US2310257A - Impregnating agent for vegetable fibrous materials - Google Patents
Impregnating agent for vegetable fibrous materials Download PDFInfo
- Publication number
- US2310257A US2310257A US368253A US36825340A US2310257A US 2310257 A US2310257 A US 2310257A US 368253 A US368253 A US 368253A US 36825340 A US36825340 A US 36825340A US 2310257 A US2310257 A US 2310257A
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- United States
- Prior art keywords
- copper
- ammonia
- solutions
- fluoride
- solution
- 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
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- 239000002657 fibrous material Substances 0.000 title description 17
- 235000013311 vegetables Nutrition 0.000 title description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 44
- 239000000243 solution Substances 0.000 description 44
- 229910021529 ammonia Inorganic materials 0.000 description 23
- 239000000126 substance Substances 0.000 description 19
- 239000000463 material Substances 0.000 description 18
- 229910021594 Copper(II) fluoride Inorganic materials 0.000 description 14
- 239000007864 aqueous solution Substances 0.000 description 14
- GWFAVIIMQDUCRA-UHFFFAOYSA-L copper(ii) fluoride Chemical compound [F-].[F-].[Cu+2] GWFAVIIMQDUCRA-UHFFFAOYSA-L 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 13
- 229910052802 copper Inorganic materials 0.000 description 13
- 239000010949 copper Substances 0.000 description 13
- 239000007788 liquid Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- -1 fluorine ions Chemical class 0.000 description 10
- 244000005700 microbiome Species 0.000 description 10
- BPQWCZKMOKHAJF-UHFFFAOYSA-N scheele's green Chemical compound [Cu+2].O[As]([O-])[O-] BPQWCZKMOKHAJF-UHFFFAOYSA-N 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 230000009471 action Effects 0.000 description 8
- 229940030341 copper arsenate Drugs 0.000 description 7
- RKYSWCFUYJGIQA-UHFFFAOYSA-H copper(ii) arsenate Chemical compound [Cu+2].[Cu+2].[Cu+2].[O-][As]([O-])([O-])=O.[O-][As]([O-])([O-])=O RKYSWCFUYJGIQA-UHFFFAOYSA-H 0.000 description 7
- 150000007530 organic bases Chemical class 0.000 description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 6
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 6
- BESJRHHIPGWPTC-UHFFFAOYSA-N azane;copper Chemical class N.[Cu] BESJRHHIPGWPTC-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 230000002522 swelling effect Effects 0.000 description 6
- 229960004418 trolamine Drugs 0.000 description 6
- 238000009736 wetting Methods 0.000 description 6
- 239000005749 Copper compound Substances 0.000 description 5
- 241000196324 Embryophyta Species 0.000 description 5
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 5
- 150000001880 copper compounds Chemical class 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 230000000087 stabilizing effect Effects 0.000 description 5
- 239000002023 wood Substances 0.000 description 5
- 240000000491 Corchorus aestuans Species 0.000 description 4
- 235000011777 Corchorus aestuans Nutrition 0.000 description 4
- 235000010862 Corchorus capsularis Nutrition 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- DJHGAFSJWGLOIV-UHFFFAOYSA-K Arsenate3- Chemical compound [O-][As]([O-])([O-])=O DJHGAFSJWGLOIV-UHFFFAOYSA-K 0.000 description 3
- 241000238631 Hexapoda Species 0.000 description 3
- 238000007792 addition Methods 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 230000002335 preservative effect Effects 0.000 description 3
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical class [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- OCUCCJIRFHNWBP-IYEMJOQQSA-L Copper gluconate Chemical class [Cu+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O OCUCCJIRFHNWBP-IYEMJOQQSA-L 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 241000607479 Yersinia pestis Species 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229940000489 arsenate Drugs 0.000 description 2
- AQLMHYSWFMLWBS-UHFFFAOYSA-N arsenite(1-) Chemical compound O[As](O)[O-] AQLMHYSWFMLWBS-UHFFFAOYSA-N 0.000 description 2
- GCPXMJHSNVMWNM-UHFFFAOYSA-N arsenous acid Chemical class O[As](O)O GCPXMJHSNVMWNM-UHFFFAOYSA-N 0.000 description 2
- 150000001642 boronic acid derivatives Chemical class 0.000 description 2
- 150000003842 bromide salts Chemical class 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 201000010099 disease Diseases 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 229930182478 glucoside Natural products 0.000 description 2
- 150000008131 glucosides Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 150000004694 iodide salts Chemical class 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- 229930182490 saponin Natural products 0.000 description 2
- 150000007949 saponins Chemical class 0.000 description 2
- 235000017709 saponins Nutrition 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 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 1
