US3028297A - Orthotitanic compound used in method for improving wet strength of paper and resulting paper - Google Patents
Orthotitanic compound used in method for improving wet strength of paper and resulting paper Download PDFInfo
- Publication number
- US3028297A US3028297A US591531A US59153156A US3028297A US 3028297 A US3028297 A US 3028297A US 591531 A US591531 A US 591531A US 59153156 A US59153156 A US 59153156A US 3028297 A US3028297 A US 3028297A
- Authority
- US
- United States
- Prior art keywords
- paper
- pulp
- filler
- wet strength
- orthotitanic
- 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
- 238000000034 method Methods 0.000 title description 9
- 150000001875 compounds Chemical class 0.000 title description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 24
- 239000010936 titanium Substances 0.000 claims description 24
- 229910052719 titanium Inorganic materials 0.000 claims description 22
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 20
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 claims description 13
- 229920000642 polymer Polymers 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 239000000835 fiber Substances 0.000 claims description 7
- 229920002678 cellulose Polymers 0.000 claims description 4
- 239000001913 cellulose Substances 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 45
- 239000000945 filler Substances 0.000 description 39
- 239000000123 paper Substances 0.000 description 38
- 230000014759 maintenance of location Effects 0.000 description 15
- 239000000243 solution Substances 0.000 description 13
- 150000002148 esters Chemical class 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 10
- -1 tri-cyano-ethyl-mono-triethanolamine Chemical compound 0.000 description 9
- 229920003043 Cellulose fiber Polymers 0.000 description 8
- 229920001131 Pulp (paper) Polymers 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- 230000003301 hydrolyzing effect Effects 0.000 description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- HOVAGTYPODGVJG-UVSYOFPXSA-N (3s,5r)-2-(hydroxymethyl)-6-methoxyoxane-3,4,5-triol Chemical group COC1OC(CO)[C@@H](O)C(O)[C@H]1O HOVAGTYPODGVJG-UVSYOFPXSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- HOVAGTYPODGVJG-UHFFFAOYSA-N methyl beta-galactoside Natural products COC1OC(CO)C(O)C(O)C1O HOVAGTYPODGVJG-UHFFFAOYSA-N 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 238000009827 uniform distribution Methods 0.000 description 4
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical group CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-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
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- YCIHPQHVWDULOY-FMZCEJRJSA-N (4s,4as,5as,6s,12ar)-4-(dimethylamino)-1,6,10,11,12a-pentahydroxy-6-methyl-3,12-dioxo-4,4a,5,5a-tetrahydrotetracene-2-carboxamide;hydrochloride Chemical compound Cl.C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H](N(C)C)C(=O)C(C(N)=O)=C(O)[C@@]4(O)C(=O)C3=C(O)C2=C1O YCIHPQHVWDULOY-FMZCEJRJSA-N 0.000 description 1
- BYACHAOCSIPLCM-UHFFFAOYSA-N 2-[2-[bis(2-hydroxyethyl)amino]ethyl-(2-hydroxyethyl)amino]ethanol Chemical compound OCCN(CCO)CCN(CCO)CCO BYACHAOCSIPLCM-UHFFFAOYSA-N 0.000 description 1
- ZSIRWYMANRZZPE-UHFFFAOYSA-N 3-[bis(2-hydroxyethyl)amino]propanenitrile Chemical compound OCCN(CCO)CCC#N ZSIRWYMANRZZPE-UHFFFAOYSA-N 0.000 description 1
- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 244000304337 Cuminum cyminum Species 0.000 description 1
- GUBGYTABKSRVRQ-CUHNMECISA-N D-Cellobiose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-CUHNMECISA-N 0.000 description 1
- YTBSYETUWUMLBZ-UHFFFAOYSA-N D-Erythrose Natural products OCC(O)C(O)C=O YTBSYETUWUMLBZ-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- YTBSYETUWUMLBZ-IUYQGCFVSA-N D-erythrose Chemical compound OC[C@@H](O)[C@@H](O)C=O YTBSYETUWUMLBZ-IUYQGCFVSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- SHZGCJCMOBCMKK-UHFFFAOYSA-N D-mannomethylose Natural products CC1OC(O)C(O)C(O)C1O SHZGCJCMOBCMKK-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-QTVWNMPRSA-N D-mannopyranose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-QTVWNMPRSA-N 0.000 description 1
- YTBSYETUWUMLBZ-QWWZWVQMSA-N D-threose Chemical compound OC[C@@H](O)[C@H](O)C=O YTBSYETUWUMLBZ-QWWZWVQMSA-N 0.000 description 1
- 206010056474 Erythrosis Diseases 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- SQUHHTBVTRBESD-UHFFFAOYSA-N Hexa-Ac-myo-Inositol Natural products CC(=O)OC1C(OC(C)=O)C(OC(C)=O)C(OC(C)=O)C(OC(C)=O)C1OC(C)=O SQUHHTBVTRBESD-UHFFFAOYSA-N 0.000 description 1
- SHZGCJCMOBCMKK-JFNONXLTSA-N L-rhamnopyranose Chemical compound C[C@@H]1OC(O)[C@H](O)[C@H](O)[C@H]1O SHZGCJCMOBCMKK-JFNONXLTSA-N 0.000 description 1
- PNNNRSAQSRJVSB-UHFFFAOYSA-N L-rhamnose Natural products CC(O)C(O)C(O)C(O)C=O PNNNRSAQSRJVSB-UHFFFAOYSA-N 0.000 description 1
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 description 1
- 229930195725 Mannitol Natural products 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- RQTDRJMAUKHGHV-UHFFFAOYSA-N P.P.I Chemical compound P.P.I RQTDRJMAUKHGHV-UHFFFAOYSA-N 0.000 description 1
- 244000137852 Petrea volubilis Species 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 240000007591 Tilia tomentosa Species 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 1
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 229910052570 clay Inorganic materials 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
- 230000000694 effects Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 150000001261 hydroxy acids Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- CDAISMWEOUEBRE-GPIVLXJGSA-N inositol Chemical compound O[C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@H](O)[C@@H]1O CDAISMWEOUEBRE-GPIVLXJGSA-N 0.000 description 1
- 229960000367 inositol Drugs 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000008101 lactose Substances 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 150000002772 monosaccharides Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- CDAISMWEOUEBRE-UHFFFAOYSA-N scyllo-inosotol Natural products OC1C(O)C(O)C(O)C(O)C1O CDAISMWEOUEBRE-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 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
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/66—Salts, e.g. alums
-
- 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
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/003—Compounds containing elements of Groups 4 or 14 of the Periodic Table without C-Metal linkages
Definitions
- This invention relates to improved papers and'in particular to novel papers having improved wet strength.
