CN114052042A - Double-solid slow-release air purifying agent - Google Patents

Double-solid slow-release air purifying agent Download PDF

Info

Publication number
CN114052042A
CN114052042A CN202111411965.6A CN202111411965A CN114052042A CN 114052042 A CN114052042 A CN 114052042A CN 202111411965 A CN202111411965 A CN 202111411965A CN 114052042 A CN114052042 A CN 114052042A
Authority
CN
China
Prior art keywords
parts
gel
purifying agent
sodium
air purifying
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.)
Pending
Application number
CN202111411965.6A
Other languages
Chinese (zh)
Inventor
申哲民
陈明
袁涛
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanghai Jiaotong University
Original Assignee
Shanghai Jiaotong University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Shanghai Jiaotong University filed Critical Shanghai Jiaotong University
Priority to CN202111411965.6A priority Critical patent/CN114052042A/en
Publication of CN114052042A publication Critical patent/CN114052042A/en
Pending legal-status Critical Current

Links

Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L9/00—Disinfection, sterilisation or deodorisation of air
    • A61L9/015—Disinfection, sterilisation or deodorisation of air using gaseous or vaporous substances, e.g. ozone
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2101/00—Chemical composition of materials used in disinfecting, sterilising or deodorising
    • A61L2101/02—Inorganic materials
    • A61L2101/06—Inorganic materials containing halogen

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Environmental Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Zoology (AREA)
  • Wood Science & Technology (AREA)
  • Dentistry (AREA)
  • Agronomy & Crop Science (AREA)
  • Plant Pathology (AREA)
  • Pest Control & Pesticides (AREA)
  • Biomedical Technology (AREA)
  • Toxicology (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Epidemiology (AREA)
  • Animal Behavior & Ethology (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Disinfection, Sterilisation Or Deodorisation Of Air (AREA)

Abstract

The invention relates to a double-solid slow-release air purifying agent, which comprises gel and an auxiliary material bag which acts with the gel and enables the gel to release chlorine dioxide, wherein the gel comprises the following raw materials in parts by weight: 1 part of sodium carbonate, 10-12 parts of sodium chlorite, 1 part of sulfate, 72 parts of water and 8-10 parts of water-absorbing resin; the auxiliary material bag comprises the following raw materials in parts by weight: 2 parts of calcium chloride, 2 parts of calcium oxide, 2 parts of sodium dihydrogen phosphate and 2 parts of sodium bicarbonate. When the purifying agent is used, the auxiliary material bag is unsealed, the content of the auxiliary material bag is poured out to cover the gel, the two materials react to release chlorine dioxide, and the release process is limited by the barrier effect of the gel formed by the water-absorbing resin, so that the chlorine dioxide can be slowly released from the gel; the calcium chloride and the calcium oxide release heat after absorbing moisture, and the decomposition reaction of the sodium chlorite is accelerated to start. Compared with the prior art, the air purifying agent can slowly release chlorine dioxide gas, and has the advantages of quick reaction start and long effective service life.