- 241001072332 Monia Species 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000003637 basic solution Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229950011260 betanaphthol Drugs 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical class [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 125000005608 naphthenic acid group Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- PTLRDCMBXHILCL-UHFFFAOYSA-M sodium arsenite Chemical compound [Na+].[O-][As]=O PTLRDCMBXHILCL-UHFFFAOYSA-M 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/52—Impregnating agents containing mixtures of inorganic and organic compounds
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
- A01N59/20—Copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/02—Processes; Apparatus
- B27K3/0278—Processes; Apparatus involving an additional treatment during or after impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K5/00—Treating of wood not provided for in groups B27K1/00, B27K3/00
- B27K5/04—Combined bleaching or impregnating and drying of wood
Definitions
- Another method of preventing the active agent from being washed away when in contact with water consists in fixing the. said agent in the fibres by a suitable addition. .
- This object can be attained by adding chromates or bichromates to the impregnating solution.
- fibrous material is treated e. g. with a fluoride solution.
- the invention provides an excellent impregnating agent for preserving vegetable fibrous materials which consists oi a solution copper fluoride, copper arsenite, or copper arsenate in ammonia, containing an organic base, aqueous or low volatility, i. e. an organic base which is practically non-volatile or only very slightly volatile.
- an organic base i. e. an organic base which is practically non-volatile or only very slightly volatile.
- Organic bases which are especially suitable for the present purpose are the hydroxy amines, e. g. triethanol-amine.
- hydroxy amines e. g. triethanol-amine.
- Substances such as triethanol-amine also have the property of increasing the wetting power of the solution so that it will more readily penetrate into the fibrous materials.
- Theorganicbases can beused as such orin the iorm oi water soluble compounds, and when the expression organic base is used in the specification and the appending' claims it is'meant to in-,
- the action oi the impregnating liquid according to the invention can further be improved by adding mordants having the property of fixing the compounds on the fibre.
- Derivatives oi phthalic acid and of naphthol and compounds with a double phenyl nucleus are suitable for A considerable improvement may be obtained by incorporating into the impregnating liquid substances which have a swelling action on the fibres without appreciably attacking the same as described in my co-pending U. S. A. application Serial No. 368,252, filed Dec. 6, 1940.
- a swelling action is generally also exerted by the organic bases or their water soluble compounds used according to the invention. This swelling action has a favourable efiect on the impregnating proces since the impregnating liquid penera'tes more easily into the fibres so that the copper fluoride is deposited more uniformly throughout the material.
- the impregnating agent according tothe invention preferably does not contain more than 7- grams of copper per litre.
- An impregnating agent orthis composition has an excellent preservative action on the fibrous material treated therewith without appreciably attacking the The invention will be illustrated by the following examples:
- reaction i finished 90 grams of ethylenediamine and 150 cm. of a 10% solution oi equal parts of ammonium rhodanide and amthis purpose. but other well known mordants may 7 ,alsobeused.
- the solution'obtained in this way is the basic liquid, which is diluted with 40-60 parts of water in order to produce the impregnating liquid properly speaking.
- Solutions having a similar preservative action are produced when substituting in the examples arsenates for arsenites or when using two or more of the said substances at the same time.
- the invention is especially valuable for preserving bags, e. g. jute bags, transport cases and perature of 38 C. for a period of 28 days.
- a jute bag is impregnated with theliquid described in Example'l, dried and, subsequently washed for a period of '7 days in running water.
- the bag is now introduced into a container Where it. is subjected to a rotting process at a tern;
- the invention is not only serving fabrics, wood and against deterioration by and insects, but also and protecting plants against insect pests.
- the preserving agent according to the invention can be sprayed on the important for premicro organisms, fungi other fibrous materials for combating plant diseases plants according to the usual methods.
- solutions used in this case are preferably diluted to a lower concentration than those employed for impregnatingfabrics and wood.
