EP2809843A1 - Roll cover with improved dynamic properties and high resilience behavior - Google Patents
Roll cover with improved dynamic properties and high resilience behaviorInfo
- Publication number
- EP2809843A1 EP2809843A1 EP13702601.9A EP13702601A EP2809843A1 EP 2809843 A1 EP2809843 A1 EP 2809843A1 EP 13702601 A EP13702601 A EP 13702601A EP 2809843 A1 EP2809843 A1 EP 2809843A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- roll cover
- parts
- rubber
- crosslinked
- 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.)
- Granted
Links
- 229920001971 elastomer Polymers 0.000 claims abstract description 96
- 239000005060 rubber Substances 0.000 claims abstract description 96
- 229920000459 Nitrile rubber Polymers 0.000 claims abstract description 81
- 239000000203 mixture Substances 0.000 claims abstract description 66
- -1 acrylate compound Chemical class 0.000 claims abstract description 50
- 239000004033 plastic Substances 0.000 claims abstract description 8
- 229920003023 plastic Polymers 0.000 claims abstract description 8
- 230000003068 static effect Effects 0.000 claims abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 24
- 239000000945 filler Substances 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 13
- 229920000642 polymer Polymers 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 12
- 238000011084 recovery Methods 0.000 claims description 11
- 239000006229 carbon black Substances 0.000 claims description 9
- 229920001577 copolymer Polymers 0.000 claims description 8
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 6
- RVSDOPPPGCJMAY-UHFFFAOYSA-M [Zn+].CC(=C)C([O-])=O Chemical class [Zn+].CC(=C)C([O-])=O RVSDOPPPGCJMAY-UHFFFAOYSA-M 0.000 claims description 5
- ACGGZEQGHMNWFM-UHFFFAOYSA-M [Zn+].[O-]C(=O)C=C Chemical class [Zn+].[O-]C(=O)C=C ACGGZEQGHMNWFM-UHFFFAOYSA-M 0.000 claims description 5
- 239000003963 antioxidant agent Substances 0.000 claims description 5
- XKMZOFXGLBYJLS-UHFFFAOYSA-L zinc;prop-2-enoate Chemical class [Zn+2].[O-]C(=O)C=C.[O-]C(=O)C=C XKMZOFXGLBYJLS-UHFFFAOYSA-L 0.000 claims description 5
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 4
- 239000003431 cross linking reagent Substances 0.000 claims description 4
- 239000004014 plasticizer Substances 0.000 claims description 4
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 4
- PIMBTRGLTHJJRV-UHFFFAOYSA-L zinc;2-methylprop-2-enoate Chemical class [Zn+2].CC(=C)C([O-])=O.CC(=C)C([O-])=O PIMBTRGLTHJJRV-UHFFFAOYSA-L 0.000 claims description 4
- JMWGZSWSTCGVLX-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;2-methylprop-2-enoic acid Chemical class CC(=C)C(O)=O.CC(=C)C(O)=O.CC(=C)C(O)=O.CCC(CO)(CO)CO JMWGZSWSTCGVLX-UHFFFAOYSA-N 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 3
- DZBOAIYHPIPCBP-UHFFFAOYSA-L magnesium;2-methylprop-2-enoate Chemical class [Mg+2].CC(=C)C([O-])=O.CC(=C)C([O-])=O DZBOAIYHPIPCBP-UHFFFAOYSA-L 0.000 claims description 3
- LLLCSBYSPJHDJX-UHFFFAOYSA-M potassium;2-methylprop-2-enoate Chemical class [K+].CC(=C)C([O-])=O LLLCSBYSPJHDJX-UHFFFAOYSA-M 0.000 claims description 3
- HSOOIVBINKDISP-UHFFFAOYSA-N 1-(2-methylprop-2-enoyloxy)butyl 2-methylprop-2-enoate Chemical class CC(=C)C(=O)OC(CCC)OC(=O)C(C)=C HSOOIVBINKDISP-UHFFFAOYSA-N 0.000 claims description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 2
- 239000004925 Acrylic resin Substances 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- MFPROKIABJECGK-UHFFFAOYSA-K aluminum;2-methylprop-2-enoate Chemical class [Al+3].CC(=C)C([O-])=O.CC(=C)C([O-])=O.CC(=C)C([O-])=O MFPROKIABJECGK-UHFFFAOYSA-K 0.000 claims description 2
- LIQDVINWFSWENU-UHFFFAOYSA-K aluminum;prop-2-enoate Chemical class [Al+3].[O-]C(=O)C=C.[O-]C(=O)C=C.[O-]C(=O)C=C LIQDVINWFSWENU-UHFFFAOYSA-K 0.000 claims description 2
- WPKYZIPODULRBM-UHFFFAOYSA-N azane;prop-2-enoic acid Chemical class N.OC(=O)C=C WPKYZIPODULRBM-UHFFFAOYSA-N 0.000 claims description 2
- DZGUJOWBVDZNNF-UHFFFAOYSA-N azanium;2-methylprop-2-enoate Chemical class [NH4+].CC(=C)C([O-])=O DZGUJOWBVDZNNF-UHFFFAOYSA-N 0.000 claims description 2
- OAKHANKSRIPFCE-UHFFFAOYSA-L calcium;2-methylprop-2-enoate Chemical class [Ca+2].CC(=C)C([O-])=O.CC(=C)C([O-])=O OAKHANKSRIPFCE-UHFFFAOYSA-L 0.000 claims description 2
