US3619234A - Process for the optical brightening of fibrous materials of synthetic polyamides or cellulose esters - Google Patents
Process for the optical brightening of fibrous materials of synthetic polyamides or cellulose esters Download PDFInfo
- Publication number
- US3619234A US3619234A US799531A US3619234DA US3619234A US 3619234 A US3619234 A US 3619234A US 799531 A US799531 A US 799531A US 3619234D A US3619234D A US 3619234DA US 3619234 A US3619234 A US 3619234A
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- US
- United States
- Prior art keywords
- weight
- carbon atoms
- percent
- alkyl
- formula
- 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
- 239000002657 fibrous material Substances 0.000 title claims abstract description 24
- 230000003287 optical effect Effects 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000005282 brightening Methods 0.000 title abstract description 15
- 239000004952 Polyamide Substances 0.000 title abstract description 13
- 229920002647 polyamide Polymers 0.000 title abstract description 13
- 229920002678 cellulose Polymers 0.000 title abstract description 9
- 150000002191 fatty alcohols Chemical class 0.000 claims abstract description 14
- 229920001515 polyalkylene glycol Polymers 0.000 claims abstract description 9
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 17
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- 125000003342 alkenyl group Chemical group 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 6
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 claims description 5
- 125000003262 carboxylic acid ester group Chemical class [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 abstract description 10
- 150000001733 carboxylic acid esters Chemical class 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 description 10
- 239000004744 fabric Substances 0.000 description 10
- -1 aliphatic radical Chemical class 0.000 description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 5
- 229920002292 Nylon 6 Polymers 0.000 description 5
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- HRKAMJBPFPHCSD-UHFFFAOYSA-N Tri-isobutylphosphate Chemical compound CC(C)COP(=O)(OCC(C)C)OCC(C)C HRKAMJBPFPHCSD-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- WJZIPMQUKSTHLV-UHFFFAOYSA-N 2-ethyldecanoic acid Chemical compound CCCCCCCCC(CC)C(O)=O WJZIPMQUKSTHLV-UHFFFAOYSA-N 0.000 description 2
- 229920002284 Cellulose triacetate Polymers 0.000 description 2
- 229920002302 Nylon 6,6 Polymers 0.000 description 2
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- 239000004808 2-ethylhexylester Substances 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 101000913968 Ipomoea purpurea Chalcone synthase C Proteins 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- 229920000571 Nylon 11 Polymers 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 101000907988 Petunia hybrida Chalcone-flavanone isomerase C Proteins 0.000 description 1
- 125000004442 acylamino group Chemical group 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000005840 aryl radicals Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 150000003219 pyrazolines Chemical class 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920006304 triacetate fiber Polymers 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
- D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
- D06L4/60—Optical bleaching or brightening
- D06L4/679—Fixing treatments in optical brightening, e.g. heating, steaming or acid shock
Definitions
- the present invention relates to a process for the optical brightening of fibrous materials consisting of synthetic polyamides or cellulose esters by impregnating the material with a liquor containing an optical brightener with subsequent fixa tion by a heat treatment which comprises fixing the brightener in the presence of an auxiliary consisting of a polyalkylene glycol of the formula in which n is 2 or 3 and x is a number of2 to 22. and a fatty alcohol oxethylate ofthe formula in which R is alkyl or alkenyl ofeight to 24 carbon atoms and z is a number of3 to 16.
- a further object of this invention is a composition of matter. useful as an auxiliary in said process. consisting of a polyalkylene glycol ofthe formula in which n is 2 or 3 and .r is a number of 2 to 22 and a fatty alcohol oxethylate ofthe formula in which R is alkyl or alkenyl ofeight to 24 carbon atoms and z is a number of3 to 16.
- thermosol process It is known to optically brighten synthetic fibrous materials of linear polyesters according to the so-called thermosol process with a satisfactory effect.
- Said method comprises padding the material at ambient temperatures with solutions or suspensions of an appropriate water-insoluble brightener and submitting it to a subsequent heat treatment.
- the heat treatment aimed at the fixation of the brightener is preferably effected at temperatures allowing simultaneous thermostabilization of the fibrous material. With polyester fibers these temperatures generally range from about l70 to 220C.
- thermosol method it has been attempted to apply the thermosol method also to the treatment of fibrous materials of synthetic polyamides. however, in that case the effects produced with the optical brighteners are essentially worse than achieved with usual exhaustive methods. Owing to this fact the thermosoling of optical brighteners on polyamide fibers has not attained yet any importance.
- the object of the invention hence is a process for the optical brightening of fibrous materials of synthetic polyamides or cellulose esters by impregnating the material with a liquor containing an optical brightener and fixing the brightener. subsequently. by a heat treatment in the presence of an auxiliary consisting of a polyethylene glycol of about 2 to 22 (C,,H,,,O)units in which n is 2 or 3 and an oxethylated fatty alcohol, the aliphatic radical of which contains at least eight to 24 carbon atoms comprising 3 to l6 ethylene glycol ether units.
