CN1385413A - Composition containing conjugated calcium linoleate and making method thereof - Google Patents
Composition containing conjugated calcium linoleate and making method thereof Download PDFInfo
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- CN1385413A CN1385413A CN02110430A CN02110430A CN1385413A CN 1385413 A CN1385413 A CN 1385413A CN 02110430 A CN02110430 A CN 02110430A CN 02110430 A CN02110430 A CN 02110430A CN 1385413 A CN1385413 A CN 1385413A
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Abstract
The compound containing conjugated calcium linoleate is a white or light yellow powder, and its composition includes (wt%) 30-80% of conjugated linolic acid acyl group containing cis-9 trans-11-conjugated linolic acid acyl group whose content is 15-40% of trans-10 cis-12-conjugated linolic acid acyl group whose content is 40-15% which are isomer of linolic acid mutually; 5-8% of calcium, 13-53% of other fatty acid acyl group and 2-9% of water. On the basis of equipment for producing conjugated linolic acid it adopts alkali isomerization, simultaneous saponification and calcification process to prepare compound containing conjugated calcium linoleate in same equipment. Said compound can be used as additive for food, functional food, cosmetics and feed, etc.
Description
(1) technical field
The present invention relates to the improvement of linolic acid technology, specifically is a kind of composition and manufacture method thereof that contains calcium conjugated linoleic acid, and it belongs to technological field of biochemistry.
(2) background technology
In the prior art, Chinese patent (publication number 1270160) being arranged, disclosed refining polyunsaturated fatty acid and polyunsaturated fatty acid calcium medicinal products, is that the form with lipid acid and calcium salt thereof exists.Preparation technology is mainly saponification, precipitation, filtration, acidifying etc., and raw material is a vegetables oil, and precipitation is to adopt ethanol, in polyunsaturated fatty acid calcium preparation technology polyunsaturated fatty acid sodium is changed into polyunsaturated fatty acid calcium through acidifying back end hydrogenation calcium oxide.The preparation of refining polyunsaturated fatty acid and polyunsaturated fatty acid calcium medicinal products for said products and pharmaceutical excipient, is made pharmaceutically acceptable formulation.These goods have saturated fatty acid and monounsaturated fatty acids content is lower, characteristics such as two unsaturated fatty acidss and linolenic acid content height.Also have Chinese patent (publication number CN1287114) to disclose the technology of preparing of utilizing glycerine to prepare conjugated linolic acid and conjugated linoleic acid microcapsule as solvent.Traditional conjugated linolic acid (being called for short CLA) all is that liquid form exists.
In the above-mentioned document, relate in the manufacture method of fatty acid calcium, do not relate to the manufacturing of calcium conjugated linoleic acid.And do not relate to the manufacturing of calcium conjugated linoleic acid among the relevant conjugated linolic acid preparation method yet.
(3) technology contents
The objective of the invention is kind and broadened application scope for further increase conjugated linolic acid product, development function food, poultry, domestic animal functional feed are developed the solid-state composition that contains calcium conjugated linoleic acid.
Task of the present invention is realized by following technical scheme, has developed a kind of composition that contains calcium conjugated linoleic acid, and this product is white or buff powder; Its weight percent consists of: contain the suitable-9 of linoleic acid isomers each other, anti--11-conjugated linolic acid acyl group, its content is 15---and 40%, and trans-10, suitable-12-conjugated linolic acid acyl group, its content is 40---and 15%; Conjugated linolic acid acyl group total content 30---80%; Calcium contents 5---8%; Other fatty acid acyl total contents 13---53%; Moisture 2---9%.Described other fatty acid acyls include: palmitinic acid acyl group, stearic acid acyl group, oleic acid acyl group, linolic acid acyl group.
Calcium conjugated linoleic acid chemical structural formula in this product:
Suitable-9, anti--the 11-calcium conjugated linoleic acid
Trans-10, suitable-the 12-calcium conjugated linoleic acid
Suitable-9, anti--the 11-trans-10, the molecular formula of suitable-12-calcium conjugated linoleic acid calcium conjugated linoleic acid: Ca (C
18H
31O
2)
2Molecular weight: 598.02.
