EP2449004A1 - Composant de fabrication à semi-conducteur - Google Patents
Composant de fabrication à semi-conducteurInfo
- Publication number
- EP2449004A1 EP2449004A1 EP10729044A EP10729044A EP2449004A1 EP 2449004 A1 EP2449004 A1 EP 2449004A1 EP 10729044 A EP10729044 A EP 10729044A EP 10729044 A EP10729044 A EP 10729044A EP 2449004 A1 EP2449004 A1 EP 2449004A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- matte
- polymer
- article
- fibers
- temperature
- 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.)
- Ceased
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 20
- 239000004065 semiconductor Substances 0.000 title claims description 11
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 7
- 239000004917 carbon fiber Substances 0.000 claims abstract description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000004513 sizing Methods 0.000 claims description 11
- 229920001169 thermoplastic Polymers 0.000 claims description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 65
- 238000000034 method Methods 0.000 abstract description 51
- 239000002131 composite material Substances 0.000 abstract description 49
- 229920002313 fluoropolymer Polymers 0.000 abstract description 11
- 239000004811 fluoropolymer Substances 0.000 abstract description 11
- 239000000835 fiber Substances 0.000 description 60
- 238000010438 heat treatment Methods 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 238000000280 densification Methods 0.000 description 11
- 239000002245 particle Substances 0.000 description 10
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000002002 slurry Substances 0.000 description 7
- 235000012431 wafers Nutrition 0.000 description 7
- 238000007906 compression Methods 0.000 description 6
- 230000006835 compression Effects 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 6
- 239000010439 graphite Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000123 paper Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 238000007596 consolidation process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 4
- 102100026256 Glycosylphosphatidylinositol-anchored high density lipoprotein-binding protein 1 Human genes 0.000 description 3
- 101001035846 Homo sapiens HMG box-containing protein 1 Proteins 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004416 thermosoftening plastic Substances 0.000 description 3
- 229920006362 Teflon® Polymers 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000001427 coherent effect Effects 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- -1 perfluoro Chemical group 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 229920005594 polymer fiber Polymers 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- KHXKESCWFMPTFT-UHFFFAOYSA-N 1,1,1,2,2,3,3-heptafluoro-3-(1,2,2-trifluoroethenoxy)propane Chemical compound FC(F)=C(F)OC(F)(F)C(F)(F)C(F)(F)F KHXKESCWFMPTFT-UHFFFAOYSA-N 0.000 description 1
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 1
- OVGRCEFMXPHEBL-UHFFFAOYSA-N 1-ethenoxypropane Chemical compound CCCOC=C OVGRCEFMXPHEBL-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000012993 chemical processing Methods 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 230000001010 compromised effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 150000001983 dialkylethers Chemical class 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000011087 paperboard Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08L27/18—Homopolymers or copolymers or tetrafluoroethene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B1/00—Cleaning by methods involving the use of tools
- B08B1/10—Cleaning by methods involving the use of tools characterised by the type of cleaning tool
- B08B1/14—Wipes; Absorbent members, e.g. swabs or sponges
- B08B1/143—Wipes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B1/00—Cleaning by methods involving the use of tools
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/042—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon fibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
- D21H13/36—Inorganic fibres or flakes
- D21H13/38—Inorganic fibres or flakes siliceous
- D21H13/44—Flakes, e.g. mica, vermiculite
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
- D21H13/36—Inorganic fibres or flakes
- D21H13/46—Non-siliceous fibres, e.g. from metal oxides
- D21H13/50—Carbon fibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2327/18—Homopolymers or copolymers of tetrafluoroethylene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
Definitions
- the field of the invention encompasses a process for the production of composites comprising reinforcing graphite fiber and fluoropolymer, having use in making semiconductor manufacture components.
- Composite articles comprising or consisting of a polymer (usually a continuous phase, and possibly comprising fluoropolymer(s) and fibers (such as glass fibers, carbon fibers, and graphite fibers) are well known in the art.