- suitable solutions may be obtained by diluting the basic solutions described in the examples with water in a pro-. portion of 100-300 parts of water on 1 part of the solution. It is advantageous to increase the proportion of ammonia and organic base in the said dilute solutions in order to keep the copper compounds better dissolved, whereas the mordants and the substances having a swelling action may be omitted in this case.
- a substance having a swelling action comprising an aqueous solution containing ammonia, a hydroxy amine of low volatility and'having a marked stabilizing effect on copper ammonia compounds in dilute aqueous solutions and improving the impregnating and wetting proper- I ties of such solutions, and at least 'one' substance of the group consisting of copper fiuoride,,cop
- composition for preserving fibrous materials by combating harmful micro-organisms 1.
- - comprising an aqueous solution containing ammonia, ethylene diamine, and at least one 'sub-. stance of the group consisting of copper fluoride, copper arsenite, and copper arsenate.
- rialsby comprising an aqueous solution containing at further ammonia
- a marked stabilizing effect comprising an aqueous solution containing at least one substance of the group consisting of copper fluoride, copper arsenite, and copper ara hydroxy amine of low volatility and having a marked stabilizing effect on copper ammonia compounds in dilute aqueous solutions and improving the impregnating and wetting properties of said solutions, and a mordant consisting'of a mixture containing phthalic acid'and naphth'ol compounds.
- a composition for preserving fibrous materials by combating harmful micro-organisms
- aqueous solution containing at least one substanceof the group consisting of, copper fluoride, copper arsenite, and copper arsenate; further ammonia, triethanolamine, and
- mordant consisting of betanaphthol, phenolphthalein, and diphenylamine.
- A'composition for preserving fibrous materials by combating harmful micp-organisms comprising an aqueous solution containing at least one substance of the group consisting of copper fiuoride,,copper arsenite, and copper arsenate; further ammonia, a. hydroxy amine of low volatility and having a marked stabilizing effect on copper ammonia compounds in dilute aqueous solutions and improving the impregnating and wetting properties'ofsuch solutions, and
- said swelling substance being one selected from a group consisting of soluble borates, cyanides, humates, saponins,glucosides, saccharates, gluconates, carboxylic acids, salts of sulphuric acids, amines and amides, and rhodanides, nitrates, iodides, bromides,-chlo rides, and chlorates.
- Acomposition for preserving fibrous materials by combating harmful micro-organisms comprising an .aqueoussolution containing at least one substance of the group consisting of copper fluoride, copper arsenite, and copper arsenate; v hydroxy amine of low volatility and having on copper ammonia compounds in dilute aqueous solutions and improving the impregnatingand wetting properties of such solutions, the said solutioncontaining less. than 7 grams of: copper per litre.
- the process for preserving fibrous materials comprising impregnating the said material sulphonic acids and alkyl' by treating it with an aqueous solution containsists in spraying against said plant an aqueous ing at least one substance oi the group consistsolution containing ammonia, triethanolamine, in: 01' copper fluoride, copper arsenite, and copper and at least one substance ofthe group consistarsenate; further ammonia and triethanolamine; ing or copper fluoride, copper arsenite, and copand dryinz'the material thus treated. 5 per arsenate.
Description
Patented Feb. 9, 1943 nvrrasemme AGENT FOR VEGETABLE .rmaoUs MATERIALS Ludwig Bitter, The Hague, Netherlands, assignor, I
by direct and mesne assignments, to Albi Chemical Corporation, New York. N. Y., a corporation of New York No Drawing.
Application December 2, 1940, Se-
rial No. 368,253. In the Netherlands September 11 Claims.
out from the material treated it the same is in contact with a large excess of water for a sumcient period. This difllculty cannot be solved by using an insoluble fluoride such as calcium fluoride because the proportion of fluorine ions produced by this compound is so small that they have practically no preserving action.
It has been tried to obviate this difficulty by storing a sumcient amount of the preserving agent in a cavity of the object to be preserved. Obviously, however, this is only possible if the said object is of a suitable size, 1. e. in the case of wood having a suflicient thickness.
Another method of preventing the active agent from being washed away when in contact with water consists in fixing the. said agent in the fibres by a suitable addition. .This object can be attained by adding chromates or bichromates to the impregnating solution.