- the invention also relates to improved papers containing fillers in which there are uniform distribution of the fillers throughout the papers.
- paper In many uses of paper it is essential that the-paper possess a high wet strength, such as packaging paper for meat, hand towels, garbage bags, sand paper backings, adhesive tape backings, etc. Papers used-for the aforementioned purposes often come in contact with moisture and must be sufiiciently resistant thereto so as, not to rapidly deteriorate in use.
- Papers to be used as printing papers in general should possess the characteristics of surface smoothness, whiteness, printability and opacity.
- the invention consists in the novel processes, steps, combinations and improvements, and compositions herein shown and described.
- a still further object of this invention is to provide improved papers having the characteristics of high wet tensile strength.
- a still further object of this invention is to provide improved papers having fillers incorporated there in wherein there is a high retention of filler by the paper fibers and in which the filler is uniformly distributed throughout the paper.
- a still further object of this invention is to provide novel methods for the production of improved papers having the characteristics set forth in accordance with the foregoing objects.
- reactive titania is meant monomeric orthotitanic acid of the structure Ti(OI-l) or a low polymer )4]n'
- a water soluble solution of reactive titania to a dilute paper stock (slurry of pulp), followed by subsequent drying of said pulpto form a paper sheet, results in the formation of a paper sheet having improved wet tensile strength.
- the reactive titania increases the'retention of the filler by the paper pulp and gives a more uniform distribution of the filler throughout the paper.
- the filler-containing papers produced in ac cordance with this invention are free of two-sideness, i.e., presence of more filler on one side of the sheet than-the other, because of the uniform distribution of the filler throughout the paper sheet.
- the water soluble reactive titania solutions useful in accordance with this invention can be prepared from a water soluble orthotitanic ester in the presence of a suitable screener to delay hydrolysis of the orthotitanate, thus producing a. highly reactive form of monomeric or low polymer orthotitanic acid.
- a suitable screener to delay hydrolysis of the orthotitanate, thus producing a. highly reactive form of monomeric or low polymer orthotitanic acid.
- These stabilized solutions are disclosed in copending application Serial No. 576,498 filed April 5, 1956, by Paul Lagally and is now Patent 2,950,174.
- the orthotitanates disclosed in Patent 2,950,- 174 are those which arerclatively stable in aqueous medium and which require a hydrolyzing agent, such as an acidor an alkali, for hydrolysis thereof. Examples of the preferred orthotitanates of this type are those of the chelated kind.
- water soluble reactive titania solutions useful in accordance with this invention can be prepared from a water-soluble orthotitanic ester in the presence of a suitable screeneras illustrated by esters containing:
- Chelated esters of this type are, for example, isopropyl-tri-triethanolamine orthotitanate, di-isopropyl-ditriethanolamine orthotitanate, di-isopropyl-di-diethanolamine orthotitanate, tetra cyanoethyldiethanolamine orthotitanate.
- Water-soluble esters or this type are, for example, tri-cyano-ethyl-mono-triethanolamine orthotitanate, tri ethyleneglycol-monotriethyleneglycol mono triethanolamine orthotitanate.
- orthotitanates which are relatively stable iii-aqueous medium and of the type indicated by the preferred esters require the addition of a suitable'hydrolyzing agent for the hydrolysis thereof to occur; Moreover, the hydrolyzing agent must be of such nature that it will not form a stable titanium complex with the hydrolyzed product.
- acids which are not useful as hydrolyzing agents because they form stable titanium complexes are- (1)hydroxy acids containing a hydroxy group in the alpha or beta position such as lactic acid or tartaric acid: (2) lower aliphatic dicarboxylic acids such as oxalic acid and malonic acid and (3) hydro-fiuoric acid.
- acids which may be used as a hydrolyzing agent are:
- bases may be used as hydrolyzing agents for certain of the orthotitanates.
- suitable bases for this purpose are sodium hydroxide, potassium hydroxide and nitrogen containing bases such as ammonium hydroxide, ethyl amine, diethyl amine, pyridine, piperidine and cyclohexylamine.
- a stabilizer is employed for controlling the hydrolysis of the orthotitanate and for preventing the precipitation of the hydrolyzed product from the aqueous solution.
- the stabilizer contains electron donating groups for temporarily screening the orthotitanic acid or ester to prevent polymerization thereof and subsequent precipitation from solution.
- any compound exhibiting the required electron donating qualities for eifeotuating the desired screening effect may be used as the stabilizer.
- Typical compounds which may be used as stabilizers include hydroxyaldehydes and hydroxy-ketones and corresponding semiacetals of the aldehydes and ketones.
- examples of such compounds are the monosaccharides such as glucose, fructose, mannose, xylose, threose, erythrose, rhamnose; the polysaccharides such as lactose and cellobiose, sugars with straight chains or as substances having oxide rings such as methyl glucoside may also be used.
- watersoluble alcohols as represented by those having straight chain or cyclic structure such as ethylene glycol, diethylene glycol, triethylene glycol, sorbitol, mannitol and inositol.
- water soluble amides such as urea, dimethylforamide; hydroxy-alkyl derivatives of aminos containing tertiary nitrogen such as triethanolamine and hydroxyalkyl-alkylenepolyamines such as tetrahydroxyethyl ethylene diamine.
