishing layer and the base layer, and the difference between the D hardness of the polishing layer and the D hardness of the intermediate layer is 20 degrees or less.
  • Non-Patent Literature 1 " CMP No Saiensu (The Science of CMP)"; Science Forum Inc.; August 20,1997; pp. 113-119
  • An object of the present invention is to provide a polishing pad with a high polishing rate that is unlikely to change with time.
  • One aspect of the present invention relates to a hard sheet including:
  • another aspect of the present invention relates to a polishing pad including the foregoing hard sheet as a polishing layer.
  • Still another aspect of the present invention relates to a production method of hard sheet including:
  • Fig. 1 is schematic sectional illustration of one embodiment of a hard sheet.
  • Fig. 1 is a schematic sectional view of a hard sheet 10 of the present embodiment.
  • the circled area schematically depicts an enlarged view of a portion of the sectional view.
  • the hard sheet 10 includes: a non-woven fabric 1 being an entangled body of ultrafine fibers 1a; and an elastic polymer 2 added into the non-woven fabric 1.
  • the R% calculated by the above equation is preferably also 0 to 20%, when JIS-D hardness measurements are made at a total of six points being three arbitrary points in the second outer layer 5 and at three arbitrary points in the intermediate layer 4, and the D hardnesses obtained at the six points are used for the calculation. Furthermore, the total content of ions capable of causing a pH change in water, is 400 ⁇ g/cm 3 or less.
  • the ultrafine fibers 1a which form the non-woven fabric 1 a plurality of the ultrafine fibers 1a form a fiber bundle 1b.
  • the fiber bundles 1b are bound together with the elastic polymer 2.
  • the ultrafine fibers 1a which form each of the fiber bundles 1b are also bound together with the elastic polymer 2.
  • the ultrafine fibers 1a which form each of the fiber bundles 1b are also bound together with the elastic polymer 2.
  • half or more of the ultrafine fibers 1a are bound together with the elastic polymer 2.
  • Such composite body comprising the non-woven fabric 1 and the elastic polymer 2 corresponds to the hard sheet 10 that is closely-packed, with a small amount of pores and a high degree of hardness.
  • Such hard sheet 10 has high rigidity due to the reinforcing effect by the fiber bundles 1b and the high packing rate (i.e., low porosity) of the hard sheet.
  • the hard sheet 10 comprises the non-woven fabric 1 of the ultrafine fibers which form the fiber bundles.
  • the fiber bundles in the non-woven fabric that are present at the surface separate into individual fibers or become fibrillated during polishing.
  • the ultrafine fibers with a high fiber density become exposed at the polishing surface.
  • These exposed ultrafine fibers come in contact with the member to be polished, over a wide area; and also can retain large amounts of slurry.
  • the exposed ultrafine fibers soften the surface of the polishing pad, selective load application to aggregates of abrasive grains is suppressed. As a result, occurrence of scratches is suppressed.
  • the hard sheet 10 is adjusted to be uniform in the thickness direction such that R% calculated by using the JIS-D hardnesses measured at a total of six points, i.e., three points in the second outer layer 5 and three points in the intermediate layer 2, also becomes 0 to 20%. As such, by adjusting to obtain a uniform degree of hardness, a uniform degree of polishing becomes possible.
  • the hard sheet 10 is adjusted such that the total content of ions capable of causing a pH change in water becomes 400 ⁇ g/cm 3 or less.
  • a gelling agent is used in order for the elastic polymer to be uniformly added into the hard sheet in the thickness direction as described above. Ions in the hard sheet may change the pH of the slurry during polishing. When the pH of the slurry changes, the polishing rate tends to decrease and abrasive grains tend to aggregate easily. In such case, by reducing ionizable compounds in the hard sheet by water washing lowering of the polishing rate caused by a pH change in the slurry can be suppressed.
  • the ions capable of causing a pH change in water correspond to all ions capable of changing the pH of water when dissolved therein.
  • the hard sheet of the present embodiment is produced by adding an elastic polymer into a closely-packed non-woven fabric of the ultrafine fibers via impregnation, uniformly and in large proportions in the thickness direction.
  • an emulsion of elastic polymer containing a gelling agent is preferably used.
  • production is made possible by water washing the non-woven fabric in the production process, such that the total content of ions in the gelling agent that are capable of causing a pH change in water becomes 400 ⁇ g/cm 3 or less.
  • the non-woven fabric in the present embodiment is formed of ultrafine fibers, and the ultrafine fibers preferably form fiber bundles.
  • the ultrafine fibers have a fineness of 0.0001 to 0.5 dtex and preferably 0.001 to 0.01 dtex.
  • the fineness of the ultrafine fibers is less than 0.0001 dtex, the ultrafine fibers in the vicinity of the surface are unlikely to sufficiently separate into individual fibers during polishing, resulting in decrease in the amount of the slurry retained.
  • the fineness of the ultrafine fibers exceeds 0.5 dtex, the surface becomes too rough, thereby causing a lower polishing rate; and also, abrasive grains tend to aggregate easily on the surface of the ultrafine fibers.
  • the ultrafine fibers are preferably long fibers (filaments), and specifically, have an average fiber length of preferably 100 mm or more and further preferably 200 mm or more.
  • the upper limit of the average fiber length is not particularly limited; and fibers with a length of, for example, several meters, several hundred meters, several kilometers, or a higher value may be included, if not cut during the entanglement process as will be described below.
  • the ultrafine fibers are long fibers, fiber density can be increased, and therefore, rigidity of the hard sheet is increased. Moreover, the long fibers are unlikely to become detached during polishing. Note that when the ultrafine fibers are short fibers, fiber density cannot be easily increased, and therefore, a high rigidity cannot be obtained for the hard sheet. Moreover, the short fibers tend to become detached easily during polishing.
  • the ultrafine fibers which form the non-woven fabric it is preferable that a plurality thereof bundled together form a fiber bundle.
  • the average sectional area of the fiber bundle present on a sectional surface of the hard sheet extending in the thickness direction thereof is preferably 80 ⁇ m 2 or more, further preferably 100 ⁇ m 2 or more, and particularly preferably 120 ⁇ m 2 or more, in terms of obtaining a hard sheet with a particularly high rigidity.
  • the proportion of the fiber bundles with a sectional area of 40 ⁇ m 2 or more is preferably 25% or more, relative to a predetermined total number of the fiber bundles on the sectional surface of the hard sheet extending in the thickness direction thereof.
  • the proportion of the fiber bundles with a sectional area of 40 ⁇ m 2 or more is preferably 40% or more, further preferably 50% or more, and particularly preferably 100%.
  • polishing rate tends to decrease and planarization performance tends to degrade.
  • the bundle density of the fiber bundles per unit area of the sectional surface of the hard sheet extending in the thickness direction thereof is preferably 600 bundles/mm 2 or more, and further preferably 1000 bundles/mm 2 or more, and moreover, preferably 4000 bundles/mm 2 or less and further preferably 3000 bundles/mm 2 or less.
  • the fiber bundles at the surface separate into individual fibers or become fibrillated, and ultrafine fibers are formed in large amounts, thereby increasing the amount of the slurry retained.
  • the polishing surface becomes soft and thus suppresses occurrence of scratches.
  • the ultrafine fibers are preferably formed of a thermoplastic resin with a glass transition temperature (T g ) of preferably 50°C or more and further preferably 60°C or more.
  • T g glass transition temperature
  • the upper limit of T g is not particularly limited, and is preferably 300°C and further preferably 150°C, considering that production is industrial.
  • T g is still further preferably 50°C or more, when measured on the ultrafine fibers that remain wet after having undergone treatment with warm water at 50°C.
  • water absorption of the thermoplastic resin is preferably 4 mass% or less and further preferably 2 mass% or less. When water absorption exceeds 4 mass%, during polishing, the ultrafine fibers gradually absorb water in the slurry and thereby cause rigidity to decrease with time. In such case, planarization performance tends to degrade easily with time, or, polishing rate and polishing uniformity tend to vary easily. Water absorption is preferably 0 to 2 mass%.
  • thermoplastic resin examples include: aromatic polyester-based resins such as polyethylene terephthalate (PET, T g : 77°C, water absorption: 1 mass%), isophthalic acid-modified polyethylene terephthalate (T g : 67 to 77°C, water absorption: 1 mass%), sulfoisophthalic acid-modified polyethylene terephthalate (T g : 67 to 77°C, water absorption: 1 to 4 mass%), polybutylene naphthalate (T g : 85°C, water absorption: 1 mass%), and polyethylene naphthalate (T g : 124°C, water absorption: 1 mass%); and semi-aromatic polyamide-based resins such as copolymerizable nylon comprising terephthalic acid, nonanediol, and methyl octanediol (T g : 125 to 140°C, water absorption: 1 to 4 mass%).
  • PET polyethylene terephthalate
  • isophthalic acid-modified polyethylene terephthalate polybutylene naphthalate
  • polyethylene naphthalate are preferred, in terms of being capable of sufficiently maintaining rigidity, water resistance, and wear resistance.
  • PET and modified PET such as isophthalic acid-modified PET become crimped to a considerable degree in the wet heat treatment process as will be described below, wherein ultrafine fibers are formed from a sheet of entangled web comprising sea-island-type conjugated fibers; and are therefore preferred in terms of being capable of forming a closely-packed, highly-dense body of entangled fibers; of tending to easily increase rigidity of the hard sheet; of tending not to easily cause progressive change in the hard sheet due to moisture, during polishing.