If the fibrous material is treated e. g. with a fluoride solution.
containing a substance of this character it appears that part oithe fluoride is present in the impregnated and dried material in such a form that it cannot be washed out to an appreciable extent with water, but that nevertheless the water coming in contact with the material is provided with a certain proportion of fluorine ions which produce a preserving action. Fully satisfactory results. however, are not always obtained by this method, since 'in some cases the fluorine ion concentration is-reduced below the limit required for a bactericide action, especially when the impregnated material treated is in contact with hard water, since in this case calcium .fluoride is produced, which is highly insoluble.
The packing materials such as cases, bags, baskets, etc., which are impregnated in this way also show the drawback that the foodstuffs contained in the same take up small amounts of fluoride so that it is generally not allowable to use the same tor thispurpose It has also been tried to preserve wood and other fibrous materials by impregnating the same with solutions of metal compounds in organic solvents from which the said metal compounds are deposited in insoluble or only very slightly soluble form in the fibres. For this purpose solutions of copper, zinc and aluminium salts of fatty-acids, naphthenic acids and the like in solvents such as naphtha can be used; emulsions oi the said substances are also suitable. For practical purposes, however, this method is generally too expensive; moreover the materials treated generally have an objectionable odour and the suppleness oi the fibres is decreased.
Other prior processes are based on the preserving action of the copper ion. It has e. 8. been proposed to impregnate jute bags by immerging the same in an ammoniacal copper oxide solution (the 'so-called Schweizer solution). This solution, however, presents the drawback that it has a dissolving action on the cellulose so that the material should only be immerged in the liquid for a very short time; e. g. 30 seconds, and
in this case it is not always possible to obtain a uniform impregnation. Moreover the-ammonia vapours produced bythe liquid render it necessary for the workmen to use gas masks and to take special precautions for protecting the skin against the liquid, while this method too is generally too expensive for practical purposes.
It has been suggested to combine the preserving action oi! the fluorine ions and the copper ions by impregnating the material to be treated with a solution of copper fluoride in ammonia. According to this process which has been described in German specification No. 226,975 the copper fluoride is precipitated from a copper salt solution with ammonium fluoride, separated from the liquid by filtration and subsequently dissolved in ammonia. When the fibrous material is impregnated with this solution the ammonia will readily evaporate, and the copper fluoride. is deposited in the fibrous'material in non-dissolved condition. v
This method too did .not'work satisfactorily. If relatively'ooncentrated solutions are used, the fibres are attacked by the ammoniacal copper solution and the material is accordingly tendered in the same way as described above in connection with the ammoniacal copper oxide solutions. If on the contrary very dilute solutions are employed the fibres are not appreciably attacked, but it has appeared that in this case the copper fluoride is already precipitated from the said dilute solution prior to the impregnating step so that it is deposited onthe fibres and not in the fibres in a form which is unsuitable for obtaining a satisfactory, uniiorm preserving action.
The invention provides an excellent impregnating agent for preserving vegetable fibrous materials which consists oi a solution copper fluoride, copper arsenite, or copper arsenate in ammonia, containing an organic base, aqueous or low volatility, i. e. an organic base which is practically non-volatile or only very slightly volatile. I have found that when using a solution 0! this character for preserving fibrous materials the insoluble copper compound is deposited in the fibres in a form which is very favorable in the present purpose. This is probably due to the fact that the copper compound remains in solution for a substantially longer period evenin very dilute solutions, so that it is slowly deposited in and on the fibres when the ammonia is evaporated from the impregnated material. Whether the said copper solutions are molecula or colloidal solutions is immaterial for the present purpose.
Owing to the very slow decomposition of the ammoniacal copper compound it is possible to use much more dilute solutions. This has the advantage that the fibres are practically not attacked by the solution, so that the material can be immerged in the said solution for a considerable period, c. g. 20-30 min. Moreover the dilute solutions are much more easy to handle since it is unnecessary to take special precautions against the ammonia vapours.
Organic bases which are especially suitable for the present purpose are the hydroxy amines, e. g. triethanol-amine. By the addition of compounds of this character to a dilute solution oi e. g. copper fiuoride in ammonia the properties of the said solution as an impregnating agent for wood and fabrics are substantially improved.