- Water-soluble reactive titania solutions can also be used which are prepared from certain water-soluble orthotitanate esters by neutralization of an aqueous solution of the ester to give a product which is not stable for long periods of time but for short intervals, long enough to be used on a practical basis.
- orthotitanates which may be used for this purpose are:
- the procedure used in accordance with this invention involves addition of reactive titania solution to a slurry of pulp (dilute stock containing cellulose fibers and which may contain filler in water, followed by formation of the paper sheet; or addition of a Water-soluble orthotitanate ester to the stock followed by hydrolysis of the ester by a suitable hydrolyzing agent to reactive titania, followed by formation of the paper sheet.
- the addition of the reactive titania alone imparts wet strength to the sheet, but the efiect may be further increased by heating after formation and drying.
- the amount of titania used will vary depending upon the structure of the orthotitanate used for making the reactive titania. A high molecular weight compound is most practical where a lower retention for wet strength is desired but where higher retentions (high wet strength) are desired, the esters of lower molecular weight are preferred.
- the retention of small amounts of titania is al-. most quantitative but when amounts greater than 2.9% Ti(OH) (2% TiO based on the weight of dry pulp are used, the retention is not quantitative and the unused titania remains in solution.
- the range of concentration of Ti(OH) will vary between 1 to 45%, and preferably 1 to 20%.
- the retention of the titania by the cellulose fibers is not quantitative.
- an amount as high as 5% may be retained quantitatively, a portion of which is retained by the cellulose fibers and a portion by the filler.
- sheets formed from paper pulp containing fillers in accordance with this invention exhibit increased retention of fillers and a lack of two-sidedness.
- Any suitable conventional paper filler may be used, such as clay, calcium carbonate, titanium oxide, silica, etc.
- the filler is in an amount from to 45% based on the dry weight of the pulp.
- Aqueous solution of wet strength agent consisting of a titanium containing agent selected from the group consisting of monomeric orthotitanic acid and water-soluble, low moleculan weight; polymers of orthotitanio acid Slurry of paper pulp containing cellulose fibers Forming paper sheet in conventional manner Drying formed sheet
- wet strength agent consisting of a titanium containing agent selected from the group consisting of monomeric orthotitanic acid and water-soluble, low moleculan weight; polymers of orthotitanio acid Slurry of paper pulp containing cellulose fibers Forming paper sheet in conventional manner Drying formed sheet
- Examples I-IV disclose the preparation of stabilized water soluble orthotitanate solutions which may be used as the source of reactive titania in accordance with the present invention.
- EXAMPLE II 120 grams of a mixture of 1 mole tetra isopropyl orthotitanate and two moles triethanolamine (containing .206 mole di-isopropyl-di-triethanolamine titanate) are dissolved in 200 ml. water and 200 of a 50% solution of urea are added. The resulting mixture is neutralized with 2 5 ml. cone. H01 and diluted with water to 600ml.
- EXAMPLE III To 10 grams of a mixture of one mole tetra-isopropylorthotitanate and four moles triethanolamine (0.0131 mole tetra-triethanolarnine titanate) are added 3.9 grams triethanolamine (0.026 mole) .20 ml. of water are added and, after neutralization, the obtained solution is diluted with water to 50 ml. The obtained mixture remains stable.
- EXAMPLE IV To a semi-bleached kraft pulpofs600cc. (S..-R.) freeness basis weight (24" x 36'. x 480:30 lbs.) was added an amount ofmethyl glucosidestabilized.diisopropyl-ditriethanolamine titanate of Example I to give 3.2% Ti(OH) based on the dry weight of pulp. The sheet was then formed in a standard T.A.P.P.I. sheet mold. Measurement of the Wet tensile showed it to be 1.8 pounds per inch before heating and 3.8 pounds per inch after heating one minute at 350 F. A sheet formed in the same manner without titania compound present would have a wet tensile of less than .1 pound/ inch.
- EXAMPLE VI To Duracel pulp of 700 cc. freeness (S.R.) basis weight (24" x 36" x 480:30 lbs.) was added an amount of methyl glucoside stabilized diisopropyl di-triethanolamine titanate of Example I calculated to give 33% Ti(OH) based on the dry weight of pulp. After formation of the sheet and drying, the Wet tensile strength was found to be 2.4 pounds per inch.
- EXAMPLE VII In the same manner as described in Example V, a quantity of methyl glucoside stabilized diisopropyl ditriethanolamine titanate of Example I was added in an amount calculated to give 17% Ti(OH) based on the weight of dry pulp. The resulting sheet when tested gave 46 pounds per inch wet tensile before heating and 7 pounds per inch after heating one minute at 350 F.
- EXAMPLE VIII To Duracel pulp of 700cc. freeness (S.R.) basis weight (24 X 36" x 480:30 lbs.) was added a quantity of di isopropyl di-triethanolamine titanate calculated to give 6.8% Ti(OH) based on dry weight of pulp. The mixture was then neutralized to pH 7 with dilute hydrochloric acid. After forming the sheet and drying, the wet tensile strength was determined to be 1 pound per inch.
- Example XVII To cellulose pulp of the same type used in Example XVI was added a 10% filler suspension (clay) to give 30% filler based on dry weight of pulp. To this slurry was added a quantity of methyl glucoside stabilized di-isopropyl ditriethanolamine titanate of Example I to give 1% Ti(OH)., based on dry pulp weight. The titania compound was then neutralized to pH 6 with dilute hydrochloric acid, and the pulp diluted to .5 consistency. The sheet was then formed. Filler retention was found to be 89.0% as determined by ash content. A sheet made without titania present showed filler retention to be only 8.7%.
- a paper sheet having improved wet strength comprising cellulose fibers held together by a wet strength agent consisting of a titanium containing agent selected from the group consisting of monomeric orthotitanic acid and water-soluble, low molecular-weight polymers of orthotitanic acid, said titanium containing agent being in an amountfrom about 1 to 45% by weight based on the dry weight of fibers.