  • the ultrafine fibers may contain ultrafine fibers formed of another thermoplastic resin.
  • thermoplastic resin for combined use include: aromatic polyesters, aliphatic polyesters, and copolymers thereof, such as polylactic acid, polybutylene terephthalate, polyhexamethylene terephthalate, polyethylene succinate, polybutylene succinate, polybutylene succinate adipate, and polyhydroxybutyrate-polyhydroxyvalerate copolymer; aliphatic nylons and copolymers thereof, such as nylon 6, nylon 66, nylon 10, nylon 11, and nylon 12; polyolefins such as polyethylene and polypropylene; modified polyvinyl alcohols containing 25 to 70 mol% of ethylene units; and elastomers such as polyurethane-based elastomer, nylon- based elastomer, and polyester- based elastomer.
  • the hard sheet includes an elastic polymer that is added into the non-woven fabric of the ultrafine fibers.
  • the elastic polymer include polyurethane, polyamide- based elastomers, (meth)acrylic ester- based elastomers, (meth)acrylic ester-styrene- based elastomers, (meth)acrylic ester-acrylonitrile- based elastomers, (meth)acrylic ester-olefin- based elastomers, (meth)acrylic ester-(hydrogenated) isoprene-based elastomers, (meth)acrylic ester-butadiene-based elastomers, styrene-butadiene-based elastomers, styrene-hydrogenated isoprene-based elastomers, acrylonitrile-butadiene-based elastomers, acrylonitrile-butadiene-styrene-based elastomers, vinyl acetate-based elastomers, (meth)acryl
  • the elastic polymer is preferably non-porous.
  • being non-porous means that there are substantially no pores (no closed cells) as those in porous or sponge-like elastic polymer.
  • the elastic polymer is not of the kind having a plurality of closed cells as in an elastic polymer obtained by solidifying a solvent-based polyurethane.
  • the elastic polymer When the elastic polymer is non-porous, high polishing stability is obtained, wearing is unlikely, and residues of the slurry and of the pad are unlikely to remain in the pores. Therefore, a high polishing rate can be maintained for long hours. Moreover, since the elastic polymer has high adhesion to the ultrafine fibers, the ultrafine fibers are unlikely to fall out. Furthermore, since a high degree of rigidity is obtained, planarization performance is excellent.
  • Water absorption of the elastic polymer is preferably 0.5 to 8 mass% and further preferably 1 to 6 mass%.
  • slurry wettability thereof decreases.
  • polishing rate, polishing uniformity, and polishing stability tend to decrease and abrasive grains tend to aggregate easily.
  • rigidity of the hard sheet decreases with time during polishing and planarization performance degrades.
  • polishing rate and polishing uniformity becomes varied easily.
  • water absorption of the elastic polymer corresponds to water absorption when a film of the elastic polymer after drying treatment is immersed in water at room temperature for saturation and swelling. Note that when two or more kinds of elastic polymers are included, water absorption is theoretically calculated by multiplying water absorption of each kind of the elastic polymer by its mass fraction and then adding together the obtained values.
  • Water absorption of the elastic polymer can be adjusted by introducing a hydrophilic functional group or by adjusting the degree of crosslinkage.
  • the hydrophilic functional group include a carboxyl group, a sulfonic acid group, and a polyalkylene glycol group with three or less carbon atoms.
  • the hydrophilic group can be introduced by copolymerization of monomers having the hydrophilic group.
  • the proportion of the monomer units having the hydrophilic group is preferably 0.1 to 20 mass% and further preferably 0.5 to 10 mass%.
  • the storage elastic modulus at 150°C [E' (150°C, dry)] is preferably 0.1 to 100 MPa and further preferably 1 to 80 MPa.
  • the storage elastic modulus of the elastic polymer can be adjusted by adjusting the degree of crosslinkage. Note that when two or more kinds of elastic polymers are included, the storage elastic modulus is theoretically calculated by multiplying the storage elastic modulus [E' (150°C, dry)] of each kind of the elastic polymer by its mass fraction and then adding together the obtained values.
  • the elastic polymer one may be used singly or two or more may be used in a combination.
  • polyurethane is preferred in terms of having excellent ability to bind to the ultrafine fibers.
  • the ultrafine fibers that form the fiber bundles are preferably bundled together by the elastic polymer; and half or more of the ultrafine fibers are further preferably bundled together by the elastic polymer.
  • the fiber bundles are preferably bound together by the elastic polymer present on the outer side of the fiber bundles; and half or more of these fiber bundles are further preferably bound together by the elastic polymer and are thus present in bulk form.
  • structural stability of the hard sheet improves and polishing stability thus improves.
  • the hard sheet with a uniform and high degree of hardness is obtained.
  • the ultrafine fibers that form the fiber bundles are not bundled together, since the ultrafine fibers obtain flexibility, it becomes difficult to obtain excellent planarization performance. Moreover, the ultrafine fibers tend to fall out easily during polishing, and abrasive grains tend to aggregate on the ultrafine fibers that have fallen out, thereby easily causing scratches.
  • To have the ultrafine fibers bundled together by the elastic polymer means that the ultrafine fibers present in the fiber bundle adhere and bond to one another via the elastic polymer present in the fiber bundle.
  • the ratio between the non-woven fabric and the elastic polymer (non-woven fabric/elastic polymer) in the resin sheet is preferably 90/10 to 55/45 and further preferably 85/15 to 65/35, in mass ratio.
  • the ratio between the non-woven fabric and the elastic polymer falls within the above range, the rigidity of the hard sheet can be easily increased.
  • the density of the ultrafine fibers that are exposed at the surface of the hard sheet can be sufficiently increased. As a result, polishing stability, polishing rate, and planarization performance can be sufficiently improved.
  • the apparent density of the hard sheet is preferably 0.5 to 1.2 g/cm 3 and further preferably 0.6 to 1.2 g/cm 3 , in terms of maintaining high rigidity.
  • the R% calculated by the above equation by using D-hardnesses measured at a total of six points, i.e., three arbitrary points on the second outer layer and three arbitrary points on the intermediate layer is also preferably 0 to 20%.
  • the JIS-D hardness of the hard sheet is 45 degrees or more, preferably 45 to 75 degrees, and further preferably 50 to 70 degrees.
  • the hardness of the first outer layer is 45 degrees or more in JIS-D hardness, excellent planarization performance is obtained.
  • the JIS-D hardness is too high, scratches tend to occur easily. Note that regarding the hard sheet of the present embodiment, since the ultrafine fibers exposed at the sheet surface have high fiber density, despite the sheet being hard, the sheet surface is soft. Therefore, scratches are unlikely to occur.
  • the R% calculated by the above equation using the D-hardnesses measured at a total of six points, i.e., three arbitrary points on the first outer layer and three arbitrary points on the intermediate layer, is 0 to 20% and preferably 0 to 15%.
  • the R% of the first outer layer and the intermediate layer falls within the above range, when the hard sheet is used as a polishing pad, the change in the polishing rate at the first outer layer and the intermediate layer becomes small and a stable polishing performance is obtained.
  • the R% exceeds 20% the change in the polishing rate thereat becomes large during polishing and a stable polishing performance is not obtained.
  • arbitrary points for JIS-D hardness measurement mean that points for measurement on each of the layers are selected arbitrarily, and that regardless of the positions of the points measured uniformly, the R% obtained would be 0 to 20%. In such case, there will be no deviation in hardness, not only in the thickness direction but also in the width direction; and therefore, there will be a uniform polishing rate and thus a stable polishing performance in the planar direction as well.
  • the R% calculated by the above equation using D-hardnesses measured at a total of six points, i.e., three arbitrary points on the second outer layer and three arbitrary points on the intermediate layer, is preferably 0 to 20% and further preferably 0 to 15%.
  • the total content of ions that cause a pH change in water is 400 ⁇ g/cm 3 or less.
  • the hard sheet of the present embodiment is produced, for example, by impregnating a non-woven fabric with an emulsion of an elastic polymer and then solidifying the elastic polymer by heating and drying, thereby to add the elastic polymer into the non-woven fabric.
  • water in the emulsion in the non-woven fabric via impregnation starts drying from the fabric surface. Therefore, as evaporation of the water progresses, there occurs migration of the emulsion from inside the non-woven fabric to the outer layer of the non-woven fabric.
  • the elastic polymer When migration occurs, the elastic polymer is unevenly distributed to the vicinity of the outer layer of the non-woven fabric, the amount of the elastic polymer in the vicinity of the intermediate layer becomes small, and voids tend to easily remain in the vicinity of the intermediate layer. Such migration is suppressed by adding a gelling agent into the emulsion, so that the emulsion would gelate before drying.
  • the present inventors found that when ions included in the gelling agent that are capable of causing a pH change in water remain in predetermined amounts or more in the hard sheet, the polishing rate decreased during polishing.
  • the total content of the ions capable of causing a pH change in water is 400 ⁇ g/cm 3 or less, preferably 350 ⁇ g/cm 3 or less, and further preferably 100 ⁇ g/cm 3 or less. Moreover, the total content of the ions is preferably 0 ⁇ g/cm 3 , but is preferably about 1 to 100 ⁇ g/cm 3 and further preferably about 10 to 50 ⁇ g/cm 3 , in terms of efficiency in industrial water washing.
  • the ions that causes a pH change in water correspond to all kinds of ions that change the pH of water when dissolved therein.