Substances such as triethanol-amine also have the property of increasing the wetting power of the solution so that it will more readily penetrate into the fibrous materials.
Theorganicbasescan beused as such orin the iorm oi water soluble compounds, and when the expression organic base is used in the specification and the appending' claims it is'meant to in-,
clude both the tree bases and their water soluble compounds.
I have found it to be adavntageous to prepare the impregnating liquid not by dissolving previously precipitated copper fluoride inthe liquid containing ammonia, but by adding a soluble fiuoride to a solution oi a soluble copper, salt containing ammonia and the organic base. Comparativctests have shown that solutions obtained in the last mentioned way have a better, more unii'orin preservative action on the fibrous material than solutions obtained from previously precipitated copper fiuoride. Similar results were obtained with the other copper compounds used according to the invention. It is not improbable j that this improvement is partly dueto the presence in the final product of the sodium sulphate or sodium chloride, produced by the interaction oi copper sulphate or copper chloride withsodium fiuoride, arsenite or arsenate.
The action oi the impregnating liquid according to the invention can further be improved by adding mordants having the property of fixing the compounds on the fibre. Derivatives oi phthalic acid and of naphthol and compounds with a double phenyl nucleus are suitable for A considerable improvement may be obtained by incorporating into the impregnating liquid substances which have a swelling action on the fibres without appreciably attacking the same as described in my co-pending U. S. A. application Serial No. 368,252, filed Dec. 6, 1940. As suitable additions for this purpose I may mention borax and other soluble borates, cyanides, humates, saponins, some glucosides, saccharates, gluconates and other salts of carboxylic acids, salts of sulphonic acids and alkyl sulphuric acids, amines and amides, and salts the anions or kations of which are indicated in the well known Hofmeister range, as exerting a swelling action, such as rhodanides, nitrates, iodides, bromides,
- chlorides and chlorates. A swelling action is generally also exerted by the organic bases or their water soluble compounds used according to the invention. This swelling action has a favourable efiect on the impregnating proces since the impregnating liquid penera'tes more easily into the fibres so that the copper fluoride is deposited more uniformly throughout the material.
The impregnating agent according tothe invention preferably does not contain more than 7- grams of copper per litre. An impregnating agent orthis composition has an excellent preservative action on the fibrous material treated therewith without appreciably attacking the The invention will be illustrated by the following examples:
Example 1 Kilograms Crystalline copper sulphate 4.5 Sodium fluoride-and 1.6 Ammonia 28% 5.0
are introduced into a'container containing stirring and cooling devices. An exothermic reaction occurs and it is necessary to cool the reaction mixture sinc'esubstantlal amounts of ammonia will be lost by evaporation ii the temperature of water in a proportion of 30-50 parts of water on 1 part of the basic liquid.
Example 2 v i i Kilograms Crystalline copper ch1oride 3.9 Sodium arsenite and-- 2.1 Ammonia 28% 6.0 v
are made to react as described in'Example 1.
when the reaction i finished 90 grams of ethylenediamine and 150 cm. of a 10% solution oi equal parts of ammonium rhodanide and amthis purpose. but other well known mordants may 7 ,alsobeused.
monium humate in dilute ammonia containing 25% 01' NH: are added.
' The solution'obtained in this way is the basic liquid, which is diluted with 40-60 parts of water in order to produce the impregnating liquid properly speaking.
Solutions having a similar preservative action are produced when substituting in the examples arsenates for arsenites or when using two or more of the said substances at the same time.
The invention is especially valuable for preserving bags, e. g. jute bags, transport cases and perature of 38 C. for a period of 28 days.
jute bag was subjected to a baskets. Packing materials of this character have often to be stored or kept in a humid atmosphere under conditions which are very favourable"'for the development of micro organisms. Especially serious diificulties are encountered when using sand bags which are often destroyedin a relatively short time.
The excellent results obtained byfthe treatment claimed are shown by the following test:
A jute bag is impregnated with theliquid described in Example'l, dried and, subsequently washed for a period of '7 days in running water. The bag is now introduced into a container Where it. is subjected to a rotting process at a tern;
non-impregnated similar rotting treatment.