- an auxiliary consisting of a polyethylene glycol of about 2 to 22 (C,,H,,,O)units in which n is 2 or 3 and an oxethylated fatty alcohol, the aliphatic radical of which contains at least eight to 24 carbon atoms comprising 3 to l6 ethylene glycol ether units.
- an aliphatic carboxylic acid ester corresponding to the general formula represent saturated or unsaturated aliphatic groups which may be identical or different. having from four to l8 carbon atoms. one or both of said groups containing at least one side chain of one to four carbon atoms which chains preferably are in the a-position in the acid radical while in the a or ,B-position in the alcohol radical.
- esters of the indicated type the following may be cited by way of example: 2-ethyl-capric acid-2-ethylhexyl ester. 2-ethyl-capric acid-2-ethyl-buityl-ester.
- the foam-depressing agents are generally added to the composition of matter of the invention each in an amount in the range of from 0.5 to 5 percent. referred to the weight of the composition.
- the instant process may be carried out by applying to the material to be brightened a solution. dispersion or emulsion containing the optical brightener. the polyalkene glycol. the oxethylated fatty alcohol and. optionally. further adjuvants. predying said material. subjecting it to a heat treatment in a thermosoling device and finishing it thereafter. in usual manner.
- the optical brightening agents can be applied from an organic or. preferably. aqueous bath. lt is likewise possible to apply the brightener and the auxiliary ofthe invention with. optionally. the foam-depressing agents to the fibrous material separately in any sequence, prior to the heat treatment.
- heat treatment for the fixation of the optical brightener is and generally conducted at temperatures between about 170 220 C.. preferably I and 210 to 60. preferably 5 to 40 seconds form of dry heating or. if desired. steam.
- polyalkylene glycols to be used according to the invention compounds ofthe general formula C. It lasts. approximately. 5 and proceeds either in the in using a small amount of However. polypropylene glycols or polyethylene-propylene glycols or mixtures of both are likewise appropriate.
- oxethylated fatty alcohols may serve compounds of the formula wherein 1 represents a number from about 3 to 16. preferably 5 to 10. and R is a saturated or unsaturated aliphatic radical of eight to 24. preferably l2 to 18 carbon atoms.
- the mixing ratio of the polyalkylene glycols and oxethylated fatty alcohols may vary within wide limits. Generally. about 0.0l to 1 part by weight. preferably 0.05 to 0.5 part. of oxethylated fatty alcohol is used per each part by weight of the polyalkylene glycol.
- the composition of matter of the invention should advantageously be applied in an amount from about 0.05 to 2.5 percent. preferably. 0.2 to 1.5 percent. calculated on the weight ofthe fibrous material.
- optical brightening agents suitable for fibrous materials of polyamide or cellulose acetate.
- Such optical brighteners have, for example. been disclosed in Belgian Pats. Nos. 631,367, 661 139, 670 161 and 701 986.
- For use on fibrous materials of synthetic polyamides predominantly water-soluble brighteners of the indicated type are employed.
- the brightening agents are applied in usual concentrations, generally, in an amount in the range of from about 0.01 to 2 percent, preferred to the weight of the fibrous material.
- the instant process is applicable to fibrous materials on the basis of polyamides, for example those prepared from adipic acid and hexa-methylene diamine (polyamide 66) or adipic acid, hexamethylene-diamine and caprolactam (polyamide 66/6). caprolactam (polyamide 6) or w-aminoundecylic acid (polyamide 11) and also to fibrous materials of cellulose esters, especially cellulose triacetate. Said process provides goods ofa uniform, high degree of whiteness.
- EXAMPLE 1 A knit fabric made of polycaprolactam (polyamide 6) was impregnated with a liquor containing per liter 15 g. of an auxiliary consisting of 85 parts of polyethylene glycol ofa molecular weight of 400, parts of an addition product of 5 mols of ethylene oxide to 1 mol ofa fatty alcohol having on an average 13 carbon atoms, 2.5 parts of triisobutyl phosphate and 2.5 parts of 2 ethylcapric acid-Z-ethyl-butyl ester, 15 g./l. of an optical brightening agent corresponding to the formula and 0.3 g./l. ofcitric acid.
- the fibrous material was squeezed off between cylinders until its moisture content represented 70 percent of its dry weight and, subjected. subsequently. for seconds to a treatment by hot air of 190C.
- the knit fabric thus treated displayed an outstanding degree of whiteness substantially higher than that produced, under equal conditions, without the use of the auxiliaries.