  • ions included in a common gelling agent such as sulfate ions, nitrate ions, carbonate ions, ammonium ions, sodium ions, calcium ions, and potassium ions.
  • a hard sheet can be produced, for example, by following steps given below.
  • an entangled fiber sheet of long fibers of ultrafine-fiber-forming fibers will be prepared.
  • the entangled fiber sheet of long fibers of ultrafine-fiber-forming fibers can be produced, for example, as follows.
  • sea-island-type conjugated fibers comprising a water-soluble thermoplastic resin as the sea component and a water-insoluble thermoplastic resin as the island components.
  • Such sea-island-type conjugated fibers correspond to ultrafine-fiber-forming fibers capable of forming ultrafine fibers which comprise the resin of the island components, by dissolution of the sea component.
  • well-known ultrafine-fiber-forming fibers such as multilayer-stack-section fibers may be used.
  • the water-soluble thermoplastic resin corresponds to a thermoplastic resin that can be removed by dissolution or decomposition by using water, an alkaline aqueous solution, an acidic aqueous solution.
  • the water-soluble thermoplastic resin include: PVA-based resins such as polyvinyl alcohol (PVA) and PVA copolymers; modified polyesters containing polyethylene glycol and/or alkali metal salt of sulfonic acid as copolymerizable components; and polyethylene oxide. Among these, PVA-based resins are preferred.
  • an ethylene-modified PVA containing preferably 4 to 15 mol% and further preferably 6 to 13 mol% of ethylene units is preferred, in terms of improving the physical properties of the sea-island-type conjugated fibers.
  • the viscosity-average degree of polymerization of the PVA-based resin is preferably 200 to 500, further preferably 230 to 470, and particularly preferably 250 to 450.
  • the melting point of the PVA-based resin is preferably 160 to 250°C, further preferably 175 to 224°C, and particularly preferably 180 to 220°C, in terms of excellent mechanical characteristics and excellent thermal stability, and thus, excellent melt spinning ability.
  • thermoplastic resin that cannot be removed by dissolution or decomposition by using water, an alkaline aqueous solution, an acidic aqueous solution, and that can undergo melt spinning, is used.
  • the various resins capable of forming ultrafine fibers as given above preferably thermoplastic resins with Tg of 50°C or more and water absorption of 4 mass% or less, are used.
  • the water-insoluble thermoplastic resin may contain additives such as a catalytic agent, an anti-coloring agent, a heat resistance modifier, a flame retardant, a lubricant, a stain inhibitor, a fluorescent whitening agent, a delustering agent, a coloring agent, a gloss enhancer, an anti-static agent, an aroma modifier, a deodorizing agent, an anti-bacterial agent, a tick repellent, and inorganic particulates.
  • additives such as a catalytic agent, an anti-coloring agent, a heat resistance modifier, a flame retardant, a lubricant, a stain inhibitor, a fluorescent whitening agent, a delustering agent, a coloring agent, a gloss enhancer, an anti-static agent, an aroma modifier, a deodorizing agent, an anti-bacterial agent, a tick repellent, and inorganic particulates.
  • the sea-island-type conjugated fibers can be produced by a conjugate spinning method wherein the water-soluble thermoplastic resin and the water-insoluble thermoplastic resin having low compatibility with the water-soluble thermoplastic resin are each melt spun and then conjugated. Thereafter, the sea-island-type conjugated fibers, remaining in long fiber form, are preferably converted into a web.
  • the web of the long fibers of the sea-island-type conjugated fibers is obtained, for example, by a spunbonding method wherein the water-soluble thermoplastic resin and the water-insoluble thermoplastic resin are each melt spun and then conjugated, and the resultant is drawn and then deposited.
  • the long fibers correspond to continuous fibers that are produced without undergoing a cutting process as in production of short fibers.
  • a detailed description will now be given of a production method of a web of long fibers of sea-island-type conjugated fibers, in one example.
  • the water-soluble thermoplastic resin and the water-insoluble thermoplastic resin are each melted and kneaded by separate extruders, and are then ejected at once from separate spinnerets, as molten resin strands. Then, the ejected strands are conjugated by a composite nozzle; and thereafter, the resultant is ejected from a nozzle opening of a spinning head, thereby to form a sea-island-type conjugated fiber.
  • the mass ratio between the water-soluble thermoplastic resin and the water-insoluble thermoplastic resin in the sea-island-type conjugated fibers is not particularly limited, and is preferably 5/95 to 50/50 and further preferably 10/90 to 40/60. It is favorable that the mass ratio between the water-soluble thermoplastic resin and the water-insoluble thermoplastic resin falls within the above range, in terms of obtaining a high-density non-woven fabric and securing excellent ultrafine fiber formability.
  • the number of islands in the sea-island-type conjugated fibers is preferably 4 to 4000 islands/fiber and further preferably 10 to 1000 islands/fiber.
  • fineness of the sea-island-type conjugated fiber is not particularly limited, and is preferably about 0.5 to 3 dtex from an industrial perspective.
  • the sea-island-type conjugated fibers are cooled by using a cooling device; and then drawn by a high-speed air flow at a rate corresponding to a take-up speed of 1000 to 6000 m/min such that a target fineness is obtained, by using a suction device such as an air-jet nozzle. Thereafter, the conjugated fibers that have been drawn are deposited on top of a mobile capturing surface, thereby to form a web of long fibers. At that time, the deposited web of the long fibers may be partially pressure bonded as necessary.
  • a silicone-based oiling agent such as an anti-needle-breakage oiling agent, an anti-static oiling agent, or an entanglement-enhancing oiling agent, or a mineral-oil-based oiling agent is added into the web. Then, the web is entangled by needle punching. The mass per unit area of the entangled web preferably falls within the range of 100 to 1500 g/m 2 , in terms of excellent handling characteristics.
  • Shrinkage treatment is preferably conducted by a wet heat shrinkage treatment such as steam heating.
  • a wet heat shrinkage treatment such as steam heating.
  • steam heating conditions for example, a condition of heating for 60 to 600 seconds at an ambient temperature of 60 to 130°C and at a relative humidity of preferably 75% or more and further preferably 90% or more, can be given.
  • the wet heat shrinkage treatment preferably causes the entangled web of the long fibers to shrink such that the area shrinkage becomes preferably 35% or more and further preferably 40% or more. By allowing such high degree of shrinkage, fiber density increases significantly.
  • the upper limit of the area shrinkage is preferably about 80% or less, in terms of shrinkage limit and treatment efficiency. Note that the area shrinkage (%) is calculated by the following equation: Area of entangled web before shrinkage treatment ⁇ Area of entangled web after shrinkage treatment / Area of entangled web before shrinkage treatment ⁇ 100.
  • the entangled web that has undergone the wet heat shrinkage treatment as above may further be hot rolled or hot pressed, thereby to further increase fiber density.
  • the mass per unit area thereafter compared to the mass per unit area therebefore is preferably 1.2 times or more and further preferably 1.5 times or more, and preferably 4 times or less and further preferably 3 times or less.
  • Such entangled fiber sheet is converted to a non-woven fabric with an apparent density of 0.35 to 0.90 g/cm 3 , due to the sea-island-type conjugated fibers subsequently forming ultrafine fibers.
  • the entangled web comprising the long fibers shrinks to a more considerable extent by wet heating, due to formation of the ultrafine fibers. Therefore, the fiber density of the ultrafine fibers is of a higher degree.
  • the water-soluble thermoplastic resin in the sea-island-type conjugated fibers is removed selectively, thereby to form a non-woven fabric comprising fiber bundles of the ultrafine fibers.
  • voids are created at portions from which the water-soluble thermoplastic resin has been extracted by dissolution.
  • the ultrafine fibers that form the fiber bundles are bundled together, and also, the fiber bundles are bound together. As such, a hard sheet with high fiber density, low porosity, and high rigidity is obtained.
  • an elastic polymer is packed in the entangled fiber sheet, uniformly in the sheet thickness direction. Since an emulsion of elastic polymer is highly concentrated, low in viscosity, and excellent in permeability via impregnation, the entangled fiber sheet can be easily filled with large proportions of the emulsion. Moreover, by including a gelling agent in the emulsion of elastic polymer, it is possible to suppress migration of the emulsion which causes uneven distribution thereof in the sheet thickness direction when dried.
  • elastic polymer capable of hydrogen bonding is preferable in terms of high adhesion to fibers.
  • Elastic polymers capable of hydrogen bonding correspond to, for example, elastomers comprising a polymer capable of crystallization or aggregation by hydrogen bonding, as with polyurethanes, polyamide-based elastomers, polyvinyl alcohol-based elastomers.
  • polyurethane examples include various kinds thereof obtained by reacting polymeric polyol having an average molecular weight of 200 to 6000, organic polyisocyanate, and a chain-elongating agent, in a predetermined molar ratio.
  • polymeric polyol examples include: polyether-based polyols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and poly(methyl tetramethylene) glycol, and copolymers thereof; polyester-based polyols such as polybutylene adipate diol, polybutylene sebacate diol, polyhexamethylene adipate diol, poly(3-methyl-1,5-pentylene adipate) diol, poly(3-methyl-1,5-pentylene sebacate) diol, and polycaprolactone diol, and copolymers thereof; polycarbonate-based polyols such as polyhexamethylene carbonate diol, poly(3-methyl-1,5-pentylene carbonate) diol, polypentamethylene carbonate diol, and polytetramethylene carbonate diol, and copolymers thereof; and polyester carbonate polyols.