- the method of forming a paper sheet having improved Wet tensile strength comprising the steps of mixing with a slurry of paper pulp including cellulose fibers, an aqueous solution of a wet strength agent consisting of a titanium containing agent selected from the group consisting of monomeric orthotitanic acid and watersoluble, low molecular-weight polymers of orthotitanic acid, said titanium containing agent being in an amount from about 1 to 45% by weight based on the dry weight of fibers.
- a paper sheet containing a filler uniformly dis tributed throughout comprising cellulose fibers and a filler held together by a Wet strength agent consisting of a titanium containing agent selected from the group consisting of monomeric orthotitanic acid and water-soluble, low molecular-weight polymers of orthotitanic acid, said titanium containing agent being in an amount from about 1 to 45 by weight based on the dry weight of fibers,
- the method of forming a paper sheet containing a filler uniformly distributed throughout comprising the steps of mixing with a slurry of paper pulp comprising cellulose fibers and filler, an aqueous solution of a Wet strength agent consisting of a titanium containing agent selected from the group consisting of monomeric orthotitanic acid and water-soluble, low molecular-weight polymers of orthotitanic acid, said titanium containing agent being in an amount from about 1 to 45% by weight based on the dry weight of fibers.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Paper (AREA)
Description
Paul Lagally, Pleasant Gap, Pa., assignor to Linden Laboratories, lnc., State College, Pa., a corporation of Pennsylvania No Drawing. Filed June 15,1956, Ser. No.- 591,531
This invention relates to improved papers and'in particular to novel papers having improved wet strength. The invention also relates to improved papers containing fillers in which there are uniform distribution of the fillers throughout the papers.
In many uses of paper it is essential that the-paper possess a high wet strength, such as packaging paper for meat, hand towels, garbage bags, sand paper backings, adhesive tape backings, etc. Papers used-for the aforementioned purposes often come in contact with moisture and must be sufiiciently resistant thereto so as, not to rapidly deteriorate in use.
Papers to be used as printing papers in general should possess the characteristics of surface smoothness, whiteness, printability and opacity.
Prior to the present invention various techniques have been used for improving the characteristics of paper. Forv example, the addition of fillers to paper pulp toimprove the surface, smoothness, whiteness, printability and opacityv of the paper sheet is well known. Unfortunately, however, it is not always possible to obtain adequate retention of the filler by the pulp and/ or uniform distribution of the filler throughout the paper sheet,
Objects and advantages of the inventionwill be setforth in part hereinafter and in part will be obvious herefrom, or may be learned by practice with the invention, the same being realized and attainedby means of the processes, steps, combinations, improvements and compositions pointed out in the appended claims.
The invention consists in the novel processes, steps, combinations and improvements, and compositions herein shown and described.
it is an object of this invention to provide improved papers having the characteristics of high wet tensile strength. A still further object of this invention is to provide improved papers having fillers incorporated there in wherein there is a high retention of filler by the paper fibers and in which the filler is uniformly distributed throughout the paper. A still further object of this invention is to provide novel methods for the production of improved papers having the characteristics set forth in accordance with the foregoing objects.
It has been found that the foregoing objects may be realized by producing paper from paper pulp utilizing water soluble solutions of reactive titania in the paper pulp. By reactive titania is meant monomeric orthotitanic acid of the structure Ti(OI-l) or a low polymer )4]n' In accordance with one aspect of the present invention, it has been found that the incorporation of a water soluble solution of reactive titania to a dilute paper stock (slurry of pulp), followed by subsequent drying of said pulpto form a paper sheet, results in the formation of a paper sheet having improved wet tensile strength.
Moreover, it has also been found that if the paper stock contains a filler, the reactive titania increases the'retention of the filler by the paper pulp and gives a more uniform distribution of the filler throughout the paper. Advantageously, the filler-containing papers produced in ac cordance with this invention are free of two-sideness, i.e., presence of more filler on one side of the sheet than-the other, because of the uniform distribution of the filler throughout the paper sheet.
States atent 'ice The water soluble reactive titania solutions useful in accordance with this invention can be prepared from a water soluble orthotitanic ester in the presence of a suitable screener to delay hydrolysis of the orthotitanate, thus producing a. highly reactive form of monomeric or low polymer orthotitanic acid. These stabilized solutions are disclosed in copending application Serial No. 576,498 filed April 5, 1956, by Paul Lagally and is now Patent 2,950,174. The orthotitanates disclosed in Patent 2,950,- 174 are those which arerclatively stable in aqueous medium and which require a hydrolyzing agent, such as an acidor an alkali, for hydrolysis thereof. Examples of the preferred orthotitanates of this type are those of the chelated kind.
The water soluble reactive titania solutions useful in accordance with this invention can be prepared from a water-soluble orthotitanic ester in the presence of a suitable screeneras illustrated by esters containing:
(1) Two, three or four ligands containing basic nitrogen. Chelated esters of this type are, for example, isopropyl-tri-triethanolamine orthotitanate, di-isopropyl-ditriethanolamine orthotitanate, di-isopropyl-di-diethanolamine orthotitanate, tetra cyanoethyldiethanolamine orthotitanate.
(2) Less than two ligands containing basic nitrogen andin addition other ligands containing electron-donating groups. Water-soluble esters or this type are, for example, tri-cyano-ethyl-mono-triethanolamine orthotitanate, tri ethyleneglycol-monotriethyleneglycol mono triethanolamine orthotitanate.
As indicated heretofore, orthotitanates which are relatively stable iii-aqueous medium and of the type indicated by the preferred esters require the addition of a suitable'hydrolyzing agent for the hydrolysis thereof to occur; Moreover, the hydrolyzing agent must be of such nature that it will not form a stable titanium complex with the hydrolyzed product.
Examples of acids which are not useful as hydrolyzing agents because they form stable titanium complexes are- (1)hydroxy acids containing a hydroxy group in the alpha or beta position such as lactic acid or tartaric acid: (2) lower aliphatic dicarboxylic acids such as oxalic acid and malonic acid and (3) hydro-fiuoric acid.