- EXAMPLE 2 A laundered and dried fabric of polyamide 6.6 was treated with a liquor containing per liter g. of an auxiliary consist ing of 75 parts of polypropyleneglycol of a molecular weight of 250. 15 parts of an addition product of 8 mols of ethylene oxide to 1 mol of a branched fatty alcohol having on an average 13 carbon atoms, 5 parts of triisobutylphosphate and 5 parts of2 ethyl-capric acid-Z-ethyl-butyl ester, 25 g./l. of an optical brightening agent having the composition specified in example 1 and 0.5 g./l. of citric acid. To the liquor moreover. mg./l.ofdyestuffC.l. No.51 319 (cf. Color Index, 2nd edition (1956))were added in order to improve the shade of the brightener.
- the fibrous material was squeezed off in usual manner between cylinders to a moisture content representing 55 percent of its dry weight. dried subsequently. during 30 seconds at C. and subjected, thereafter, for 20 seconds to a treatmentin hot air at 200 C.
- the fabric thus treated showed an excellent degree of whiteness essentially superior to that produced, under equal conditions, without the auxiliaries.
- EXAMPLE 3 A knit fabric made from polyamide 6 was treated with a liquor containing per liter 25 g. of an auxiliary consisting of 85 parts of polyethylene glycol of a molecular weight of 200, 10 parts of an addition product of 5 mols of ethylene oxide to 1 mol of stearyl alcohol, 2.5 parts of triisobutyl phosphate and 2.5 parts of 2-ethyl capric acid-Z-ethylbutyl ester, 5.7 g./l. of an optical brightening agent corresponding to the formula l SOJNB OCH; 2
- the knit fabric thus handled displayed a high degree of whiteness.
- EXAMPLE 4 A fabric of triacetate fibers was impregnated with a liquor containing per liter 20 g. of the auxiliary specified in example 1. 2.25 g./l. ofan optical brightening agent ofthe formula and S g./l. of an addition product of8 mols of ethylene oxides to 1 mol of nonylphenol. The fibrous material was squeezed off between cylinders to a moisture content of 60 percent of its dry weight and exposed during 20 seconds to a temperature of 190 C. The fabric exhibited an excellent degree of whiteness.
- EXAMPLE 5 A knit fabric of polyamide 6 was treated with a liquor containing per liter 25 g. of an auxiliary consisting of 85 parts of polyethylene glycol ofa molecular weight of 200, 10 parts of an addition product of 5 mols of ethylene oxide to 1 mol of olealcohol, 2.5 parts oftriisobutyl phosphate and 2.5 parts of 2-ethyl capric acid 2-ethy1-butyl ester. 5.7 g./l. of an optical brightening agent of the formula specified in example 1 and 0.5 g./l. of citric acid.
- the fibrous material thus wetted was squeezed off between cylinders until having a moisture content of 50 percent of its dry weight and subjected. thereafter. for 20 seconds to a hot air treatment at 190 C.
- the knit fabric thus treated displays an excellent degree of whiteness.
- a process for the optical brightening of a fibrous material of a synthetic polyamide or cellulose ester which comprises impregnating the fibrous material with a liquor containing an optical brightener. and subsequently fixing the optical brightener by a heat treatment in the consisting essentially of a. a polyalkylene glycol of the formula wherein n represents 2 or 3 and 1: represents a number from 2 to 22, and b. a fatty alcohol oxethylate of the formula presence of an auxiliary wherein R represents an alkyl or alkenyl group containing eight to 24 carbon atoms and z represents a number from 3 to l6, the ratio of the components being about 0.01 to 1 part by weight of oxethylate per one part by weight of glycol.
- x represents a number b.
- R represents an alkyl or alkenyl group containing eight to 24 carbon atoms and z represents a number from 3 to 16, the ratio of the components being about 0.01 to 1 weight of oxethylate per one part by weight of glycol.
- composition defined in claim 4 wherein the ratio of components is 0.05 to 0.5 parts by weight oxethylate to one part by weight glycol.
- composition defined in claim 4 which additionally contains from 0.5 to 5 percent by weight of an aliphatic carboxylic acid ester of the formula part by wherein R, and R are alkyl or alkenyl of four to 18 carbon atoms, at least one of R and R being branched.
- composition defined in claim 4 which additionally contains from 0.5 to 5 percent by weight of a phosphoric acid alkyl ester, the alkyl radicals of which contain four to eight carbon atoms.
- composition defined in claim 4 which additionally contains a. from 0.5 to 5 percent by weight of an aliphatic carboxylic acid ester of the formula wherein R and R are alkyl or alkenyl of four to 18 carbon atoms, at least one of R, and R being branched. and b. from 0.5 to 5 percent by weight ofa phosphoric acid alkyl ester, the alkyl radicals of which contain four to eight carbon atoms.