  • these may be used in a combination with a polyfunctional alcohol such as a trifunctional alcohol, e.g., trimethylolpropane, or a tetrafunctional alcohol, e.g., pentaerythritol; or a short-chain alcohol such as ethylene glycol, propylene glycol, 1,4-butanediol, or 1,6-hexanediol.
  • a polyfunctional alcohol such as a trifunctional alcohol, e.g., trimethylolpropane, or a tetrafunctional alcohol, e.g., pentaerythritol
  • a short-chain alcohol such as ethylene glycol, propylene glycol, 1,4-butanediol, or 1,6-hexanediol.
  • Such polymeric polyols may be used singly or in a combination of two or more.
  • amorphous polycarbonate-based polyol, alicyclic polycarbonate-based polyol, linear polycarbonate-based polyol, a mixture of any one of these polycarbonate-based polyols and polyether-based polyol, and polyester-based polyol are preferred in terms of obtaining a hard sheet that is excellent in durability characteristics such as hydrolysis resistance and oxidation resistance.
  • polyurethane having a polyalkylene glycol group with five carbon atoms or less and particularly three carbon atoms or less is preferred, in terms of water wettability becoming particularly favorable.
  • organic polyisocyanate examples include: non-yellowing diisocyanates such as aliphatic or alicyclic diisocyanates, e.g., hexamethylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, and 4,4'-dicyclohexylmethane diisocyanate; and aromatic diisocyanates such as 2,4-tolylene diisocyanate, 2,6- tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and xylylene diisocyanate polyurethane.
  • non-yellowing diisocyanates such as aliphatic or alicyclic diisocyanates, e.g., hexamethylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, and 4,4'-dicyclohexylmethane diisocyanate
  • aromatic diisocyanates
  • these may be used in a combination with a multifunctional isocyanate such as a trifunctional isocyanate or a tetrafunctional isocyanate.
  • a multifunctional isocyanate such as a trifunctional isocyanate or a tetrafunctional isocyanate.
  • organic polyisocyanates may be used singly or in a combination of two or more.
  • 4,4'-dicyclohexylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and xylylene diisocyanate are preferred, in terms of high adhesion to fibers and of obtaining a hard sheet with a high degree of hardness.
  • chain-elongating agent examples include: diamines such as hydrazine, ethylenediamine, propylenediamine, hexamethylenediamine, nonamethylenediamine, xylylenediamine, isophoronediamine, piperazine and derivatives thereof, adipic dihydrazide, and isophthalic dihydrazide; triamines such as diethylenetriamine; tetramines such as triethylenetetramine; diols such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,4-bis( ⁇ -hydroxyethoxy)benzene, and 1,4-cyclohexanediol; triols such as trimethylolpropane; pentanols such as pentaerythritol; and amino alcohols such as aminoethyl alcohol and aminopropyl alcohol.
  • diamines such as hydrazine,
  • monoamines such as ethylamine, propylamine, or butylamine
  • monoamine compounds having a carboxyl group such as 4-aminobutanoic acid and 6-aminohexanoic acid
  • monools such as methanol, ethanol, propanol, or butanol
  • a compound such as a diol having a carboxyl group such as 2,2-bis(hydroxymethyl)propionic acid, 2,2-bis(hydroxymethyl)butanoic acid, or 2,2-bis(hydroxymethyl)valeric acid, can be used in a combination with the polyurethane, thereby to introduce an ionic group such as a carboxyl group into the polyurethane skeleton. This can further improve water wettability.
  • a crosslinking agent having molecules that contain two or more of a functional group capable of reacting with a functional group included in monomer units that form polyurethane, or a self-crosslinking compound such as a polyisocyanate-based compound or a polyfunctional blocked isocyanate-based compound, is added, thereby to form a crosslinked structure.
  • Examples of the combination of the functional group with monomer units and the functional group in the crosslinking agent include: a carboxyl group and an oxazoline group; a carboxyl group and a carbodiimide group; a carboxyl group and an epoxy group; a carboxyl group and a cyclocarbonate group; a carboxyl group and an aziridine group; and a carbonyl group and a hydrazine or hydrazide derivative.
  • a combination of monomer units having a carboxyl group and a crosslinking agent having an oxazoline group, a carbodiimide group, or an epoxy group; a combination of monomer units having a hydroxyl group or an amino group and a crosslinking agent having a blocked isocyanate group; and a combination of monomer units having a carbonyl group and a hydrazine or hydrazide derivative, are particularly preferred in terms of allowing easy formation of crosslinks as well as excellent rigidity and wear resistance of the hard sheet.
  • the crosslinked structure is preferably formed in the heat treatment process conducted after the polyurethane is added into the entangled fiber sheet, in terms of being able to maintain stability of the emulsion of elastic polymer.
  • a carbodiimide group and/or an oxazoline group that allow excellent crosslinking performance and pot life of the emulsion, and that are problem-free in regard to safety, are particularly preferred.
  • the crosslinking agent having a carbodiimide group include water-dispersion carbodiimide-based compounds such as "CARBODILITE E-01", “CARBODILITE E-02", and “CARBODILITE V-02" all available from Nisshibo Industries, Inc.
  • examples of the crosslinking agent having an oxazoline group include water-dispersion oxazoline-based compounds such as "EPOCROS K-2010E”, “EPOCROS K-2020E”, and “EPOCROS WS-500” all available from Nippon Shokubai Co., Ltd.
  • effective components of the crosslinking agent relative to the polyurethane is preferably 1 to 20 mass%, further preferably 1.5 to 1 mass%, and still further preferably 2 to 10 mass%.
  • the content of the components of the polymeric polyol in the polyurethane is preferably 65 mass% or less and further preferably 60 mass% or less. Moreover, the content thereof in the polyurethane is preferably 40 mass% or more and further preferably 45 mass% or more, in terms of being able to suppress occurrence of scratches due to imparting of moderate elasticity.
  • the method for preparing an emulsion of the polyurethane is not particularly limited and a known method can be used. Specifically, for example, a method for imparting an ability of self-emulsification in water to the polyurethane, by using monomers having a hydrophilic group such as a carboxyl group, a sulfone group, or a hydroxyl group, as copolymerizable components; or a method for emulsifying the polyurethane by adding a surfactant thereto, can be given.
  • An elastic polymer that include monomeric units having a hydrophilic group as copolymerizable components have excellent water wettability and therefore can retain large amounts of slurry.
  • surfactant used for emulsification include: anionic surfactants such as sodium lauryl sulfate, ammonium lauryl sulfate, polyoxyethylene tridecyl ether sodium acetate, sodium dodecylbenzenesulfonate, sodium alkyldiphenyletherdisulfonate, and sodium dioctylsulfosuccinate; and non-ionic surfactants such as polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene-polyoxypropylene block copolymer.
  • anionic surfactants such as sodium lauryl sulfate, ammonium lauryl sulfate, polyoxyethylene tridecyl ether sodium acetate, sodium dodecylbenzenesulfonate, sodium alkyldiphenyletherdisulfonate, and
  • a surfactant having reactivity i.e., a reactive surfactant may be used.
  • a thermosensitive gelation ability also can be imparted to the emulsion.
  • the solidifying concentration of the emulsion is preferably 15 to 40 mass% and further preferably 25 to 35 mass%, in terms of being able to pack the entangled fiber sheet with the elastic polymer, highly and uniformly in the sheet thickness direction.
  • the particle size of the emulsion is preferably 0.01 to 1 ⁇ m and further preferably 0.03 to 0.5 ⁇ m.
  • a first emulsion includes a gelling agent containing ions that cause a pH change in water.
  • the gelling agent is used in order to allow gelation of the emulsion particles by heating, by causing change in the pH of the emulsion.
  • the water in the emulsion included in the non-woven fabric via impregnation starts drying from the surface of the non-woven fabric. Therefore, as evaporation of the water progresses, migration of the emulsion from inside the non-woven fabric to the outer layer of the non-woven fabric tends to easily occur.
  • the elastic polymer When migration of the emulsion inside the non-woven fabric occurs, the elastic polymer is unevenly distributed to the vicinity of the outer layer of the non-woven fabric, the amount of the elastic polymer in the vicinity of the intermediate layer becomes small, and voids tend to easily remain in the vicinity of the intermediate layer. When voids remain in the vicinity of the intermediate layer, hardness at the intermediate layer lowers and also becomes non-uniform. Such migration is suppressed by adding the gelling agent into the emulsion, so that the emulsion would gelate before drying.
  • any kind can be used without particular limitation, as long as the gelling agent is a water-soluble salt capable of changing the pH of the emulsion to the extent that the emulsion particles would gelate by heating.
  • Specific examples of the gelling agent include monovalent or bivalent inorganic salts such as sodium sulfate, ammonium sulfate, sodium carbonate, calcium chloride, calcium sulfate, calcium nitrate, zinc oxide, zinc chloride, magnesium chloride, potassium chloride, potassium carbonate, sodium nitrate, and lead nitrate.
  • the proportion of the gelling agent in the first emulsion is preferably 0.5 to 5 parts by mass and further preferably 0.6 to 4 parts by mass, relative to 100 parts by mass of the elastic polymer, in terms of being able to moderately impart a gelation ability.
  • the first emulsion may further contain a penetrating agent, an antifoam, a lubricant, a water repellant, an oil repellant, a viscous agent, an extender, a curing accelerator, an antioxidant, an ultraviolet absorber, a fluorescing agent, an antifungal agent, a foaming agent, a water-soluble polymeric compound such as polyvinyl alcohol or carboxymethyl cellulose, a dye, a pigment, inorganic particulates.
  • the method for impregnating the entangled fiber sheet with the first emulsion is not particularly limited, and for example, a method of dipping and nipping, knife coating, bar coating, or roll coating can be used.