It appeared that at the end of'the period of 28 days the tensile strength of the-impregnatedbag was reduced to about 75% of. the original strength,--whereas the same-value for the nonimpregnated bag after a rotting period of only 7 days was not'more than although in this case the preliminary treatment with water during 7 days was omitted. This experiment shows that the mechanical properties of the impregnated bag were only slightly affected although the conditions in this test were much harder than they will ever be in practice.
The invention is not only serving fabrics, wood and against deterioration by and insects, but also and protecting plants against insect pests. For the last mentioned purposes the preserving agent according to the invention can be sprayed on the important for premicro organisms, fungi other fibrous materials for combating plant diseases plants according to the usual methods. The
solutions used in this case are preferably diluted to a lower concentration than those employed for impregnatingfabrics and wood. By way of Example I may mention that suitable solutions may be obtained by diluting the basic solutions described in the examples with water in a pro-. portion of 100-300 parts of water on 1 part of the solution. It is advantageous to increase the proportion of ammonia and organic base in the said dilute solutions in order to keep the copper compounds better dissolved, whereas the mordants and the substances having a swelling action may be omitted in this case.
I claim: q l 1. A composition for preserving fibrous mate-' rials by combating harmful micro-organisms,
a substance having a swelling action comprising an aqueous solution containing ammonia, a hydroxy amine of low volatility and'having a marked stabilizing effect on copper ammonia compounds in dilute aqueous solutions and improving the impregnating and wetting proper- I ties of such solutions, and at least 'one' substance of the group consisting of copper fiuoride,,cop
per arsenite, and copper arsenate.
2. A composition for preserving fibrous-materials by combating harmful: micro-organisms, comprising an aqueous solution containing am,-
monia, triethanolamine, and at least one substance of the group consisting of copper fluoride,
copper arsenite, and copper arsenate'.
3. A composition for preserving fibrous materials by combating harmful micro-organisms,
- comprising an aqueous solution containing ammonia, ethylene diamine, and at least one 'sub-. stance of the group consisting of copper fluoride, copper arsenite, and copper arsenate.
4:. A composition for preserving fibrous matesenate; further ammonia,
rialsby comprising an aqueous solution containing at further ammonia, and "a a marked stabilizing effect comprising an aqueous solution containing at least one substance of the group consisting of copper fluoride, copper arsenite, and copper ara hydroxy amine of low volatility and having a marked stabilizing effect on copper ammonia compounds in dilute aqueous solutions and improving the impregnating and wetting properties of said solutions, and a mordant consisting'of a mixture containing phthalic acid'and naphth'ol compounds.
5. A composition for preserving fibrous materials by combating harmful micro-organisms,
comprising an aqueous solution containing at least one substanceof the group consisting of, copper fluoride, copper arsenite, and copper arsenate; further ammonia, triethanolamine, and
a mordant consisting of betanaphthol, phenolphthalein, and diphenylamine.
6. A composition for preserving fibrous matecombating harmful micro-organisms,
least one substance of the group consisting of copperfiuoride, copper arsenite, and copper ar senate; a hydroxy amine of low volatility and having a marked stabilizing effect on copper ammonia compounds in dilute aqueous solutions and improving the impregnating and wetting properties of such solutions, and a swelling substance harmless to the fibres and improvin the penetration of said solution of copper ammonia compounds into said fibres.
'l. A'composition for preserving fibrous materials by combating harmful micp-organisms, comprising an aqueous solution containing at least one substance of the group consisting of copper fiuoride,,copper arsenite, and copper arsenate; further ammonia, a. hydroxy amine of low volatility and having a marked stabilizing effect on copper ammonia compounds in dilute aqueous solutions and improving the impregnating and wetting properties'ofsuch solutions, and
materials and being harmless thereto,' said swelling substance being one selected from a group consisting of soluble borates, cyanides, humates, saponins,glucosides, saccharates, gluconates, carboxylic acids, salts of sulphuric acids, amines and amides, and rhodanides, nitrates, iodides, bromides,-chlo rides, and chlorates. 8. Acomposition for preserving fibrous materials by combating harmful micro-organisms, comprising an .aqueoussolution containing at least one substance of the group consisting of copper fluoride, copper arsenite, and copper arsenate; v hydroxy amine of low volatility and having on copper ammonia compounds in dilute aqueous solutions and improving the impregnatingand wetting properties of such solutions, the said solutioncontaining less. than 7 grams of: copper per litre.
9. The process of producing a compound for preserving fibrous materials by combating harm-,- ful micro-organisms, which consists in adding a substance of the group of soluble fluorides, arsenites, and
. ties of such solutions.
rials by combating harmful micro-organisms,
10. The process for preserving fibrous materials, comprising impregnating the said material sulphonic acids and alkyl' by treating it with an aqueous solution containsists in spraying against said plant an aqueous ing at least one substance oi the group consistsolution containing ammonia, triethanolamine, in: 01' copper fluoride, copper arsenite, and copper and at least one substance ofthe group consistarsenate; further ammonia and triethanolamine; ing or copper fluoride, copper arsenite, and copand dryinz'the material thus treated. 5 per arsenate.
11. The method for combating plant diseases, LUDWIG RI'I'IER. insect pests, and micro-organisms; which con-
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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NL2310257X | 1940-09-11 |
Publications (1)
Publication Number | Publication Date |
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US2310257A true US2310257A (en) | 1943-02-09 |
Family
ID=19874059
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US368253A Expired - Lifetime US2310257A (en) | 1940-09-11 | 1940-12-02 | Impregnating agent for vegetable fibrous materials |
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Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2417388A (en) * | 1944-08-10 | 1947-03-11 | Chemical Lab Inc | Sericeous fibers |
US2446682A (en) * | 1944-05-10 | 1948-08-10 | Chemical Lab Inc | Modifying cellulose textiles with an alkylolamine-copper complex |
US2467540A (en) * | 1945-01-15 | 1949-04-19 | Carey Philip Mfg Co | Manufacture of asbestos sheet material |
US2512558A (en) * | 1944-12-20 | 1950-06-20 | Chemical Lab Inc | Treating cellulose fibers with alkali metal hydroxide and copper-alkylolamine complex |
US3945835A (en) * | 1972-12-12 | 1976-03-23 | Canadian Patents And Development Limited | Heavy duty aqueous wood preservative |
US4011090A (en) * | 1972-09-01 | 1977-03-08 | Canadian Patents And Development Limited | Aqueous ammoniacal zinc oxide compositions for lumber treatment |
US4038086A (en) * | 1972-12-12 | 1977-07-26 | Canadian Patents And Development Limited | Aqueous ammoniacal zinc arsenic or zinc/copper arsenic wood preservative solutions |
EP0211181A1 (en) * | 1985-06-07 | 1987-02-25 | Dr. Wolman GmbH | Wood preservative |
EP0252366A1 (en) * | 1986-06-26 | 1988-01-13 | Dr. Wolman GmbH | Wood protecting agents containing copper and organotin compounds |
-
1940
- 1940-12-02 US US368253A patent/US2310257A/en not_active Expired - Lifetime
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2446682A (en) * | 1944-05-10 | 1948-08-10 | Chemical Lab Inc | Modifying cellulose textiles with an alkylolamine-copper complex |
US2417388A (en) * | 1944-08-10 | 1947-03-11 | Chemical Lab Inc | Sericeous fibers |
US2512558A (en) * | 1944-12-20 | 1950-06-20 | Chemical Lab Inc | Treating cellulose fibers with alkali metal hydroxide and copper-alkylolamine complex |
US2467540A (en) * | 1945-01-15 | 1949-04-19 | Carey Philip Mfg Co | Manufacture of asbestos sheet material |
US4011090A (en) * | 1972-09-01 | 1977-03-08 | Canadian Patents And Development Limited | Aqueous ammoniacal zinc oxide compositions for lumber treatment |
US3945835A (en) * | 1972-12-12 | 1976-03-23 | Canadian Patents And Development Limited | Heavy duty aqueous wood preservative |
US4038086A (en) * | 1972-12-12 | 1977-07-26 | Canadian Patents And Development Limited | Aqueous ammoniacal zinc arsenic or zinc/copper arsenic wood preservative solutions |
EP0211181A1 (en) * | 1985-06-07 | 1987-02-25 | Dr. Wolman GmbH | Wood preservative |
EP0252366A1 (en) * | 1986-06-26 | 1988-01-13 | Dr. Wolman GmbH | Wood protecting agents containing copper and organotin compounds |
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