CN103027105B - Fruit wax for fresh-keeping of fruits and vegetables and preparation method and application - Google Patents
Fruit wax for fresh-keeping of fruits and vegetables and preparation method and application Download PDFInfo
- Publication number
- CN103027105B CN103027105B CN2012105814204A CN201210581420A CN103027105B CN 103027105 B CN103027105 B CN 103027105B CN 2012105814204 A CN2012105814204 A CN 2012105814204A CN 201210581420 A CN201210581420 A CN 201210581420A CN 103027105 B CN103027105 B CN 103027105B
- Authority
- CN
- China
- Prior art keywords
- wax
- fruit
- vegetables
- fruits
- fruit wax
- 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.)
- Active
Links
Landscapes
- Storage Of Fruits Or Vegetables (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention discloses fruit wax for fresh-keeping of fruits and vegetables and a preparation method and an application. The preparation method comprises the steps of adopting a phase inversion emulsion method, selecting high-quality oleic acid, myristate, morpholine, potassium hydroxide, polydimethyl siloxane, and deionized water according to characteristics of oxidized polyethylene and carnauba wax, choosing appropriate emulsification temperature and time for emulsifying the wax and the adding quantity and speed of the deionized water, obtaining an O/W type emulsion, and obtaining the oxidized polyethylene and carnauba wax composite fruit wax for the fresh-keeping of the fruits and the vegetables. The fruit wax synthesized by the method is high in film-forming strength and extremely high in glossiness after film forming, can be comparable to imported wax liquid, and is good in water retention property and air permeability; the outstanding performance of the fruit wax completely surpass that of imported high-gloss fruit wax at present; and the fruit wax meets the requirements of green, safe and mechanical waxing of food. The fruit wax can be widely used for waxing the fruits and the vegetables such as citrus, apples, peaches and tomatoes.
Description
Technical field
The invention belongs to the postharvest fruit and vegetable biological technical field, be specifically related to a kind of preserving fruit and vegetable utilizing fruit wax, the preparation method who also relates to a kind of preserving fruit and vegetable utilizing fruit wax, also relate to a kind of application of preserving fruit and vegetable utilizing fruit wax, and this fresh-keeping wax liquid is suitable for the fruit and vegetables such as oranges and tangerines, apple, peach, tomato.
Background technology
Raising along with domestic and international people's living standard, for freshness and the year-round supply thereof of realizing fruits and vegetables, wax and fresh-keepingly as a kind of new fresh-keeping mode, arise at the historic moment, it is artificial at fruit and vegetable surfaces, to smear thin film, in order to pore of regulating the fruits and vegetables epidermis etc., reduce the fruits and vegetables moisture loss, delaying the fruits and vegetables dehydration wilts, restriction fruits and vegetables and the exchange of external environment gas, suppress the fruits and vegetables respiratory metabolism, slow down nutrient loss and aging, extend fruit vegetables storing period and shelf life (Bai etc., Alternatives to shellaccoaings provide comparable benefits in terms of gloss, internal gases modification, and qualityfor ' Delicious ' apple fruit.HortSciene 2002, 37:559-563.), can also increase simultaneously the gloss of fruits and vegetables, beautify outward appearance, thereby improve the fruits and vegetables commodity value.China just has ' with the base of a fruit of sealing with wax ' to reduce the record of oranges and tangerines dehydration as far back as 12nd century, the U.S. just starts to the thirties in 20th century paraffin melted by heat and is coated with by fruits and vegetables such as oranges and tangerines, fruit waxing is both at home and abroad till now processed the history of more than 70 year has been arranged, and is widely used in fresh-keeping on the fruits and vegetables such as oranges and tangerines, apple, pears, tomato.Most of wax liquid of early stage commercial use are to using paraffin and Brazil wax as basic material, because paraffin can be controlled dehydration well, and Brazil wax can make fruit produce tempting gloss.Fruit wax is generally used in most countries and area now, and the fruit wax product that oneself is arranged, series fruit wax as bright as the celestial being of U.S. DECCO company (211,402,402F), U.S. FMC series fruit wax (Sta-fresh 890HS), Spain FOMESA fruit wax series (prestige guarantor, big spy, good fortune are auspiciousness).This class fruit wax can meet healthy requirement, because contain higher lac resin, can improve significantly the fruits and vegetables glossiness, very soon in countries use such as the U.S., China, Spain, Japan, Australia, Israel, South Africa again.The research that our country's fruits and vegetables waxing is at present processed lags significantly behind developed country, although our the domestic processing requirements of commercialization to fruits and vegetables is more and more higher, commercialization is processed the fruit wax overwhelming majority of using and relied on from the U.S., Japan, Spain's import.