  • heating is conducted to allow the first emulsion to gelate inside the entangled fiber sheet.
  • heating conditions for such gelation for example, a condition of holding heating for about 0.5 to 5 minutes at preferably 40 to 90°C and further preferably 50 to 80°C, is preferably used.
  • heating is preferably conducted with steam, in terms of being able to uniformly heat the inner layer, while also suppressing migration of the emulsion that is due to rapid evaporation of water from the outer layer.
  • heating and drying for example, a method for heating and drying in a dryer such as a hot-air dryer, or a method for heating and drying in the dryer after conducting infrared heating, can be given.
  • heating and drying conditions for example, a condition of heating in 2 to 10 minutes such that the maximum temperature becomes preferably 130 to 160°C and further preferably 135 to 150°C, can be given.
  • the sea-island-type conjugated fibers included in the entangled fiber sheet into which the elastic polymer has been added via impregnation, are subjected to an ultrafine-fiber-forming treatment, thereby to form a first composite body comprising a non-woven fabric of the ultrafine fibers and the elastic polymer included therein.
  • the present step involves forming ultrafine fibers by an ultrafine-fiber-forming treatment whereby the water-soluble thermoplastic resin is removed from the sea-island-type conjugated fibers which comprise the water-soluble thermoplastic resin as the island components and the water-insoluble thermoplastic resin as the sea component.
  • the ultrafine-fiber-forming treatment is a treatment whereby the entangled fiber sheet comprising the sea-island-type conjugated fibers undergoes hot water heat treatment by using water, alkaline aqueous solution, acidic aqueous solution, thereby to remove the water-soluble thermoplastic resin forming the sea component, by dissolution or decomposition.
  • the entangled fiber sheet is immersed in hot water at 65 to 90°C for 5 to 300 seconds; and then, at the second stage, the entangled fiber sheet is immersed in hot water at 85 to 100°C for 100 to 600 seconds.
  • a treatment such as nipping with rollers, high-pressure water jetting, ultrasonication, showering, stirring, rubbing, may be conducted.
  • the water-soluble thermoplastic resin dissolves from the sea-island-type conjugated fibers, resulting in formation of ultrafine fibers.
  • the ultrafine fibers become crimped to a considerable degree. Such crimping causes the ultrafine fibers to have a higher fiber density.
  • voids are created at portions where the water-soluble thermoplastic resin had been present. These voids are packed with the elastic polymer by a subsequent process.
  • the gelling agent included in the sheet is also removed by dissolution in hot water. As such, a first composite body is formed.
  • Step of forming a second composite body by impregnating the first composite body with a second emulsion comprising a gelling agent and an elastic polymer; allowing the second emulsion to gelate; and then solidifying the elastic polymer by heating and drying
  • the voids in the first composite body are packed with the elastic polymer, thereby to bind the ultrafine fibers together.
  • the ultrafine fibers are bundled together and the porosity of the hard sheet can thus be lowered.
  • the ultrafine fibers form fiber bundles, the emulsion tends to permeate easily due to capillary action.
  • a second emulsion is selected from those listed for the first emulsion. Note that the second emulsion and the first emulsion may have the same composition or different compositions.
  • the second emulsion is added and undergoes gelation, such that when the second composite body formed is evenly divided into three parts in the thickness direction thereof and the three parts correspond to a first outer layer, an intermediate layer, and a second outer layer in order from any one surface side thereof, the difference in porosity between the first outer layer and the intermediate layer is preferably 5% or less and further preferably 3% or less.
  • the difference in porosity between the first outer layer and the intermediate layer is preferably 5% or less and further preferably 3% or less.
  • the porosity of each of the layers is obtained as follows. An image of a sectional surface of the second composite body extending in the thickness direction thereof, magnified 30X, is taken by a scanning electron microscope. Then, by using an image analysis software Popimaging (available from Digital being kids.Co), the image obtained is binarized by dynamic thresholding to determine the void portions. Then, a circle is inscribed in each of the void portions; and the total area of the inscribed circles is referred to as the total amount of voids in all of the layers in total.
  • Popimaging available from Digital being kids.Co
  • Step of water washing such that the total content of ions that cause a pH change in the second composite body becomes 400 ⁇ g/cm 3 or less
  • the hard sheet of the present embodiment used the emulsion containing the gelling agent, in order to suppress migration of the emulsion to the outer layer at the time of adding the elastic polymer into the non-woven fabric.
  • the present inventors found that when considerable amounts of ions that had been in the gelling agent remained in the hard sheet obtained, the polishing rate lowered at the time of polishing. Moreover, they found that by conducting water washing and making the remaining amount of the ions 400 ⁇ g/cm 3 or less, lowering of the polishing rate was able to be suppressed.
  • the process of water washing is such that the total content of the ions that cause a pH change in water included in the hard sheet becomes 400 ⁇ g/cm 3 or less, preferably 350 ⁇ g/cm 3 or less, and further preferably 100 ⁇ g/cm 3 or less.
  • heated water washing treatment is preferable in terms of excellent water washing efficiency.
  • specific conditions for example, a condition of immersing the second composite body in hot water at 80°C or more, can be given. In detail, for example, at the first stage, the second composite body is immersed in hot water at 65 to 90°C for 5 to 300 seconds; and then, at the second stage, the second composite body is immersed in hot water at 85 to 100°C for 100 to 600 seconds.
  • a treatment such as nipping with rollers, high-pressure water jetting, ultrasonication, showering, stirring, rubbing, may be conducted.
  • the voids present in the hard sheet lower the degree of hardness as well as hardness uniformity of the sheet.
  • the first composite body, the second composite body, and/or the hard sheet as described above are hot pressed to reduce the number of voids.
  • a preferable condition is of pressing at a linear pressure of 30 to 100 kg/cm by using metal rollers heated to, for example, 160 to 180°C as the temperature not allowing decomposition of the ultrafine fibers and the elastic polymer.
  • the hard sheet of the present embodiment is obtained.
  • the hard sheet of the present embodiment is preferably used as a polishing layer of a polishing pad.
  • the hard sheet can be processed as desired as necessary to form a polishing layer.
  • the hard sheet is subjected to a napping treatment by using sandpaper, card clothing, diamond, or to a brushing by reverse sealing, hot press treatment, or emboss processing.
  • grooves in a grid pattern, a concentric pattern, a spiral pattern, or holes may be formed on the surface of the hard sheet.
  • an elastic layer such as that of a knitted fabric, a woven fabric, a non-woven fabric, an elastic resin film, or an elastic sponge-like body, may be stacked on the hard sheet serving as the polishing layer.
  • elastic film and such elastic sponge-like body include: non-woven fabrics impregnated with a kind of polyurethane currently widely used (e.g., "SUBA400" (available from Nitta Haas Incorporated)); rubbers such as natural rubber, nitrile rubber, polybutadiene rubber, and silicone rubber; thermoplastic elastomers such as polyester-based thermoplastic elastomer, polyamide-based thermoplastic elastomer, and fluorine-based thermoplastic elastomer; foamed plastic; and polyurethane.
  • polyurethane currently widely used
  • rubbers such as natural rubber, nitrile rubber, polybutadiene rubber, and silicone rubber
  • thermoplastic elastomers such as polyester-based thermoplastic elastomer, polyamide-based
  • polishing pad in addition to the kind comprising the polishing layer and the elastic layer directly joined to each other by fusion bonding there are also the kind comprising such two layers adhering to each other via an adhesive, a double-sided adhesive tape, and furthermore, the kind comprising such two layers with another layer further interposed therebetween.
  • the polishing pad which uses the hard sheet of the present embodiment can be used for chemical mechanical polishing (CMP) wherein the surface to be polished and the polishing pad are brought in contact with each other under pressure at a certain rate for a certain amount of time, via a slurry, by using a known CMP equipment.
  • the slurry contains, for example, a liquid medium such as water, oil, an abrading agent such as silica, aluminum oxide, cerium oxide, zirconium oxide, silicon carbide and a component such as a base, an acid, a surfactant.
  • a lubricant, a coolant may be used in a combination with the slurry.
  • the product for polishing is not particularly limited and examples include crystal, silicon, glass, optical substrates, electronic circuit boards, multilayer wiring boards, and hard disks. Particularly, for polishing, silicon wafers and semiconductor wafers are preferred. Specific examples of semiconductor wafers include those having on the surface, for example, an insulating film of silicon oxide, silicon fluoride oxide, organic polymer, a film comprising metal for wiring material such as copper, aluminum, tungsten, or a barrier film of metal such as tantalum, titanium, tantalum nitride, titanium nitride.
  • the value obtained by dividing the mass per unit area (g/cm 2 ) of the hard sheet by the thickness (cm) thereof was referred to as the apparent density (g/cm 3 ).
  • apparent density measurements were made at ten arbitrary points in the hard sheet, and the arithmetic average of the obtained values was calculated as the apparent density. Note that the thickness was measured with an applied load of 240 gf/cm 2 in compliance with JISL1096.