- TXTCTCUXLQYGLA-UHFFFAOYSA-L calcium;prop-2-enoate Chemical class [Ca+2].[O-]C(=O)C=C.[O-]C(=O)C=C TXTCTCUXLQYGLA-UHFFFAOYSA-L 0.000 claims description 2
- VZWHXRLOECMQDD-UHFFFAOYSA-L copper;2-methylprop-2-enoate Chemical class [Cu+2].CC(=C)C([O-])=O.CC(=C)C([O-])=O VZWHXRLOECMQDD-UHFFFAOYSA-L 0.000 claims description 2
- XPLSDXJBKRIVFZ-UHFFFAOYSA-L copper;prop-2-enoate Chemical class [Cu+2].[O-]C(=O)C=C.[O-]C(=O)C=C XPLSDXJBKRIVFZ-UHFFFAOYSA-L 0.000 claims description 2
- RLQOUIUVEQXDPW-UHFFFAOYSA-M lithium;2-methylprop-2-enoate Chemical class [Li+].CC(=C)C([O-])=O RLQOUIUVEQXDPW-UHFFFAOYSA-M 0.000 claims description 2
- XSAOIFHNXYIRGG-UHFFFAOYSA-M lithium;prop-2-enoate Chemical class [Li+].[O-]C(=O)C=C XSAOIFHNXYIRGG-UHFFFAOYSA-M 0.000 claims description 2
- 229920001568 phenolic resin Polymers 0.000 claims description 2
- 239000005011 phenolic resin Substances 0.000 claims description 2
- 239000000049 pigment Substances 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 229920000098 polyolefin Polymers 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical class [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 2
- SONHXMAHPHADTF-UHFFFAOYSA-M sodium;2-methylprop-2-enoate Chemical class [Na+].CC(=C)C([O-])=O SONHXMAHPHADTF-UHFFFAOYSA-M 0.000 claims description 2
- DWLAVVBOGOXHNH-UHFFFAOYSA-L magnesium;prop-2-enoate Chemical class [Mg+2].[O-]C(=O)C=C.[O-]C(=O)C=C DWLAVVBOGOXHNH-UHFFFAOYSA-L 0.000 claims 1
- 239000002657 fibrous material Substances 0.000 abstract 1
- 239000006185 dispersion Substances 0.000 description 15
- 239000006087 Silane Coupling Agent Substances 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000011159 matrix material Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 238000004073 vulcanization Methods 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate group Chemical group C(C(=C)C)(=O)[O-] CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 150000008040 ionic compounds Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920003052 natural elastomer Polymers 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- 239000012763 reinforcing filler Substances 0.000 description 2
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical class CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- DVNPFNZTPMWRAX-UHFFFAOYSA-N 2-triethoxysilylethanethiol Chemical compound CCO[Si](CCS)(OCC)OCC DVNPFNZTPMWRAX-UHFFFAOYSA-N 0.000 description 1
- LOSLJXKHQKRRFN-UHFFFAOYSA-N 2-trimethoxysilylethanethiol Chemical compound CO[Si](OC)(OC)CCS LOSLJXKHQKRRFN-UHFFFAOYSA-N 0.000 description 1
- BUZICZZQJDLXJN-UHFFFAOYSA-N 3-azaniumyl-4-hydroxybutanoate Chemical compound OCC(N)CC(O)=O BUZICZZQJDLXJN-UHFFFAOYSA-N 0.000 description 1
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical class CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229940006460 bromide ion Drugs 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- 229940006461 iodide ion Drugs 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- ZUBIJGNKOJGGCI-UHFFFAOYSA-M potassium;prop-2-enoate Chemical class [K+].[O-]C(=O)C=C ZUBIJGNKOJGGCI-UHFFFAOYSA-M 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical class [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- FPBXRRDHCADTAL-UHFFFAOYSA-N triethoxy(3-nitropropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCC[N+]([O-])=O FPBXRRDHCADTAL-UHFFFAOYSA-N 0.000 description 1
- ASAOXGWSIOQTDI-UHFFFAOYSA-N triethoxy-[2-(2-triethoxysilylethyltetrasulfanyl)ethyl]silane Chemical compound CCO[Si](OCC)(OCC)CCSSSSCC[Si](OCC)(OCC)OCC ASAOXGWSIOQTDI-UHFFFAOYSA-N 0.000 description 1
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 description 1
- KLFNHRIZTXWZHT-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltrisulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSCCC[Si](OCC)(OCC)OCC KLFNHRIZTXWZHT-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- QPPXVBLDIDEHBA-UHFFFAOYSA-N trimethoxy(3-nitropropyl)silane Chemical compound CO[Si](OC)(OC)CCC[N+]([O-])=O QPPXVBLDIDEHBA-UHFFFAOYSA-N 0.000 description 1