- a polymer usually a continuous phase, and possibly comprising fluoropolymer(s) and fibers (such as glass fibers, carbon fibers, and graphite fibers)
- fibers such as glass fibers, carbon fibers, and graphite fibers
- the addition of fiber to a matrix polymer can improve certain properties of the polymer. These properties can include creep resistance, tensile strength and modulus, and flexural strength and modulus.
- the reinforcing fiber chosen generally has a higher tensile modulus and strength than the polymer alone.
- the resulting composite When a fluoropolymer is used as the matrix polymer, as described herein, the resulting composite often has many of the attributes of fluoropolymers such as high temperature resistance and chemical resistance, which make such composites useful as parts, for example, for the chemical processing industry. It is among the objects of this invention to provide a method for the production of such polymer composites that exhibit improved properties and to provide articles made by the method.
- Additional known related methods and articles include but are not necessarily limited to United States Patent No. 5,759,927 to Meeker, issued June 2, 1998, entitled “Glass-fiber-containing non-woven polymer web, and process for preparing same,” and United States Patent No. 5,460,764 to Held, issued October 24, 1995, entitled “Method and apparatus for making highly densified sheets”.
- Figure 1 shows schematically some mattes of the known art.
- Figure 2 shows elevation views of a matte and two composite articles according to the present disclosure.
- an article wherein said article is semiconductor manufacture component comprising:
- thermoplastic polymer (a) about 70 wt% to about 90 wt% of a thermoplastic polymer
- a sizing agent selected from the group consisting of polyvinylpyrrolidone, polyvinyl alcohol, copolyvinyl alcohol, copolyvinly acetate, copolyvinly alcohol-acetate and sodium carboxymethyl cellulose, optionally further comprising (d) less than 2 000 nanomoles per gram of sodium, potassium, calcium, and aluminum, combined; wherein the wt% in each of (a), (b) and (c) is based on the total weight of the component.
- the method disclosed herein comprises providing a matte comprising: about 1 to about 91 weight percent fiber and about 9 to about 99 weight percent of said polymer.
- the matte has a density of Dm, and is less than Dc, wherein said polymer has a softening temperature.
- the matte is densified by compressing the matte to a that is density greater than 1.1 times Dm and less than 0.999 times Dc, while at least a portion of the matte is at a temperature less than said softening temperature, to provide a compressed matte. Thereafter the compressed matte is heated throughout to a temperature greater than said softening temperature while at a consolidated density greater than 1.1 times Dm and less than 0.999 times Dc, to provide a pre-consolidated matte.
- At least a portion of the pre-consolidated matter is cooled to a temperature less than said softening temperature, to provide a consolidated matte.
- the next step is stacking heightwise a plurality of the consolidated matte to provide an unconsolidated article.
- the unconsolidated article is then consolidated by compressing the height of said unconsolidated article and heating it throughout to a temperature greater than said softening
- At least a portion of the consolidated composite article is cooled to a temperature that is less than said softening temperature.
- the invention can combine elements known to the art in a new manner to achieve one or more unexpected or
- Single elements of such art may include US Patents 5506052, 6066395, 20090062426, 7094468, 7150913, 5589055, 4420512, 4975321 , 4555446 , 52272385, 4448910, 4,455,343, 20070082199,
- Density of composite articles can be determined by ASTM D 792 - 08
- Thickness of mattes can be determined by TAPPI T41 1 Thickness (Caliper) of Paper, Paperboard and Combined Board, and weight per volume can be determined by cutting an area of known size (e.g. 16 cm by 16 cm) and thickness as determined by TAPPI T411 , and weighing that known volume of matte.
- a typical matte of polymer flake or particles and fibers (17 of figure 1A or 1 T of figure 1 B) or a composite article may have a density of about 0.2 g/mL or less to about 1.9 g/mL or more, depending somewhat on the weighted density of the polymer and fibers used.