  • D hardness measurements were made on the surface, the first outer layer, and the intermediate layer of the hard sheet in compliance with JIS K 7311. Specifically, for the D hardness of the surface of the hard sheet, eight hard sheets each with a thickness of about 1.25 mm were overlapped and D hardness measurements were made at three points at regular intervals in the width direction; and the average of the obtained values was referred to as the D hardness of the surface of the hard sheet.
  • a hard sheet with a thickness of about 1.25 mm was abraded starting from the second outer layer side, thereby obtaining a 0.40 mm-thick sheet for the first outer layer.
  • 25 sheets of the sheet for the first outer layer thus obtained were overlapped and hardness measurements were made at three points at regular intervals in the width direction; and the average of the obtained values was referred to as the JIS-D hardness of the first outer layer.
  • a hard sheet was abraded starting from the first outer layer side and the second outer layer side, evenly, thereby obtaining a 0.40 mm-thick sheet for the intermediate layer.
  • R(%) D hardness maximum ⁇ D hardness minimum / D hardness average ⁇ 100.
  • a piece of the hard sheet cut into a rectangle and 10 mL of water were put in a screw-cap test tube. Then, the screw-cap test tube was heated at 90°C for 2 hours with a block heater, thereby to extract water-soluble substances in the hard sheet by hot water extraction. Then, ion components in the liquid extract were detected by ion chromatography (ICS-1600). The total content of sulfate ions and ammonium ions, i.e., ions capable of causing a pH change in water, was measured and then converted to the amount of the ions included per unit volume of the hard sheet.
  • ICS-1600 ion chromatography
  • the hard sheet was cut into a 51 cm-diameter circle, and a grid pattern of 1.0 mm-wide, 0.5 mm-deep grooves spaced 15.0 mm apart from one another was created on the surface, thereby to produce a polishing pad. Then, after an adhesive tape was attached to the back surface of the polishing pad, the back surface was attached to a CMP polishing machine ("PPO-60S" available from Nomura Machine Tool Works, Ltd.).
  • polishing rate measurements were made on the first outer layer of a hard sheet about 1.25 mm thick, and also on a hard sheet 0.70 mm thick with the intermediate layer exposed.
  • Water-soluble PVA was used as a sea component, and isophthalic acid-modified PET with a degree of modification of 6 mol% was used as island components.
  • the water-soluble PVA and the isophthalic acid-modified PET were ejected from a spinneret for conjugate melt spinning (number of islands: 25 islands/fiber) at 260°C, such that the water-soluble PVA and the isophthalic acid-modified PET would be 25/75 (mass ratio). Then, the ejector pressure was adjusted so that the spinning rate would be 3700 m/min, long fibers with a fineness of 3 dtex were captured on a net, and a web with a mass per unit area of 35 g/m 2 was obtained.
  • the entangled web was treated with steam for 70 seconds under the conditions of 110°C and 23.5% RH. The area shrinkage at that time was 44%. Then, the entangled web was dried in an oven at 90 to 110°C and then hot pressed at 115°C, thereby to obtain an entangled fiber sheet with a mass per unit area of 1312 g/m 2 , an apparent density of 0.544 g/cm 3 , and a thickness of 2.41 mm.
  • the entangled fiber sheet was impregnated with a polyurethane emulsion serving as a first emulsion.
  • the polyurethane was a non-yellowing polyurethane including: a polyol component being a mixture of polycarbonate-based polyol and polyalkylene glycol with 2 to 3 carbon numbers in a molar ratio of 99.8 : 0.2; and 1.5 mass% of carboxyl group-containing monomers.
  • the polyurethane was a non-porous polyurethane capable of forming a crosslinked structure by heat treatment.
  • the first emulsion was prepared so as to contain 4.6 parts by mass of a carbodiimide-based crosslinking agent and 1.8 parts by mass of ammonium sulfate as a gelling agent, both relative to 100 parts by mass of the polyurethane; and also so that the solidifying content in the polyurethane would be 20%.
  • the entangled fiber sheet impregnated with the first emulsion was heated at 90°C in a 30% RH atmosphere to allow the first emulsion to gelate; and this was followed by drying treatment at 150°C. Then, the entangled fiber sheet was hot pressed at 140°C, thereby to adjust the mass per unit area to 1403 g/m 2 , the apparent density to 0.716 g/cm 3 , and the thickness to 1.96 mm.
  • nipping treatment and high-pressure water jetting treatment were used to immerse the entangled fiber sheet with the polyurethane added therein in hot water at 95°C for 10 minutes, thereby to dissolve and thus remove the water-soluble PVA, thereby to convert ultrafine fibers with a fineness of 0.09 dtex; and this was followed by drying.
  • a first composite body with a mass per unit area of 1009 g/m 2 , an apparent density of 0.538 g/cm 3 , and a thickness of 1.87 mm was obtained.
  • the first composite body was impregnated with a polyurethane emulsion (solid content: 30 mass%) serving as a second emulsion.
  • a polyurethane emulsion solid content: 30 mass% serving as a second emulsion.
  • the second emulsion was prepared so as to contain 4.6 parts by mass of a carbodiimide-based crosslinking agent and 1.0 part by mass of ammonium sulfate, both relative to 100 parts by mass of the polyurethane; and also so that the solidifying content in the polyurethane would be 30%.
  • the first composite body impregnated with the second emulsion was heated at 90°C in a 60% RH atmosphere, to allow the second emulsion to gelate; and this was followed by drying treatment at 150°C.
  • a second composite body with a mass per unit area of 1245 g/m 2 , an apparent density of 0.748 g/cm 3 , and a thickness of 1.66 mm was obtained.
  • the difference in porosity between the first outer layer and the intermediate layer in the second composite body was 1.8%.
  • nipping treatment and high-pressure water jetting treatment were used to water wash the second composite body by immersion in hot water at 95°C for 10 minutes. This was followed by drying at 180°C. Then, the second composite body was hot pressed under the conditions of a linear pressure of 100 kg/cm and 160°C, thereby to obtain an intermediary body for a hard sheet, with a mass per unit area of 1212 g/m 2 , an apparent density of 0.795 g/cm 2 , and a thickness of 1.53 mm.
  • the outer layer on both sides of the intermediary body for a hard sheet was abraded with a #100 paper to reduce the outer layer thicknesses by 0.15 mm each, thereby finishing to obtain a hard sheet with a mass per unit area of 994 g/m 2 , an apparent density of 0.788 g/cm 3 , and a thickness of 1.26 mm.
  • JIS-D hardness of the hard sheet was 52 degrees.
  • R% of the JIS-D hardness was 11.3%.
  • the total content of sulfate ions and ammonium ions, i.e., ions capable of causing a pH change was 26.9 ⁇ g/cm 3 .
  • Example 1 Except that the first composite body before addition of the second emulsion was hot pressed under the conditions of a linear pressure of 100 kg/cm and 160°C, a hard sheet was produced as in Example 1 and then evaluated. Note that the hard sheet obtained had a mass per unit area of 996 g/m 2 , an apparent density of 0.808 g/cm 3 , and a thickness of 1.23 mm. The results are shown in Table 1.
  • Example 1 Except that the second composite body was water washed to a lesser degree, a hard sheet was produced as in Example 1 and then evaluated.
  • the total content of sulfate ions and ammonium ions, i.e., ions capable of causing a pH change was 300 ⁇ g/cm 3 .
  • the results are shown in Table 1.
  • Example 1 Except that the second composite body was not water washed instead of being water washed by immersion in hot water at 95°C for 10 minutes, a hard sheet was produced as in Example 1 and then evaluated. The results are shown in Table 1.
  • Example 1 Except that the first composite body was further hot pressed under the conditions of a linear pressure of 100 kg/cm and 160°C; and that the first composite body was impregnated with an emulsion with a similar composition as the second emulsion but not including the gelling agent, instead of being impregnated with the second emulsion including the gelling agent, a hard sheet was produced as in Example 1 and then evaluated. Note that the hard sheet obtained had a mass per unit area of 969 g/m 2 , an apparent density of 0.817 g/cm 3 , and a thickness of 1.19 mm. The results are shown in Table 1.
  • Example 1 Except that the second composite body was water washed to a lesser degree, a hard sheet was produced as in Example 1 and then evaluated.
  • the results are shown in Table 1.
  • Example 1 Except that the second composite body was water washed to a lesser degree, a hard sheet was produced as in Example 1 and then evaluated.
  • the results are shown in Table 1.
  • the polishing pads according to the present invention which used the hard sheets obtained in Example 1, 2 and 3, respectively, wherein the JIS-D hardnesses were 45 degrees or more, the R%s were 0 to 20%, and the total contents of the ions capable of causing a pH change in water were 400 ⁇ g/cm 3 or less, each exhibited a polishing rate at the first outer layer, i.e., the initial polishing rate, of 120 nm/min; and maintained 90% or more of the initial polishing rate based on the average thereof of until after five hours.
  • the polishing rate at the first outer layer was significantly low, being 93 nm/min.
  • the hard sheet of Comparative Example 2 an effort was made to uniformly pack the hard sheet with the elastic polymer by hot pressing, instead of doing so by adding the gelling agent into the second emulsion.
  • the total content of the ions was small but the R% was 30.2%, thus exhibiting non-uniformity. As a result, only 89% of the initial polishing rate based on the average thereof of until after five hours, could be maintained.
  • Comparative Examples 3 and 4 wherein the total contents of the ions were 404 ⁇ g/cm 3 and 504 ⁇ g/cm 3 , respectively, only about 84% of each of the initial polishing rates based on the averages thereof of until after five hours, could be maintained.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
  • Nonwoven Fabrics (AREA)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Reinforced Plastic Materials (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Mechanical Treatment Of Semiconductor (AREA)
  • Laminated Bodies (AREA)