Originally the manufacture method that contains the composition of calcium conjugated linoleic acid, be that proper amount of sodium hydroxide or potassium hydroxide are added in the non-aqueous solvent of glycerol or ethylene glycol or propylene glycol, this solvent with contain linoleic vegetables oil, part by weight by solvent and oil is 2-4: 1, the alkali consumption is the 10-50% of weight of oil, after joining in the retort together, tight-closed this jar, carry out following steps again:
I, vacuum outgas: in the apparent vacuum tightness of the table of this jar be: under the 600-700mmHg post, the degassing time of this material in this jar is: 20-60 minute;
Ii, 150-190 ℃ of down reaction 2-5 hour, lower the temperature after reacting completely;
Iii, when being cooled to, add calcium chloride water, stir, make precipitin reaction complete less than 100 ℃;
The throw out of iv, generation is through centrifugation;
V, wash isolating material, to neutral;
Behind the drying materials after vi, the washing, be ground to granularity, must contain the additive granules product of calcium conjugated linoleic acid at 150-400 μ.
Originally the manufacture method that contains the composition of calcium conjugated linoleic acid describedly contains linoleic vegetables oil, comprising: common seepweed seeds oil, artemisia capillaris thunb seed oil, safflower oil, sunflower seed oil, water white gourd oil, soybean oil or Semen Maydis oil.
Originally the manufacture method that contains the composition of calcium conjugated linoleic acid, described calcium chloride, its add-on is the 10-30% of oily reacting weight.
The present invention is the conjugated linolic acid product of exploitation on disclosed Chinese patent (publication number CN1287114) basis.Adopt alkali isomerization, saponification simultaneously and Calcific technology, preparation contains the product of calcium conjugated linoleic acid in same equipment, and technology is easy, is easy to suitability for industrialized production.Originally the composition that contains calcium conjugated linoleic acid surpasses the standard of international like product.
The present invention contains the composition of calcium conjugated linoleic acid owing to contain suitable-9 of linoleic acid isomers each other; instead-11-conjugated linolic acid acyl group (abbreviating c9.t11CLA as) and trans-10; suitable-12-conjugated linolic acid acyl group (abbreviating t10.c12CLA as)---therefore this class active substance can be used for additives such as food, functional foodstuff, makeup and feed.Human body and poultry, domestic animal metabolism of fat there is special role.This active substance can improve body fat to be piled up, prevention of obesity, and the content effect slims the abdomen; Can also be used for functional feedstuff additive, poultry, domestic animal metabolism of fat are had special role.Said composition is used for cow feed additive, can significantly reduce lipid content in the milk.The lowfat milk product can improve milk preparation on market in benefit.With said composition feeding cow 50g/d, demonstrate fat reduction in the milk after five days, effect is inculcated the conjugated linolic acid unanimity with abomasum.When off-test, butterfat reduces to 2.69% from 4.08%, and CLA content is brought up to 10.1mg/g from 6.2mg/g.Said composition is to milk cow ingestion of food and the influence useless of milk proteins content.Feed for a long time and add the feed of said composition, can increase milk crop.For the early stage milk cow of lactation, can improve energy state, increase milk crop and strengthen energy balance.Said composition is used for pig feed, can obviously improve pork quality, reduces pig back fat and total lipid content.Said composition is used for the chicken feed, has obvious reduction effect for egg cholesterol, and 1.0% fed 30 days, and cholesterol can reduce by 40%.The composition that contains calcium conjugated linoleic acid of the present invention has broad application prospects in food service industry, cosmetic industry, feedstuff industry.
(4) embodiment
Protection scope of the present invention not only is confined among the embodiment.
Originally contain the manufacturing of the composition of calcium conjugated linoleic acid, be that proper amount of sodium hydroxide or potassium hydroxide are added in the non-aqueous solvent of glycerol or ethylene glycol or propylene glycol, this solvent with contain linoleic vegetables oil, part by weight by solvent and oil is 2-4: 1, the alkali consumption is the 10-50% of weight of oil, after joining in the retort together, tight-closed this jar, carry out following steps again:
I, vacuum outgas: in the apparent vacuum tightness of the table of this jar be: under the 650-680mmHg post, the degassing time of this material in this jar is: 30 minutes;
Ii, 150-190 ℃ of down reaction 2-5 hour, lower the temperature after reacting completely;
Iii, when being cooled to, add calcium chloride water, stir, make precipitin reaction complete less than 100 ℃;
The throw out of iv, generation is through centrifugation;
V, wash isolating material, to neutral;
Behind the drying materials after vi, the washing, be ground to granularity, obtain: scentless white or lurid evengranular powder at 150-400 μ---contain the composition of calcium conjugated linoleic acid.
The processing condition of specific embodiments of the invention and the results are shown in following table 1---4:
Example 1-18: get safflower oil, ethylene glycol, sodium hydroxide, carry out respectively at processing condition by table 1 experiment number, under 160-190 ℃, to react 1-4 hour, reaction product is reduced to less than 100 ℃, add an amount of calcium chloride water, the precipitation that generates, centrifugal, washing, oven dry is ground to such an extent that granularity is the product of 150-400 μ.Table 1, contain the composition embodiment of calcium conjugated linoleic acid:
| The experiment number | Stock oil (g) | Solvent (g) | Alkali (g) | The isomerization reaction temperature (℃) | Reaction times (h) | The metathesis temperature (℃) | Calcium chloride (g) | CLA acyl group total content % | C9.t 11CL A content % | T10. c12C LA content % | Other CLA acyl group content % | Other fatty acid acyl % |
| ????1 | ????100 | ????200 | ????20 | ????190 | ????3.0 | ????80 | ????22 | ????70.6 | ????32.9 | ????32.6 | ????5.1 | ????16.4 |
| ????2 | ????100 | ????200 | ????20 | ????190 | ????3.0 | ????80 | ????22 | ????71.2 | ????33.6 | ????33.1 | ????4.5 | ????15.9 |
| ????3 | ????100 | ????300 | ????20 | ????190 | ????3.0 | ????80 | ????22 | ????71.9 | ????33.5 | ????32.5 | ????5.9 | ????15.1 |
| ????4 | ????100 | ????400 | ????20 | ????190 | ????3.0 | ????70 | ????22 | ????71.3 | ????31.8 | ????34.9 | ????4.6 | ????15.7 |
| ????5 | ????100 | ????200 | ????20 | ????190 | ????3.0 | ????70 | ????22 | ????71.2 | ????32.3 | ????31.5 | ????7.4 | ????15.8 |
| ????6 | ????100 | ????200 | ????12 | ????190 | ????3.0 | ????70 | ????14 | ????32.9 | ????12.5 | ????14.3 | ????6.1 | ????14.1 |
| ????7 | ????100 | ????200 | ????15 | ????190 | ????3.0 | ????60 | ????16.4 | ????53.9 | ????24.1 | ????22.5 | ????7.3 | ????33.1 |
| ????8 | ????100 | ????200 | ????20 | ????190 | ????3.0 | ????60 | ????22 | ????73.3 | ????35.6 | ????33.1 | ????4.6 | ????13.7 |
| ????9 | ????100 | ????200 | ????25 | ????190 | ????3.0 | ????60 | ????28 | ????73.5 | ????34.2 | ????32.9 | ????6.4 | ????13.5 |
| ????10 | ????100 | ????200 | ????20 | ????160 | ????3.0 | ????60 | ????22 | ????63.3 | ????29.5 | ????28.1 | ????5.7 | ????23.7 |
| ????11 | ????100 | ????200 | ????20 | ????170 | ????3.0 | ????60 | ????22 | ????66.2 | ????30.2 | ????29.3 | ????6.7 | ????20.8 |
| ????12 | ??100 | ??200 | ??20 | ????180 | ????3.0 | ????70 | ????22 | ????70.5 | ????32.5 | ????33.6 | ????4.4 | ????16.5 |
| ????13 | ??100 | ??200 | ??20 | ????190 | ????3.0 | ????70 | ????22 | ????71.5 | ????33.4 | ????32.1 | ????6.0 | ????15.5 |
| ????14 | ??100 | ??200 | ??20 | ????190 | ????1.0 | ????70 | ????22 | ????63.7 | ????30.5 | ????29.7 | ????3.5 | ????23.3 |
| ????15 | ??100 | ??200 | ??20 | ????190 | ????1.5 | ????70 | ????22 | ????69.7 | ????31.2 | ????30.8 | ????5.7 | ????19.3 |
| ????16 | ??100 | ??200 | ??20 | ????190 | ????2.0 | ????70 | ????22 | ????71.3 | ????33.2 | ????32.8 | ????4.3 | ????16.7 |
| ????17 | ??100 | ??200 | ??20 | ????190 | ????3.0 | ????70 | ????22 | ????72.5 | ????35.6 | ????33.7 | ????3.2 | ????14.5 |
| ????18 | ??100 | ??200 | ??20 | ????190 | ????4.0 | ????70 | ????22 | ????73.6 | ????36.1 | ????34.3 | ????3.2 | ????13.4 |
Example 19: get 300g soybean oil, 600g propylene glycol, 120g sodium hydroxide, in 180 ℃ of reactions 2 hours, reaction product was reduced to less than 100 ℃, adds an amount of calcium chloride water, and the precipitation of generation is centrifugal, and washing is dried, grind product.With products measure result such as the following table 2 that obtains:
Table 2
| Product parameters | Content (%) |
| Conjugated linolic acid acyl group total content (%) | ????40.7 |
| C9.t11CLA content (%) | ????17.5 |
| T10.c12CLA content (%) | ????16.3 |
| Calcium (%) | ????6.6 |
| Moisture (%) | ????2.0 |
| Other fatty acid acyls (%) are wherein: palmitinic acid acyl group (%) stearic acid acyl group (%) oleic acid acyl group (%) linolic acid acyl group (%) | ????50.7 ????12.4 ????4.7 ????24.4 ????9.2 |
Example 20: get 25kg Trisun Oil R 80,75kg propylene glycol, 14kg potassium hydroxide, in 170 ℃ of reactions 5 hours, reaction product was reduced to less than 100 ℃, adds an amount of calcium chloride water, and the precipitation of generation is centrifugal, and washing is dried, grind product.With products measure result such as the following table 3 that obtains:
Table 3
| Product parameters | Content (%) |
| Conjugated linolic acid acyl group total content (%) | ????57.7 |
| C9.t11CLA content (%) | ????26.6 |
| T10.c12CLA content (%) | ????25.8 |
| Calcium (%) | ????6.5 |
| Moisture (%) | ????5.3 |
| Other fatty acid acyls (%) are wherein: palmitinic acid acyl group (%) stearic acid acyl group (%) oleic acid acyl group (%) linolic acid acyl group (%) | ????30.5 ????6.6 ????2.1 ????20.4 ????1.4 |
Example 21: get 25kg common seepweed seeds oil, 75kg ethylene glycol, 7.5kg potassium hydroxide, in 180 ℃ of reactions 5 hours, reaction product was reduced to less than 100 ℃, adds an amount of calcium chloride water, and the precipitation of generation is centrifugal, and washing is dried, grind product.With products measure result such as the following table 4 that obtains:
Table 4
| Product parameters | Content (%) |
| Conjugated linolic acid acyl group total content (%) | ????70.2 |
| C9.t11CLA content (%) | ????33.21 |
| T10.c12CLA content (%) | ????32.6 |
| Calcium (%) | ????5.5 |
| Moisture (%) | ????3.0 |
| Other fatty acid acyls (%) are wherein: palmitinic acid acyl group (%) stearic acid acyl group (%) oleic acid acyl group (%) linolic acid acyl group (%) | ????21.3 ????5.1 ????2.2 ????12.8 ????1.2 |
Fatty acid compositional analysis in the composition that contains calcium conjugated linoleic acid of the present invention: get additive samples of the present invention, decompose with hydrochloric acid and obtain free fatty acids,, be converted into fatty acid methyl ester further through esterification.Form with gas chromatographic analysis lipid acid.The operational condition of gas chromatographic analysis: chromatographic instrument: GC-112 gas chromatograph (Shanghai analytical instrument factory); Glass capillary column: A30QC2/AC20 fusion silicon capillary post (30m * 0.25mmi.d. * 0.20 μ m; SGE, Australia produces); The detector flame ionization ditector; Chromatographic condition: 195 ℃ of column temperatures, 250 ℃ of sampler temperature, 250 ℃ of detector temperatures, carrier gas (nitrogen) flow velocity 9ml/min, hydrogen flow rate 22.5ml/min, air velocity 80ml/min, splitting ratio 60: 1; Sample size 0.5-1 μ l.
Claims (5)
1, a kind of composition that contains calcium conjugated linoleic acid is characterized in that: this product is white or buff powder; Its weight percent consists of: contain the suitable-9 of linoleic acid isomers each other, anti--11-conjugated linolic acid acyl group, its content is 15---and 40%, and trans-10, suitable-12-conjugated linolic acid acyl group, its content is 40---and 15%; Conjugated linolic acid acyl group total content 30---80%; Calcium contents 5---8%; Other fatty acid acyl total contents 13---53%; Moisture 2---9%.
2, according to the described composition that contains calcium conjugated linoleic acid of claim 1, it is characterized in that: described other fatty acid acyls include: palmitinic acid acyl group, stearic acid acyl group, oleic acid acyl group, linolic acid acyl group.
3, according to the described manufacture method that contains the composition of calcium conjugated linoleic acid of claim 1, be that proper amount of sodium hydroxide or potassium hydroxide are added in the non-aqueous solvent of glycerol or ethylene glycol or propylene glycol, this solvent with contain linoleic vegetables oil, part by weight by solvent and oil is 2-4: 1, the alkali consumption is the 10-50% of weight of oil, after joining in the retort together, tight-closed this jar, carry out following steps again:
I, vacuum outgas: in the apparent vacuum tightness of the table of this jar be: under the 600-700mmHg post, the degassing time of this material in this jar is: 20-60 minute;
Ii, 150-190 ℃ of down reaction 2-5 hour, lower the temperature after reacting completely; It is characterized in that:
Iii, when being cooled to, add calcium chloride water, stir, make precipitin reaction complete less than 100 ℃;
The throw out of iv, generation is through centrifugation;
V, wash isolating material, to neutral;
Behind the drying materials after vi, the washing, be ground to granularity, must contain the additive granules product of calcium conjugated linoleic acid at 150-400 μ.
4, according to the described manufacture method that contains the composition of calcium conjugated linoleic acid of claim 3, it is characterized in that: describedly contain linoleic vegetables oil, comprising: common seepweed seeds oil, artemisia capillaris thunb seed oil, safflower oil, sunflower seed oil, water white gourd oil, soybean oil or Semen Maydis oil.
5, according to the described manufacture method that contains the composition of calcium conjugated linoleic acid of claim 3, it is characterized in that: described calcium chloride, its add-on are the 10-30% of oily reacting weight.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008006284A1 (en) * | 2006-07-07 | 2008-01-17 | Hui Zhang | Use of calcium salt of polyenoic acid in medical and cosmetic field |
| CN100539999C (en) * | 2007-06-01 | 2009-09-16 | 中山市尤利卡天然药物有限公司 | Be used for fat-reducing, blood fat reducing, blood sugar lowering, blood pressure lowering, the osteoporotic compound preparation of control |
| CN101849960A (en) * | 2010-04-15 | 2010-10-06 | 广东海洋大学 | Conjugated linoleic acid combination preparation and preparation method thereof |
| CN101032278B (en) * | 2007-02-08 | 2011-11-30 | 大连医诺生物有限公司 | Combination including calcium conjugated linoleic acid and producing method thereof |
| CN101443437B (en) * | 2006-04-13 | 2013-08-07 | 脂质营养品有限公司 | Process for producing isomer enriched conjugated linoleic acid compositions |
| CN105566090A (en) * | 2014-10-13 | 2016-05-11 | 浙江医药股份有限公司新昌制药厂 | Preparation method for calcium polyunsaturated fatty acid |
| CN110075012A (en) * | 2019-05-20 | 2019-08-02 | 湖北大学 | The application of idesia oil and cosmetics and tyrosinase activity inhibitor |
-
2002
- 2002-05-31 CN CNB021104301A patent/CN1159281C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101443437B (en) * | 2006-04-13 | 2013-08-07 | 脂质营养品有限公司 | Process for producing isomer enriched conjugated linoleic acid compositions |
| WO2008006284A1 (en) * | 2006-07-07 | 2008-01-17 | Hui Zhang | Use of calcium salt of polyenoic acid in medical and cosmetic field |
| CN101032278B (en) * | 2007-02-08 | 2011-11-30 | 大连医诺生物有限公司 | Combination including calcium conjugated linoleic acid and producing method thereof |
| CN100539999C (en) * | 2007-06-01 | 2009-09-16 | 中山市尤利卡天然药物有限公司 | Be used for fat-reducing, blood fat reducing, blood sugar lowering, blood pressure lowering, the osteoporotic compound preparation of control |
| CN101849960A (en) * | 2010-04-15 | 2010-10-06 | 广东海洋大学 | Conjugated linoleic acid combination preparation and preparation method thereof |
| CN105566090A (en) * | 2014-10-13 | 2016-05-11 | 浙江医药股份有限公司新昌制药厂 | Preparation method for calcium polyunsaturated fatty acid |
| CN110075012A (en) * | 2019-05-20 | 2019-08-02 | 湖北大学 | The application of idesia oil and cosmetics and tyrosinase activity inhibitor |
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| CN1159281C (en) | 2004-07-28 |
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