- a typical consolidate matte of polymer flake, or particles, combined with fibers (17'" of figure 1C) should have a density greater than the matte it was made from, and may have a density of about 0.3 g/mL to about 2.9 g/mL, depending somewhat on the weighted density of the polymer and fibers used.
- Figures 1A-D represent the prior art and aid in the understanding the invention.
- Figure 1A shows a matte
- FIG. 17 comprising polymer particles 102 and fibers 101 situated between two platens 60,62.
- Release films 61 ,63 can optionally be placed between two platens 60, 62 and the matte 17 composed of fibers 101 and polymer particles 102, or the platens can optionally otherwise be treated to prevent sticking of the matte to a platen.
- the matte 17 can optionally be initially under low contact pressure from the platens as heat is applied to the mattes, for example through the platens.
- the polymer particles will soften and typically change shape upon exceeding the softening temperature of the polymer.
- Figure 1 B illustrates a matte that can be obtained as the temperature exceeds the softening temperature and as the formation of beads 102 on (optionally wetting) the fibers within the layer 17'. Not all the original polymer particles need be heated above their softening temperature. Pressure can be applied to platens 60,62 causing the height of the matte to decrease
- the matte as illustrated is in a relatively unconstrained state at the edges of the platens, i.e., in the in-plane directions, therefore the fibers can be moved, along with the polymer, in those directions, giving the fibers an arrangement more perpendicular to the height direction of the matte (the height direction being the z direction) and more parallel to the platen surfaces.
- the consolidated matte can optionally be cooled under pressure, particularly to below the softening temperature. This same sequence of events can be achieved on a continuous basis using a heated belt press or similarly a heating zone and nip rolls. The process can include the polymer being heated above the softening temperature at some point; this can occur before or after the application of pressure that produces significant densification.
- the composite can be cooled under pressure.
- Belt press pre-consolidation matte or (debulked plies) result in a very flat product versus the incumbent platen press pre-consolidated/debulking ply method.
- Very flat plies eases the ability to load debulked plies for molding steps.
- a consolidated matte 17" of figure 1C can be further consolidated as above to form a more densified matte or composite article 17'" of figure 1 D.
- the apparatus used for further consolidation may be the same or different than that used for the initial densification.
- Figure 2 shows elevation views of an oriented matte and two composite articles comprising such oriented mattes.
- Figure 2A shows an oriented matte 2001 ; for clarity, fibers are shown as imbedded.
- a coordinate axis set x-y-z 2002 is defined so that the height of the matte is oriented parallel to the z axis. Since fibers 2003 are aligned, on average, along one direction perpendicular to the z axis, one can assign that direction to correspond to the x axis. Perpendicular to z and x axes is the y axis.
- the matte illustrated in Figure 2A has been cut from a larger matte, to make two cut faces (2006 and 2007) parallel to the z axis, and parallel to the y and x axes respectively.
- fibers 2004 can be cut with relatively circular cross section by the xz face 2006
- fibers 2005 can be cut with relatively elliptical cross section (or ultimately nearly a parallelogram) by the xz face 2006.
- Figure 2B shows a portion of an oriented composite article that can be made by stacking mattes corresponding to figure 2A.
- the composite article illustrates mattes (e.g. 2022, 2023) can have different orientations, such as an orientation with each z axis parallel (heightwise stacked), and the fiber orientation of each immediately adjacent and contacting matte being at right angles. If a matte is made by consolidating two thin mattes with fiber orientation stacked at right angles, such a matte or analogous mattes can be stacked with each z axis parallel (heightwise stacked), to obtain a composite article of Figure 2B.
- Figure 2C shows a portion of an oriented composite article 2030 that can be made by stacking mattes corresponding to figure 2A (e.g., 2031 and 2032). Note the grouping of pluralities of mattes into groups (2037, 2039, 2035, where the plurality is a triplet of mattes). Some mattes are oriented parallel, some are oriented at right angles.