Claims (16)

  1. Feuille rigide comprenant :
    une toile non tissée de fibres ultrafines ayant une finesse de 0,0001 à 0,5 dtex ; et
    un polymère élastique ajouté dans la toile non tissée,
    la feuille rigide ayant :
    une dureté JIS-D de 45 degrés ou plus ;
    un pourcentage R calculé par une équation R(%) = (dureté D maximale - dureté D minimale) / moyenne de la dureté D x 100 de 0 à 20 %, lorsqu'une surface en coupe de la feuille rigide s'étendant dans une direction de l'épaisseur de la feuille rigide est divisée uniformément en trois parties correspondant à une première couche externe, une couche intermédiaire, et une seconde couche externe dans l'ordre en partant de n'importe quel côté de la surface ; les mesures de dureté JIS-D sont réalisées sur un total de six points qui sont trois points arbitraires sur la première couche externe et trois points arbitraires sur la couche intermédiaire ; et ensuite les duretés JIS-D obtenues sur les six points sont utilisées pour le calcul ; et
    une teneur totale en ions susceptible de provoquer un changement de pH dans l'eau de 400 µg/cm3 ou moins.
  2. Feuille rigide selon la revendication 1, dans laquelle la teneur totale en ions est de 1 à 100 µg/cm3.
  3. Feuille rigide selon la revendication 1, dans laquelle les fibres ultrafines sont des fibres longues ayant une longueur de fibre moyenne de 100 mm ou plus et forment des faisceaux de fibres.
  4. Feuille rigide selon la revendication 3, dans laquelle une masse volumique apparente de la toile non tissée est de 0,35 à 0,90 g/cm3.
  5. Feuille rigide selon la revendication 3, dans laquelle, sur la surface en coupe de la feuille rigide s'étendant dans la direction de l'épaisseur de la feuille rigide, les fibres ultrafines formant les faisceaux de fibres sont, partiellement au moins, regroupées en faisceaux par le polymère élastique.
  6. Feuille rigide selon la revendication 5, dans laquelle, sur la surface en coupe de la feuille rigide s'étendant dans la direction de l'épaisseur de la feuille rigide, les faisceaux de fibres sont, partiellement au moins, liées entre elles par le polymère élastique.
  7. Feuille rigide selon la revendication 3, dans laquelle la moitié ou plus des fibres ultrafines formant les faisceaux de fibres sont liées entre elles par le polymère élastique.
  8. Feuille rigide selon la revendication 7, dans laquelle sur la surface en coupe de la feuille rigide s'étendant dans la direction de l'épaisseur de la feuille rigide, la moitié ou plus des faisceaux de fibres sont liés entre eux par le polymère élastique.
  9. Feuille rigide selon la revendication 1, dans laquelle le polymère élastique est un polymère élastique non poreux.
  10. Feuille rigide selon la revendication 1, dans laquelle un rapport de masse de la toile non tissée sur le polymère élastique (toile non tissée/polymère élastique) est de 90/10 à 55/45.
  11. Feuille rigide selon la revendication 10, dans laquelle une masse volumique apparente de la feuille est de 0,50 à 1,2 g/cm3.
  12. Feuille rigide selon la revendication 1,
    dans laquelle la seconde couche externe a une dureté JIS-D de 45 degrés ou plus, et
    le pourcentage R calculé par l'équation R(%) = (dureté D maximale - dureté D minimale) / moyenne de la dureté D x 100 est de 0 à 20 %, lorsque les mesures de dureté JIS-D sont réalisées sur un total de six points qui sont trois points arbitraires sur la seconde couche externe et trois points arbitraires sur la couche intermédiaire, et ensuite les duretés JIS-D obtenues sur les six points sont utilisées pour le calcul.
  13. Tampon à polir comprenant la feuille rigide selon l'une quelconque des revendications 1 à 12 en tant que couche de polissage.
  14. Procédé de production de feuille rigide comprenant :
    (1) une étape incluant de préparer une feuille de fibres entremêlées comprenant des fibres longues ayant une longueur de fibre moyenne de 100 mm ou plus de fibres de formation de fibres ultrafines, la feuille de fibres entremêlées étant susceptible de former une toile non tissée d'une masse volumique apparente de 0,35 g/cm3 ou plus comprenant des fibres ultrafines d'une finesse de 0,5 dtex ou moins, par soumission à un traitement de formation de fibres ultrafines ;
    (2) une étape incluant d'imprégner la feuille de fibres entremêlées avec une première émulsion incluant un polymère élastique et un agent gélifiant contenant des ions susceptibles de provoquer un changement de pH dans l'eau, puis de laisser la première émulsion gélifier, et puis de solidifier le polymère élastique par chauffage et séchage ;
    (3) une étape incluant de former un premier corps composite comprenant la toile non tissée et le polymère élastique en soumettant les fibres de formation de fibres ultrafines au traitement de formation de fibres ultrafines ;
    (4) une étape incluant de former un second corps composite par imprégnation du premier corps composite avec une seconde émulsion incluant un polymère élastique et un agent gélifiant puis de solidifier le polymère élastique par chauffage et séchage, le second corps composite ayant une différence de porosité entre une première couche externe et une couche intermédiaire de 5 % ou moins, lorsque le second corps composite formé est divisé uniformément en trois parties dans la direction de l'épaisseur du second corps composite, les trois parties correspondant à la première couche externe, à la couche intermédiaire, et à une seconde couche externe dans l'ordre en partant de n'importe quel côté de la surface ;
    (5) une étape incluant de laver à l'eau le second corps composite de telle sorte qu'une teneur totale en ions passe à 400 µg/cm3 ou moins pour obtenir une feuille rigide ; et
    (6) une étape incluant de comprimer à chaud au moins l'un choisi parmi le premier corps composite, le second corps composite, et la feuille rigide, de telle sorte qu'une dureté de surface de la feuille rigide passe à une dureté JIS-D de 45 degrés ou plus.
  15. Procédé de production de feuille rigide selon la revendication 14, dans lequel la teneur totale en ions est de 1 à 100 µg/cm3.
  16. Procédé de production de feuille rigide selon la revendication 14,
    dans lequel les fibres de formation des fibres ultrafines sont des fibres conjuguées de type Sea-Island comprenant une résine thermoplastique hydrosoluble à base d'alcool polyvinylique en tant que composante Sea et une résine thermoplastique hydro-insoluble en tant que composante Island ; et
    le traitement de formation de fibres ultrafines de l'étape (3) est un processus moyennant lequel la résine thermoplastique hydrosoluble à base d'alcool polyvinylique est dissoute dans de l'eau chaude et éliminée de manière sélective.
EP14752242.9A 2013-02-12 2014-02-05 Feuille rigide et procédé pour sa fabrication Not-in-force EP2957672B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2013024525 2013-02-12
PCT/JP2014/000616 WO2014125797A1 (fr) 2013-02-12 2014-02-05 Feuille rigide et procédé pour la fabrication de feuille rigide