Recent domestic is developed a variety of wax liquid, but these fruit waxes are mainly the high brightness fruit wax that contains shellac, although this class fruit wax can increase the fruits and vegetables outward appearance, make fruit produce tempting gloss, reduce the loss in weight of fruits and vegetables in storage and transportation, strengthen its competitiveness on market, but after the fruits and vegetables waxing, gloss can not be permanent, and after fruits and vegetables were processed in waxing, gas permeability was poor, easily produce anaerobic respiration, under normal temperature, storage can cause the effumability smell substances such as ethanol, acetaldehyde, methyl alcohol to accumulate in a large number in 1-2 week.When ethanol content is low as the fruits and vegetables aromatic substance, but when content surpasses 1500 μ l/L, fruits and vegetables just easily produce peculiar smell (Hagenmaier etc. such as ' vinasse ', Changes in volatile components of stored tangerines and other specialtycitrus fruits with different coatings.J.Food Sci.2002,67:1742-1745).By studying the impact of different wax liquid on apple and oranges and tangerines gas permeability and smell substance content, conclude that OPE is better than shellac wax (Hagenmaier, R.D.The flavor of mandarin hybrids with different coatings.Postharvest Biol.Technol.2002,24:79-87).Although the OPE gas permeability is quite a lot of a little, in many fruit and vegetable varieties, its water-retaining property is poor, process fruits and vegetables after glossiness lower, and still can improve significantly smell substance in fruit and gather way.Although developed country drops into great effort research, improve wax liquid gas permeability and glossiness, some new materials are used to the transformation of wax liquid, effectively do not go to change this situation.
China is world's fruits and vegetables output and consumption big country, for improving fruits and vegetables domestic market or the competitiveness on the outlet overseas market, is badly in need of developing high gloss fruit wax, luminosity is lasting, and can obviously reduce the smell substance content such as ethanol, acetaldehyde, Shelf-life, the commodity value of raising fruits and vegetables.
Summary of the invention
The object of the present invention is to provide a kind of preserving fruit and vegetable utilizing fruit wax, it is main wax liquid material that this fruit wax has been selected the reasonable oxidic polyethylene of gas permeability and the high Brazil wax of glossiness, invent out a kind of high gloss, can in fruit vegetables storing and shelf life, reduce to greatest extent the fruits and vegetables weight-loss ratio, good permeability, can obviously reduce the smell substance accumulation such as ethanol, acetaldehyde, the Novel fruit wax of water-holding fresh-keeping successful.
Another object of the present invention has been to provide a kind of preparation method of preserving fruit and vegetable utilizing fruit wax, adopt and change mutually emulsion process, easy to implement the method, easy to operate, characteristic for oxidic polyethylene, Brazil wax, select high-quality oleic acid, myristic acid, morpholine, potassium hydroxide, dimethyl silicone polymer, deionized water, select emulsifying temperature, the time of suitable emulsifying wax, and the deionized water amount and the speed that add, form O/W type emulsion, can obtain the compound fruit and vegetable preservative fruit waxes such as oxidic polyethylene, Brazil wax.The synthetic fruit wax of this method becomes film-strength high, after film forming, not only glossiness is high, can match in excellence or beauty with import wax liquid phase, and water-retaining property and good permeability, its excellent properties has surmounted the high glaze fruit wax of current import fully, meets green safe of food and mechanized waxing requirement.This product can be widely used on the fruits and vegetables such as oranges and tangerines, apple, peach, tomato and wax.