- This composite article shows a pattern of stacking that can be termed an orientation pattern of 0, 0, 0, 90, 90, 90 degrees.
- a matte can be prepared by any known techniques. For instance, using a paper making process, fibers can be mixed with a polymer to form a mixture or slurry.
- any mixing means may be used, but preferably the fibrous components are mixed at about a 0.001 % to 5% consistency or solids content (e.g. comprising 0.01-5 parts solids to 99.009-95 parts aqueous solution or water).
- the slurry may then be diluted with water to enhance formation, and it may finally be flocculated with flocculating agent and drainage retention aid chemicals.
- the flocculated mixture or slurry may be placed onto a paper making machine to be formed into a wet matte, possibly with orientation of fibers or without orientation of the fibers, possibly oriented in the direction of movement of the matte during the paper making process, or perpendicular to that direction.
- the matte may be formed by vacuum casting the slurry or other methods.
- Mattes can be formed by dewatering a slurry, for example using a belt press.
- a belt press manufacturer is Bright Technologies, Hopkins, Michigan. Mattes can be dried, for example in ovens, on rotating drums, or by moving air.
- Mattes can be formed by dewatering a slurry, for example using a belt press.
- a belt press manufacturer is Bright Technologies, Hopkins, Michigan. Mattes can be dried, for example in ovens, on rotating drums, or by moving air.
- Densifying can be carried out by compression or other known methods, which may be upon one or more axes, simultaneously or
- the axes may be mutually orthogonal, such as x, y, and z axes.
- Mattes may have any convenient dimensions of length, width, or height. Mattes can be more than 1 cm in height, or less than 0.8, 0.6, 0.4, 0.2, 0.1 , 0.05, or 0.01 cm in height.
- Densification can be carried out at pressures as low as 100 kPa, and as high as 100 MPa, and at interval pressures between about 10OkPa and about 100MPa. Densification, heating, cooling, or combinations of such can be carried out from about 0.1 , 1 , 2, 5, 10, 20, 100 minutes or many hours, up to about 135 hours, or more.
- Any method of densifying can, and may, break at least some of the fibers during processing. Accordingly the length of the fibers can be reduced. It is usually advantageous to maintain a high fiber length, but this goal may be advantageously compromised for certain applications if other properties of the composite article are improved.
- a matte may be made by other means, such as dry air laying optionally with polymer particles present.
- a matte may be densified by dry needling.
- the polymer of the invention can be a fluoropolymer and any polymer of the invention can comprise repeat units or monomers of
- tetrafluoroethylene perfluoro (alkoxyalkane) of 3 to 14 carbon atoms such as perfluoro(vinyl propyl ether), hexafluoropropylene, chlorotrifluoroethylene, ethylene, propylene, or combinations thereof (copolymers).
- Any polymer of the invention can optionally flow upon heating, particularly above the polymer melting point or glass transition temperature (Tg).
- Tg glass transition temperature
- the polymer can optionally wet the fibers, particularly after softening.
- Polymer that is useful herein is a thermoplastic, and is present in an amount of from about 70 wt% to about 90wt%, based on the total weight of the component.
- the softening temperature of the polymer is a temperature at which the polymer can be slowly but permanently deformed typically without breaking, chipping, or separating.
- Examples of the softening temperature include the melting point, the lowest temperature of a melting range, the highest temperature of a melting range, or the glass transition temperature.
- Particles are small pieces or parts, or tiny portions or flecks. Particles can be free-flowing or stuck to fibers. Types of particles include flakes, grains, shreds, fragments, crumbs, chips, pellets, specks, shavings, etc.
- Fibers include, but are not limited to, those composed of: glass;
- graphite carbon; fluorinated graphite; aramid such as poly(p- phenyleneterephthtalamide); boron nitride; silicon carbide; polyester; and polyamide.
- Carbon, graphite and fluorinated graphite fibers are preferred fibers. Fibers of the present disclosure can also be chopped.