Publications (3)

Publication Number Publication Date
EP2957672A1 EP2957672A1 (fr) 2015-12-23
EP2957672A4 EP2957672A4 (fr) 2016-07-27
EP2957672B1 true EP2957672B1 (fr) 2018-05-02

Family

ID=51353810

Family Applications (1)

Application Number Title Priority Date Filing Date
EP14752242.9A Not-in-force EP2957672B1 (fr) 2013-02-12 2014-02-05 Feuille rigide et procédé pour sa fabrication

Country Status (7)

Country Link
US (1) US20160002835A1 (fr)
EP (1) EP2957672B1 (fr)
JP (1) JP6220378B2 (fr)
KR (1) KR102136441B1 (fr)
CN (1) CN105008614B (fr)
TW (1) TWI607832B (fr)
WO (1) WO2014125797A1 (fr)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6531824B2 (ja) * 2015-04-17 2019-06-19 株式会社村田製作所 共振回路、帯域阻止フィルタおよび帯域通過フィルタ
DE102016222063A1 (de) * 2016-11-10 2018-05-17 Siltronic Ag Verfahren zum beidseitigen Polieren einer Halbleiterscheibe
US20180134918A1 (en) * 2016-11-11 2018-05-17 Jh Rhodes Company, Inc. Soft polymer-based material polishing media
JP6951895B2 (ja) * 2017-07-25 2021-10-20 ニッタ・デュポン株式会社 研磨布
US12104317B2 (en) * 2018-08-27 2024-10-01 Kuraray Co., Ltd. Artificial leather base material, method for production thereof, and napped artificial leather
JP7111609B2 (ja) * 2018-12-27 2022-08-02 株式会社クラレ 繊維複合研磨パッドおよびそれを用いたガラス系基材の研磨方法
EP4079962B1 (fr) * 2019-12-20 2024-12-04 Toray Industries, Inc. Article stratiforme et son procédé de production
US12338575B2 (en) * 2019-12-20 2025-06-24 Toray Industries, Inc. Sheet material and method for producing same
EP4083314A4 (fr) * 2019-12-26 2024-01-10 Kuraray Co., Ltd. Feuille de type cuir pleine fleur

Family Cites Families (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03234475A (ja) 1990-02-08 1991-10-18 Kanebo Ltd 研磨布
JPH10128674A (ja) 1996-10-28 1998-05-19 Rooder Nitta Kk 研磨用パッド
JPH10225864A (ja) 1997-02-17 1998-08-25 Sony Corp 研磨パッドとその製造方法並びにその研磨パッドを用いたウエハの研磨方法
JPH1199479A (ja) 1997-09-30 1999-04-13 Teijin Ltd 研磨パッド
JPH11322878A (ja) 1998-05-13 1999-11-26 Dainippon Ink & Chem Inc 泡含有ポリウレタン成形物の製造方法、泡含有成形物用ウレタン樹脂組成物及びそれを用いた研磨パッド
JP3516874B2 (ja) 1998-12-15 2004-04-05 東洋ゴム工業株式会社 ポリウレタン発泡体の製造方法及び研磨シート
JP2000248034A (ja) 1999-03-02 2000-09-12 Mitsubishi Chemicals Corp 研磨材用ポリウレタン系樹脂組成物及びその発泡体
US6130163A (en) * 1999-06-03 2000-10-10 Promos Technologies, Inc. Stabilization of slurry used in chemical mechanical polishing of semiconductor wafers by adjustment of PH of deionized water
JP3558273B2 (ja) 1999-09-22 2004-08-25 東洋ゴム工業株式会社 ポリウレタン発泡体の製造方法及び研磨シート
JP2002009026A (ja) 2000-06-21 2002-01-11 Toray Ind Inc 研磨用パッドおよびそれを用いた研磨装置及び研磨方法
JP3901939B2 (ja) 2000-12-05 2007-04-04 帝人コードレ株式会社 研磨用基布および研磨方法
US20030100250A1 (en) 2001-10-29 2003-05-29 West Thomas E. Pads for CMP and polishing substrates
JP3992483B2 (ja) 2001-12-06 2007-10-17 帝人コードレ株式会社 研磨基布の製造方法
JP3921085B2 (ja) 2001-12-28 2007-05-30 大日精化工業株式会社 研磨用基材の製造方法
JP4356056B2 (ja) * 2002-05-15 2009-11-04 東レ株式会社 樹脂含浸体および研磨パッドおよびその研磨パッドを用いた研磨装置と研磨方法
JP2004130395A (ja) 2002-10-08 2004-04-30 Toray Ind Inc ガラステクスチャー加工用研磨布及びそれを用いた磁気記録媒体の製造方法
US7829486B2 (en) * 2003-02-06 2010-11-09 Kuraray Co., Ltd. Stretchable leather-like sheet substrate and process for producing same
JP2004311731A (ja) 2003-04-08 2004-11-04 Hitachi Chem Co Ltd 研磨用パッド及びそれを用いた被研磨物の研磨方法
JP2005212055A (ja) 2004-01-30 2005-08-11 Kanebo Ltd 不織布ベースの研磨布及びその製造方法
JP4455161B2 (ja) * 2004-05-25 2010-04-21 旭化成せんい株式会社 研磨パッド用不織布および研磨パッド
JP4420761B2 (ja) * 2004-07-27 2010-02-24 日華化学株式会社 研磨用シートの製造方法及び研磨用シート
JP4645361B2 (ja) 2005-08-24 2011-03-09 東レ株式会社 研磨布
JP5204502B2 (ja) 2007-02-01 2013-06-05 株式会社クラレ 研磨パッド及び研磨パッドの製造方法
KR101146966B1 (ko) * 2007-02-01 2012-05-23 가부시키가이샤 구라레 연마 패드 및 연마 패드의 제조 방법
KR100943244B1 (ko) * 2007-12-28 2010-02-18 대원화성 주식회사 표면 연마용 폴리우레탄 패드 및 그 제조방법
JP2009241184A (ja) * 2008-03-31 2009-10-22 Kuraray Co Ltd 研磨パッドおよびそれを用いた研磨方法
JP2010058170A (ja) * 2008-08-08 2010-03-18 Kuraray Co Ltd 研磨パッド
JP2011200984A (ja) * 2010-03-26 2011-10-13 Toray Ind Inc 研磨パッド

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Also Published As

Publication number Publication date
EP2957672A4 (fr) 2016-07-27
CN105008614A (zh) 2015-10-28
CN105008614B (zh) 2017-06-13
JPWO2014125797A1 (ja) 2017-02-02
KR20150116876A (ko) 2015-10-16
US20160002835A1 (en) 2016-01-07
EP2957672A1 (fr) 2015-12-23
KR102136441B1 (ko) 2020-07-21
JP6220378B2 (ja) 2017-10-25
WO2014125797A1 (fr) 2014-08-21
TW201440956A (zh) 2014-11-01
TWI607832B (zh) 2017-12-11

Similar Documents

Publication Publication Date Title
EP2957672B1 (fr) Feuille rigide et procédé pour sa fabrication
KR101146966B1 (ko) 연마 패드 및 연마 패드의 제조 방법
JP5411862B2 (ja) 研磨パッド及び研磨パッドの製造方法
JP5204502B2 (ja) 研磨パッド及び研磨パッドの製造方法
JP5289787B2 (ja) 研磨パッド及び研磨パッドの製造方法
JP5629266B2 (ja) 研磨パッド及びケミカルメカニカル研磨方法
JP5143518B2 (ja) 繊維複合研磨パッド
JP6180873B2 (ja) 繊維複合シート、研磨パッド及びその製造方法
JP2010064153A (ja) 研磨パッド
JP7111609B2 (ja) 繊維複合研磨パッドおよびそれを用いたガラス系基材の研磨方法
JP5356149B2 (ja) 研磨パッドの表面加工方法およびそれによって得られる研磨パッド
JP5789557B2 (ja) ガラス系基材の研磨方法
JP2010058170A (ja) 研磨パッド
JP5415700B2 (ja) 研磨パッド及び研磨パッドの製造方法
JP5502661B2 (ja) 化合物半導体ウエハの研磨方法
HK1154828B (en) Polishing pad and method for manufacturing the polishing pad

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20150912

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAX Request for extension of the european patent (deleted)
A4 Supplementary search report drawn up and despatched

Effective date: 20160629

RIC1 Information provided on ipc code assigned before grant

Ipc: B24B 37/24 20120101ALI20160623BHEP

Ipc: D06N 3/00 20060101AFI20160623BHEP

Ipc: C08J 5/14 20060101ALI20160623BHEP

Ipc: D04H 1/4382 20120101ALI20160623BHEP

Ipc: H01L 21/304 20060101ALI20160623BHEP

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20170310

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20171027

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAJ Information related to disapproval of communication of intention to grant by the applicant or resumption of examination proceedings by the epo deleted

Free format text: ORIGINAL CODE: EPIDOSDIGR1

GRAL Information related to payment of fee for publishing/printing deleted

Free format text: ORIGINAL CODE: EPIDOSDIGR3

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

GRAR Information related to intention to grant a patent recorded

Free format text: ORIGINAL CODE: EPIDOSNIGR71

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

INTC Intention to grant announced (deleted)
AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

INTG Intention to grant announced

Effective date: 20180326

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

Ref country code: AT

Ref legal event code: REF

Ref document number: 995371

Country of ref document: AT

Kind code of ref document: T

Effective date: 20180515

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602014024880

Country of ref document: DE

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602014024880

Country of ref document: DE

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20180502

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180502

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180802

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180802

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180502

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180502

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180502

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180803

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180502

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180502

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180502

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180502

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 995371

Country of ref document: AT

Kind code of ref document: T

Effective date: 20180502

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180502

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180502

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180502

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180502

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180502

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180502

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180502

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602014024880

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180502

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20190205

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180502

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190205

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180502

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20190228

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180502

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190228

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190228

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190205

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190228

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180502

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20200121

Year of fee payment: 7

Ref country code: IT

Payment date: 20200128

Year of fee payment: 7

Ref country code: GB

Payment date: 20200129

Year of fee payment: 7

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190205

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180903

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20200113

Year of fee payment: 7

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180502

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180902

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20140205

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 602014024880

Country of ref document: DE

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20210205

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210205

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210228

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210901

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210205

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180502