In order to achieve the above object, the present invention takes following technical measures:
A kind of preserving fruit and vegetable utilizing fruit wax, it is made by following material quality percentage:
A kind of preserving fruit and vegetable utilizing fruit wax, it makes (preferable range is) by following material quality percentage:
A kind of preserving fruit and vegetable utilizing fruit wax, it makes (optimum range) by following raw material weight percentage:
A kind of preparation method of preserving fruit and vegetable utilizing fruit wax, it comprises the steps:
(1), matched the preservative fruit wax raw material: each raw material is matched by composition and weight;
(2), add raw material: adopt phase conversion emulsifying, oxidic polyethylene, Brazil wax, oleic acid, myristic acid, morpholine, potassium hydroxide, dimethyl silicone polymer, fraction deionized water (approximately 1/3 oxidic polyethylene and Brazil wax weight) raw material are dropped in reactor;
(3), filler heating melts: after 120 ℃ of left and right heating and meltings, stir, mixing speed 200-300r/min, about 20min of stirring and emulsifying time, form the w/o type emulsion;
(4) be diluted with water: in whipping process, slowly add the hot water more than 95 ℃, phase inversion can accelerate to add remaining hot water after forming O/W type emulsion, finally cools fast below 50 ℃, can obtain a kind of preserving fruit and vegetable utilizing fruit wax;
(5), check: by the quality standard check;
(6), metering packing: finished product is packed by weight, obtain fruit wax.
Excellent properties of the present invention has surmounted the high glaze fruit wax of current import fully, is better than especially other domestic fruit wax, meets green safe of food and mechanized waxing requirement.This product can be widely used on the fruits and vegetables such as oranges and tangerines, apple, peach, tomato and wax.Compared with prior art, the present invention has the following advantages:
1, fruit wax is translucent brown emulsion, the rear fruits and vegetables water white transparency of filming, and glossiness is high and luminosity is lasting;
2, fruit wax quick-drying, and stable performance, the fruit face does not whiten;
3, fruit wax viscosity is low, and it is better more evenly more smooth that machinery sprays atomizing effect, prevents plug nozzle, simultaneously than being easier to clean waxing equipment;
4, the lyophobic dust that contains of fruit wax makes it to have the high waterproof energy, can reduce the moisture evaporation, prevents that the fruits and vegetables dehydration from wilting;
5, fruit wax has higher gas permeability, and storage is not easy to cause anaerobic respiration, can obviously reduce the accumulation of ' vinasse ' smell substances such as ethanol, acetaldehyde, has suppressed simultaneously the breathing of fruits and vegetables, has delayed the fruits and vegetables aging, has extended the shelf life of fruits and vegetables.
6, fruit wax is obviously checked the fruits and vegetables brown stain, keeps the fresh color and luster of fruits and vegetables, the economic worth of continuity fruits and vegetables;
7, fruit wax effectively reduces the cross-infection chance of pathogenic microorganism, controls the rotting rate of fruits and vegetables, improves fruit-vegetable quality.
The specific embodiment
Embodiment 1-11
A kind of fruit freshness preserving fruit wax is prepared from by following raw material: oxidic polyethylene AC629(U.S. Honeywell Inc.), Brazil wax NO3(Suzhou exceedes the century bio tech ltd), morpholine (German BASF joint-stock company), oleic acid (Chemical Reagent Co., Ltd., Sinopharm Group), myristic acid (safe Ke's brown (Zhangjiagang) Co., Ltd), dimethyl silicone polymer (Changzhou Tao Shi chemical industry Co., Ltd), potassium hydroxide (Chemical Reagent Co., Ltd., Sinopharm Group), deionized water.
