CA2202624A1 - Process for producing an aqueous amine oxide solution - Google Patents
Process for producing an aqueous amine oxide solutionInfo
- Publication number
- CA2202624A1 CA2202624A1 CA002202624A CA2202624A CA2202624A1 CA 2202624 A1 CA2202624 A1 CA 2202624A1 CA 002202624 A CA002202624 A CA 002202624A CA 2202624 A CA2202624 A CA 2202624A CA 2202624 A1 CA2202624 A1 CA 2202624A1
- Authority
- CA
- Canada
- Prior art keywords
- amine
- oxide
- cellulose
- solution
- aqueous
- 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.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B1/00—Preparatory treatment of cellulose for making derivatives thereof, e.g. pre-treatment, pre-soaking, activation
- C08B1/003—Preparation of cellulose solutions, i.e. dopes, with different possible solvents, e.g. ionic liquids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B1/00—Preparatory treatment of cellulose for making derivatives thereof, e.g. pre-treatment, pre-soaking, activation
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F13/00—Recovery of starting material, waste material or solvents during the manufacture of artificial filaments or the like
- D01F13/02—Recovery of starting material, waste material or solvents during the manufacture of artificial filaments or the like of cellulose, cellulose derivatives or proteins
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
- Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Biochemistry (AREA)
- Health & Medical Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Paper (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Compounds (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention relates to a process for producing an aqueous amine oxide solution used in the amine oxide process for producing a mouldable cellulose solution, in which aqueous amine oxide-containing solutions occurring in the amine oxide process especially as regenerating baths are purified and concentrated, where a microbicidal agent is added to the aqueous amine oxidecontaining solutions before, during or after purification.
Description
CA 02202624 l997-04-l4 PROCESS FOR THE PRODUCTION OF AN AQUEOUS SOi;UTION OF A
TERTIARY AMI~E-oxIDE
The present invention is concerned with a process f or the production of an aqueous amine-oxide solution used in the amine-oxide process for the production of a mouldable cellulose solution, wherein aqueous, amine-oxide containing solutions produced in the amine-oxide process particularly as precipitation baths are purified and concentrated.
For some decades there has been searched for processes for the production of cellulose moulded bodies able to substitute the viscose process, today widely employed. As an alternative which is interesting for its reduced environmental impact among other reasons, it has been found to dissolve cellulose without derivatisation in an organic solvent and extrude from this solution moulded bodies, e.g. fibres, films and other moulded bodies. Fibres thus extruded have received by BISFA
(The International Bureau for the Standardization of man made fibers) the generic name Lyocell. By an organic solvent, BISFA understands a mixture of an organic chemical and water.
It has turned out that as an organic solvent, a mixture of a tertiary amine-oxide and water is particularly appropriate for the production of cellulose moulded bodies. As the amine-oxide, primarily N-methylmorpholine-N-oxide lNM~O) is used.
Other amine-oxides are described e.g. in EP-A - 0 553 070. A
process for the production of mouldable cellulose solutions is known e.g. from EP-A - 0 356 419. For the purposes of the present specification and the present claims, the production of cellulose moulded bodies using tertiary amine-oxides generally is referred to as amine-oxide process.
In EP-A - O 356 419, an amine-oxide process for the production of spinnable cellulose solutions is described, wherein as a starting material among others a suspension of cellulose in liquid, aqueous N-methylmorpholine-N-oxide (NlqMO) is used. This process consists in transforming the suspension in a thin-film treatment apparatus in one single step and continuously into a mouldable solution. Finally, the mouldable solution is spun into fi 1. ~s by a forming tool such as a spinneret and the ~i 7 ~r t.S are passed through a precipitation bath.
In the precipitation bath the cellulose is precipitated. The tertiary amine-oxide is accumulated in the precipitation bath. The precipitation bath may contain up to 30~ by weight of amine-oxide. For the economy of the amine-oxide process it is of vital importance to recover the amine-oxide as completely as possible and reuse it for the production of a mouldable cellulose solution. Thus it is necessary to recover NMMO from the precipitation bath.
In addition to the amine-oxide however, degradation products of the amine-oxide are also accumulated in the precipitation bath. These degradation products may be intensively coloured, thus deteriorating the quality of the cellulose moulded bodies produced. On the other hand, other substances may represent an additional safety risk, since under certain conditions the amine-oxide tends to show highly exothermic decomposition reactions and these d~ i tion reactions may be induced or accelerated by certain substances. These substances have to be removed f rom the precipitation bath which is to be regenerated before the N~O is concentrated and separated.
In addition to these substances, in the amine-oxide process also substances in a colloidal state may occur. Moreover, coatings may form at the walls of pipes and the like which may impair the flow and may even lead to an obstruction of the pipe.
After removing these unwanted substances, water is withdrawn from the purified precipitation bath which optionally is combined with other process liquids of the amine-oxide process such as vapour condensates formed during the production of the cellulose solution. This may be carried out CA ~2202624 l997-04-l4 for instance by means of evaporation. In the residue of this evaporation, highly concentrated aqueous amine-oxide is produced which is rècycled again into the amine-oxide process .
In the state of the art, no step is known whereby the above formation of coatings at walls of pipes can be effectively prevented. It is the object of the present invention to carry out the amine-oxide process such that the formation of these coatings ls prevented.
The process according to the invention f or the production of an aqueous amine-oxide solution used in the amine-oxide process for the production of a mouldable cellulose solution, wherein aqueous, amine-oxide containing solutions produced in the amine-oxide process particularly as precipitation baths are purified and concentrated, is characterized in that a microbicide agent is added to the aqueous, amine-oxide containing solutions before, during or after purification.
The invention is based on the finding that the formation of coatings is caused by microorganisms and consists substantially of biological substances. As microorganisms, particularly bacteria, yeasts, fungi and algae have been found. This is surprising since for some decades it was considered that tertiary amine-oxides generally have a microbicide effect ~Stupavska, S., Acta Fac. Rer. Nat. Univ.
Comen, 1980, pages 85ff) and that they are not biodegradable.
Only recently it has been found out that NMMO can be degraded in a biological sewage plant (H. Firgo, M. Eibl, W. Ralt, G.
Meister: Rritische Fragen zur Zukunft der ~MMO-Technologie", Lenzinger Berichte 9/94, pages 81ff). Therefore it is all the more surprising for those skilled in the art that microorganisms are capable of surviving in a variety of NMMO
solutions of the amine-oxide process wherein ~MMO is present in a much higher concentration than in a sewage plant, may even propagate and~ thus cause the formation of coatings.
When a microbicide agent acting on these microorganisms is added to the amine-oxide process, the formation of the unwanted biological substances and thus the formation of wall coatings may be effectively prevented.
As microbicide agents, preferably fungicides, algicides and bactericides are used.
As microbicide agents, the following agents have shown particularly good results: agents of the aliphatic aldehyde group, aromatic aldehydes, thi~l;R7;n derivatives, tetramethylolacetylen urea, hydroxy ethylphenyl ethers, organobromine ~ ullds, polyhexamethylene-biguanide-hydrochloride, sodium azide, 11YdLUY~il peroxide and peracetic acid, ortho-phth~ lohyde or glutaraldehyde being particularly pref erred .
It is evident to those skilled in the art that the type and concentration of the microbicide agents will vary for each individual case. The effective dosage for each individual case however may be easily determined by testing. It has been shown that the effective amount generally lies in the range of from 10 to 500 ppm.
The invention is further concerned with a process for the production of cellulose moulded bodies according to the amine-oxide process, wherein a cellulose suspension and finally a mouldable solution are produced from an aqueous solution of an amine-oxide and shredded cellulose, which solution is moulded and passed into a precipitation bath, a spent precipitation bath and cellulose moulded bodies being produced, said spent precipitation bath being purified and repassed to an aqueous solution ûf the amine-oxide which is repassed to the amine-oxide process, characterized in that the process is carried out at least partially in the presence of a microbicide agent.
By means of the following Examples, the invention will be described in more detail.
Example 1 ( Control ) A spent precipitation bath of the NM~qO process containing 20%
by weight of NMMO was lightly shaken for 24 hours at 25 C.
Afterwards, the germination index/ml was detl~rm; nf~d by means of the test described below.
Determination of the germination index/ml To determine the germination index/ml, 1 ml of each of the solutions was pipetted into a sterile Petri dish and carefully mixed with agar medium. Afterwards the samples were incubated for 3 days at 37C. After incubation, the entire surface of the Petri dish was counted for germs with the naked eye, and the number obtained was based on 1 ml of sample . -- -Dishes exhibiting 20 to 300 germs may be evaluated. When moregerms were present, the determination was repeated in an appropriate dilution.
A germination index/ml of 2,200,000 was determined.
To determine the effect of microbicide agents, Example 1 was repeated with the substances indicated in the Table using the indicated concentratlons.- The germination indices obtained in each case are also shown in the Table.
Tabl e Example Substance Concentration (ppm) Germination index/ml ------ ------ 2,200,000 2 A 1,000 0 B 1,000 0 CA 02202624 l997-04-l4 6 s loO ~ 3 8 C l,OOo o g C 1oo 160,000 lo c 20 790,000 11 D 1,000 1,800 12 D loo 460,000 13 D 20 1,330,ooo 14 E 1,000 8,200 15 F l, ooo 87 A = ortho-phthalaldehyde;
s = glutaraldehyde;
C = 3,5-dimethylperhydro-1,3,5-~h;~ 7ine-2-thion;
D = tetramethylolacetylendiurea F = 2, 2-dibromo-3-nitrilo-propionamide .
Similarly good results could be obtained with polyhexamethyle~biguanid-hydrochloride and sodium azide.
TERTIARY AMI~E-oxIDE
The present invention is concerned with a process f or the production of an aqueous amine-oxide solution used in the amine-oxide process for the production of a mouldable cellulose solution, wherein aqueous, amine-oxide containing solutions produced in the amine-oxide process particularly as precipitation baths are purified and concentrated.
For some decades there has been searched for processes for the production of cellulose moulded bodies able to substitute the viscose process, today widely employed. As an alternative which is interesting for its reduced environmental impact among other reasons, it has been found to dissolve cellulose without derivatisation in an organic solvent and extrude from this solution moulded bodies, e.g. fibres, films and other moulded bodies. Fibres thus extruded have received by BISFA
(The International Bureau for the Standardization of man made fibers) the generic name Lyocell. By an organic solvent, BISFA understands a mixture of an organic chemical and water.
It has turned out that as an organic solvent, a mixture of a tertiary amine-oxide and water is particularly appropriate for the production of cellulose moulded bodies. As the amine-oxide, primarily N-methylmorpholine-N-oxide lNM~O) is used.
Other amine-oxides are described e.g. in EP-A - 0 553 070. A
process for the production of mouldable cellulose solutions is known e.g. from EP-A - 0 356 419. For the purposes of the present specification and the present claims, the production of cellulose moulded bodies using tertiary amine-oxides generally is referred to as amine-oxide process.
In EP-A - O 356 419, an amine-oxide process for the production of spinnable cellulose solutions is described, wherein as a starting material among others a suspension of cellulose in liquid, aqueous N-methylmorpholine-N-oxide (NlqMO) is used. This process consists in transforming the suspension in a thin-film treatment apparatus in one single step and continuously into a mouldable solution. Finally, the mouldable solution is spun into fi 1. ~s by a forming tool such as a spinneret and the ~i 7 ~r t.S are passed through a precipitation bath.
In the precipitation bath the cellulose is precipitated. The tertiary amine-oxide is accumulated in the precipitation bath. The precipitation bath may contain up to 30~ by weight of amine-oxide. For the economy of the amine-oxide process it is of vital importance to recover the amine-oxide as completely as possible and reuse it for the production of a mouldable cellulose solution. Thus it is necessary to recover NMMO from the precipitation bath.
In addition to the amine-oxide however, degradation products of the amine-oxide are also accumulated in the precipitation bath. These degradation products may be intensively coloured, thus deteriorating the quality of the cellulose moulded bodies produced. On the other hand, other substances may represent an additional safety risk, since under certain conditions the amine-oxide tends to show highly exothermic decomposition reactions and these d~ i tion reactions may be induced or accelerated by certain substances. These substances have to be removed f rom the precipitation bath which is to be regenerated before the N~O is concentrated and separated.
In addition to these substances, in the amine-oxide process also substances in a colloidal state may occur. Moreover, coatings may form at the walls of pipes and the like which may impair the flow and may even lead to an obstruction of the pipe.
After removing these unwanted substances, water is withdrawn from the purified precipitation bath which optionally is combined with other process liquids of the amine-oxide process such as vapour condensates formed during the production of the cellulose solution. This may be carried out CA ~2202624 l997-04-l4 for instance by means of evaporation. In the residue of this evaporation, highly concentrated aqueous amine-oxide is produced which is rècycled again into the amine-oxide process .
In the state of the art, no step is known whereby the above formation of coatings at walls of pipes can be effectively prevented. It is the object of the present invention to carry out the amine-oxide process such that the formation of these coatings ls prevented.
The process according to the invention f or the production of an aqueous amine-oxide solution used in the amine-oxide process for the production of a mouldable cellulose solution, wherein aqueous, amine-oxide containing solutions produced in the amine-oxide process particularly as precipitation baths are purified and concentrated, is characterized in that a microbicide agent is added to the aqueous, amine-oxide containing solutions before, during or after purification.
The invention is based on the finding that the formation of coatings is caused by microorganisms and consists substantially of biological substances. As microorganisms, particularly bacteria, yeasts, fungi and algae have been found. This is surprising since for some decades it was considered that tertiary amine-oxides generally have a microbicide effect ~Stupavska, S., Acta Fac. Rer. Nat. Univ.
Comen, 1980, pages 85ff) and that they are not biodegradable.
Only recently it has been found out that NMMO can be degraded in a biological sewage plant (H. Firgo, M. Eibl, W. Ralt, G.
Meister: Rritische Fragen zur Zukunft der ~MMO-Technologie", Lenzinger Berichte 9/94, pages 81ff). Therefore it is all the more surprising for those skilled in the art that microorganisms are capable of surviving in a variety of NMMO
solutions of the amine-oxide process wherein ~MMO is present in a much higher concentration than in a sewage plant, may even propagate and~ thus cause the formation of coatings.
When a microbicide agent acting on these microorganisms is added to the amine-oxide process, the formation of the unwanted biological substances and thus the formation of wall coatings may be effectively prevented.
As microbicide agents, preferably fungicides, algicides and bactericides are used.
As microbicide agents, the following agents have shown particularly good results: agents of the aliphatic aldehyde group, aromatic aldehydes, thi~l;R7;n derivatives, tetramethylolacetylen urea, hydroxy ethylphenyl ethers, organobromine ~ ullds, polyhexamethylene-biguanide-hydrochloride, sodium azide, 11YdLUY~il peroxide and peracetic acid, ortho-phth~ lohyde or glutaraldehyde being particularly pref erred .
It is evident to those skilled in the art that the type and concentration of the microbicide agents will vary for each individual case. The effective dosage for each individual case however may be easily determined by testing. It has been shown that the effective amount generally lies in the range of from 10 to 500 ppm.
The invention is further concerned with a process for the production of cellulose moulded bodies according to the amine-oxide process, wherein a cellulose suspension and finally a mouldable solution are produced from an aqueous solution of an amine-oxide and shredded cellulose, which solution is moulded and passed into a precipitation bath, a spent precipitation bath and cellulose moulded bodies being produced, said spent precipitation bath being purified and repassed to an aqueous solution ûf the amine-oxide which is repassed to the amine-oxide process, characterized in that the process is carried out at least partially in the presence of a microbicide agent.
By means of the following Examples, the invention will be described in more detail.
Example 1 ( Control ) A spent precipitation bath of the NM~qO process containing 20%
by weight of NMMO was lightly shaken for 24 hours at 25 C.
Afterwards, the germination index/ml was detl~rm; nf~d by means of the test described below.
Determination of the germination index/ml To determine the germination index/ml, 1 ml of each of the solutions was pipetted into a sterile Petri dish and carefully mixed with agar medium. Afterwards the samples were incubated for 3 days at 37C. After incubation, the entire surface of the Petri dish was counted for germs with the naked eye, and the number obtained was based on 1 ml of sample . -- -Dishes exhibiting 20 to 300 germs may be evaluated. When moregerms were present, the determination was repeated in an appropriate dilution.
A germination index/ml of 2,200,000 was determined.
To determine the effect of microbicide agents, Example 1 was repeated with the substances indicated in the Table using the indicated concentratlons.- The germination indices obtained in each case are also shown in the Table.
Tabl e Example Substance Concentration (ppm) Germination index/ml ------ ------ 2,200,000 2 A 1,000 0 B 1,000 0 CA 02202624 l997-04-l4 6 s loO ~ 3 8 C l,OOo o g C 1oo 160,000 lo c 20 790,000 11 D 1,000 1,800 12 D loo 460,000 13 D 20 1,330,ooo 14 E 1,000 8,200 15 F l, ooo 87 A = ortho-phthalaldehyde;
s = glutaraldehyde;
C = 3,5-dimethylperhydro-1,3,5-~h;~ 7ine-2-thion;
D = tetramethylolacetylendiurea F = 2, 2-dibromo-3-nitrilo-propionamide .
Similarly good results could be obtained with polyhexamethyle~biguanid-hydrochloride and sodium azide.
Claims (5)
1. A process for the production of an aqueous amine-oxide solution used in the amine-oxide process for the production of a mouldable cellulose solution, wherein aqueous, amine-oxide containing solutions produced in said amine-oxide process particularly as precipitation baths are purified and concentrated, characterized in that a microbicide agent is added to said aqueous, amine-oxide containing solutions before, during or after purification.
2. A process according to Claim 1, characterized in that a microbicide agent selected from the group of fungicides, algicides and bactericides is used.
3. A process according to Claim 2, characterized in that said microbicide agent is selected from the group of aliphatic aldehydes, aromatic aldehydes, thiadiazin derivatives, tetramethylolacetylen urea, hydroxy ethylphenyl ethers, organobromine compounds, polyhexamethylene-biguanide-hydrochloride, sodium azide, hydrogen peroxide and peracetic acid.
4. A process according to Claim 3, characterized in that as said microbicide agent ortho-phthalaladehyde or glutaraldehyde is used.
5. A process for the production of cellulose moulded bodies according to the amine-oxide process, wherein a cellulose suspension and finally a mouldable solution are produced from an aqueous solution of an amine-oxide and shredded cellulose, said solution being moulded and passed into a precipitation bath, a spent precipitation bath and cellulose moulded bodies being produced, said spent precipitation bath being purified and regenerated to an aqueous solution of said amine-oxide which is repassed to said amine-oxide process, characterized in that said process is carried out at least partially in the presence of a microbicide agent.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT0139995A AT402511B (en) | 1995-08-18 | 1995-08-18 | METHOD FOR PRODUCING AN AQUEOUS AMINOXIDE SOLUTION |
| ATA1399/95 | 1995-08-18 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2202624A1 true CA2202624A1 (en) | 1997-02-27 |
Family
ID=3513045
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002202624A Abandoned CA2202624A1 (en) | 1995-08-18 | 1996-08-16 | Process for producing an aqueous amine oxide solution |
Country Status (15)
| Country | Link |
|---|---|
| EP (1) | EP0787152B1 (en) |
| JP (1) | JPH10507489A (en) |
| KR (2) | KR100430919B1 (en) |
| CN (2) | CN1078890C (en) |
| AT (2) | AT402511B (en) |
| BR (1) | BR9606590A (en) |
| CA (1) | CA2202624A1 (en) |
| DE (1) | DE59600070D1 (en) |
| ES (1) | ES2114756T3 (en) |
| GR (1) | GR3026140T3 (en) |
| MY (1) | MY118332A (en) |
| NO (1) | NO310834B1 (en) |
| TW (2) | TWI243180B (en) |
| WO (1) | WO1997007137A1 (en) |
| ZA (1) | ZA966709B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3051709B2 (en) * | 1997-09-30 | 2000-06-12 | 憲司 中村 | Antimicrobial cellulose fiber and method for producing the same |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8819603D0 (en) * | 1988-08-17 | 1988-09-21 | Elopak Systems | Filling of containers |
| AT396930B (en) * | 1992-01-23 | 1993-12-27 | Chemiefaser Lenzing Ag | AMINOXIDE |
| AT399348B (en) * | 1993-05-05 | 1995-04-25 | Chemiefaser Lenzing Ag | FORM- OR SPIDING MASS CONTAINING CELLULOSE AND USE OF CERTAIN SUBSTANCES FOR YOUR STABILIZATION |
-
1995
- 1995-08-18 AT AT0139995A patent/AT402511B/en not_active IP Right Cessation
-
1996
- 1996-07-30 TW TW088105439A patent/TWI243180B/en not_active IP Right Cessation
- 1996-07-30 TW TW085109298A patent/TW379229B/en not_active IP Right Cessation
- 1996-08-02 MY MYPI96003187A patent/MY118332A/en unknown
- 1996-08-07 ZA ZA9606709A patent/ZA966709B/en unknown
- 1996-08-16 WO PCT/AT1996/000149 patent/WO1997007137A1/en active IP Right Grant
- 1996-08-16 KR KR1019970702555A patent/KR100430919B1/en not_active IP Right Cessation
- 1996-08-16 AT AT96926963T patent/ATE161853T1/en not_active IP Right Cessation
- 1996-08-16 KR KR10-2003-7016959A patent/KR100451306B1/en not_active IP Right Cessation
- 1996-08-16 DE DE59600070T patent/DE59600070D1/en not_active Expired - Lifetime
- 1996-08-16 CA CA002202624A patent/CA2202624A1/en not_active Abandoned
- 1996-08-16 BR BR9606590A patent/BR9606590A/en not_active IP Right Cessation
- 1996-08-16 JP JP9508736A patent/JPH10507489A/en not_active Ceased
- 1996-08-16 EP EP96926963A patent/EP0787152B1/en not_active Expired - Lifetime
- 1996-08-16 ES ES96926963T patent/ES2114756T3/en not_active Expired - Lifetime
- 1996-08-16 CN CN96190931A patent/CN1078890C/en not_active Expired - Lifetime
-
1997
- 1997-04-15 NO NO19971722A patent/NO310834B1/en not_active IP Right Cessation
-
1998
- 1998-02-12 GR GR980400313T patent/GR3026140T3/en unknown
-
2001
- 2001-06-30 CN CNB011225173A patent/CN1214138C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| GR3026140T3 (en) | 1998-05-29 |
| TWI243180B (en) | 2005-11-11 |
| ZA966709B (en) | 1997-02-18 |
| CN1358888A (en) | 2002-07-17 |
| CN1161044A (en) | 1997-10-01 |
| ATE161853T1 (en) | 1998-01-15 |
| EP0787152B1 (en) | 1998-01-07 |
| AU714801B2 (en) | 2000-01-13 |
| NO310834B1 (en) | 2001-09-03 |
| CN1078890C (en) | 2002-02-06 |
| WO1997007137A1 (en) | 1997-02-27 |
| DE59600070D1 (en) | 1998-02-12 |
| BR9606590A (en) | 1997-11-18 |
| MY118332A (en) | 2004-10-30 |
| NO971722L (en) | 1997-06-10 |
| EP0787152A1 (en) | 1997-08-06 |
| KR100430919B1 (en) | 2004-09-04 |
| JPH10507489A (en) | 1998-07-21 |
| CN1214138C (en) | 2005-08-10 |
| NO971722D0 (en) | 1997-04-15 |
| ATA139995A (en) | 1996-10-15 |
| KR100451306B1 (en) | 2004-10-11 |
| AU6695796A (en) | 1997-03-12 |
| AT402511B (en) | 1997-06-25 |
| TW379229B (en) | 2000-01-11 |
| ES2114756T3 (en) | 1998-06-01 |
| KR20040020941A (en) | 2004-03-09 |
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