Specific examples of acids which may be used as a hydrolyzing agent are:
Acid Formula Hydrochlcnm H01 Acetic, CHsCOOH TllfitlOlOflCQlllG- CFSCOOH Perfluorobutyri O F COOH Cyanoaeetic. CH2CNCOOH Chloroacetie. 01120 100011 Triehloroacetic 0 C 0 OH Maleict (CHCOOHM Succimm (CHZCOOHM Polyncryllcu (CHzCHCOOI-I)n Thmglycohc, CHZCOOH Thiornalic OHZCOOH 0 SEC 0 OH Garboxynlethyl-mereaptosuceinie 011120 0 OH Si GHCOOH CH2COOH Toluenesulfonic CH3C5H1SO H Sulfanillc NH O5H4SO3H In addition .to acids, bases may be used as hydrolyzing agents for certain of the orthotitanates. Examples of suitable bases for this purpose are sodium hydroxide, potassium hydroxide and nitrogen containing bases such as ammonium hydroxide, ethyl amine, diethyl amine, pyridine, piperidine and cyclohexylamine.
As indicated heretofore, a stabilizer is employed for controlling the hydrolysis of the orthotitanate and for preventing the precipitation of the hydrolyzed product from the aqueous solution. The stabilizer contains electron donating groups for temporarily screening the orthotitanic acid or ester to prevent polymerization thereof and subsequent precipitation from solution. Hence, any compound exhibiting the required electron donating qualities for eifeotuating the desired screening effect may be used as the stabilizer.
Typical compounds which may be used as stabilizers include hydroxyaldehydes and hydroxy-ketones and corresponding semiacetals of the aldehydes and ketones. Examples of such compounds are the monosaccharides such as glucose, fructose, mannose, xylose, threose, erythrose, rhamnose; the polysaccharides such as lactose and cellobiose, sugars with straight chains or as substances having oxide rings such as methyl glucoside may also be used. Also, suitable as stabilizers for this purpose are watersoluble alcohols as represented by those having straight chain or cyclic structure such as ethylene glycol, diethylene glycol, triethylene glycol, sorbitol, mannitol and inositol. Also, operable are water soluble amides such as urea, dimethylforamide; hydroxy-alkyl derivatives of aminos containing tertiary nitrogen such as triethanolamine and hydroxyalkyl-alkylenepolyamines such as tetrahydroxyethyl ethylene diamine.
In addition to the aforementioned stabilized watersoluble reactive titania solutions, Water-soluble reactive titania solutions can also be used which are prepared from certain water-soluble orthotitanate esters by neutralization of an aqueous solution of the ester to give a product which is not stable for long periods of time but for short intervals, long enough to be used on a practical basis. Examples of orthotitanates which may be used for this purpose are:
Tetra-triethanolamine orthotitanate Tetra-diethanolamine orthotitanate Isopropyl-tri-triethanolamine orthotitanate D-iisopropyl di-triethanolamine orthotitauate Dicyanoethyl-di-triethanolamine orthotitanate Tetra-aminoethauolamine orthotitanate Tetra-diethylethanolamine orthotitanate In general, the procedure used in accordance with this invention involves addition of reactive titania solution to a slurry of pulp (dilute stock containing cellulose fibers and which may contain filler in water, followed by formation of the paper sheet; or addition of a Water-soluble orthotitanate ester to the stock followed by hydrolysis of the ester by a suitable hydrolyzing agent to reactive titania, followed by formation of the paper sheet. The addition of the reactive titania alone imparts wet strength to the sheet, but the efiect may be further increased by heating after formation and drying.
The amount of titania used will vary depending upon the structure of the orthotitanate used for making the reactive titania. A high molecular weight compound is most practical where a lower retention for wet strength is desired but where higher retentions (high wet strength) are desired, the esters of lower molecular weight are preferred. The retention of small amounts of titania is al-. most quantitative but when amounts greater than 2.9% Ti(OH) (2% TiO based on the weight of dry pulp are used, the retention is not quantitative and the unused titania remains in solution.
In general, the range of concentration of Ti(OH) will vary between 1 to 45%, and preferably 1 to 20%. As,
indicated hereinabove, when amounts of greater than i 2.9% are used the retention of the titania by the cellulose fibers is not quantitative. When the pulp contains a filler, an amount as high as 5% may be retained quantitatively, a portion of which is retained by the cellulose fibers and a portion by the filler.
As indicated heretofore, it has been found that sheets formed from paper pulp containing fillers in accordance with this invention exhibit increased retention of fillers and a lack of two-sidedness. Any suitable conventional paper filler may be used, such as clay, calcium carbonate, titanium oxide, silica, etc. In general, the filler is in an amount from to 45% based on the dry weight of the pulp.
Aqueous solution of wet strength agent consisting of a titanium containing agent selected from the group consisting of monomeric orthotitanic acid and water-soluble, low moleculan weight; polymers of orthotitanio acid Slurry of paper pulp containing cellulose fibers Forming paper sheet in conventional manner Drying formed sheet In order to illustrate the invention more specifically the following examples are given hereinbelow. Unless otherwise indicated, the percentages or parts given are by weight.
The following Examples I-IV disclose the preparation of stabilized water soluble orthotitanate solutions which may be used as the source of reactive titania in accordance with the present invention.
EXAMPLE I EXAMPLE II 120 grams of a mixture of 1 mole tetra isopropyl orthotitanate and two moles triethanolamine (containing .206 mole di-isopropyl-di-triethanolamine titanate) are dissolved in 200 ml. water and 200 of a 50% solution of urea are added. The resulting mixture is neutralized with 2 5 ml. cone. H01 and diluted with water to 600ml.