Unit: mass percent
A kind of preparation method of preserving fruit and vegetable utilizing fruit wax, it comprises the steps:
(1), matched the preservative fruit wax raw material: choose and weighing example 1 ~ 11 in each component described in any a group;
(2), add raw material: adopt phase conversion emulsifying, oxidic polyethylene, Brazil wax, oleic acid, myristic acid, morpholine, potassium hydroxide, dimethyl silicone polymer, fraction deionized water (approximately 1/3 oxidic polyethylene and Brazil wax weight) raw material are dropped in reactor;
(3), filler heating melts: after 120 ℃ of left and right heating and meltings, stir, mixing speed 200-300r/min, about 20min of stirring and emulsifying time, form the w/o type emulsion;
(4) be diluted with water: in whipping process, slowly add the hot water more than 95 ℃, phase inversion can accelerate to add remaining hot water after forming O/W type emulsion, finally cools fast below 50 ℃, can obtain a kind of preserving fruit and vegetable utilizing fruit wax;
(5), check: by the quality standard check;
(6), metering packing: finished product is packed by weight, obtain fruit wax.
Embodiment 12:
After mechanized waxing of the present invention was processed satsuma orange, glossiness was equally matched with import wax liquid, 20 ℃ of normal temperature, and under 70-75%RH, after 2 weeks of storage, weight-loss ratio is 6.83%; The inner CO of fruit
2Content is 6.64kPa, O
2For 9.29kPa, good permeability, be not easy to cause anaerobic respiration; Ethanol content is 1707.8 μ l/L, and acetaldehyde is 25.3 μ l/L, and methanol content is 24.6 μ l/L, and after the celestial bright 402D processing satsuma orange of business wax, weight-loss ratio is 6.80%, the inner CO of fruit
2Content is 9.54kPa, O
2For 4.32kPa; Ethanol content 3200.3 μ l/L, acetaldehyde are 29.7 μ l/L, and methanol content is 31.5 μ l/L.Seasoning good permeability under normal temperature after this product treatment satsuma orange, the smell substance content such as ethanol, acetaldehyde are lower, and the vinasse flavor is lower, can obviously extend the shelf life of satsuma orange.
Embodiment 13
The present invention manually soaks the fruit waxing and processes Xia Chenghou, 20 ℃, under 70-75%RH, room temperature storage is after 3 weeks, weight-loss ratio is 3.07%, soluble solid is 11.2%, titratable acid is 0.55%, Vc content is 58.8mg/100g, ethanol content is 1351.4 μ l/L, be starkly lower than 1500 μ l/L(ethanol contents when low as the oranges and tangerines aromatic substance, when content surpasses 1500 μ l/L, oranges and tangerines just easily produce peculiar smell such as ' vinasse '), acetaldehyde is that 16.7 μ l/L methanol contents are 80.2 μ l/L, and the celestial bright 402D of the business wax of the more import of domestic use processes Xia Chenghou, weight-loss ratio is 5.97%, soluble solid 11.4%, titratable acid 0.62%, Vc 58.3mg/100g, ethanol content 1199.7 μ l/L after one week, after three weeks, content is up to 7943 μ l/L, acetaldehyde is that 58.7 μ l/L methanol contents are 134.3 μ l/L.Above result shows, after the present invention processed summer orange fruit, the smell substance content such as ethanol, acetaldehyde, methyl alcohol were lower, and fruit quality is better, and compared with the control, obviously Shelf-life is about 1 week.
Embodiment 14
After this product mechanized waxing is processed the Niu Heer navel orange, glossy, luminosity lastingly, do not whiten, water-holding fresh-keeping, 20 ℃ of normal temperature, under 70-75%RH, the smell substance content such as all ethanol of seasoning 3, acetaldehyde are lower, the vinasse flavor is lower, can obviously extend the shelf life of navel orange.Under 20 ℃ of normal temperature, after three weeks of storage, weight-loss ratio is 4.79%, and respiratory intensity is 56.62ml CO
2Kg
-1H
-1, ethanol content is 2879.5 μ l/L, and acetaldehyde is 17.9 μ l/L, and methanol content is 61.5 μ l/L, and after the business wax FMC890HS of the more import of domestic use processed navel orange, weight-loss ratio was 5.14%, respiratory intensity is 59.26ml CO
2Kg
-1H
-1, ethanol content is up to 4734.6 μ l/L, and acetaldehyde is 27.3 μ l/L, and methanol content is 90.5 μ l/L.