- JSXKIRYGYMKWSK-UHFFFAOYSA-N trimethoxy-[2-(2-trimethoxysilylethyltetrasulfanyl)ethyl]silane Chemical compound CO[Si](OC)(OC)CCSSSSCC[Si](OC)(OC)OC JSXKIRYGYMKWSK-UHFFFAOYSA-N 0.000 description 1
- JTTSZDBCLAKKAY-UHFFFAOYSA-N trimethoxy-[3-(3-trimethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CO[Si](OC)(OC)CCCSSSSCCC[Si](OC)(OC)OC JTTSZDBCLAKKAY-UHFFFAOYSA-N 0.000 description 1
- KOFGNZOFJYBHIN-UHFFFAOYSA-N trimethoxy-[3-(3-trimethoxysilylpropyltrisulfanyl)propyl]silane Chemical compound CO[Si](OC)(OC)CCCSSSCCC[Si](OC)(OC)OC KOFGNZOFJYBHIN-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21F—PAPER-MAKING MACHINES; METHODS OF PRODUCING PAPER THEREON
- D21F3/00—Press section of machines for making continuous webs of paper
- D21F3/02—Wet presses
- D21F3/08—Pressure rolls
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21F—PAPER-MAKING MACHINES; METHODS OF PRODUCING PAPER THEREON
- D21F5/00—Dryer section of machines for making continuous webs of paper
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21G—CALENDERS; ACCESSORIES FOR PAPER-MAKING MACHINES
- D21G1/00—Calenders; Smoothing apparatus
- D21G1/02—Rolls; Their bearings
- D21G1/0233—Soft rolls
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21G—CALENDERS; ACCESSORIES FOR PAPER-MAKING MACHINES
- D21G1/00—Calenders; Smoothing apparatus
- D21G1/02—Rolls; Their bearings
- D21G1/0246—Hard rolls
-
- 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
- D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
- D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
- D21H23/22—Addition to the formed paper
- D21H23/52—Addition to the formed paper by contacting paper with a device carrying the material
- D21H23/56—Rolls
- D21H23/58—Details thereof, e.g. surface characteristics, peripheral speed
Definitions
- the present invention relates to a roll, in particular for a roll for treating a paper, board or other fibrous web in a machine for producing and / or finishing the same suitable roll cover, a method for producing such a roll cover, a roll comprising this roll cover and the use such a roller.
- rolls and in particular rubber rolls having an elastic surface are used in a plurality of process steps, such as sheet formation in the wire section of the paper machine, dewatering in the press section of the paper machine, and painting, drying and smoothing in the final section of the paper machine paper machine.
- a large number of the rolls used in papermaking are in each case pressed against a counter-roll during their operation, wherein a fibrous web or paper web is carried out in the nip between the roll and the counter-roll.
- Film press for example, which is used for the surface treatment of paper webs, is produced on rapidly rotating applicator rollers, for example by means of roller blades each a film of example glue or coating color, which is transferred in the nip on the guided through the nip roll paper web.
- rollers are subjected to enormous loads during their use and therefore have to meet a variety of both mechanical and dynamic properties.
- such rolls must, in addition to good me- chanical properties, such as high tensile strength, abrasion resistance, tear resistance, tear propagation resistance, compressive strength and impact resistance, also have excellent dynamic properties, in particular a low hysteresis and a low tan5, among other things, the heat build-up during roll operation is sufficiently low.
- rollers must have a good and fast recovery behavior. These good dynamic properties and in particular the good and quick restoring behavior are also necessary so that the surface area of the roller deformed in the nip by the pressure of the counter roller returns to its original shape and dimension as quickly and completely as possible after leaving the nip, namely even after a very long service life of the roller.
- rolls are usually provided on their surface with a roll cover arranged on a roll core, the material of which is formulated with regard to the required application properties.
- roll covers are composed of materials which contain a matrix of a rubber or of a mixture of two or more rubbers in which one or more fillers are embedded.
- a roll cover in particular for a roll for treating a paper, board or another fibrous web in a machine for producing and / or finishing the same, which comprises at least one layer, the at least one layer containing a rubber composition, which comprises a rubber component comprising at least one crosslinked hydrogenated nitrile rubber and at least one (meth) acrylate compound, and wherein the at least one layer
- This solution is based on the surprising discovery that it is possible to obtain a roll cover made of a rubber composition having not only excellent mechanical properties, but at the same time excellent dynamic properties, namely a low tan5 value and a low hysteresis, and in particular with an excellent recovery behavior to get by a
- the rubber forms the rubber component which forms the matrix of the at least one layer of the roll cover, in which the at least one (meth) acrylate compound and optionally other fillers and additives are embedded. Due to the excellent mechanical and dynamic properties and in particular the excellent recovery behavior, the roll cover according to the invention is particularly suitable for use in a roller which is used in a fast-running glue or coating unit of a paper or board machine and in their use enormous centrifugal forces and deformation forces is exposed.
- rubber means any vulcanized rubber, irrespective of whether this is a vulcanized natural rubber or a vulcanized synthetic rubber.
- rubber component denotes the sum of all crosslinked and uncrosslinked rubbers contained in the rubber composition, that is to say the matrix of the at least one layer of the roll cover, whereas the term Rubber compound the sum of all in the at least one
- Layer of the roll cover compounds that is, the sum of the crosslinked and uncrosslinked rubbers, embedded therein embedded at least one (meth) acrylate compound and the optional other fillers and additives.
- (Meth) acrylate compound all compounds understood which have at least one acrylate group and / or at least one methacrylate group, ie in particular all at least one acrylate group and / or at least one methacrylate group-containing molecular compounds, ionic compounds or salts and complex compounds.
- the at least one layer of the roll cover according to the invention has a recovery speed of at least 12 mm / sec, which, as stated above, can be achieved by the at least one (meth) acrylate compound with a disconnectedrei - High degree of dispersion or finely divided with the at least one crosslinked hydrogenated nitrile rubber comprehensive rubber component is mixed. Corresponding concrete production methods are described below.
- the at least one layer of the roll cover has a return speed of at least 14 mm / sec, preferably a return speed of at least 16 mm / sec and particularly preferably a return speed of at least 18 mm / sec. having.
- the recovery speed in accordance with the present invention is determined as follows: First, five cylindrical test specimens each having a diameter of 13 mm and a height of 6 mm each are machined out of the at least one layer of the roll cover. Then the exact height of each specimen is determined with a vernier caliper. The test specimens are then subjected to pressure in succession in a dynamic testing device, eg a MTS-831 dynamic testing device from MTS, at 30 ° C.
- a dynamic testing device eg a MTS-831 dynamic testing device from MTS, at 30 ° C.
- 1 is an example of a diagram showing a plurality of path and force signals for one cycle at a force of 100 N (curve A) and one cycle at a force of 200 N (curve B) is.
- the at least one layer of the roll cover according to the invention has a maximum plastic deformation degree of 0.9%.
- the at least one (meth) acrylate compound having a sufficiently high degree of dispersion or finely divided with the rubber component comprising at least one crosslinked hydrogenated nitrile rubber.
- Specific manufacturing methods will be described below. Particularly good results are obtained in this embodiment, if the at least one layer has a plastic deformation of not more than 0.7%, preferably of at most 0.5% and more preferably of at most 0.3%.
- the degree of deformation is determined to be ((H a -H n ) / H a ) -100, where H a denotes the initial height of the sample body and H n denotes the height of the sample body after performing the force cycles. From the thus determined five degrees of deformation then the arithmetic mean is calculated. This value corresponds to the degree of deformation specified above.
- the at least one layer of the roll cover according to the invention both has a return speed of at least 12 mm / sec, preferably at least 14 mm / sec, more preferably at least 16 mm / sec and all more preferably of at least 18 mm / sec., as well as a plastic deformation rate of ma- ximal 0.9%, preferably of at most 0.7%, more preferably of at most 0.5% and most preferably of at most 0.3%.
- the at least one layer of the roll cover according to the invention additionally has a tan ⁇ value of not more than 0.16, determined according to DIN 53513 at 60 ° C., tension, 10 Hz, 15% static elongation and 1% dynamic elongation on.
- the tan ⁇ value is a measure of the heat buildup of the rubber composition, which in turn correlates with the hysteresis of the rubber composition, with a low tan ⁇ value correlating with low hysteresis and low heat build-up property.
- this low tan ⁇ value can be achieved by mixing the at least one (meth) acrylate compound with a sufficiently high degree of dispersion or finely divided with the rubber component comprising at least one crosslinked hydrogenated nitrile rubber becomes. Particularly good results are achieved if the at least one layer has a tan ⁇ value of at most 0, 14, preferably of at most 0, 12 and particularly preferably of not more than 0.10.
- the at least one layer of the roll cover according to the invention has a tear propagation resistance of more than 14 N / mm, preferably more than 15 N / mm N / mm and more preferably more than 16 N / mm N / mm.
- the tear resistance is determined according to DIN ISO 34-1, Method B, Method B.
- the at least one layer of the roll cover according to the invention comprises at least one contains hydrogenated nitrile rubber in which the at least one (meth) acrylate compound is finely distributed embedded.
- Hydrogenated nitrile rubber in this context means both completely hydrogenated and partially hydrogenated nitrile rubber.
- the crosslinked hydrogenated nitrile rubber is preferably crosslinked, partially hydrogenated nitrile rubber, the degree of hydrogenation preferably being from 85 to less than 100% and particularly preferably from 90 to less than 100%.
- the rubber composition of the at least one layer of the roll cover comprises a crosslinked hydrogenated nitrile rubber having an acrylonitrile content between 20 and 50% by weight, preferably between 30 and 40% by weight. % and more preferably between 33 and 37 wt .-% and accordingly with a butadiene content between 50 and 80 wt .-%, preferably between 60 and 70 wt .-% and particularly preferably between 67 and 63 wt .-%.
- the at least one crosslinked hydrogenated nitrile rubber has a Mooney viscosity determined according to DIN 53253-3 between 20 and 80 and preferably between 30 and 70.
- the rubber component of the rubber composition may be wholly composed of a crosslinked hydrogenated nitrile rubber or of two or more different crosslinked hydrogenated nitrile rubbers, that is, the rubber component and thus also the rubber composition contain no other rubber except a crosslinked hydrogenated nitrile rubber or more crosslinked hydrogenated nitrile rubbers.
- the rubber composition may be prepared by mixing the at least one (meth) acrylate compound into the uncrosslinked hydrogenated nitrile rubber and finely dispersing with a high degree of dispersion before the mixture thus prepared vulcanized.
- the rubber composition may be prepared so that the at least one of
- (Meth) acrylate compound is first mixed into a first, uncrosslinked hydrogenated nitrile rubber and finely divided with a high degree of dispersion before a second and optionally one or more further uncrosslinked hydrogenated nitrile rubber (s) is mixed into the mixture thus prepared are finally vulcanized and the mixture thus prepared is vulcanized.
- the at least one (meth) acrylate compound is first mixed into a first crosslinked hydrogenated nitrile rubber and finely divided with a high degree of dispersion before mixing this mixture with a second crosslinked hydrogenated nitrile rubber ,
- the rubber component of the rubber composition contains, in addition to the at least one crosslinked hydrogenated nitrile rubber, at least one further rubber other than crosslinked hydrogenated nitrile rubber which is preferably selected from the group consisting of crosslinked nitrile rubber. Schuken, crosslinked carboxylated nitrile rubbers, crosslinked styrene-butadiene rubbers and any copolymers and / or mixtures of two or more of the aforementioned crosslinked rubbers.
- the preparation of the rubber composition can be carried out analogously to the variants described above with respect to the embodiment in which the rubber component consists exclusively of hydrogenated / hydrogenated nitrile rubber (s).
- the rubber composition can be made so that the at least one
- (Meth) acrylate compound is first mixed in an uncrosslinked hydrogenated nitrile rubber and finely divided with a high degree of dispersion before a second and optionally one or more further uncrosslinked (r) of hydrogenated nitrile rubber of different rubber is mixed in the thus prepared mixture and / the mixture thus produced is finally vulcanized.
- a second and optionally one or more further uncrosslinked (r) of hydrogenated nitrile rubber of different rubber is mixed in the thus prepared mixture and / the mixture thus produced is finally vulcanized.
- first the at least one To mix (meth) acrylate compound in a non-crosslinked hydrogenated nitrile rubber and finely divided with a high degree of dispersion before this mixture is vulcanized and then mixed with a second and optionally one or more other rubber other than hydrogenated nitrile rubber.
- the rubber component contains 1 to 60 wt .-%, particularly preferably 5 to 50 wt .-% and most preferably 15 to 40 wt .-% of one or more different crosslinked hydrogenated nitrile rubber (s) and preferably 40 bis 99% by weight, particularly preferably 50 to 95% by weight and very particularly preferably 60 to 85% by weight of one or more rubbers selected from the group consisting of crosslinked nitrile rubbers, crosslinked carborylated nitrile rubbers, crosslinked styrene-butadiene Rubbers and any copolymers and / or mixtures of two or more of the aforementioned crosslinked rubbers.
- s crosslinked hydrogenated nitrile rubber
- (Meth) acrylate compound may be any molecular compound having at least one acrylate group and / or at least one methacrylate group, ionic compound or complex compound.
