US3810772A - Fluorochemical compositions for organophobic sizing of paper products - Google Patents
Fluorochemical compositions for organophobic sizing of paper products Download PDFInfo
- Publication number
- US3810772A US3810772A US00273980A US27398072A US3810772A US 3810772 A US3810772 A US 3810772A US 00273980 A US00273980 A US 00273980A US 27398072 A US27398072 A US 27398072A US 3810772 A US3810772 A US 3810772A
- Authority
- US
- United States
- Prior art keywords
- compositions
- fluorochemical
- cellulosic
- composition
- phosphate
- 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.)
- Expired - Lifetime
Links
- 239000000203 mixture Substances 0.000 title abstract description 74
- 238000004513 sizing Methods 0.000 title description 9
- 229910019142 PO4 Inorganic materials 0.000 abstract description 38
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract description 28
- 239000010452 phosphate Substances 0.000 abstract description 27
- 239000002904 solvent Substances 0.000 abstract description 21
- 239000002738 chelating agent Substances 0.000 abstract description 10
- 239000004094 surface-active agent Substances 0.000 abstract description 9
- 239000000758 substrate Substances 0.000 abstract description 7
- 230000000536 complexating effect Effects 0.000 abstract description 5
- 239000004519 grease Substances 0.000 abstract description 5
- 150000001455 metallic ions Chemical class 0.000 abstract description 4
- 230000002708 enhancing effect Effects 0.000 abstract description 2
- 235000021317 phosphate Nutrition 0.000 description 36
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 32
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 28
- 239000000123 paper Substances 0.000 description 24
- 229910052731 fluorine Inorganic materials 0.000 description 22
- 150000001875 compounds Chemical class 0.000 description 20
- 239000000463 material Substances 0.000 description 19
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 18
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 16
- 239000011737 fluorine Substances 0.000 description 16
- 239000011734 sodium Substances 0.000 description 14
- 229910052708 sodium Inorganic materials 0.000 description 14
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 14
- 239000003921 oil Substances 0.000 description 13
- 235000019198 oils Nutrition 0.000 description 13
- FSVCELGFZIQNCK-UHFFFAOYSA-N N,N-bis(2-hydroxyethyl)glycine Chemical compound OCCN(CCO)CC(O)=O FSVCELGFZIQNCK-UHFFFAOYSA-N 0.000 description 11
- 235000019483 Peanut oil Nutrition 0.000 description 11
- -1 alkyl phosphates Chemical class 0.000 description 11
- 239000000312 peanut oil Substances 0.000 description 11
- 150000003863 ammonium salts Chemical class 0.000 description 10
- 239000000460 chlorine Substances 0.000 description 10
- 239000008199 coating composition Substances 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 239000003960 organic solvent Substances 0.000 description 10
- 239000003352 sequestering agent Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000000654 additive Substances 0.000 description 8
- 229910052783 alkali metal Inorganic materials 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- 239000004615 ingredient Substances 0.000 description 8
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 8
- 238000009736 wetting Methods 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 7
- 150000001340 alkali metals Chemical class 0.000 description 7
- 229940037003 alum Drugs 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 7
- 239000002655 kraft paper Substances 0.000 description 7
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 6
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 6
- 150000001768 cations Chemical class 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical class OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 5
- CDMADVZSLOHIFP-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane;decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 CDMADVZSLOHIFP-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 235000010339 sodium tetraborate Nutrition 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000004576 sand Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000008961 swelling Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 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 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 150000003973 alkyl amines Chemical class 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- WZEMSIKSCALWJZ-UHFFFAOYSA-N azane;ethanol Chemical group N.CCO.CCO WZEMSIKSCALWJZ-UHFFFAOYSA-N 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000008139 complexing agent Substances 0.000 description 3
- RDMZIKMKSGCBKK-UHFFFAOYSA-N disodium;(9,11-dioxido-5-oxoboranyloxy-2,4,6,8,10,12,13-heptaoxa-1,3,5,7,9,11-hexaborabicyclo[5.5.1]tridecan-3-yl)oxy-oxoborane;tetrahydrate Chemical compound O.O.O.O.[Na+].[Na+].O1B(OB=O)OB(OB=O)OB2OB([O-])OB([O-])OB1O2 RDMZIKMKSGCBKK-UHFFFAOYSA-N 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- 239000011087 paperboard Substances 0.000 description 3
- 150000003141 primary amines Chemical class 0.000 description 3
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 3
- 229920003043 Cellulose fiber Polymers 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical class C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical group C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical group C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 244000010375 Talinum crassifolium Species 0.000 description 2
- 235000015055 Talinum crassifolium Nutrition 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 235000011180 diphosphates Nutrition 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000012456 homogeneous solution Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- CAAULPUQFIIOTL-UHFFFAOYSA-N methyl dihydrogen phosphate Chemical compound COP(O)(O)=O CAAULPUQFIIOTL-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229960003975 potassium Drugs 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 239000001509 sodium citrate Substances 0.000 description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 2
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 2
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 2
- 230000002522 swelling effect Effects 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- RKIMETXDACNTIE-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6-dodecafluorocyclohexane Chemical group FC1(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C1(F)F RKIMETXDACNTIE-UHFFFAOYSA-N 0.000 description 1
- LXOFYPKXCSULTL-UHFFFAOYSA-N 2,4,7,9-tetramethyldec-5-yne-4,7-diol Chemical compound CC(C)CC(C)(O)C#CC(C)(O)CC(C)C LXOFYPKXCSULTL-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- URDCARMUOSMFFI-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(2-hydroxyethyl)amino]acetic acid Chemical compound OCCN(CC(O)=O)CCN(CC(O)=O)CC(O)=O URDCARMUOSMFFI-UHFFFAOYSA-N 0.000 description 1
- BDOYKFSQFYNPKF-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetic acid;sodium Chemical compound [Na].[Na].OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O BDOYKFSQFYNPKF-UHFFFAOYSA-N 0.000 description 1
- PQAMFDRRWURCFQ-UHFFFAOYSA-N 2-ethyl-1h-imidazole Chemical compound CCC1=NC=CN1 PQAMFDRRWURCFQ-UHFFFAOYSA-N 0.000 description 1
- NJBCRXCAPCODGX-UHFFFAOYSA-N 2-methyl-n-(2-methylpropyl)propan-1-amine Chemical compound CC(C)CNCC(C)C NJBCRXCAPCODGX-UHFFFAOYSA-N 0.000 description 1
- NECRQCBKTGZNMH-UHFFFAOYSA-N 3,5-dimethylhex-1-yn-3-ol Chemical compound CC(C)CC(C)(O)C#C NECRQCBKTGZNMH-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical class OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 1
- DJEQZVQFEPKLOY-UHFFFAOYSA-N N,N-dimethylbutylamine Chemical compound CCCCN(C)C DJEQZVQFEPKLOY-UHFFFAOYSA-N 0.000 description 1
- OTRAYOBSWCVTIN-UHFFFAOYSA-N OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N Chemical compound OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N OTRAYOBSWCVTIN-UHFFFAOYSA-N 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical class [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 235000010338 boric acid Nutrition 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000002285 corn oil Substances 0.000 description 1
- 235000005687 corn oil Nutrition 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000019820 disodium diphosphate Nutrition 0.000 description 1
- GYQBBRRVRKFJRG-UHFFFAOYSA-L disodium pyrophosphate Chemical compound [Na+].[Na+].OP([O-])(=O)OP(O)([O-])=O GYQBBRRVRKFJRG-UHFFFAOYSA-L 0.000 description 1
- RHPXYIKALIRNFA-UHFFFAOYSA-L disodium;2-[carboxylatomethyl(carboxymethyl)amino]acetate Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CC([O-])=O RHPXYIKALIRNFA-UHFFFAOYSA-L 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 244000144992 flock Species 0.000 description 1
- 229940083124 ganglion-blocking antiadrenergic secondary and tertiary amines Drugs 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- UWNADWZGEHDQAB-UHFFFAOYSA-N i-Pr2C2H4i-Pr2 Natural products CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000010699 lard oil Substances 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- SMBYUOXUISCLCF-UHFFFAOYSA-N n-ethyl-n-methylpropan-1-amine Chemical compound CCCN(C)CC SMBYUOXUISCLCF-UHFFFAOYSA-N 0.000 description 1
- XWCCTMBMQUCLSI-UHFFFAOYSA-N n-ethyl-n-propylpropan-1-amine Chemical compound CCCN(CC)CCC XWCCTMBMQUCLSI-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 239000001508 potassium citrate Substances 0.000 description 1
- 229960002635 potassium citrate Drugs 0.000 description 1
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 description 1
- 235000011082 potassium citrates Nutrition 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 230000003389 potentiating effect Effects 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000001044 red dye Substances 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 230000000284 resting effect Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 230000009919 sequestration Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- NTWXWSVUSTYPJH-UHFFFAOYSA-M sodium;1,4-bis(2-methylpropoxy)-1,4-dioxobutane-2-sulfonate Chemical compound [Na+].CC(C)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(C)C NTWXWSVUSTYPJH-UHFFFAOYSA-M 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 1
- 239000003021 water soluble solvent Substances 0.000 description 1
Classifications
-
- 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
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/091—Esters of phosphoric acids with hydroxyalkyl compounds with further substituents on alkyl
Definitions
- the invention relates to functional surface coating compositions having fluorine-containing phosphate materials useful in treating paper and other cellulosic materials for improved oil and grease repellency.
- Compositions comprising such fluorochemicals in combination with nonfiuorinated organic and inorganic wetting or swelling and sequestering agents demonstate enhanced oleophobic properties when applied to cellulosic materials. They are especially useful for application to paper stock which has been previously sized.
- Fluorine-containing monomeric and polymeric materials have been generally acknowledged as useful for application to cellulosic substrates.
- certain types of stocks treated with fluorochemical sizing agents perform erratically in terms of imparting oleophobic properties thereto, and accordingly, have not received wide acceptance in industry.
- the performance of fiuorochemicals employed in treating paper was unexpectedly diminished on certain base stocks. For example, in the case of rosin/ alum sized stock, papers treated with sulphite or in the case of stocks containing lignin and/or groundwood, excessive amounts of fluorochemical sizing were necessary in order to impart satisfactory oleophobic properties.
- a still further object is to provide a series of cellulosic materials which have been coated with improved oleophobic compositions.
- functional surface coating compositions are prepared by incorporating from 0.025 to about 2.0 percent by weight of an active fluorine-containing phosphate material with about 0. 01 to about 20.0 percent by weight of nonfiuorinated organic and inorganic wetting or swelling agents either alone or in combination with sequestering agents which function to complex and/or chelate metal ions.
- an active fluorine-containing phosphate material with about 0. 01 to about 20.0 percent by weight of nonfiuorinated organic and inorganic wetting or swelling agents either alone or in combination with sequestering agents which function to complex and/or chelate metal ions.
- the additive-potentiators include various sequestering agents, water miscible organic solvents, surfactants and alkalis, each serving to either complex, wet or swell fibers of a cellulosic substrate for more favorable fluorochemical application.
- the additives are preferably employed in combinations, such as a plurality ofwater miscible solvents, like mixtures consisting of an aliphatic alcohol and dioxane or tetrahydrofuran (THF) or a monohydric alcohol such as n-butanol with THF and a chelating agent, such as DEG (the sodium salt of diethanol glycine).
- Fluorochemicals found specially adaptable for use in the subject-compositions are fluorine-containing linear, branched and cyclic structured phosphates consisting of polyfluorocyclo'alkyl phosphates and polyfiuoroalkyl phos- R (CF where R is F or H and a is an integer of from 1 to 20;
- CF CR (CF where R; is F or H and b is and R is F when b is an integer of from 1 to 18;
- R (c-C F where R; is F or C F and n is an integer of from 1 to 4 and where cdesignates an alicyclic structure;
- R is an alkyl group having 1 to 10 carbon atoms
- y is an integer of 1 or 2
- x is an integer of 1, 2 or mixtures thereof and M is a water-solubilizing cation of the group consisting of alkali metal (sodium, potassium or lithium), ammonium and substituted ammonium when x is 1, and each M is independently selected from the group consisting of hydrogen, alkali metal, ammonium and substituted ammonium when x is 2.
- polyfiuoroalkyl phosphates are compounds known in the art and are well documented in the literature.
- alkali metal, ammonium and substituted ammonium salts of polyfiuoroalkyl phosphates are taught in US. Pats. 2,559,749; 3,083,224; and 3,112,- 241.
- Perfiuoroalkylsulfonamidoalkyl phosphate materials are disclosed in US. 3,094,547.
- the above compounds are also described in US. 3,664,987 as well as copending applications S.N. 222,329 and S.N. 222,360, both filed On Jan. 31, 1972.
- the polyfluorocycloalkyl phosphates are disclosed in copending application S.N. 236,978, filed Mar. 22, 1972.
- the foregoing patents, applications and their respective enabling disclosures are incorporated-byreference herein.
- Particular polyfluorocycloalkyl phosphates of special interest may also be represented by Formula I depicting mono and his type compounds and (II) as pyroesters:
- K is fluorine or a C to C perfiuoroalkyl group substituted on the 2, 3, or 4 position of the perfluorocyclohexane ring
- n is an integer of from 1 to 4
- a is an integer of from 1 to 2
- X in each occurrance is independently selected from chlorine or any member of OM
- M is a water-solubilizing cation of the group consisting of hydrogen, alkali metal (sodium or potassium), ammonium or substituted ammonium.
- Monoesters wherein a is 1 and his esters when a is 2 may be used independently of the other.
- such products are prepared as reaction mixtures containing mono, bis and pyroesters, they can be conveniently used without first separating.
- fiuorochemicals prepared with phosphorous pentoxide also include pyroesters (II), which in turn serve to further improve the oleophobic activity of the fluorochemical coating compositions:
- oil and grease resistant polyfiuorocycloalkyl phosphate compositions typically may contain, only by way of illustration, one or more of the following: monoundecafiuorocyclohexanemethyl phosphate (monoester), bis-undecafluorocyclohexanemethyl phosphate (bis-ester) and/or his undecafluorocyclohexanemethyl pyrophosphate (pyrocster), either as the free acid or diethanolamine salt, e.g.
- Monoester T QFn-CHz-Oh-P-OH Blsester 2 C F11CH;OPOPOCH105F Pyroester
- Other polyphosphate esters may also be present, out at lower concentrations (e.g. 3%) for products prepared with a molar ratio of 3 moles of perfiuorocyclohexane alkanol to each mole of phosphorus pentoxide.
- Substituted ammonium salts of polyfiuoroalkyl and polyfluorocycloalkyl phosphates are readily prepared from commonly available, water soluble primary, secondary and tertiary amines which are inclusive only by way of example of organic amines, such as alkyl amines, alkanolamines, nitrogen containing heterocyclics, cyclic amines, polyamines, and the like.
- Alkyl amines may be primary, secondary or tertiary and may have alkyl groups having 1 to 6 carbon atoms.
- the alkyl portion of the amines may be straight chain or branched like methylamine, ethylamine, diethylamine, triethylamine, tripropylamine, diisobutylamine.
- Alkyl amines also encompass mixed amines such as N-ethyl-dipropylamine, N- ethyl-N-methyl propylamine, N,N-dimethyl butylamine, etc.
- Alkanolamines which form substituted ammonium salts with the taught compounds usually have from 1 to 3 hydroxyl groups and may also be primary, secondary, or tertiary amines.
- alkanolamines examples include monoethanolamine, diethanolamine, triethanolamine, bis(2-hydroxypropyl) amine and pentanolamine and related compounds having 2 and 3 hydroxy groups and in the range of from 2 to carbon atoms.
- Substituted ammonium salts also may be prepared from nitrogencontaining heterocyclic compounds including aromatic and non-aromatic types which may or may not be substituted, like imidazole, morpholine, piperidine and alkyl substituted heterocyclics having 1 to 6 carbon atoms like 2-ethyl imidazole.
- Cyclic amines and especially bicyclic compounds like triethylenediamine are useful salt forming agents.
- Suitable polyamines are ethylenediamine, 1,2- propanediamine, diethylene triamine, etc.
- Functional surface coating compositions will generally contain from about 0.025 to about 2.0 percent by weight of the fluorine-containing material, and most frequently, from about 0.05 to about 1.0 percent. However, more optimal quantities of fiuorochemical will range from about 0.05 to about 0.5 percent by weight.
- the non-fluorinated materials used in combination with the aforementioned fluorochemicals are mainly organic compounds providing wetting or swelling effect when in contact with cellulosic fibers.
- Inorganic compounds may also be used for enhanced oleophobic properties, for example, alkali metal hydroxides, carbonates and acids, such as boric acid and the like.
- certain of these non-fluorinated materials function as sequestering agents which form complexes when in contact with cations, such as those commonly found, for example, in clay and alum sizing. They also operate by sequestering or chelating these ions for more efiicient deposition, orientation and distribution of the fiuorochemical on the substrate.
- Particularly useful non-fluorinated materials falling within this definition are water-miscible organic solvents, chelating agents, non-ionic surfactants and alkali metal hydroxides.
- water-miscible organic solvents are recommended including readily available alcohols, such as methanol, ethanol, propanol, butanol, amyl alcohol and the like.
- the alcohols are preferably aliphatic, monohydric compounds having from about 1 to about 7 carbon atoms.
- Other available water miscible solvents include inter alia dimethylformamide (DMF), tetrahydrofuran (THF), dioxane, acetone, methyl ethyl ketone and the like.
- a cellulosic wetting amount of solvent or an amount suflicient to cause a swelling of cellulose fibers should be added to the fiuorochemical. Excessive quantities of solvent are neither required nor recommended.
- the water miscible organic solvents may be used in amounts from about 1 to about percent, and more preferably, from about 4 to about 8 percent by weight.
- sequestering agents operate by complexing or chelating cations commonly found in cellulosic sizing.
- sequestering agents are inclusive of complexing compounds, such as chelating agents which include both organic and inorganic materials capable of reacting with metallic ions to form complex molecules.
- Typical examples include compounds and salts, such as sodium tetraborate decahydrate, ammonium pentaborate, disodium octaborate tetrahydrate, sodium salt of diethanol glycine (DEG), sodium citrate, potassium citrate, the alkali metal salts of ethylenediaminetetraacetic acid, diethylenetriaminepentacetic acid-pentasodium salt, nitrilotriacetic acid disodium salt (monohydrate), N-hydroxyethyl ethylenediaminetriacetic acid (trisodium salt), oxalic acid, citric acid, boric acid and sodium hexametaphosphate, sodium acid pyrophosphate, monosodium phosphate, sodium carbonate, and the like.
- DEG diethanol glycine
- sequestering agents of the present invention are used with fluorochemicals in an amount ranging from about 0.1 to about 2.0 percent by weight, and most advantageously, from 0.25 to about 0.75 percent by weight.
- Enhanced oleophobic properties are also attainable using combinations of different sequestering agents or mixtures of sequestering agents and water miscible organic solvents.
- Representatives of this preferred combination only by way of example include, n-butanol and diethylenetriaminepentacetic acid pentasodium, n-butanol and ethylenediaminetetraacetic acid disodium, diethanol glycine sodium salt, n-butanol and THF, sodium citrate and n-butan01, sodium hexametaphosphate and n-butanol, etc.
- Combinations such as boric acid and sodium tetraborate decahydrate are but one example of potentiating combinations of chelate-sequestering compositions. Proportional amounts of each chelant, where a plurality of such materials are used, is not critical, however, the total quantity in compositions containing more than one of such agents or in blends with solvents should be from about 0.25 to about 0.75 percent by weight.
- various surface active agents and alkali metal hydroxides like sodium and potassium hydroxides impart favorable properties in terms of enhanced oleophobic activity to cellulosic fibers.
- Various types, including anionic, cationic and amphoteric type surface active agents are satisfactory, however, non-ionic surfactants stand out as being specially preferred. Oleophobic properties of the fluorochemicals are further improved when such surfactants are employed with water miscible organic solvents.
- Typical non-ionic types include a series of emulsifiers known as Surfynols which are ethylene oxide adducts of acetylenic glycols of the formula:
- R and R are alkyl radicals containing from 3 7 to carbon atoms, R and R are selected from the group consisting of methyl and ethyl, x and y have a sum in the range of 3 to 60.
- Representative Surfynols include among others Surfynol 440 which is the ethylene oxide adduct 2,4,7,9-tetramethyl-5-decyne-4,7-diol.
- Nonionics also include the polyoxyethylene nonylphenyl ethers available under the trade name Igepal.
- Igepal C0-630 is a polyoxyethylene nonylphenyl ether having a cloud point of between 126 and 133 F.
- Other representative examples include esters of sulfonsuccinic acid, as for example, the sodium dioctyl ester available under the trade name Aerosol OT or Monowet MO-70-E and the sodium diisobutyl ester sold under the names Aerosol IB and Monowet MB-70.
- Other esters, such as di-tridecyl sodium, and di-hexyl sodium are well adaptable to the subject-compositions and are also commercially available through ordinary channels of commerce.
- Surface-active agents are generally added to fluorochemicals in an amount sufiicient to provide a wetting or swelling effect upon the cellulosic fibers, and more specifically, in an amount from about 0.01 to about 1.0 percent by weight. However, as in the case of chelating agents they are most advantageously used in combination with the water miscible organic solvents for more optimal performance of the fluorochemical.
- the ratio of surfactant to solvent should generally range from about 1:40 to about 1:400 and more preferably from about 1:40 to about 1:160.
- the functional surface coating compositions of the instant invention are well adapted for application to virtually all types of cellulosic materials, such as paper and paperboard, sized and unsized stock prepared from sulphite, Kraft, soda, groundwood and other types of nonchemical and semichemical grades.
- aqueous compositions of the present invention can be applied to paper or paperboard, either onmachine or off-machine, most commonly they would be applied to at least one or perhaps both sides by means of an on-machine size press or at the calender stack.
- the composition is sprayed, cascaded or transfer rolled onto the web, or the web is immersed in the size bath, and the excess size is then metered off by either a wire wound rod or by nip rolls or both.
- the wet web then feeds through a circulating hot air oven, infrared bank or over a hot drum and/or hot calender to dry the treated paper at from 180 to 450 F., depending on the rate at which the web travels.
- the dried treated stock is roll wound or cut to size and stacked ready for use.
- cationic retention aids are added thereto.
- the stock is then sheeted and dried as above.
- compositions of the present invention in terms of their ability to impart enhanced oleophobic properties to cellulosic materials and to demonstrate their superiority over conventional surface coating products, the following test procedure was adopted:
- a tube of any rigid material 2.5 cm. (1 in.) ID and at least 2.5 cm. (1 in.) in height, the ends of which have been smoothed.
- a stop watch or laboratory timer The reagents, peanut oil, nujol, liquid lard and corn oil are separately placed in bottles ml. in each bottle) with 1.0 gram of an oil soluble red dye.
- Each specimen is then placed on a sheet of book paper resting on a smooth fiat surface.
- An end of the tube is placed on the specimen and 5 grams of sand is placed in the tube.
- the purpose of the tube is solely to insure a uniform area of the sand pile.
- compositions and processes of the instant invention illustrate the compositions and processes of the instant invention and their improved oleophobic properties when applied to cellulosic substrates. It is to be understood, however, that these examples are for illustrative purposes only and do not purport to be wholly definitive as to conditions and scope.
- the ingredients were blended together in a vessel in the order shown until a homogeneous mixture resulted.
- the bath had 0.15% fiuorochemical content.
- Part (A) which compositions contain both PC and additives of the present invention and those of part (B) which contain no additives demonstrate that in spite of higher FC concentrations on weight of paper for the latter, more efficient deposition, orientation and distribution of PC can be achieved for more enhanced oil repellency with the former.
- the results are especially dramatic when taken in light of part (A) which had a bath concentration of only 0.15% FC, whereas part (B) composition had a PC bath concentration of 0.6%.
- EXAMPLE II A composition was prepared corresponding to that outllned in Example I (A), however, 0.5% diethanol glycine sodium salt was used in place of the sodium tetraborate decahydrate. Using 50# southern kraft (0.6% rosin/ alum sized), creased holdout was increased to 50 hours at 60 C. for paper found to contain 0.16% active FC.
- a control solution containing no diethanol glycine sodium salt had a creased peanut oil holdout of less than 0.25 hour.
- a composition was prepared by admixing the above ingredients in the order shown until a homogeneous solution having 0.4% fluorochemicals resulted.
- a sheet of 50 lb. natural southern kraft (0.6% rosin/alum sized) was immersed, drained and oven dried at 180 F.
- the percent fluorochemical on weight of paper was 0.70% and the creased peanut oil holdout was 25 hours at 60 C.
- an aqueous composition was also prepared with 0.4% active fluorochemical in the bath along with 4% n-butanol and no surfactant.
- the percent fluorochemical on weight of paper was 0.72 and the creased peanut oil holdout was 7 hours at 60 C.
- a functional surface coating composition consisting essentially of (1) from about 0.01 to about 20.0 percent by weight of noniluorinated material selected from mixtures consisting of alkali metal hydroxides and carbonates, dimethylformamide and tetrahydrofuran and (2) from about 0.025 to about 2.0 percent by weight of a fluorine containing phosphate material consisting essentially of polyfluoroalkyl and cycloalkyl phosphates of the formula (R,L) ,Z where:
- R is:
- R (CF where R; is H and a is an integer of from 1 to 20; (CF CR (CF where R if For H and b is 0 and R is F when b is an integer of from 1 to 18; or R (c-C F where R, is F or C 'F and n is an integer of from 1 to 4 and where cdesignates an alicyclic structure; L is:
- R is an alkyl group having 1 to carbon atoms
- y is an integer of 1 or 2
- composition of claim 1 wherein the fluorine containing phosphate is 2)7 2 J2 2 2 2 )2]- 4.
- the composition of claim 1 wherein the fluorine containing phosphate is 5.
- the composition of claim 1 wherein the fluorine containing phosphate is 6.
- the solvent and chelating agents comprise a m'urture of n-butanol, diethanol glycine sodium salt and tetrahydrofuran.
- composition of claim 1 wherein the solvents comprise a mixture of n-butanol and tetrahydrofuran.
- a functional surface coating composition comprising (1) from about 0.01 to about 20.0 percent by weight of a nonfiuorinated material selected from the group consisting of alkali metal hydroxides and carbonates, chelating agents, nonionic, anionic and cationic surfactants, alcohols containing 1-7 carbon atoms, dimethylformamide, tetrahydrofuran, dioxane, acetone, methyl ethyl ketone and mixtures thereof and (2) from about 0.025 to about 2.0 percent by weight of a polyfluorocyclohexyl phosphate comprising a mixture of mono, his and pyroesters of the formula:
- K is fluorine or a C to C perfluoroalkyl group substituted on the 2, 3 or 4 position of the cyclohexane ring
- n is an integer of from 1 to 4
- a is an integer of from 1 to 2
- X in each occurance is independently selected from chlorine or any member of OM
- M is a watersolubilizing cation of the group consisting of hydrogen, alkali metal, ammonium and substituted ammonium.
- composition of claim 8 wherein the polyfiuorocyclohexyl phosphate comprises mixtures of compounds in which X is OM, M is hydrogen, a is 1, n is 2 and K, is F.
- composition of claim 8 wherein the polyfiuorocyclohexyl phosphate comprises mixtures of compounds in which X is OM, M is hydrogen, a is 1, n is 1 and K, is F.
- composition of claim 8 wherein the polyfiuorocyclohexyl phosphate comprises mixtures of compounds in which X is Cl, a is 1, n is 1 and K is F.
- composition of claim 8 wherein the polyfiuorocyclohexyl phosphate comprises mixture of compounds in which X is Cl, a is 2, n is 1 and K; is F.
- composition of claim 8 wherein the polyfiuorocyclohexyl phosphate comprises mixtures of compounds in which X is OM, M is diethanol ammonium, a is 2, n is 4 and K is F.
- composition of claim 8 wherein the polyfiuorocyclohexyl phosphate comprises mixtures of compounds in which X is OM, M is diethanol ammonium, a is 1, n is 1 and K is F.
- composition of claim 8 wherein the polyfiuorocyclohexyl phosphate comprises mixtures of compounds in which X is OM, M is diethanol ammonium, a is 1 and 2, n is 1 and K; is F.
- a functional surface coating composition comprising (1) from about 0.01 to about 20.0 percent by weight of water miscible organic solvents and sequestering agents selected from the group consisting essentially of nbutanol, tetrahydrofuran, dioxane, diethanol glycine sodium salt, sodium tetraborate decahydrate, disodium octaborate tetrahydrate and mixtures thereof and (2) from about 0.025 to about 2.0 'percent by weight of a polyfluorocyclohexyl phosphate comprising a mixture of mono, bis and pyroesters of the formulas:
- K is fluorine or a C to C perfluoroalkyl group substituted on the 2, 3 or 4 position of the cyclohexane ring
- n is an integer of from 1 to 4
- a is an integer of from 1 to 2
- X in each occurrance is independently selected from chlorine or any member of OM where M is a watersolubilizing cation of the group consisting of hydrogen, alkali metal, ammonium and substituted ammonium.
- composition of claim 16 wherein the solvents comprise a mixture of n-butanol and tetrahydrofuran.
- composition of claim 16 wherein the solvents comprise a mixture of n-butanol and dioxane.
- composition of claim 16 wherein the solvent and complexing agents comprise a mixture of n-butanol and diethanol glycine sodium salt.
- composition of claim 19 including tetrahydrofuran.
- composition of claim 16 wherein the solvent and complexing agents comprise a mixture of n-butanol and sodium tetraborate decahydrate.
- composition of claim 16 wherein the solvent and complexing agents comprise a mixture of n-butanol and disodium octaborate tetrahydrate.
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Abstract
IMPROVED FLUORINE-CONTAINING PHOSPHATE COMPSITIONS PROVIDE ENHANCED OIL AND GREASE RESISTANT PROPERTIES TO CELLULOSIC SUBSTRATES. FLUOROCHEMICALS LIKE POLYFLUOROCYCLOALKYL PHOSPHATES WHEN APPLIED IN COMBINATION WITH SOLVENTS, SURFACTANTS, CHELATING AGENT AND/OR ALKALI PRODUCE A COMPLEXING OF METALLIC IONS AND A WETTING EFECT OF CELLULOSIC FIBROUS BODIES THEREBY ENHANCING THEIR OLEOPHOBIC PROPERTIES. SUCH COMPOSITIONS ARE PARTICULARLY ADAPTABLE FOR ECONOMICAL APPLICATION TO CELLULOSIC STOCKS WHICH HAVE BEEN PREVIOUSLY SIZED.
Description
United States Patent Ofiice 3,810,772 FLUOROCHEMICAL COMPOSITIONS FOR ORGANOPHOBIC SIZING OF PAPER PRODUCTS Melville Willard Ufiner, Media, Pa., assignor to Air Products and Chemicals, Inc., Allentown, Pa.
No Drawing. Continuation-impart of application Ser. No. 163,417, July 16, 1971, now Patent No. 3,736,164. This application July 21, 1972, Ser. No. 273,980
Int. Cl. C09k 3/00, 3/18 U.S. Cl. 106-287 R 22 Claims ABSTRACT OF THE DISCLOSURE Improved fluorine-containing phosphate compositions provide enhanced oil and grease resistant properties to cellulosic substrates. Fluorochemicals like polyfluorocycloalkyl phosphates when applied in combination with solvents, surfactants, chelating agents and/or alkali produce a complexing of metallic ions and a wetting effect of cellulosic fibrous bodies thereby enhancing their oleophobic properties. Such compositions are particularly adaptable for economical application to cellulosic stocks which have been previously sized.
CROSS REFERENCE TO RELATED APPLICATION This application is a continuation-in-part of application Ser. No. 163,417 filed July 16, 1971, now U.S. Pat. 3,736,164.
BACKGROUND OF THE INVENTION The invention relates to functional surface coating compositions having fluorine-containing phosphate materials useful in treating paper and other cellulosic materials for improved oil and grease repellency. Compositions comprising such fluorochemicals in combination with nonfiuorinated organic and inorganic wetting or swelling and sequestering agents demonstate enhanced oleophobic properties when applied to cellulosic materials. They are especially useful for application to paper stock which has been previously sized.
Fluorine-containing monomeric and polymeric materials have been generally acknowledged as useful for application to cellulosic substrates. However, it has been found that certain types of stocks treated with fluorochemical sizing agents perform erratically in terms of imparting oleophobic properties thereto, and accordingly, have not received wide acceptance in industry. More specifically, it has been discovered the performance of fiuorochemicals employed in treating paper was unexpectedly diminished on certain base stocks. For example, in the case of rosin/ alum sized stock, papers treated with sulphite or in the case of stocks containing lignin and/or groundwood, excessive amounts of fluorochemical sizing were necessary in order to impart satisfactory oleophobic properties.
-In many instances, certain cellulosic stocks showed a tendency to preferentially absorb fluorine-containing chemicals disproportionately to the size-tub concentration resulting in pre-mature exhaustion of the size bath, so that pickup at the end of the run was significantly less than experienced at the beginning of the run. Consequently, fluorochemical sizing agents have not received universal acceptance, simply because they were too costly for economical use on all types of stock. That is to say, heretofore, the application of fluorochemical agents has been restricted almost exclusively to waterleaf or unsized stock, and as a result, manufacturers customarily avoided their use on previously sized cellulosics.
3,810,772 Patented May 14, 1974 One remedy suggested for more economical use was to employ dilute aqueous solutions of fluorochemicals, since they were generally felt to offer better wetting of the stock. In spite of some improvement, dilute aqueous compositions of fiuorochemicals nevertheless failed to provide a total solution to the problem. Such compositions had a tendency to flock, and therefore, a loss of potency upon standing resulted.
It has now been discovered that a group of fluorinecontaining phosphate compositions when used in conjunction with a particular group of additives, either singly or in combination, are capable of inducing a cellulose swelling or wetting effect or a sequestration of metal ions when in contact with cellulosic fibers thereby providing enhanced fluorochemical activity. This is demonstrated by the fact that fluorochemical concentration of a bath at the beginning of a coating operation remains substantially undiminished at the time of completion. By employing the foregoing additives in an aqueous fluorochemical bath, the activity of the oleophobic ingredients is potentiated over corresponding compositions used in the absence of such additives. The treated stock is also more uniformly oleophobic, and therefore, all paper and paperboard stock, regardless of the type and source of pulp, method of making, particular pigment or binder content, will now respond economically to fluorochemical application.
Accordingly, it is a principal object of the present invention to provide a series of novel fluorine-containing phosphate sizing compositions which can be employed economically to virtually any type of cellulosic stock.
It is a further object of the instant invention to provide potentiated fluorochemical compositions having improved oil and grease repellent properties when applied to sized cellulosics.
A still further object is to provide a series of cellulosic materials which have been coated with improved oleophobic compositions.
These and other objects, features and advantages of this invention will become apparent to those skilled in the art after a reading of the following more detailed description.
PREFERRED EMBODIMENTS OF THE INVENTION In accordance with the present invention, functional surface coating compositions are prepared by incorporating from 0.025 to about 2.0 percent by weight of an active fluorine-containing phosphate material with about 0. 01 to about 20.0 percent by weight of nonfiuorinated organic and inorganic wetting or swelling agents either alone or in combination with sequestering agents which function to complex and/or chelate metal ions. With the presence of a sufiicient amount of the nonfluorine containing additive, fibers of a cellulosic substrate become more receptive to efiicient fluorochemical distribution and deposition. The additive-potentiators include various sequestering agents, water miscible organic solvents, surfactants and alkalis, each serving to either complex, wet or swell fibers of a cellulosic substrate for more favorable fluorochemical application. Though satisfactorily used individually, the additives are preferably employed in combinations, such as a plurality ofwater miscible solvents, like mixtures consisting of an aliphatic alcohol and dioxane or tetrahydrofuran (THF) or a monohydric alcohol such as n-butanol with THF and a chelating agent, such as DEG (the sodium salt of diethanol glycine).
Fluorochemicals found specially adaptable for use in the subject-compositions are fluorine-containing linear, branched and cyclic structured phosphates consisting of polyfluorocyclo'alkyl phosphates and polyfiuoroalkyl phos- R (CF where R is F or H and a is an integer of from 1 to 20;
(CF CR (CF where R; is F or H and b is and R is F when b is an integer of from 1 to 18;
R (c-C F where R; is F or C F and n is an integer of from 1 to 4 and where cdesignates an alicyclic structure;
where R is an alkyl group having 1 to 10 carbon atoms;
(CH O, where n is the integer l or 2;
y is an integer of 1 or 2, and
Z is:
-P (O) (OM)x, where x is an integer of 1, 2 or mixtures thereof and M is a water-solubilizing cation of the group consisting of alkali metal (sodium, potassium or lithium), ammonium and substituted ammonium when x is 1, and each M is independently selected from the group consisting of hydrogen, alkali metal, ammonium and substituted ammonium when x is 2.
The following compounds illustrate only but a few of the fluorine-containing phosphate materials falling within the purview of the above formula:
1 cdesignates an allcycllc structure.
The foregoing polyfiuoroalkyl phosphates are compounds known in the art and are well documented in the literature. For example, alkali metal, ammonium and substituted ammonium salts of polyfiuoroalkyl phosphates are taught in US. Pats. 2,559,749; 3,083,224; and 3,112,- 241. Perfiuoroalkylsulfonamidoalkyl phosphate materials are disclosed in US. 3,094,547. The above compounds are also described in US. 3,664,987 as well as copending applications S.N. 222,329 and S.N. 222,360, both filed On Jan. 31, 1972. The polyfluorocycloalkyl phosphates are disclosed in copending application S.N. 236,978, filed Mar. 22, 1972. The foregoing patents, applications and their respective enabling disclosures are incorporated-byreference herein.
Particular polyfluorocycloalkyl phosphates of special interest may also be represented by Formula I depicting mono and his type compounds and (II) as pyroesters:
wherein K; is fluorine or a C to C perfiuoroalkyl group substituted on the 2, 3, or 4 position of the perfluorocyclohexane ring, n is an integer of from 1 to 4, a is an integer of from 1 to 2 and X in each occurrance is independently selected from chlorine or any member of OM where M is a water-solubilizing cation of the group consisting of hydrogen, alkali metal (sodium or potassium), ammonium or substituted ammonium.
Monoesters wherein a is 1 and his esters when a is 2 may be used independently of the other. Alternatively, because such products are prepared as reaction mixtures containing mono, bis and pyroesters, they can be conveniently used without first separating. Furthermore,
fiuorochemicals prepared with phosphorous pentoxide (P 0 also include pyroesters (II), which in turn serve to further improve the oleophobic activity of the fluorochemical coating compositions:
wherein the values of K n and X for the pyrophosphates of (II) are the same as Formula I. Although a and m of (II) may be integers of one or more, in most instances their values will be preferably 1.
From Formulas I and II, it can be seen that certain compounds will have only a single X, in which case they may have a value of chlorine or an OM radical where M is hydrogen, alkali metal, ammonium or substituted ammonium derived from primary, secondary or tertiary amines. However, pyroesters (II) and bisesters (I) have at least two Xs present. In this instance, X may then be independently selected from chlorine or OM and any of the values for M. This naturally includes individual compounds where each of the Xs have radicals which are the same as well as compounds having a plurality of Xs where each is different from the other.
The following table illustrates other polyfluorocyclohexanealkyl phosphates falling within the purview of Formulas I and II:
Thus, oil and grease resistant polyfiuorocycloalkyl phosphate compositions typically may contain, only by way of illustration, one or more of the following: monoundecafiuorocyclohexanemethyl phosphate (monoester), bis-undecafluorocyclohexanemethyl phosphate (bis-ester) and/or his undecafluorocyclohexanemethyl pyrophosphate (pyrocster), either as the free acid or diethanolamine salt, e.g.
Monoester T (QFn-CHz-Oh-P-OH Blsester 2 C F11CH;OPOPOCH105F Pyroester Other polyphosphate esters may also be present, out at lower concentrations (e.g. 3%) for products prepared with a molar ratio of 3 moles of perfiuorocyclohexane alkanol to each mole of phosphorus pentoxide.
Substituted ammonium salts of polyfiuoroalkyl and polyfluorocycloalkyl phosphates are readily prepared from commonly available, water soluble primary, secondary and tertiary amines which are inclusive only by way of example of organic amines, such as alkyl amines, alkanolamines, nitrogen containing heterocyclics, cyclic amines, polyamines, and the like. Alkyl amines may be primary, secondary or tertiary and may have alkyl groups having 1 to 6 carbon atoms. The alkyl portion of the amines may be straight chain or branched like methylamine, ethylamine, diethylamine, triethylamine, tripropylamine, diisobutylamine. Alkyl amines also encompass mixed amines such as N-ethyl-dipropylamine, N- ethyl-N-methyl propylamine, N,N-dimethyl butylamine, etc. Alkanolamines which form substituted ammonium salts with the taught compounds usually have from 1 to 3 hydroxyl groups and may also be primary, secondary, or tertiary amines. Examples of suitable alkanolamines are monoethanolamine, diethanolamine, triethanolamine, bis(2-hydroxypropyl) amine and pentanolamine and related compounds having 2 and 3 hydroxy groups and in the range of from 2 to carbon atoms. Substituted ammonium salts also may be prepared from nitrogencontaining heterocyclic compounds including aromatic and non-aromatic types which may or may not be substituted, like imidazole, morpholine, piperidine and alkyl substituted heterocyclics having 1 to 6 carbon atoms like 2-ethyl imidazole. Cyclic amines and especially bicyclic compounds like triethylenediamine are useful salt forming agents. Suitable polyamines are ethylenediamine, 1,2- propanediamine, diethylene triamine, etc.
Preparation of the foregoing salts are described in copending patent application S.N. 236,978, filed Mar. 22, 1972. The fiuorochemical compounds and salts disclosed therein and methods for their manufacture are hereby incorporated-by-reference into the present application.
Functional surface coating compositions will generally contain from about 0.025 to about 2.0 percent by weight of the fluorine-containing material, and most frequently, from about 0.05 to about 1.0 percent. However, more optimal quantities of fiuorochemical will range from about 0.05 to about 0.5 percent by weight.
The non-fluorinated materials used in combination with the aforementioned fluorochemicals are mainly organic compounds providing wetting or swelling effect when in contact with cellulosic fibers. Inorganic compounds may also be used for enhanced oleophobic properties, for example, alkali metal hydroxides, carbonates and acids, such as boric acid and the like. In addition, certain of these non-fluorinated materials function as sequestering agents which form complexes when in contact with cations, such as those commonly found, for example, in clay and alum sizing. They also operate by sequestering or chelating these ions for more efiicient deposition, orientation and distribution of the fiuorochemical on the substrate. Particularly useful non-fluorinated materials falling within this definition are water-miscible organic solvents, chelating agents, non-ionic surfactants and alkali metal hydroxides.
A wide range of water-miscible organic solvents are recommended including readily available alcohols, such as methanol, ethanol, propanol, butanol, amyl alcohol and the like. The alcohols are preferably aliphatic, monohydric compounds having from about 1 to about 7 carbon atoms. Other available water miscible solvents include inter alia dimethylformamide (DMF), tetrahydrofuran (THF), dioxane, acetone, methyl ethyl ketone and the like. Generally, a cellulosic wetting amount of solvent or an amount suflicient to cause a swelling of cellulose fibers should be added to the fiuorochemical. Excessive quantities of solvent are neither required nor recommended. More specifically, the water miscible organic solvents may be used in amounts from about 1 to about percent, and more preferably, from about 4 to about 8 percent by weight.
It is also specially advantageous to employ combinations of such water miscible organic solvents with the fluorochemicals disclosed herein. For example, blended admixtures of n-butanol and THF, DMF or dioxane are particularly effective when employed with the oleophobic fluorochemicals. N-amyl-alcohol can also be satisfactorily used in combination with DMF for enhanced oleophobicity. Other variations of organic solvent combinations too numerous to mention, provide acceptable results. However, in selecting a particular solvent or combination of solvents for use with the fiuorochemical ingredient preferably they should be readily miscible in aqueous solutions. The proportional range of each solvent used in a given combination of solvents is not critical, however, the combined quantities employed in a coating composition will not ordinarily exceed those amounts set-forth above for homogeneous solvent containing compositions.
As previously mentioned, the sequestering agents operate by complexing or chelating cations commonly found in cellulosic sizing. For purposes of the present invention, sequestering agents are inclusive of complexing compounds, such as chelating agents which include both organic and inorganic materials capable of reacting with metallic ions to form complex molecules. Typical examples include compounds and salts, such as sodium tetraborate decahydrate, ammonium pentaborate, disodium octaborate tetrahydrate, sodium salt of diethanol glycine (DEG), sodium citrate, potassium citrate, the alkali metal salts of ethylenediaminetetraacetic acid, diethylenetriaminepentacetic acid-pentasodium salt, nitrilotriacetic acid disodium salt (monohydrate), N-hydroxyethyl ethylenediaminetriacetic acid (trisodium salt), oxalic acid, citric acid, boric acid and sodium hexametaphosphate, sodium acid pyrophosphate, monosodium phosphate, sodium carbonate, and the like. Ordinarily, all that is needed is a complexing amount or an amount sufiicient to bind or sequester the metallic ions on the cellulose fibers. More particularly, sequestering agents of the present invention are used with fluorochemicals in an amount ranging from about 0.1 to about 2.0 percent by weight, and most advantageously, from 0.25 to about 0.75 percent by weight.
Enhanced oleophobic properties are also attainable using combinations of different sequestering agents or mixtures of sequestering agents and water miscible organic solvents. Representatives of this preferred combination, only by way of example include, n-butanol and diethylenetriaminepentacetic acid pentasodium, n-butanol and ethylenediaminetetraacetic acid disodium, diethanol glycine sodium salt, n-butanol and THF, sodium citrate and n-butan01, sodium hexametaphosphate and n-butanol, etc. Combinations, such as boric acid and sodium tetraborate decahydrate are but one example of potentiating combinations of chelate-sequestering compositions. Proportional amounts of each chelant, where a plurality of such materials are used, is not critical, however, the total quantity in compositions containing more than one of such agents or in blends with solvents should be from about 0.25 to about 0.75 percent by weight.
In addition to water soluble solvents and chelating agents, various surface active agents and alkali metal hydroxides like sodium and potassium hydroxides impart favorable properties in terms of enhanced oleophobic activity to cellulosic fibers. Various types, including anionic, cationic and amphoteric type surface active agents are satisfactory, however, non-ionic surfactants stand out as being specially preferred. Oleophobic properties of the fluorochemicals are further improved when such surfactants are employed with water miscible organic solvents.
Typical non-ionic types include a series of emulsifiers known as Surfynols which are ethylene oxide adducts of acetylenic glycols of the formula:
wherein R and R are alkyl radicals containing from 3 7 to carbon atoms, R and R are selected from the group consisting of methyl and ethyl, x and y have a sum in the range of 3 to 60. Representative Surfynols include among others Surfynol 440 which is the ethylene oxide adduct 2,4,7,9-tetramethyl-5-decyne-4,7-diol.
Nonionics also include the polyoxyethylene nonylphenyl ethers available under the trade name Igepal. Igepal C0-630 is a polyoxyethylene nonylphenyl ether having a cloud point of between 126 and 133 F. Other representative examples include esters of sulfonsuccinic acid, as for example, the sodium dioctyl ester available under the trade name Aerosol OT or Monowet MO-70-E and the sodium diisobutyl ester sold under the names Aerosol IB and Monowet MB-70. Other esters, such as di-tridecyl sodium, and di-hexyl sodium are well adaptable to the subject-compositions and are also commercially available through ordinary channels of commerce.
Surface-active agents are generally added to fluorochemicals in an amount sufiicient to provide a wetting or swelling effect upon the cellulosic fibers, and more specifically, in an amount from about 0.01 to about 1.0 percent by weight. However, as in the case of chelating agents they are most advantageously used in combination with the water miscible organic solvents for more optimal performance of the fluorochemical. The ratio of surfactant to solvent should generally range from about 1:40 to about 1:400 and more preferably from about 1:40 to about 1:160.
The functional surface coating compositions of the instant invention are well adapted for application to virtually all types of cellulosic materials, such as paper and paperboard, sized and unsized stock prepared from sulphite, Kraft, soda, groundwood and other types of nonchemical and semichemical grades.
Although the aqueous compositions of the present invention can be applied to paper or paperboard, either onmachine or off-machine, most commonly they would be applied to at least one or perhaps both sides by means of an on-machine size press or at the calender stack. In these processes, the composition is sprayed, cascaded or transfer rolled onto the web, or the web is immersed in the size bath, and the excess size is then metered off by either a wire wound rod or by nip rolls or both.
The wet web then feeds through a circulating hot air oven, infrared bank or over a hot drum and/or hot calender to dry the treated paper at from 180 to 450 F., depending on the rate at which the web travels. The dried treated stock is roll wound or cut to size and stacked ready for use.
Where it is convenient to add a known quantity of the fiuorochemical composition directly to the furnish at the beater or repulper, cationic retention aids, known in the art, are added thereto. The stock is then sheeted and dried as above.
In order to evaluate the effectiveness of the compositions of the present invention in terms of their ability to impart enhanced oleophobic properties to cellulosic materials and to demonstrate their superiority over conventional surface coating products, the following test procedure was adopted:
OIL PENETRATION TEST Apparatus requirements:
1. A tube of any rigid material, 2.5 cm. (1 in.) ID and at least 2.5 cm. (1 in.) in height, the ends of which have been smoothed.
2. Al pipet or medicine dropper, calibrated to deliver 1.1
3. Round-grained sand, Ottawa cement testing sand screened to pass a No. and be retained on a No. 3 sieve.
4. Sheets of white coated and calendered 80 lb. book paper, 104 grams/m. exponent to, 70 lb. at least the same size as the test specimen, preferably much larger.
5. A stop watch or laboratory timer. The reagents, peanut oil, nujol, liquid lard and corn oil are separately placed in bottles ml. in each bottle) with 1.0 gram of an oil soluble red dye.
Each specimen is then placed on a sheet of book paper resting on a smooth fiat surface. An end of the tube is placed on the specimen and 5 grams of sand is placed in the tube. The purpose of the tube is solely to insure a uniform area of the sand pile. Using the pipet or a medicine dropper, 1.1 ml. of the colored oil or greases were added to the sand, the tube is removed, and the timing device is started. The test proceeds for 72 hours at 60 C. or until the stain strikes through the treated paper and stains the book paper beneath it.
The following specific examples illustrate the compositions and processes of the instant invention and their improved oleophobic properties when applied to cellulosic substrates. It is to be understood, however, that these examples are for illustrative purposes only and do not purport to be wholly definitive as to conditions and scope.
EXAMPLE I A size bath composition having the following ingredients was prepared:
1% solution diethanolamine salts of mono, bis and pyroesters of 1,1 dihydroperfluorocyclohexanemethyl phosphate 15.0
The ingredients were blended together in a vessel in the order shown until a homogeneous mixture resulted. The bath had 0.15% fiuorochemical content.
(A) A sheet of 50 lb. southern kraft having 0.6% rosin/alum sized was completely immersed in the bath containing 0.15 fluorochemical phosphate (FC). After removal, it was padded to drain off excess fluid, dried for 15 minutes at F. in a circulating hot air oven, and found to contain 0.19% active PC on the weight of paper. The dried 'fluorochemical treated sheet was tested in accordance with AST M Standard Method F87-68 outlined above using peanut oil. Average creased peanut oil holdout was 23 hours at 60 C.
(B) For purposes of comparison, an aqueous bath was prepared with a 0.6% concentration of the same fluorochemical phosphate. However, no solvents or chelating agents were added. A sheet of 50 lb. southern kraft with 0.6% rosin/alum sized was immersed and dried in accordance with the method of part A and found to contain 0.46% active PC on the Weight of paper. Using the same method of testing the average creased peanut oil holdout was less than M; hour at 60 C.
Part (A) which compositions contain both PC and additives of the present invention and those of part (B) which contain no additives demonstrate that in spite of higher FC concentrations on weight of paper for the latter, more efficient deposition, orientation and distribution of PC can be achieved for more enhanced oil repellency with the former. The results are especially dramatic when taken in light of part (A) which had a bath concentration of only 0.15% FC, whereas part (B) composition had a PC bath concentration of 0.6%.
EXAMPLE II A composition was prepared corresponding to that outllned in Example I (A), however, 0.5% diethanol glycine sodium salt was used in place of the sodium tetraborate decahydrate. Using 50# southern kraft (0.6% rosin/ alum sized), creased holdout was increased to 50 hours at 60 C. for paper found to contain 0.16% active FC.
9 I EXAMPLE n1 A sizing bath having the following ingredients was prepared:
The above ingredients were combined and mixed in the order shown. A sheet of 50# southern kraft (0.6% rosin/alum sized) was entirely immersed in the composition, excess FC squeezed off and the sheet dried at 180 F. The average creased peanut oil holdout was 41 hours at 603 C. based upon 0.25% active fluorochemical on weight of paper. In comparison, when n-butanol is excluded from the composition, 0.31% active F is picked up and average creased peanut oil holdout is less than A hour at 60 C.
Compositions corresponding to those in Example III were also prepared, however, the quantity of fluorochem ical was gradually increased. Results are shown in the table below.
TABLE I Percent Greased fluoropeanut oil Percent chemical holdout. fluorochemical on weight (hours a in bath of paper 60 C.)
TABLE II Percent Greased fluoropeanut. oil Percent chemical holdout fluorochemical on weight (he in bath paper at 60 C Table II provides evidence that conventional aqueous fluorochemical coating compositions applied to sized stock, regardless of the fluorochemical concentration, does not impart acceptable oil repellency properties to such cellulosics. In contradistinction, the compositions of Examples I(A), II and III all prepared with the nonfiuorinated additives of the subject invention for improved deposition, orientation and distribution of the F0 on cellulose stock, provided a fluorochemical on weight of paper at a percentage well within the range shown in Table II, however, the average creased peanut oil holdout ranged from 23 to 50 hours rather than the hour or less holdouts of Table II.
10 EXAMPLE IV Parts by weight Water 79.5 Diethanol glycine sodium salt 0.5
1% solution diethanolamine salts of mono, bis and pyroesters of 1,1 dihydroperfluorocyclohexane methyl phosphate 20.0
The ingredients were mixed in the order shown until a homogeneous solution was prepared. A sheet of 41# Reg. waterleaf (bleached kraft) was immersed completely into the solution having a fluorochemical concentration of 0.2%. Upon removal, excess fluid was allowed to drain oil and the sheet dried at F. in a circulating hot air oven. The sheet was tested for oil repellency according to the above method. The percent fluorochemical on weight of paper was 0.23 and the creased peanut oil holdout was 72+ hours at 60 C.
A control solution containing no diethanol glycine sodium salt had a creased peanut oil holdout of less than 0.25 hour.
1% solution diethanolamine salts of mono, his
and pyroesters of 1,1 dihydroperfluorocyclohexane methyl phosphate 40.0
A composition was prepared by admixing the above ingredients in the order shown until a homogeneous solution having 0.4% fluorochemicals resulted. In order to determine its oleophobic properties a sheet of 50 lb. natural southern kraft (0.6% rosin/alum sized) was immersed, drained and oven dried at 180 F. The percent fluorochemical on weight of paper was 0.70% and the creased peanut oil holdout was 25 hours at 60 C.
As a control, an aqueous composition was also prepared with 0.4% active fluorochemical in the bath along with 4% n-butanol and no surfactant. The percent fluorochemical on weight of paper was 0.72 and the creased peanut oil holdout was 7 hours at 60 C.
While the invention has been described in conjunction with specific examples thereof, they are illustrative only. Accordingly, many alternatives, modifications and variations will be apparent to those skilled in the art in light of the foregoing description, and it is therefore intended to embrace all such alternatives, modifications and variations as to fall within the spirit and broad scope of the appended claims.
I claim:
1. A functional surface coating composition consisting essentially of (1) from about 0.01 to about 20.0 percent by weight of noniluorinated material selected from mixtures consisting of alkali metal hydroxides and carbonates, dimethylformamide and tetrahydrofuran and (2) from about 0.025 to about 2.0 percent by weight of a fluorine containing phosphate material consisting essentially of polyfluoroalkyl and cycloalkyl phosphates of the formula (R,L) ,Z where:
R, is:
R (CF where R; is H and a is an integer of from 1 to 20; (CF CR (CF where R if For H and b is 0 and R is F when b is an integer of from 1 to 18; or R (c-C F where R, is F or C 'F and n is an integer of from 1 to 4 and where cdesignates an alicyclic structure; L is:
where R is an alkyl group having 1 to carbon atoms; or
(CH O, where n is the integer 1 or 2;
y is an integer of 1 or 2, and
3. The composition of claim 1 wherein the fluorine containing phosphate is 2)7 2 J2 2 2 2 )2]- 4. The composition of claim 1 wherein the fluorine containing phosphate is 5. The composition of claim 1 wherein the fluorine containing phosphate is 6. The composition of claim 1 wherein the solvent and chelating agents comprise a m'urture of n-butanol, diethanol glycine sodium salt and tetrahydrofuran.
7. The composition of claim 1 wherein the solvents comprise a mixture of n-butanol and tetrahydrofuran.
8. A functional surface coating composition comprising (1) from about 0.01 to about 20.0 percent by weight of a nonfiuorinated material selected from the group consisting of alkali metal hydroxides and carbonates, chelating agents, nonionic, anionic and cationic surfactants, alcohols containing 1-7 carbon atoms, dimethylformamide, tetrahydrofuran, dioxane, acetone, methyl ethyl ketone and mixtures thereof and (2) from about 0.025 to about 2.0 percent by weight of a polyfluorocyclohexyl phosphate comprising a mixture of mono, his and pyroesters of the formula:
wherein K, is fluorine or a C to C perfluoroalkyl group substituted on the 2, 3 or 4 position of the cyclohexane ring, n is an integer of from 1 to 4, a is an integer of from 1 to 2 and X in each occurance is independently selected from chlorine or any member of OM where M is a watersolubilizing cation of the group consisting of hydrogen, alkali metal, ammonium and substituted ammonium.
9. The composition of claim 8 wherein the polyfiuorocyclohexyl phosphate comprises mixtures of compounds in which X is OM, M is hydrogen, a is 1, n is 2 and K, is F.
10. The composition of claim 8 wherein the polyfiuorocyclohexyl phosphate comprises mixtures of compounds in which X is OM, M is hydrogen, a is 1, n is 1 and K, is F.
11. The composition of claim 8 wherein the polyfiuorocyclohexyl phosphate comprises mixtures of compounds in which X is Cl, a is 1, n is 1 and K is F.
12. The composition of claim 8 wherein the polyfiuorocyclohexyl phosphate comprises mixture of compounds in which X is Cl, a is 2, n is 1 and K; is F.
13. The composition of claim 8 wherein the polyfiuorocyclohexyl phosphate comprises mixtures of compounds in which X is OM, M is diethanol ammonium, a is 2, n is 4 and K is F.
14-. The composition of claim 8 wherein the polyfiuorocyclohexyl phosphate comprises mixtures of compounds in which X is OM, M is diethanol ammonium, a is 1, n is 1 and K is F.
15. The composition of claim 8 wherein the polyfiuorocyclohexyl phosphate comprises mixtures of compounds in which X is OM, M is diethanol ammonium, a is 1 and 2, n is 1 and K; is F.
16. A functional surface coating composition comprising (1) from about 0.01 to about 20.0 percent by weight of water miscible organic solvents and sequestering agents selected from the group consisting essentially of nbutanol, tetrahydrofuran, dioxane, diethanol glycine sodium salt, sodium tetraborate decahydrate, disodium octaborate tetrahydrate and mixtures thereof and (2) from about 0.025 to about 2.0 'percent by weight of a polyfluorocyclohexyl phosphate comprising a mixture of mono, bis and pyroesters of the formulas:
wherein K; is fluorine or a C to C perfluoroalkyl group substituted on the 2, 3 or 4 position of the cyclohexane ring, n is an integer of from 1 to 4, a is an integer of from 1 to 2 and X in each occurrance is independently selected from chlorine or any member of OM where M is a watersolubilizing cation of the group consisting of hydrogen, alkali metal, ammonium and substituted ammonium.
17. The composition of claim 16 wherein the solvents comprise a mixture of n-butanol and tetrahydrofuran.
18. The composition of claim 16 wherein the solvents comprise a mixture of n-butanol and dioxane.
19. The composition of claim 16 wherein the solvent and complexing agents comprise a mixture of n-butanol and diethanol glycine sodium salt.
20. The composition of claim 19 including tetrahydrofuran.
21. The composition of claim 16 wherein the solvent and complexing agents comprise a mixture of n-butanol and sodium tetraborate decahydrate.
22. The composition of claim 16 wherein the solvent and complexing agents comprise a mixture of n-butanol and disodium octaborate tetrahydrate.
References Cited UNITED STATES PATENTS 3,664,987 5/1972 Moyer 260-29.6 H 2,597,702 5/ 1952 Benning 260-924 3,245,816 4/1966 Schwaibe 106213 3,039,886 6/1962 Masley 106214 3,736,164 5/1973 Utfner 106213 OTHER REFERENCES Surface Active Agents-Schwartz, 1949.
THEODORE MORRIS, Primary Examiner US. Cl. X.R. 117154 o-mso 9 Patent Nom 3,810,772 Dated May 14, 1974 Inventorfi Melville W9 Uffner It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:
Column 4 line 57, within the formula, after "C "H 3 should be=--F Column 9, line 17, "603C" should be--6OC-- Inthe Claims: a H I I Claim 1 Column 10, line 75, within the formula, "'F should beF Claim 2 Column 11, line -24: in the formula, before "C'F Q and after insert-F-- Claim 5 -Column ll, line 35, OH should be-CH Q r I lgned an Sealzd this twenty-seventh Day Of April 1976 [SEAL] 0 Arrest:
RUTH C. M SON C. MARSHALL DANN Am'flmg OUR? (WWII-"1'0"" flarenrs and Trademarks
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0170461A1 (en) * | 1984-07-16 | 1986-02-05 | General Foods Corporation | Infusion bag material treatment with fluoro-chemical sizing agent |
US4898700A (en) * | 1983-05-14 | 1990-02-06 | Toho Rayon Co., Ltd. | Process for producing preoxidized fibers from acrylic fibers |
US5330622A (en) * | 1991-07-25 | 1994-07-19 | Aussedat-Rey | Composition for rendering a paper or textile base resistant to water, oil and solvents, treated base and process for the production of the treated base |
WO2000003089A1 (en) * | 1998-07-08 | 2000-01-20 | Upm-Kymmene Corporation | Release liner paper |
US20050163998A1 (en) * | 2001-05-01 | 2005-07-28 | Sanjay Kashikar | Fiber size, sized reinforcements, and articles reinforced with such reinforcements |
-
1972
- 1972-07-21 US US00273980A patent/US3810772A/en not_active Expired - Lifetime
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4898700A (en) * | 1983-05-14 | 1990-02-06 | Toho Rayon Co., Ltd. | Process for producing preoxidized fibers from acrylic fibers |
EP0170461A1 (en) * | 1984-07-16 | 1986-02-05 | General Foods Corporation | Infusion bag material treatment with fluoro-chemical sizing agent |
US5330622A (en) * | 1991-07-25 | 1994-07-19 | Aussedat-Rey | Composition for rendering a paper or textile base resistant to water, oil and solvents, treated base and process for the production of the treated base |
WO2000003089A1 (en) * | 1998-07-08 | 2000-01-20 | Upm-Kymmene Corporation | Release liner paper |
US20050163998A1 (en) * | 2001-05-01 | 2005-07-28 | Sanjay Kashikar | Fiber size, sized reinforcements, and articles reinforced with such reinforcements |
US7585563B2 (en) * | 2001-05-01 | 2009-09-08 | Ocv Intellectual Capital, Llc | Fiber size, sized reinforcements, and articles reinforced with such reinforcements |
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