- the median length of the fibers can be longer or shorter or the same as the median height of the matte containing the fibers.
- Fibers may be sized as known in the art. Sizing may comprise, for example, epoxy resins or polymers, urethane-modified epoxy resins or polymers, polyester resins or polymers, phenol resins or polymers, polyamide resins or polymers, polyurethane resins or polymers, polycarbonate resins or polymers, polyetherimide resins or polymers, polyamideimide resins or polymers, polystylylpyridine resins or polymers, polyimide resin, bismaleimide resins or polymers, polysulfone resins or polymers, polyethersulfone resins or polymers, epoxy-modified urethane resins or polymers, polyvinyl alcohol resins or polymers, polyvinyl pyrrolidone resins or polymers, resins or polymers and mixtures thereof.
- Sizing may comprise, for example, epoxy resins or polymers, urethane-modified epoxy resins or polymers, polyester resins or polymers, phenol resins or polymers, polyamide
- Sizings may be solvent compatible or water compatible, and may be solvent soluble or water soluble.
- Polyvinylpyrrolidone (PVP) a known sizing agent, is a water-soluble polymer made from the monomer N-vinylpyrrolidone.
- Known sizing agents are disclosed in US Pub. 20080299852; U.S. Pat. Nos. 5,393,822 and 7,135,516.
- the flakes, or the co-disppersed flakes and fiber in water, used to make a matte by paper-making techniques can have a Canadian Standard Freeness of greater than 200 up to the Freeness test maximum of 2000.
- the flakes, or the co-dispersed flakes and fiber in water, used to make a matte by paper-making techniques can have settling times of from 1 to 13 000 seconds or more.
- Settling time is measured, optionally with the fiber content ratio by weight to be used in a matte, in an aqueous solution (i.e., less than 1 % based on weight of polymer solids suitable to form an apparently homogeneous slurry appropriate for feeding to a screen to ultimately form a matte, observed until such time a new layer is formed on the bottom or the top discernable to the naked eye).
- an aqueous solution i.e., less than 1 % based on weight of polymer solids suitable to form an apparently homogeneous slurry appropriate for feeding to a screen to ultimately form a matte, observed until such time a new layer is formed on the bottom or the top discernable to the naked eye.
- Settling time can be greater than from about to 2 to about 12 000 seconds.
- removing most water from matte to form a wet matte removing more water from the layer to form a dry matte; drying the layer to form a self-supporting planar matte; optionally thermally tacking the web to improve dry strength for handling and preconsolidating said matte by heating said matte above the polymer melt temperature to form a different matte, then applying sufficient pressure normal to the plane of said matte to cause the polymer to flow to form a preconsolidated matte; and cooling that matte.
- the aqueous slurry can be substantially free of other constituents.
- the fiber content in the composite of the present invention is from about 10 wt% to about 30 wt%, based on the total weight of the component.
- Suitable belt presses are well known, for example in US Patents 3,159,526; 3,298,887; 4,369,083; 5,112,209; 5,433,145; 5,454,304; 5460764, 5,520,530; 5,546,857; 5,555,799; 5592874; 5759927; 5,895,546 each of which is hereby incorporated by reference in their entirety.
- a manufacturer of suitable belt presses, particularly isobaric double belt presses, is Held
- Suitable platen presses are well known, for example US Patent 5,775,214, 5,253,571 , 5,323,696 and 5,333,541 each of which is hereby incorporated by reference in their entirety. Manufacturers of suitable presses include Maschinenfabrik Herbert Meyer GmbH in Germany (vertical presses or laminating presses, e.g. models APV, Fusing Press AHV-Bm, or AHV-S with up to 20 tons pressure and heating plates up to 673 K).
- Suitable methods of applying heat include but are not limited to contacting a matte or composite article with a hot surface (e.g. conduction); using a hot gas jet (e.g. convection); and using radiation (e.g. infrared or microwave radiation).
- a hot surface e.g. conduction
- a hot gas jet e.g. convection
- radiation e.g. infrared or microwave radiation
- Consolidation can be carried out under the same conditions as densification.
- heating to a temperature above the softening temperature or heating to a temperature below the softening temperature, or both in various combinations as known in the art can be carried out optionally as defined herein, during consolidation.
- the first matte may be a matter comprised of thin mattes. In either case the matte comprises 1 to 91weight percent fiber" and "9 to 99 weight percent polymer.
- the first matte having a density of Dm is less than Dc.
- the first matte is densified by compressing to a density greater than 1.1 times Dm and less than 0.999 times Dc while at least a portion of the first matte is at a temperature less than said softening temperature. This will provide a compressed matte. Thereafter, the compressed matte is heated throughout to a temperature greater than the softening temperature of the polymer, while at a consolidated density greater than 1.1 times Dm and less than 0.999 times Dc. This will provide a preconsolidated matte, which is then cooled, or a least a portion is cooled to a temperature less than said softening temperature of the polymer to provide a consolidated matte. A plurality of consolidated matte is then stacked heightwise to provide an unconsolidated article.
- the height of the unconsolidated article is compressed and heated throughout to a temperature greater than the polymer softening temperature, to provide a consolidated composite article. At least a portion of the consolidated composite article is cooled to a temperature less than the softening temperature of the polymer.
- Disclosed herein is a method for making an composite article with orientation, by preconsolidating said stack by: heating said stack to above the melt temperature of the polymer, then applying sufficient pressure normal to the plane of the matte while the matte is unconstrained in the in-plane direction to cause the fluoropolymer to flow orienting the fibers in substantially the plane of the layer by means of said flow to form a preconsolidated sheet;
- Composite articles can be used for chucks, for example spin chucks used in coater chambers to hold wafers, or for CMP chucks for holding wafers or polishing pads during chemical mechanical polishing
- CMP CMP
- chucks which are rotated about their z axis at high rates of speed, where strength in the x-y plane of the composite allows higher diameters or higher rates of speed to be used, allowing for larger chucks or larger wafers or faster processing or more robust processing.
- composites that resist deformation, thereby holding the wafer in a planar position for precision processing. Cleanliness (e.g. low metal content, low or slow elution of metal or ions) in composites is also prized in semiconductor manufacturing articles, including in spin, rinse, and dry modules and chucks.
- Composites are valued as a support structure for the semiconductor wafer, e.g., such support structures also known as wafer chucks, susceptors, or wafer pedestals.
- Semiconductor manufacturing articles are well known, for example in US Patents 7357842; 20090033898; 5451784; 5824177; 5803968; and 6520843 each of which is hereby incorporated by reference in their entirety.
- Composite articles are useful in sealing elements, for example in compressor valves as disclosed in US Patent 7,011 ,111 ; each of which is hereby incorporated by reference in their entirety.
- the present invention is useful in at least one, or a combination, of (including but not limited to): a simplified process of manufacture; a robust and/or reproducible process of manufacture that can produce robust and/or reproducible product; a process to produce an article of increased density; an article of increased density; a process to produce products having fewer metal, metallic, ionic, or related impurities, particularly for processes that include a solvent or water; a process for using fibers that preserves fiber length; a process to produce product having a uniform property throughout a useful volume; any process to produce a composite product having a directional property (such as tensile strength, compressive strength, or elongation to break) that is uniform or superior regardless of the direction of measurement (or uniform or superior in one direction, or uniform or superior in two orthogonal directions), and the like.
- a simplified process of manufacture a robust and/or reproducible process of manufacture that can produce robust and/or reproducible product
- a process to produce an article of increased density an article of increased density
- a composite article of the invention can used for known applications, e.g. equipment for semiconductor manufacture, in aircraft parts, in automotive parts, in gaskets, in seals, and the like.
- the article of the present invention may be a spin disk.
- Teflon® PFA is a registered trademark of and available from E. I. du Pont de Nemours and Company, Wilmington, Delaware, and can include a polymer containing about 99 mole percent tetrafluoroethylene and about 1 mole percent perfluoro(propyl vinyl ether).
- a carbon fiber CF1 used was polyacrylonitrile based, had a length of about 6.0 mm, a diameter of about 5 to 7 microns, a bulk density of approximately 200 g/L, approximately 4 weight percent water compatible sizing, a carbon density of approximately 1.8 g/cm3 by ASTM D1505, a tensile strength of at least about 500 ksi (greater than 3450 MPa) and tensile modulus of at least approximately 31.6 Msi by ASTM D4018. Elemental analysis of the fiber for metal content in units of nanomoles per gram fiber showed results of approximately 170 000 for sodium, 770 for potassium, 180 for calcium, and 22 for aluminum.
- a similar fiber CF2 had lower content of metals. Elemental analysis of the fiber for metal content in units of nanomoles per gram fiber showed results of approximately 830 for sodium, 510 for potassium, less than 10 for calcium, and 3 for aluminum. Tensile strength was > 500 ksi (>3.45 GPa), tensile modulus was > 30 Msi (> 207 GPa), and the fiber appeared to be somewhat stronger than CF1. The sizing level was 3.8 weight percent; the sizing was characterized as water soluble.
- Teflon® PFA pellets PFAP1 (tetrafluoroethylene- perfluoro(propyl vinyl ether) copolymer, CAS 26655-00-5) have a melting point of approximately 305 C, a flow rate of 14 g/(10 min) and tensile yield strength of approximately 13.8 MPa and tensile strength of approximately 25 MPa at 25 C and 12 MPa at 250 C by ASTM D3307, and a specific gravity of approximately 2.15 g/mL.
- PFA flakes (PFAF1 ) from PFAP1 were made using a disc mill of the type manufactured by Andritz Sprout (Muncy, PA) as taught in
- Patent/Publication Number US5506052A by Deakyne by Deakyne.
- a wet matte Mw1 was made from 20% by weight CF1 and 80% by weight PFAF1 according to the methods of US5506052A.
- the dry matte Md1 made from Mw1 (before notable compression of Mw1 ) has a width of approximately 16.75 inches, a length of over 18 inches, and a basis weight of approximately 0.12 Ib/ft2.
- the coherent matte Md made from Md1 (before notable compression of Md1) has a thickness of approximately 0.095 inches (approximately 2.4 mm , 2400 microns) and approximately the same basis weight.
- a preconsolidated article CAp1-24 was made on a platen press from cut portions of coherent matte type Md . Squares of approximately 16.5 inches were cut, making note of the original length direction. Approximately 24 squares were stacked one upon the other with the length directions each orthogonally oriented to their one (for top or bottom matte) or two (for internal matte) nearest neighbors to produce a stack about 2.2 inches thick.
- the stack at essentially ambient temperature was placed in a temperature-controlled platen press and heated so that the temperature throughout the stack was greater than 310 C (583 K, 590 F) while the stack was minimally compressed along the thickness (z) direction at a pressure less than 90 psi (4310 Pa), while being unconstrained by any added pressure in the length and width (x and y) directions.
- the completely heated stack was then further compressed along the thickness direction while heating was ended and cooling was begun.
- the stack was thus consolidated to a thickness of about 0.285 inches and the temperature was decreased throughout the article to less than 290 C (563 K, 554 F). Then the temperature of and pressure on the stack were reduced to ambient conditions to obtain the article CA1-24.
- Articles CA2-24 and CA3-24 were made as for CA1-24 by substitution of carbon fibers CF2 and CF3 respectively for CF1.
- the wet matte Mw3 incorporating CF3 (free of sizing) was notably different in processing and appearance compared to Mw1 and Mw2 incorporating CF2.
- the composite material made from the sized carbon fibers CF2 demonstrated superior tensile strength and appearance.
- a heatable belt press HBP1 or HPB2 was used to make
- HBP1 was a continuous dual belt press with a working width of about 30 inches and a working length of about 10 feet.
- the constant gap working height was adjustable.
- the belt press temperature was adjustable in multiple zones.
- the entrance zones of HBP1 were set to 500 F, the internal transport zones were set to 700 F, and the later cooling zones within the working length were cooled by water entering the zones at approximately 32 F and exiting the final cooling zone at less than 100 F.
- the gap between the two belts was set to about 0.028 inches as measured the thickness after exit by a length of solder passed through the press. Both belts were coated by a release formulation.
- a single sheet of matte about 0.095 inches in height was passed through the press to continuously produce a preconsolidated matte about 0.015 inches in height. The matte was fed into the belt press at 12 inches per minute. In trial BP2, the feed rate of matte was increased to 15 inches per minute.
- the preconsolidated mattes from each belt press process were separately cut into portions, assembled mutually orthogonally into stacks as for the platen-press-made material, and finally compressed as follows.
- Preconsolidated matte made on the platen press at a density of 1.85 g/mL has been noted to expand so as to lower its density to about 1.4 g/mL during heating to above 300 C while restrained by [80 tons on 16 sq inch].
- Preconsolidated matte made on the constant gap belt press had a density of about 1.4 g/mL and did not undergo noticeable expansion during heating to 300 C while restrained by the same pressure. Final densification was higher in the case of reconsolidated matte made on the constant gap belt press under identical conditions of exposed pressure and temperature profiles in the article press.
- a composite article can a coefficient of thermal expansion in the XY direction of about 10 ppm/K; the coefficient of thermal expansion in the Z direction can be greater or less than in the XY direction.
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- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
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Abstract
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US22277009P | 2009-07-02 | 2009-07-02 | |
PCT/US2010/040574 WO2011002867A1 (fr) | 2009-07-02 | 2010-06-30 | Composant de fabrication à semi-conducteur |
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JP (2) | JP2012532217A (fr) |
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EP4030466A4 (fr) * | 2019-10-23 | 2023-11-08 | Daikin Industries, Ltd. | Élément pour dispositif de nettoyage de semi-conducteurs |
JP7549155B2 (ja) | 2021-03-04 | 2024-09-10 | デュポン スペシャルティ プロダクツ ユーエスエー リミテッド ライアビリティ カンパニー | 複合材料及び複合材料を形成する方法 |
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- 2010-06-30 JP JP2012517886A patent/JP2012532217A/ja active Pending
- 2010-06-30 KR KR1020127002824A patent/KR20120106712A/ko not_active Application Discontinuation
- 2010-06-30 WO PCT/US2010/040574 patent/WO2011002867A1/fr active Application Filing
- 2010-06-30 CN CN201510144427.3A patent/CN104844993A/zh active Pending
- 2010-06-30 KR KR1020177003661A patent/KR20170018479A/ko not_active Application Discontinuation
- 2010-06-30 CN CN201080029578.XA patent/CN102471501B/zh active Active
- 2010-06-30 EP EP10729044A patent/EP2449004A1/fr not_active Ceased
- 2010-06-30 SG SG2011097458A patent/SG177442A1/en unknown
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2015
- 2015-04-24 JP JP2015089342A patent/JP2015131976A/ja active Pending
Non-Patent Citations (1)
Title |
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See references of WO2011002867A1 * |
Also Published As
Publication number | Publication date |
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JP2015131976A (ja) | 2015-07-23 |
KR20170018479A (ko) | 2017-02-17 |
JP2012532217A (ja) | 2012-12-13 |
CN102471501B (zh) | 2015-04-29 |
CN104844993A (zh) | 2015-08-19 |
WO2011002867A1 (fr) | 2011-01-06 |
SG177442A1 (en) | 2012-02-28 |
CN102471501A (zh) | 2012-05-23 |
KR20120106712A (ko) | 2012-09-26 |
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