- the at least one (meth) acrylate compound is selected from the group consisting of zinc monoacrylates, zinc diacrylates, zinc monomethacrylates, zinc dimethacrylates, thacrylates, lithium acrylates, lithium methacrylates, sodium acrylates, sodium methacrylates, potassium acrylates, potassium methacrylates, magnesium methacrylates, magnesium methacrylates, magnesium methacrylates, calcium acrylates, calcium methacrylates, aluminum acrylates, aluminum methacrylates, copper acrylates, copper methacrylates, ammonium acrylates, ammonium methacrylates, quaternary ammonium acrylates, quaternary ammonium methacrylates, Alkyl diol monoacrylates, alkyl diol diacrylates, alkyl diol mono methacrylates, alkyl dio
- the at least one (meth) acrylate compound is particularly preferably selected from the group consisting of zinc monoacrylates, zinc diacrylates, zinc monomethacrylates, zinc dimethacrylates, butanediol dimethacrylates, trimethylolpropane trimethacrylates and any desired mixtures of two or more of the abovementioned compounds.
- the zinc monoacrylates and zinc monomethacrylates have a monovalent (meth) acrylate anion and a divalent zinc ion, and may have as a second negative group for generating the charge neutrality any monovalent anion, such as preferably a hydroxide ion, a chloride ion, a bromide ion or an iodide ion.
- the rubber composition based on 100 parts by weight of the rubber component, 1 to 20 parts by weight, preferably 5 to 15 parts by weight and particularly preferably 7, 5 to 12.5 parts by weight, such as 10 parts by weight, of the at least one
- the rubber composition of the at least one layer of the roll cover according to the invention may optionally contain further fillers and / or additives.
- the reinforcing filler can be, for example, carbon black and / or silica, but also an inorganic compound such as calcium carbonate, or a mineral such as mica.
- the at least one layer of the roll cover according to the invention based on 100 parts by weight of the rubber component, 1 to 150 parts by weight, preferably 10 to 100 parts by weight, more preferably 20 to 70 parts by weight and most preferably 40 to 50 parts by weight of carbon black, such as 45 parts by weight of carbon black.
- carbon black it is possible to use all types of carbon black known to the person skilled in the art and preferably carbon black having a BET specific surface area of between 5 and 120 m 2 / g.
- the at least one layer of the invention based on 100 parts by weight of the rubber component, 1 to 100 parts by weight, preferably 5 to 40 parts by weight and particularly preferably 10 to 20 parts by weight of silica, such as 15 parts by weight of silica.
- All the types of silica known to the person skilled in the art can be used as silica and preferably silica with a BET specific surface area between 5 and 210 m 2 / g.
- the at least one layer of the roll cover of the present invention contains silica, it is preferable to use it in combination with a silicone coupling agent to increase the compatibility of the rubber matrix with the silica to improve dispersion of the silica in the matrix.
- silane coupling agents of the sulfide type such as bis (3-triethoxysilylpropyl) - tetrasulfide, bis (2-triethoxysilylethyl) tetrasulfide, bis (3-trimethoxysilylpropyl) tetrasulfide, bis (2-trimethoxysilylethyl ) tetrasulfide, bis (3-triethoxysilylpropyl) trisulfide, bis (3-trimethoxysilylpropyl) trisulfide and the like, mercapto-type silane coupling agents such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane,
- 2-mercaptoethyltriethoxysilane and the like vinyl type silane coupling agents such as vinyltriethoxysilane, vinyltrimethoxysilane and the like, amino-type silane coupling agents such as 3-aminopropyltriethoxysilane,
- 3-aminopropyltrimethoxysilanes and the like glycidoxy type silane coupling agents such as ⁇ -glycidoxypropyltriethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane and the like, nitrone-type silane coupling agents such as 3-nitropropyltrimethoxysilane, 3-nitropropyltriethoxysilane and the like, and chorine type silane coupling agents such as 3-chloropropylpyrimethoxysilane , 3-Chloropropyl pyltriethoxysilane and the like.
- the rubber composition may contain, as an alternative or in addition to carbon black and / or silica, at least one filler and / or additive, which is preferably selected from the group consisting of plasticizers, antioxidants, resins, polymer fillers, pigments and any Mixtures of two or more of the aforementioned compounds.
- the rubber composition of the at least one layer of the roll cover according to the invention may be added to all plasticizers and / or antioxidants known to those skilled in the art, the plasticizer preferably being present in an amount between 0 and 30 parts by weight, preferably between 0 and 15 parts by weight and Antioxidants are preferably present in an amount between 0 and 5 parts by weight and preferably between 1 and 4 parts by weight, based in each case on 100 parts by weight of the gum component.
- the at least one resin is a phenolic resin and / or an acrylate resin.
- the amount of the at least one resin in this embodiment is preferably more than 0 to 80 parts by weight, more preferably 2 to 40 parts by weight, and most preferably 5 to 30 parts by weight based on 100 parts by weight of the rubber component.
- the rubber composition based on 100 parts by weight of the rubber component, between more than 0 and 80 parts by weight, preferably between 2 and 40 parts by weight and more preferably between 5 and 30 parts by weight of at least one polymer filler.
- the at least one polymer filler is preferably selected from the group consisting of polyolefins, polyamides, Polyurethanes, polyesters, gums and any mixtures of two or more of the aforementioned compounds.
- suitable rubbers for the polymer filler are crosslinked natural rubbers, crosslinked styrene-butadiene rubbers, crosslinked chloroprene rubbers, crosslinked nitrile rubbers, crosslinked hydrogenated nitrile rubbers, crosslinked carboxylated nitrile rubbers and any desired copolymers and / or mixtures of two or more of the aforementioned crosslinked rubbers.
- the polymer filler is particularly preferably composed of polyethylene or of polypropylene and very particularly preferably of a high-density polyethylene.
- the average particle diameter (d 50) of the polymer filler is preferably between 1 ⁇ m and 500 ⁇ m, and preferably between 10 ⁇ m and 150 ⁇ m.
- the mean particle diameter d 50 of the polymer filler is understood to be the value of the particle diameter which is less than 50% of the particles present from the polymer filler, ie 50% of all particles of the polymer filler have a smaller particle diameter than
- the roll cover comprises at least one layer consisting of the previously described rubber composition. Since this layer has very good mechanical properties as well as excellent dynamic properties, in particular a low tan5 value, and in particular an excellent recovery behavior, this at least one layer preferably forms the cover layer of the roll cover. Good results are achieved in this embodiment in particular when the at least one layer has a thickness between 5 and 25 mm.
- the roll cover consists of the at least one layer, wherein in this embodiment it is particularly preferred that the roll cover has a thickness of between 5 and 25 mm.
- the roll cover according to the invention can be produced in particular by a process in which the at least one (meth) acrylate compound having a high degree of dispersion is mixed in undiluted hydrogenated nitrile rubber and finely divided therein before the mixture thus produced is optionally further uncrosslinked hydrogenated nitrile rubber or another uncrosslinked rubber is added and the mixture thus produced is vulcanized.
- a further subject of the present invention is a method for producing the above-described roll cover according to the invention, which comprises the following steps:
- Nitrile rubbers uncrosslinked styrene-butadiene rubbers and any copolymers and / or mixtures of two or more of the aforementioned crosslinked rubbers, and
- step d) vulcanizing the mixture prepared in step c).
- the steps a) and b) can also be carried out simultaneously.
- the uncrosslinked hydrogenated nitrile rubber added in step c) may be identical to the uncrosslinked hydrogenated nitrile rubber provided in step a) or may differ therefrom, for example with regard to the molecular weight or the acrylonitrile content. Further, steps b) and c) may be performed simultaneously or sequentially.
- a method for producing the roll cover according to the invention described above comprises the following steps:
- step c) vulcanizing the mixture prepared in step b) and d) mixing the mixture obtained in step c) with a rubber which is preferably selected from the group consisting of crosslinked hydrogenated nitrile rubbers, crosslinked nitrile rubbers, crosslinked carboxylated nitrile rubbers, crosslinked styrene-butadiene rubbers and any copolymers and / or mixtures of two or more of the aforementioned crosslinked rubbers.
- a rubber which is preferably selected from the group consisting of crosslinked hydrogenated nitrile rubbers, crosslinked nitrile rubbers, crosslinked carboxylated nitrile rubbers, crosslinked styrene-butadiene rubbers and any copolymers and / or mixtures of two or more of the aforementioned crosslinked rubbers.
- steps a) and b) can be performed simultaneously.
- the crosslinked hydrogenated nitrile rubber added in the step d) may be the same as or different from the crosslinked hydrogenated nitrile rubber produced by vulcanization in the step c), for example, in terms of molecular weight or acrylonitrile content.
- step b) the mixing of the at least one crosslinking agent simultaneously or separately, ie before or after, the mixing of the at least one
- any compound known to the person skilled in the art for this purpose can be used as the vulcanizing agent, in particular sulfur, one or more vulcanizing agents based on polysulfides, one or more vulcanizing agents based on thiourea compounds, one or more vulcanizing agents based on of triazine derivatives and / or one or more vulcanizing agents based on peroxide compounds, wherein vulcanizing agents based on peroxide compounds are particularly preferred.
- one or more vulcanization accelerators may be added in addition to the vulcanizing agent.
- sulfenamide compounds such as N-cyclohexyl-2-benzothiazyl sulfenamide
- thiazole compounds such as 2-mercaptobenzothiazole
- thiuram compounds such as tetramethylthiuram monosulfide and tetramethylthiuram disulfide.
- the vulcanization can be carried out under the customary pressure and temperature conditions known to the person skilled in the art for example, in an autoclave at a temperature between 40 and 170 ° C and preferably between 90 and 160 ° C and at a pressure between 2 and 10 bar and preferably between 3 and 5 bar.
- the present invention relates to a roll cover obtainable by any of the methods described above.
- the roll cover according to the invention is characterized in that the at least one (meth) acrylate compound is finely dispersed in the rubber component, whereby the above-described excellent mechanical and dynamic properties and in particular the excellent recovery behavior described above are obtained.
- Another object of the present invention is a roll with a roll core and a formed on the roll core elastic see roll cover, which is composed as previously described.
- the present invention relates to the use of the roller described above in a paper or board machine and preferably in a film press, in a size press, in a coater or in a coater.
Landscapes
- Rolls And Other Rotary Bodies (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE102012201310A DE102012201310A1 (en) | 2012-01-31 | 2012-01-31 | Roll cover with improved dynamic properties and high resilience |
PCT/EP2013/051313 WO2013113608A1 (en) | 2012-01-31 | 2013-01-24 | Roll cover with improved dynamic properties and high resilience behavior |
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EP2809843A1 true EP2809843A1 (en) | 2014-12-10 |
EP2809843B1 EP2809843B1 (en) | 2017-03-01 |
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EP13702601.9A Active EP2809843B1 (en) | 2012-01-31 | 2013-01-24 | Roll cover with improved dynamic properties and high resilience behavior |
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US (1) | US9290887B2 (en) |
EP (1) | EP2809843B1 (en) |
CN (1) | CN104093899A (en) |
DE (1) | DE102012201310A1 (en) |
WO (1) | WO2013113608A1 (en) |
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DE102012205206A1 (en) * | 2012-03-30 | 2013-10-02 | Voith Patent Gmbh | roll cover |
DE102016114013A1 (en) * | 2016-07-29 | 2018-02-01 | Voith Patent Gmbh | Roll cover and roller and their use |
CN111058327A (en) * | 2019-11-06 | 2020-04-24 | 福建省青山纸业股份有限公司 | Method for improving roller coating |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2657823B2 (en) * | 1988-06-09 | 1997-09-30 | 日本ゼオン株式会社 | Vulcanizable rubber composition |
JPH086007B2 (en) * | 1988-06-10 | 1996-01-24 | 日本ゼオン株式会社 | Vulcanizable rubber composition |
US6328681B1 (en) | 1999-01-21 | 2001-12-11 | Stowe Woodward Inc. | Elastomeric roll cover with ultra high molecular weight polyethylene filler |
DE19942743A1 (en) | 1999-09-07 | 2001-03-08 | Bayer Ag | Rubber compounds for roller coverings |
CN100362072C (en) * | 2000-06-20 | 2008-01-16 | 三洋化成工业株式会社 | Adhesive for resin roll assembly and resin roll |
DE10102047A1 (en) * | 2001-01-17 | 2002-07-18 | Bayer Ag | Rubber mixture, useful for the production of coatings for rollers, contains a carboxylated nitrile rubber, a metal acrylate salt, a liquid acrylate and a silane |
US7008513B2 (en) * | 2002-12-31 | 2006-03-07 | Albany International Corp. | Method of making a papermaking roll cover and roll cover produced thereby |
CN1532333A (en) * | 2003-03-26 | 2004-09-29 | 精进机材公司 | Coated roller of resin dipped dense fiber inner lining layer for improving strength and adhesive property |
US6874232B2 (en) * | 2003-05-21 | 2005-04-05 | Stowe Woodward, Llc | Method for forming cover for industrial roll |
DE102005023213A1 (en) * | 2005-05-16 | 2006-11-23 | Rhein Chemie Rheinau Gmbh | Microgel-containing vulcanizable composition |
DE102007042781A1 (en) * | 2007-09-07 | 2009-03-12 | Voith Patent Gmbh | PU roller |
CN102414459B (en) * | 2009-04-21 | 2015-07-15 | 维美德技术有限公司 | A roll for a fibre web machine |
DE102012201314A1 (en) * | 2012-01-31 | 2013-08-01 | Voith Patent Gmbh | Roll cover with improved mechanical properties and high resilience |
-
2012
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- 2013-01-24 US US14/375,928 patent/US9290887B2/en active Active
- 2013-01-24 CN CN201380007532.1A patent/CN104093899A/en active Pending
- 2013-01-24 EP EP13702601.9A patent/EP2809843B1/en active Active
- 2013-01-24 WO PCT/EP2013/051313 patent/WO2013113608A1/en active Application Filing
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US20140345821A1 (en) | 2014-11-27 |
DE102012201310A1 (en) | 2013-08-01 |
WO2013113608A1 (en) | 2013-08-08 |
EP2809843B1 (en) | 2017-03-01 |
CN104093899A (en) | 2014-10-08 |
US9290887B2 (en) | 2016-03-22 |
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