Embodiment 15
After the present invention manually soaked fruit waxing processing apple, the apple glossiness was high, 20 ℃ of normal temperature, and under 70-75%RH, after 2 weeks of storage, weight-loss ratio is 6.74%; The inner CO of fruit
2Content is 8.36kPa, O
2For 8.34kPa, good permeability, be not easy to cause anaerobic respiration; Ethanol content is 1528.7 μ l/L, and acetaldehyde is 30 μ l/L, and methanol content is 34.9 μ l/L, and after business wax AppleLustr 221Shellac Based Coating processing apple, weight-loss ratio is 6.80%, the inner CO of fruit
2Content is 11.54kPa, O
2For 4.32kPa; Ethanol content 2444 μ l/L, acetaldehyde are 29.2 μ l/L, and methanol content is 31.9 μ l/L.After this product treatment apple under normal temperature the smell substance content such as seasoning ethanol, acetaldehyde lower, vinasse flavors is lower, can obviously extend the shelf life of apple.
Embodiment 16
After the present invention manually soaks fruit waxing processing tomato, the tomato glossiness is high, 20 ℃ of normal temperature, after under 70-75%RH, preserving for 2 weeks, weight-loss ratio is 6.12%, soluble solid is 8.8%, titratable acid is 0.35%, Vc content is 22.3mg/100g, ethanol content is 1034.5 μ l/L, acetaldehyde is 17.2 μ l/L, methanol content is 22.3 μ l/L, and after business wax DECCOTomakote 8 processing tomatoes, weight-loss ratio is 6.83%, soluble solid is 9.2%, titratable acid is 0.33%, Vc content is 19.6mg/100g, ethanol content 1430.4 μ l/L, acetaldehyde is 16.4 μ l/L, methanol content is 28.2 μ l/L.After this product treatment tomato under normal temperature the smell substance content such as seasoning ethanol, acetaldehyde lower, vinasse flavors is lower, can obviously delay the decline of Tomato Quality.
Claims (4)
1. preserving fruit and vegetable utilizing fruit wax, it is made by the raw material of following mass percent:
Described preserving fruit and vegetable utilizing fruit wax, its preparation process is:
(1), matched the preservative fruit wax raw material: each raw material is matched by composition and weight;
(2), add raw material: adopt phase conversion emulsifying, by the deionized water of oxidic polyethylene, Brazil wax, oleic acid, myristic acid, morpholine, potassium hydroxide, dimethyl silicone polymer, 1/3 oxidic polyethylene and Brazil wax weight, drop in reactor; (3), filler heating melts: after 120 ℃ of heating and meltings, stir, mixing speed 200-300r/min, about 20min of stirring and emulsifying time, form the w/o type emulsion;
(4), be diluted with water: in whipping process, slowly add the hot water more than 95 ℃, phase inversion adds remaining hot water after forming O/W type emulsion, finally cools fast below 50 ℃;
(5), check: by the quality standard check;
(6), metering packing: finished product is packed by weight, obtain fruit wax.