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19681719355 DE1719355B2 (de) | 1968-03-02 | 1968-03-02 | Verfahren zum optischen aufhellen von fasermaterialien aus synthetischen polyamiden oder celluloseestern |
Publications (1)
Publication Number | Publication Date |
---|---|
US3619234A true US3619234A (en) | 1971-11-09 |
Family
ID=5689694
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US799531A Expired - Lifetime US3619234A (en) | 1968-03-02 | 1969-02-14 | Process for the optical brightening of fibrous materials of synthetic polyamides or cellulose esters |
Country Status (9)
Country | Link |
---|---|
US (1) | US3619234A (enrdf_load_stackoverflow) |
AT (1) | AT294001B (enrdf_load_stackoverflow) |
BE (1) | BE729261A (enrdf_load_stackoverflow) |
CH (3) | CH560790A (enrdf_load_stackoverflow) |
DE (1) | DE1719355B2 (enrdf_load_stackoverflow) |
FR (1) | FR2003125A1 (enrdf_load_stackoverflow) |
GB (1) | GB1248319A (enrdf_load_stackoverflow) |
NL (1) | NL6901054A (enrdf_load_stackoverflow) |
SE (1) | SE358911B (enrdf_load_stackoverflow) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4426298A (en) | 1981-11-27 | 1984-01-17 | Shell Oil Company | Textile processing oils |
US4904794A (en) * | 1987-03-05 | 1990-02-27 | Ciba-Geigy Corporation | Pyrazoline compounds |
US6274756B1 (en) * | 1996-07-18 | 2001-08-14 | Exxon Chemicals Patents, Inc. | Esters, ethers, and compositions comprising them |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3033276A1 (de) | 1980-09-04 | 1982-04-08 | Basf Ag, 6700 Ludwigshafen | Druckpaste |
DE3046482A1 (de) * | 1980-12-10 | 1982-07-15 | Bayer Ag, 5090 Leverkusen | Verfahren zum weisstoenen von fasermaterialien |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3156655A (en) * | 1960-08-02 | 1964-11-10 | Lever Brothers Ltd | Heavy duty liquid detergent composition |
US3284462A (en) * | 1963-11-25 | 1966-11-08 | Ciba Ltd | 2-aroxazolyl-5-aryl-thiophene compounds |
-
1968
- 1968-03-02 DE DE19681719355 patent/DE1719355B2/de active Granted
-
1969
- 1969-01-22 NL NL6901054A patent/NL6901054A/xx unknown
- 1969-02-14 US US799531A patent/US3619234A/en not_active Expired - Lifetime
- 1969-02-27 CH CH299769A patent/CH560790A/xx not_active IP Right Cessation
- 1969-02-27 CH CH299769D patent/CH299769A4/xx unknown
- 1969-02-27 CH CH357474A patent/CH561322A5/xx not_active IP Right Cessation
- 1969-02-27 GB GB00619/69A patent/GB1248319A/en not_active Expired
- 1969-02-28 AT AT02021/69A patent/AT294001B/de not_active IP Right Cessation
- 1969-02-28 SE SE02803/69A patent/SE358911B/xx unknown
- 1969-03-03 FR FR6905635A patent/FR2003125A1/fr active Granted
- 1969-03-03 BE BE729261D patent/BE729261A/xx not_active IP Right Cessation
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3156655A (en) * | 1960-08-02 | 1964-11-10 | Lever Brothers Ltd | Heavy duty liquid detergent composition |
US3284462A (en) * | 1963-11-25 | 1966-11-08 | Ciba Ltd | 2-aroxazolyl-5-aryl-thiophene compounds |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4426298A (en) | 1981-11-27 | 1984-01-17 | Shell Oil Company | Textile processing oils |
US4904794A (en) * | 1987-03-05 | 1990-02-27 | Ciba-Geigy Corporation | Pyrazoline compounds |
US6274756B1 (en) * | 1996-07-18 | 2001-08-14 | Exxon Chemicals Patents, Inc. | Esters, ethers, and compositions comprising them |
Also Published As
Publication number | Publication date |
---|---|
DE1719355B2 (de) | 1973-09-20 |
SE358911B (enrdf_load_stackoverflow) | 1973-08-13 |
FR2003125A1 (fr) | 1969-11-07 |
DE1719355A1 (de) | 1968-08-05 |
GB1248319A (en) | 1971-09-29 |
CH561322A5 (enrdf_load_stackoverflow) | 1975-04-30 |
DE1719355C3 (enrdf_load_stackoverflow) | 1974-05-02 |
AT294001B (de) | 1971-10-15 |
CH299769A4 (enrdf_load_stackoverflow) | 1974-03-29 |
FR2003125B1 (enrdf_load_stackoverflow) | 1973-11-16 |
NL6901054A (enrdf_load_stackoverflow) | 1969-09-04 |
BE729261A (enrdf_load_stackoverflow) | 1969-09-03 |
CH560790A (enrdf_load_stackoverflow) | 1975-04-15 |
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