EXAMPLE III To 10 grams of a mixture of one mole tetra-isopropylorthotitanate and four moles triethanolamine (0.0131 mole tetra-triethanolarnine titanate) are added 3.9 grams triethanolamine (0.026 mole) .20 ml. of water are added and, after neutralization, the obtained solution is diluted with water to 50 ml. The obtained mixture remains stable.
precipitates insoluble titania quickly. EXAMPLE IV EXAMPLE V To a semi-bleached kraft pulpofs600cc. (S..-R.) freeness basis weight (24" x 36'. x 480:30 lbs.) was added an amount ofmethyl glucosidestabilized.diisopropyl-ditriethanolamine titanate of Example I to give 3.2% Ti(OH) based on the dry weight of pulp. The sheet was then formed in a standard T.A.P.P.I. sheet mold. Measurement of the Wet tensile showed it to be 1.8 pounds per inch before heating and 3.8 pounds per inch after heating one minute at 350 F. A sheet formed in the same manner without titania compound present would have a wet tensile of less than .1 pound/ inch.
EXAMPLE VI To Duracel pulp of 700 cc. freeness (S.R.) basis weight (24" x 36" x 480:30 lbs.) was added an amount of methyl glucoside stabilized diisopropyl di-triethanolamine titanate of Example I calculated to give 33% Ti(OH) based on the dry weight of pulp. After formation of the sheet and drying, the Wet tensile strength was found to be 2.4 pounds per inch.
EXAMPLE VII In the same manner as described in Example V, a quantity of methyl glucoside stabilized diisopropyl ditriethanolamine titanate of Example I was added in an amount calculated to give 17% Ti(OH) based on the weight of dry pulp. The resulting sheet when tested gave 46 pounds per inch wet tensile before heating and 7 pounds per inch after heating one minute at 350 F.
EXAMPLE VIII To Duracel pulp of 700cc. freeness (S.R.) basis weight (24 X 36" x 480:30 lbs.) was added a quantity of di isopropyl di-triethanolamine titanate calculated to give 6.8% Ti(OH) based on dry weight of pulp. The mixture was then neutralized to pH 7 with dilute hydrochloric acid. After forming the sheet and drying, the wet tensile strength was determined to be 1 pound per inch.
EXAMPLE IX In the same manner as in Example VIII, a quantity of diisopropyl di-aminoethylethanolamine titanate calculated to give 12% Ti(OH) based on dry weight of pulp gave 2.2 pounds per inch wet tensile before heating and 2.8 pounds per inch after heating.
EXAMPLE X In the same manner as in Example VIII, a quantity of diisopropyl di-diethanolmethyl amine titanate calculated to give 11% Ti(OH) gave 4.4 pounds per inch wet tensile before heating and 5.4 pounds per inch after heating.
In the same manner as in Example VIII, additional sheets were prepared, using the ingredients and having the properties indicated in below Table I.
ized aqueous solution of tetra-triethanolamine titanate Table I Percent TKOH); Wet Wet Compound Based'on Tensile, Tensile Dry lbs/in. after Weight Heating, of Pulp lbs/in;
Ex. XI Tetra-E thanoldiethyl- 8 4 5. 3
amine Titanate. Ex. XII Tetra-Triisopropanol- 6 4. 2 5. 3
amine Titanate. Ex. XIII Tetra-D.iisopropanol;v 8 3. 6 4. 8.
amine Titanate. Ex. XIV.. Tetra-Dietliylamlncg 14 1. 5 1. 7
Titanate.
The following examples XV toXVII serve todisclose the preparation of paperv sheets containing fillersin ac cordance with this invention.
EXAMPLE XV- To cellulose pulp from type ordinarily used for book papers (60% soda, 25% sulfite, 15% old paper) 015.600 cc. Schopper-Riegler freeness basis weight including filler (24" x 36" x 480: lbs.) at 2% consistency was added 10% filler suspension (clay) to give 30% filler based on dry weight of pulp. To this slurry was added a quantity of urea stabilized di-isopropyl di-triethanolamine titanate of Example I to give 2% Ti(OH) based on dry weight of pulp. The pulp was diluted to .5% consistency and the sheet formed. Filler retention was found to be 70% determined by ash content of the finished sheet. A sheet made in the same manner but using no reactive titania showed filler retention to be only 30%.
EXAMPLE XVI To cellulose pulp from the type ordinarily used for book papers 60% soda, 25% sulfite, 15% old paper) of 600 cc. Schopper-Riegler freeness basis weight including filler (24" x 36" X 480:100 lbs.) was added a 10% filler suspension (CaCO to give 30% filler based on dry weight of pulp. To this slurry was added a quantity of methyl glucoside stabilized di-isopropyl ditriethanolamine titanate of Example I to give 1% Ti(OH) based on dry weight of pulp. The pulp was diluted to .5 consistency and the sheet formed. Filler retention was found to be 81% determined by ash content. A sheet made similarly but using no reactive titania showed filler retention to be only 22%.
EXAMPLE XVII To cellulose pulp of the same type used in Example XVI was added a 10% filler suspension (clay) to give 30% filler based on dry weight of pulp. To this slurry was added a quantity of methyl glucoside stabilized di-isopropyl ditriethanolamine titanate of Example I to give 1% Ti(OH)., based on dry pulp weight. The titania compound was then neutralized to pH 6 with dilute hydrochloric acid, and the pulp diluted to .5 consistency. The sheet was then formed. Filler retention was found to be 89.0% as determined by ash content. A sheet made without titania present showed filler retention to be only 8.7%.
The invention in its broader aspects is not limited to the specific steps, processes, compositions, combinations and improvements shown and described, but departures may be made therefrom within the scope of the accompanying claims without departing from the principles of the invention and without sacrificing its chief advantages.
The present application is a continuation-in-part of application Serial No. 576,498, filed April 5, 1956, now U.S. Patent No. 2,950,174.
What is claimed is:
1. A paper sheet having improved wet strength comprising cellulose fibers held together by a wet strength agent consisting of a titanium containing agent selected from the group consisting of monomeric orthotitanic acid and water-soluble, low molecular-weight polymers of orthotitanic acid, said titanium containing agent being in an amountfrom about 1 to 45% by weight based on the dry weight of fibers.
2. The method of forming a paper sheet having improved Wet tensile strength comprising the steps of mixing with a slurry of paper pulp including cellulose fibers, an aqueous solution of a wet strength agent consisting of a titanium containing agent selected from the group consisting of monomeric orthotitanic acid and watersoluble, low molecular-weight polymers of orthotitanic acid, said titanium containing agent being in an amount from about 1 to 45% by weight based on the dry weight of fibers.
3. A paper sheet containing a filler uniformly dis tributed throughout comprising cellulose fibers and a filler held together by a Wet strength agent consisting of a titanium containing agent selected from the group consisting of monomeric orthotitanic acid and water-soluble, low molecular-weight polymers of orthotitanic acid, said titanium containing agent being in an amount from about 1 to 45 by weight based on the dry weight of fibers,
4. The method of forming a paper sheet containing a filler uniformly distributed throughout comprising the steps of mixing with a slurry of paper pulp comprising cellulose fibers and filler, an aqueous solution of a Wet strength agent consisting of a titanium containing agent selected from the group consisting of monomeric orthotitanic acid and water-soluble, low molecular-weight polymers of orthotitanic acid, said titanium containing agent being in an amount from about 1 to 45% by weight based on the dry weight of fibers.
References Cited in the tile of this patent UNITED STATES PATENTS 2,345,985 McKinney Apr. 4, 1944 2,378,193 Cummins June 12, 1945 2,564,365 Kingsbury Aug. 14, 1951 2,579,413 Boyd Dec. 18, 1951 2,643,262 Bostwick June 23, 1953 2,680,108 Schmidt June 1, 1954 2,689,858 Boyd Sept. 21, 1954 2,721,787 Hettrick Oct. 25, 1955 2,749,248 Benson June 5, 1956 2,785,995 Kress Mar. 19, 1957 2,824,114 Bostwick Feb. 18, 1958 2,930,106 Wrotnowski Mar. 29, 1960
Claims (1)
1. A PAPER SHEET HAVING IMPROVED WET STRENGTH COMPRISING CELLULOSE FIBERS HELD TOGETHER BY A WET STRENGTH AGENT CONSISTING OF A TITANIUM CONTAINING AGENT SELECTED FROM THE GROUP CONSISTING OF MONOMERIC ORTHOTITANTIC ACID AND WATER-SOLUBLE, LOW MOLECULAR-WEIGHT POLYMERS OF ORTHOTITANIC ACID, SAID TITANIUM CONTAINING AGENT BEING IN AN AMOUNT FROM ABOUT 1 TO 45% BY WEIGHT BASED ON THE DRY WEIGHT OF FIBERS.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US591531A US3028297A (en) | 1956-06-15 | 1956-06-15 | Orthotitanic compound used in method for improving wet strength of paper and resulting paper |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US591531A US3028297A (en) | 1956-06-15 | 1956-06-15 | Orthotitanic compound used in method for improving wet strength of paper and resulting paper |
Publications (1)
Publication Number | Publication Date |
---|---|
US3028297A true US3028297A (en) | 1962-04-03 |
Family
ID=24366841
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US591531A Expired - Lifetime US3028297A (en) | 1956-06-15 | 1956-06-15 | Orthotitanic compound used in method for improving wet strength of paper and resulting paper |
Country Status (1)
Country | Link |
---|---|
US (1) | US3028297A (en) |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3419406A (en) * | 1964-02-27 | 1968-12-31 | Eastman Kodak Co | Coating compositions |
US3679721A (en) * | 1969-03-18 | 1972-07-25 | British Titan Products | Titanium compounds |
US3694475A (en) * | 1969-03-18 | 1972-09-26 | British Titan Products | Titanium compounds |
EP0092755A1 (en) * | 1982-04-22 | 1983-11-02 | KAY-FRIES, Inc. | Bis alkyl bis(trialkanolamine)zirconates |
EP0148647A1 (en) * | 1984-01-11 | 1985-07-17 | Kemira Oy | A paper-making method and a combination of ingredients to be used in it |
US4609746A (en) * | 1983-10-12 | 1986-09-02 | Dynamit Nobel Ag | Titanium chelates and preparation of these chelates |
US4621148A (en) * | 1983-10-12 | 1986-11-04 | Dynamit Nobel Ag | Water-soluble triethanolamine titanates |
US4744973A (en) * | 1985-11-29 | 1988-05-17 | Westinghouse Electric Corp. | Inorganic polymeric cationic ion exchange matrix |
US4845134A (en) * | 1987-01-23 | 1989-07-04 | Phillips Petroleum Company | Gelable compositions and use thereof in steam treatment of wells |
US5080759A (en) * | 1990-09-04 | 1992-01-14 | Quaker Chemical Corporation | Method for controlling stickies in pulp and papermaking processes using recycled paper |
US5474964A (en) * | 1994-09-16 | 1995-12-12 | Phillips Petroleum Company | Hydrocarbon isomerization catalyst and use thereof |
Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2345985A (en) * | 1938-11-29 | 1944-04-04 | Du Pont | Production of titanium oxide pigments |
US2378193A (en) * | 1941-11-14 | 1945-06-12 | Johns Manville | Paper and method of manufacturing same |
US2564365A (en) * | 1949-12-21 | 1951-08-14 | Nat Lead Co | Method for producing orthotitanic acid |
US2579413A (en) * | 1949-10-21 | 1951-12-18 | Monsanto Chemicals | Amides of ortho titanic acid |
US2643262A (en) * | 1950-04-28 | 1953-06-23 | Du Pont | Organic compounds of titanium |
US2680108A (en) * | 1951-08-08 | 1954-06-01 | Bayer Ag | Process of producing reaction products from higher molecular compounds containing hydroxyl groups and a titanium complex |
US2689858A (en) * | 1952-01-25 | 1954-09-21 | Monsanto Chemicals | Organotitanium polymers |
US2721787A (en) * | 1950-10-23 | 1955-10-25 | American Cyanamid Co | Free-flowing, nondusting titania |
US2749248A (en) * | 1952-05-09 | 1956-06-05 | Du Pont | Organophilic titania powders containing a polymerizable ethylenic monomer bound to fractured surfaces thereof and their preparation |
US2785995A (en) * | 1955-05-13 | 1957-03-19 | Quaker Chemical Products Corp | Process of improving the wet strength and dimensional stability of cellulose paper fibers and regenerated cellulose films by reacting them with acetals and products produced thereby |
US2824114A (en) * | 1952-09-09 | 1958-02-18 | Du Pont | Water soluble group iv-a metal esters of amino alcohols and their preparation |
US2930106A (en) * | 1957-03-14 | 1960-03-29 | American Felt Co | Gaskets |
-
1956
- 1956-06-15 US US591531A patent/US3028297A/en not_active Expired - Lifetime
Patent Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2345985A (en) * | 1938-11-29 | 1944-04-04 | Du Pont | Production of titanium oxide pigments |
US2378193A (en) * | 1941-11-14 | 1945-06-12 | Johns Manville | Paper and method of manufacturing same |
US2579413A (en) * | 1949-10-21 | 1951-12-18 | Monsanto Chemicals | Amides of ortho titanic acid |
US2564365A (en) * | 1949-12-21 | 1951-08-14 | Nat Lead Co | Method for producing orthotitanic acid |
US2643262A (en) * | 1950-04-28 | 1953-06-23 | Du Pont | Organic compounds of titanium |
US2721787A (en) * | 1950-10-23 | 1955-10-25 | American Cyanamid Co | Free-flowing, nondusting titania |
US2680108A (en) * | 1951-08-08 | 1954-06-01 | Bayer Ag | Process of producing reaction products from higher molecular compounds containing hydroxyl groups and a titanium complex |
US2689858A (en) * | 1952-01-25 | 1954-09-21 | Monsanto Chemicals | Organotitanium polymers |
US2749248A (en) * | 1952-05-09 | 1956-06-05 | Du Pont | Organophilic titania powders containing a polymerizable ethylenic monomer bound to fractured surfaces thereof and their preparation |
US2824114A (en) * | 1952-09-09 | 1958-02-18 | Du Pont | Water soluble group iv-a metal esters of amino alcohols and their preparation |
US2785995A (en) * | 1955-05-13 | 1957-03-19 | Quaker Chemical Products Corp | Process of improving the wet strength and dimensional stability of cellulose paper fibers and regenerated cellulose films by reacting them with acetals and products produced thereby |
US2930106A (en) * | 1957-03-14 | 1960-03-29 | American Felt Co | Gaskets |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3419406A (en) * | 1964-02-27 | 1968-12-31 | Eastman Kodak Co | Coating compositions |
US3679721A (en) * | 1969-03-18 | 1972-07-25 | British Titan Products | Titanium compounds |
US3694475A (en) * | 1969-03-18 | 1972-09-26 | British Titan Products | Titanium compounds |
EP0092755A1 (en) * | 1982-04-22 | 1983-11-02 | KAY-FRIES, Inc. | Bis alkyl bis(trialkanolamine)zirconates |
US4609746A (en) * | 1983-10-12 | 1986-09-02 | Dynamit Nobel Ag | Titanium chelates and preparation of these chelates |
US4621148A (en) * | 1983-10-12 | 1986-11-04 | Dynamit Nobel Ag | Water-soluble triethanolamine titanates |
EP0148647A1 (en) * | 1984-01-11 | 1985-07-17 | Kemira Oy | A paper-making method and a combination of ingredients to be used in it |
US4744973A (en) * | 1985-11-29 | 1988-05-17 | Westinghouse Electric Corp. | Inorganic polymeric cationic ion exchange matrix |
US4845134A (en) * | 1987-01-23 | 1989-07-04 | Phillips Petroleum Company | Gelable compositions and use thereof in steam treatment of wells |
US5080759A (en) * | 1990-09-04 | 1992-01-14 | Quaker Chemical Corporation | Method for controlling stickies in pulp and papermaking processes using recycled paper |
WO1992004501A1 (en) * | 1990-09-04 | 1992-03-19 | Quaker Chemical Corporation | Method for controlling stickies in pulp and papermaking processes using recycled paper |
US5474964A (en) * | 1994-09-16 | 1995-12-12 | Phillips Petroleum Company | Hydrocarbon isomerization catalyst and use thereof |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US3028297A (en) | Orthotitanic compound used in method for improving wet strength of paper and resulting paper | |
JP2607219B2 (en) | Paper manufacturing method | |
EP0804382B1 (en) | Novel temperature-activated polysilicic acids and their use in paper production processes | |
JPH04505315A (en) | Silica sol and how to use silica sol | |
DE69908938T2 (en) | METHOD FOR PRODUCING PAPER | |
EP2173944B1 (en) | Filler composition | |
FI114724B (en) | Procedure for making paper | |
JPH0611957B2 (en) | Paper manufacturing method | |
DE3780532T2 (en) | AMPHOTERIC STRENGTH AND METHOD FOR THE PRODUCTION THEREOF. | |
JPH08502016A (en) | Silica sol, method for preparing silica sol and use of sol | |
US3006806A (en) | Sized paper and process therefor | |
JPH0327676B2 (en) | ||
US4056432A (en) | Process for making paper products of improved dry strength | |
KR20130062946A (en) | A composition comprising microfibrillated cellulose and a process for the production of a composition | |
JPS6038473A (en) | Modified inorganic filler | |
US3562103A (en) | Process of making paper containing quaternary ammonium starch ethers containing anionic covalent phosphorus and paper made therefrom | |
FI121120B (en) | Composition for use as a filler in papermaking | |
US3392085A (en) | Method of sizing paper with a fatty acid and carbohydrate | |
JP2607161B2 (en) | Paper manufacturing method | |
KR20030047901A (en) | Fluorescent brightener pigment compositions | |
US4935062A (en) | Kaolinite aggregation using organo-silicon compounds | |
US3258392A (en) | Color stabilized paper containing fluorescent dye and titanate | |
US3615795A (en) | Method for sizing paper | |
US2786824A (en) | Cationic urea-formaldehyde resins and preparation thereof | |
US3151019A (en) | Filler retention in paper making by addition of carboxyalkyl starch ether |