2. a kind of preserving fruit and vegetable utilizing fruit wax according to claim 1, it is made by the raw material of following mass percent:
3. a kind of preserving fruit and vegetable utilizing fruit wax according to claim 1, it is made by the raw material of following mass percent:
4. the application of a kind of preserving fruit and vegetable utilizing fruit wax claimed in claim 1 in preserving fruit and vegetable utilizing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012105814204A CN103027105B (en) | 2012-12-27 | 2012-12-27 | Fruit wax for fresh-keeping of fruits and vegetables and preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012105814204A CN103027105B (en) | 2012-12-27 | 2012-12-27 | Fruit wax for fresh-keeping of fruits and vegetables and preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103027105A CN103027105A (en) | 2013-04-10 |
| CN103027105B true CN103027105B (en) | 2013-11-27 |
Family
ID=48014927
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012105814204A Active CN103027105B (en) | 2012-12-27 | 2012-12-27 | Fruit wax for fresh-keeping of fruits and vegetables and preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103027105B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107897353A (en) * | 2017-11-30 | 2018-04-13 | 钟山佳园生态农业有限公司 | Citrus anti-rot and fresh-keeping method |
| CN108077416A (en) * | 2017-11-30 | 2018-05-29 | 钟山佳园生态农业有限公司 | Citrus preservative fruit wax |
| CN108244231B (en) * | 2018-02-22 | 2021-11-09 | 宁波市农业科学研究院 | Nano fruit and vegetable fresh-keeping film coating agent and preparation method and application thereof |
| CN112535207B (en) * | 2019-09-23 | 2021-12-31 | 华中农业大学 | Edible fresh fruit coating preservative and preparation method and application thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101305749A (en) * | 2008-06-30 | 2008-11-19 | 王永勤 | Molecular film fruit and vegetable fresh-keeping agent prepared by edible material |
| CN101642159A (en) * | 2008-08-06 | 2010-02-10 | 天津市赛奥农产品保鲜科技有限公司 | Film-coating fresh-keeping fruit wax for fruits and vegetables and preparation method thereof |
| CN101884349A (en) * | 2010-07-21 | 2010-11-17 | 乔恩战 | Fresh-keeping film coating fruit wax for fruits and vegetables |
| CN101884350A (en) * | 2010-07-21 | 2010-11-17 | 乔恩战 | Method for preparing fresh-keeping film coating fruit wax for fruits and vegetables |
-
2012
- 2012-12-27 CN CN2012105814204A patent/CN103027105B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN103027105A (en) | 2013-04-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103039600B (en) | Formula, preparation method and application thereof of fruit freshness-retaining wax | |
| CN108514026B (en) | Fresh-cut fruit and vegetable composite preservative and using method thereof | |
| CN101946841B (en) | Treating method and product of organic osmanthus green tea | |
| CN102266024B (en) | Preparation method of convenient instant purple potato food | |
| CN103027105B (en) | Fruit wax for fresh-keeping of fruits and vegetables and preparation method and application | |
| CN100455201C (en) | 1-methyl cyclopropene and chitosan combined processing fresh-keeping method for special tropical fruits | |
| CN102805168B (en) | Marine plant tea and preparation method thereof | |
| CN101690514A (en) | Preparation method for honey peach fresh-keeping emulsion and application of honey peach fresh-keeping emulsion | |
| CN101921515B (en) | Edible coating taking starch and polysaccharide compound modified product as matrixes and preparation method thereof | |
| CN104705392A (en) | Preservative fruit wax containing bleached lac as well as preparation method and application thereof | |
| Flores-Gallegos et al. | Tuba, a fermented and refreshing beverage from coconut palm sap | |
| CN104286156A (en) | Tomato coating compound preservative and preparation method thereof | |
| CN105285088B (en) | A kind of preservative fruit wax and preparation method and application containing sumac wax ingredient | |
| CN101803716B (en) | Garlic juice flavoring and preparation method thereof | |
| CN103305400A (en) | Grape skin residue and yam fruit vinegar powder and preparation method thereof | |
| CN108244231A (en) | Nanometer fruits and vegetables fresh-keeping film-coating agent and its preparation method and application | |
| CN106579173A (en) | Fermentation accessory ingredients for preparing pickled vigna unguiculata and natural fermentation technological method of pickled vigna unguiculata | |
| CN106720263A (en) | A kind of freshness preserving agent for fruit and vegetable and preparation method thereof | |
| Sivakumar et al. | Postharvest management on quality retention of litchi during storage | |
| CN105285077A (en) | Composite coating film fresh keeping agent containing persimmon leaf flavones as well as preparation method and application of composite coating film fresh keeping agent | |
| CN107027879A (en) | A kind of fruit freshness preserving fruit wax and preparation method thereof | |
| CN103013802A (en) | Fresh red bayberry wine and winey red bayberries | |
| CN109805088A (en) | A kind of fruit freshness preserving fruit wax | |
| CN110140764A (en) | A kind of fruit freshness preserving fruit wax and preparation method and application | |
| CN101336733A (en) | Squid rice roll and processing method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |