CN86107461A - Method for preparing fish skin - Google Patents
Method for preparing fish skin Download PDFInfo
- Publication number
- CN86107461A CN86107461A CN86107461.0A CN86107461A CN86107461A CN 86107461 A CN86107461 A CN 86107461A CN 86107461 A CN86107461 A CN 86107461A CN 86107461 A CN86107461 A CN 86107461A
- Authority
- CN
- China
- Prior art keywords
- skin
- fish
- leather
- tanning
- body lotion
- 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.)
- Withdrawn
Links
- 238000000034 method Methods 0.000 title claims abstract description 27
- 241000251468 Actinopterygii Species 0.000 title abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 150000003839 salts Chemical class 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 7
- 238000005238 degreasing Methods 0.000 claims abstract description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 5
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 238000005554 pickling Methods 0.000 claims abstract description 5
- 102000004190 Enzymes Human genes 0.000 claims abstract description 3
- 108090000790 Enzymes Proteins 0.000 claims abstract description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 3
- 239000011651 chromium Substances 0.000 claims abstract description 3
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 3
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 3
- 239000010985 leather Substances 0.000 claims description 32
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 18
- 239000006210 lotion Substances 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 239000007859 condensation product Substances 0.000 claims description 8
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 6
- 239000000839 emulsion Substances 0.000 claims description 6
- 238000011049 filling Methods 0.000 claims description 6
- 150000002191 fatty alcohols Chemical class 0.000 claims description 4
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 3
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 3
- -1 alkali metal hydrosulfide Chemical class 0.000 claims description 3
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 239000004571 lime Substances 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 206010040844 Skin exfoliation Diseases 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 150000001449 anionic compounds Chemical class 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 239000000991 leather dye Substances 0.000 claims description 2
- 229910052976 metal sulfide Inorganic materials 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 208000010744 skin desquamation Diseases 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- 238000004043 dyeing Methods 0.000 abstract description 3
- 159000000013 aluminium salts Chemical class 0.000 abstract description 2
- 229910000329 aluminium sulfate Inorganic materials 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract description 2
- 229940124091 Keratolytic Drugs 0.000 abstract 1
- 150000001340 alkali metals Chemical class 0.000 abstract 1
- 125000000129 anionic group Chemical group 0.000 abstract 1
- 125000003118 aryl group Chemical group 0.000 abstract 1
- 150000001844 chromium Chemical class 0.000 abstract 1
- 230000001530 keratinolytic effect Effects 0.000 abstract 1
- 238000003756 stirring Methods 0.000 abstract 1
- 102000008186 Collagen Human genes 0.000 description 6
- 108010035532 Collagen Proteins 0.000 description 6
- 241000124008 Mammalia Species 0.000 description 6
- 229920001436 collagen Polymers 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- 241000938605 Crocodylia Species 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 241000251730 Chondrichthyes Species 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 235000011116 calcium hydroxide Nutrition 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- 235000013311 vegetables Nutrition 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- FEPBITJSIHRMRT-UHFFFAOYSA-N 4-hydroxybenzenesulfonic acid Chemical compound OC1=CC=C(S(O)(=O)=O)C=C1 FEPBITJSIHRMRT-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 241000283707 Capra Species 0.000 description 1
- 241000628997 Flos Species 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- 102000011782 Keratins Human genes 0.000 description 1
- 108010076876 Keratins Proteins 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 241001494479 Pecora Species 0.000 description 1
- 241000269799 Perca fluviatilis Species 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 241000282898 Sus scrofa Species 0.000 description 1
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 210000003038 endothelium Anatomy 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- YZMHQCWXYHARLS-UHFFFAOYSA-N naphthalene-1,2-disulfonic acid Chemical compound C1=CC=CC2=C(S(O)(=O)=O)C(S(=O)(=O)O)=CC=C21 YZMHQCWXYHARLS-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C3/00—Tanning; Compositions for tanning
- C14C3/02—Chemical tanning
- C14C3/28—Multi-step processes
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
A method of preparing fish skin comprising: descaling and at least partially degreasing in an aqueous liquid containing one or more surface-active anionic, nonionic or amphoteric organic compounds, treating the fish skin in a second bath comprising a keratolytic enzyme or an alkali metal sulphide by stirring, then degreasing, pretanning the fish skin with an aromatic syntan at a temperature below 20 ℃ and a pH of 5-8, pickling the fish skin in a pickling bath comprising acid and salt, pH1.5-4, tanning the fish skin with a chromium salt and/or syntan liquid, washing with water after standing, retanning the fish skin with chromium or aluminium salt and/or syntan, dyeing, oiling, and drying.
Description
The present invention relates to a kind of method for preparing fish-skin.
The preparation of animal's leather generally includes the exposure of endothelium or corium, can optionally select for use to give again and tan, and then is that tanning and the leather that comprises dyeing, emulsion oil-filling, drying, ornamenting and mechanical workout etc. are handled afterwards.
Although there is high development now, prepare the technology of leather by skin of mammal such as ox, pig, sheep and goat for example,, except that the shark skin, all difficulties that cause owing to the special construction by collagen within the fish make people ignore the fish-skin process hides.Anticorrosion by comprising, dry, immersion is softening and use lime treatment respectively in water-bath, promptly decompose keratic removing and remove floss (depilating) by calcium hydroxide and sodium sulphite, deliming, the so-called sashimi (raw fish) skin of washing and pickling etc. in containing the acid and the liquid of salt respectively give treatment process and containing chromic salts for example or the tanning drum of the flexibility material of vegetable tanning material in tanning, further washing, emulsion oil-filling, dry, optional dyeing and mechanical treatment (ornamenting) etc. can make soft easily bent fish-skin leather or very hard usually, be similar to the fish-skin leather of Reptilia leather, have flexibility and the good fish-skin leather of intensity simultaneously but can not make.
Know for No. 2700590 by United States Patent (USP), at the problem of fish skin collagen facile hydrolysis and use tanning agent with high converging action, for example the composition of certain plants extract and Phenylsulfonic acid/formaldehyde condensation products carries out tanning to teleost, shark and mammiferous skin.Thereby this makes leather tanning also to play preservative activity, but this leather becomes very hard, and it is similar to the Reptilia leather, lacks pliability and flexibility.In addition, silent skin de-scaling and remove Keratin sulfate and other protein etc. have then constituted the subject matter in the tanning fish skin.
Also have, carry out tanning fish skin in the following manner No. 4379708 according to United States Patent (USP): the pH value of skin is adjusted to 1.5～3.5 tannings in two steps then, at first be no more than under 35 ℃ the temperature with rare owse tanning, using the stock liquor tanning above under 35 ℃ the temperature at last, then be washing, emulsion oil-filling and the pH value of skin adjusted to be at least 6 that prepared leather has certain flexibility.The aspects such as necessary intensity of leather products chemical astringent matter effect in good breaking strength, plentiful feel and pliability and anti-technological process all do not reach requirement.
In No. 729242, French Patent, disclose a kind of method of tanning fish-skin, used synthetic tanning agent earlier, then used vegetable tanning agent or both mixtures carry out tanning, thereupon with chrome tanning according to this method.Yet, both do not reached desired leather softness in this way and failed to reach desired leather flexure degree yet.
Because the molecular structure of fish skin collagen and the molecular structure difference of Mammals collagen are very big, so the method for the method of tanning fish-skin and tanning skin of mammal is very inequality.Fish skin collagen has the linear chain structure opposite with the branched structure of Mammals collagen.This point is closed by the chain of tanning with regard to having illustrated at them, exists marked difference with regard to the intensity of hydrolysis temperature and tensile strength.Also have, serious difference is also arranged between the hydrolysis temperature of their skins.Its hydrolysis temperature of the fish-skin of nearly all fish is lower about 20 ℃ than skin of mammal.This means that with regard to fish-skin all process steps before its tanning all must be to carry out than recommending to be used for giving the low temperature below 20 ℃ of processing skin of mammal temperature.
The purpose of this invention is to provide and a kind ofly prepare softness by fish-skin and easily rub and still have the method for high-intensity leather.
Another purpose of the present invention provides a kind of method that can processing be subject to the fish-skin of processing conditions influence, and this class fish-skin is can not be with the additive method processing known in the prior art.
The inventive method is characterised in that:
A) be at least degreasing partly with the fish-skin desquamation and in the body lotion that in a spot of water, contains one or more surface-active negatively charged ion, nonionic or both sexes organic compound.
B) handle fish-skin by being stirred in the second kind of body lotion that contains dissolved ceratinase or alkali metalsulphide and/or alkali metal hydrosulfide, lime and water, further can be optionally by adding the sulfide precipitation agent removing sulfide,
C) with having surface-active nonionic and/or anionic compound and/or solvent and/or enzyme, with step (b) simultaneously or in independent body lotion with the fish-skin degreasing,
D) be to give the fish-skin of tanning under 5～8 the condition at the temperature, the pH value that are lower than 20 ℃ with the aromatics synthetic tanning agent,
E) contain acid and salt, pH value be in 1.5～4 the body lotion with the fish-skin pickling,
F) itself being known mode with chromic salts and/or synthetic tanning agent liquid tanning fish-skin, and
G) at the after dates that leaves standstill of a few hours, can choose wantonly and wash and, follow, if necessary with chromium or aluminium salt and/or synthetic tanning agent retanning fish-skin, leather dyes and carries out emulsion oil-filling with itself oneself for known mode, dry then with make further mechanical treatment.
According to a preferred embodiment of the present invention, in step a), alkylene oxide and C arranged as what surface active cpd used
5～C
20Condenses, high-grade aliphatic ester and the C of alkanol
5～C
20The sulfonate or the vitriol of condenses, fat or Fatty Alcohol(C12-C14 and C12-C18) of alkanol.
According to another preferred embodiment, carry out giving in the step d) with the condensation product of aromatics one, two or trisulfonic acid and formaldehyde and tan.Preferred one, two or ternary sulfonic acid be the derivative of phenol, naphthalene and/or lignin.
Although the present invention uses oneself knows in the leather production chemicals and treatment solution, the present invention is in the order of using and to be at least aspect the processing condition partly be that leather production with routine is different.Fish-skin can be processed to and can be surprising and really not be conspicuous for the high-quality leather of any purposes.
Embodiment:
The inventive method is used to Brazil's thorn perch skin that tanning belongs to Seranidae family.
The amount that provides is meant the consumption when handling 1000 gram fresh hides or moisture regain skin.
A) skin is being contained 5～12 alkylene oxide and the C that restrain
8～C
12The rotary drum for processing 15～60 minutes of the mixture of the condensation product of alkanol and 50～100 gram water reaches 100～300% and carries out the washing of leather by adding water to liquor ratio then.
B) in order to make collegen filament loose before tanning, the skin in rotary drum adds 1000～3000 gram water, 3～5 gram sodium sulphite and 6～14 gram calcium hydroxides, and this body lotion is rotated 20～60 minutes, reaches 20 minutes at least with big water gaging flushing leather subsequently.
C) add 1000～2000 gram water and 15～30 gram inorganic salt to the leather that cleaned, the alkaline sulfides that adds in this salt and the preceding operation reacts and forms insoluble salt, for example lime carbonate.And then add the soluble sodium salt of 3～8 gram organic acids (being sulfocarbolic acid), body lotion was rotated 20～30 minutes, until the chemicals that in step b), uses whole when precipitated till, the leather of water flushing after this 15 minutes.
A) add 1000 gram water and 5～15 grams can be in the temperature below 19 ℃ to the leather that cleaned, pH value is the formaldehyde and the condensation product of phenol or naphthalene that works under the condition between 5～8, continues the rotation rotary drum and makes this processing process repeat 15～45 minutes.Add 2000 gram water and 140 gram sodium-chlor subsequently, and rotary drum was further rotated 15 minutes.Add 18 gram acid then, preferably organic acid is that formic acid (other acid for example mineral acid also can be used) makes pH value reach 1.5～3.5, body lotion is rotated 120～180 minutes again.
E) add 25～40 gram tanning agents to body lotion, preferably basicity is 33% chromium sulphate.Hocket static and rotation, be about whole process periods of 12 hours until finishing.Though body lotion can be used further at subsequent processing, but it is removed and further process with new body lotion
F) use alkalization in due form, basicity is that 33% concentration is that 9% the new body lotion of chromic salts carries out conventional chrome tanning, leather is placed on leaves standstill 8 hours on the shelf then.
G) with the mixture retanning leather of two kinds of synthetic tanning agentes, this two kinds of condensation products that synthetic tanning agent is formaldehyde and different organic acids, i.e. mixture of glutaraldehyde and naphthalene disulfonic acid/formaldehyde condensation products.
After this use usual method ornamenting leather, leather is carried out emulsion oil-filling and mechanical treatment.
Finished product leather has the intensity that is similar to the Reptilia leather, but it is flexible and flexible at aspect such as wrinkling as the high-quality leather.
Claims (6)
1. prepare the method for fish-skin leather, it is characterized in that:
A), and in the body lotion that in a spot of water, contains one or more surface-active negatively charged ion, nonionic or both sexes organic compound, be at least degreasing partly with the fish-skin desquamation,
B) handle fish-skin by being stirred in to contain in dissolved ceratinase or alkali metalsulphide and/or alkali metal hydrosulfide, lime and second kind of body lotion of water, and then can optionally remove sulfide by adding the sulfide precipitation agent, and the washing fish-skin,
C) with surface-active nonionic and/or anionic compound and/or solvent and/or enzyme, with step b) simultaneously or in independent body lotion with the fish-skin degreasing,
D) with the aromatics synthetic tanning agent in the temperature that is lower than 20 ℃, pH value is to give the fish-skin of tanning under 5～8 the condition,
E) contain acid and salt, pH value be in 1.5～4 the body lotion with the fish-skin pickling,
F) with itself with by known mode with chromic salts and/or synthetic tanning agent liquid tanning fish-skin, and
G) at the after date that leaves standstill of a few hours, can choose washing wantonly and with chromium or salt and/or synthetic tanning agent retanning fish-skin, then, if necessary, the mode that leather dyes and oneself knows with itself is carried out emulsion oil-filling, dry then and make further mechanical treatment.
2. as said method in the claim 1, that it is characterized in that in step a) using as surface active cpd is a kind of alkylene oxide and C
5～C
20The sulfonate of the condensation product of alkanol or a kind of fat or Fatty Alcohol(C12-C14 and C12-C18) or vitriol.
3. as said method in the claim 1, it is characterized in that condensation product with aromatics one, two or trisulfonic acid and formaldehyde carries out giving in the step d) and tans.
4. as said method in the claim 3, it is characterized in that aromatics one, two or trisulfonic acid are by phenol, naphthalene and xylogen deutero-.
5. as said method in the claim 1, it is characterized in that step d) and f) in same body lotion, carry out.
6. according to the fish-skin leather of said method preparation in the claim 1～5.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3534353.2 | 1985-09-26 | ||
| DE19853534353 DE3534353A1 (en) | 1985-09-26 | 1985-09-26 | METHOD FOR PRODUCING FISH LEATHER |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN86107461A true CN86107461A (en) | 1987-07-29 |
| CN1004078B CN1004078B (en) | 1989-05-03 |
Family
ID=6282023
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN86107461.0A Expired CN1004078B (en) | 1985-09-26 | 1986-09-24 | Method for preparing fish skin |
Country Status (4)
| Country | Link |
|---|---|
| KR (1) | KR870003208A (en) |
| CN (1) | CN1004078B (en) |
| ES (1) | ES2000622A6 (en) |
| ZA (1) | ZA867268B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103284211A (en) * | 2013-05-10 | 2013-09-11 | 德炎水产食品股份有限公司 | Pickled chili fish skin and preparation method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2447158C1 (en) * | 2010-09-30 | 2012-04-10 | Российская Федерация, От Имени Которой Выступает Министерство Промышленности И Торговли Российской Федерации | Method of processing sheepskins |
-
1986
- 1986-09-24 ZA ZA867268A patent/ZA867268B/en unknown
- 1986-09-24 CN CN86107461.0A patent/CN1004078B/en not_active Expired
- 1986-09-26 ES ES8602228A patent/ES2000622A6/en not_active Expired
- 1986-09-26 KR KR1019860008086A patent/KR870003208A/en not_active Application Discontinuation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103284211A (en) * | 2013-05-10 | 2013-09-11 | 德炎水产食品股份有限公司 | Pickled chili fish skin and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1004078B (en) | 1989-05-03 |
| ES2000622A6 (en) | 1988-03-01 |
| KR870003208A (en) | 1987-04-15 |
| ZA867268B (en) | 1987-05-27 |
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| C13 | Decision | ||
| GR02 | Examined patent application | ||
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| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
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