Description

Double-solid slow-release air purifying agent
Technical Field
The invention belongs to the technical field of air disinfection, and relates to a double-solid slow-release air purifying agent.
Background
Air purification, odor removal and germ eradication are problems that are often encountered in life and work. The indoor formaldehyde pollution is serious and the human health is influenced due to the indoor decoration and furniture. The existing main methods for removing formaldehyde and peculiar smell are an adsorption method, a neutralization method by spraying a medicament, a coating sealing method and the like. However, these methods, such as adsorption and neutralization by spraying chemicals, only remove formaldehyde temporarily, and then formaldehyde is emitted from the source.
Chlorine dioxide can oxidize formaldehyde into formic acid to CO2And formaldehyde is removed, and N201710727467.X discloses a preparation method of a long-acting slow-release type solid chlorine dioxide air purifying agent, wherein the slow-release type chlorine dioxide air purifying agent is prepared by using super absorbent resin prepared by grafting PVP (polyvinylpyrrolidone) on carboxymethyl cellulose and chlorine dioxide solution, and has low slow-release capacity. CN111567552A discloses a slow-release chlorine dioxide air purification gel and a preparation method thereof, wherein the gel is prepared from sodium chlorite, citric acid, sodium chloride, sodium bicarbonate, magnesium sulfate, sodium dihydrogen phosphate, polyethylene glycol and sodium carboxymethylcellulose citrate. CN201711444568.2 discloses a slow-release air purifying agent and a preparation method thereof, wherein the air purifying agent comprises chlorine dioxide, a molecular sieve, a sodium chlorite solution and the like as raw materials. These scavengers are slow to start reaction when used and the raw materials are not fully utilized.
Disclosure of Invention
The invention aims to provide a double-solid slow-release air purifying agent to overcome the defects of unstable release of chlorine dioxide, slow reaction start and the like in the prior art.
The purpose of the invention can be realized by the following technical scheme:
the invention provides a double-solid slow-release air purifying agent which comprises gel and an auxiliary material bag which acts with the gel and enables the gel to release chlorine dioxide, wherein the gel comprises the following raw materials in parts by weight: 1 part of sodium carbonate, 10-12 parts of sodium chlorite, 1 part of sulfate, 72 parts of water and 8-10 parts of water-absorbing resin; the auxiliary material bag comprises the following raw materials in parts by weight: 2 parts of calcium chloride, 2 parts of calcium oxide, 2 parts of sodium dihydrogen phosphate and 2 parts of sodium bicarbonate.
Further, the sulfate is sodium sulfate or magnesium sulfate.
Further, the water-absorbing resin is polyethylene glycol, sodium polyacrylate, polyvinyl alcohol or polyacrylamide.
Further, the preparation process of the gel comprises the following steps:
and (3) dispersing sodium carbonate, sodium chlorite and sulfate in water, and then mixing with water absorption resin to obtain the gel.
Furthermore, the mass ratio of the sodium carbonate to the sodium chlorite to the sulfate to the water-absorbing resin is 1: 10: 1: 72: 8.
furthermore, the mass ratio of the sodium carbonate to the sodium chlorite to the sulfate to the water-absorbing resin is 1: 12: 1: 72: 10.
further, the raw material of the gel further includes an indicator for indicating the reaction speed and the degree of utilization of the raw material.
Further, sodium carbonate, sodium chlorite and sulfate are dispersed in water, indicator is dripped, and the mixture is mixed with water-absorbent resin to obtain the gel.
Further, the indicator is a bromothymol blue indicator or an alpha-naphthol phthalein indicator.
Further, the preparation process of the auxiliary material bag comprises the following steps:
and (3) uniformly mixing calcium chloride, calcium oxide, sodium dihydrogen phosphate and sodium bicarbonate, and hermetically packaging to obtain the auxiliary material bag.
Further, when the purifying agent is used, the auxiliary material bag is unsealed, the content of the auxiliary material bag is poured out to cover the gel, and the gel slowly releases chlorine dioxide.
Chlorine dioxide can oxidize formaldehyde into formic acid to CO2The formaldehyde is removed, and according to the principle, the invention develops the chlorine dioxide capable of continuously releasing a small amount of chlorine dioxide for a long time based on sodium chloriteAn air purifier for gases. Chlorine dioxide generated by the decomposition of sodium chlorite can oxidize and degrade formaldehyde, viruses and other organic pollutants in the air.
When the purifying agent is used, the auxiliary material bag is unsealed, the content of the auxiliary material bag is poured out and covered on the gel, the two materials react to release chlorine dioxide, and the release process is limited by the barrier effect of the gel formed by the water-absorbing resin, so that the chlorine dioxide can be slowly released from the gel. To indicate the reaction rate and the degree of raw material utilization, an indicator was added at the time of preparing the gel.
In the raw material components, sodium chlorite is decomposed to generate chlorine dioxide, which is a main provider of an oxidant; sodium carbonate and sulfate are used for protecting sodium chlorite from decomposition in the transportation and storage processes; the sodium dihydrogen phosphate and the sodium bicarbonate release hydrogen ions when meeting water to promote the decomposition of sodium chlorite to generate chlorine dioxide; the calcium chloride and the calcium oxide are mainly used for absorbing moisture in air, and the calcium chloride and the calcium oxide release heat while absorbing the moisture, so that the release of hydrogen ions of sodium dihydrogen phosphate and sodium bicarbonate is accelerated, the decomposition reaction of sodium chlorite is accelerated, and chlorine dioxide is generated.
The present invention sets a certain range for the addition amount of sodium chlorite and water-absorbent resin. If the addition amount of sodium chlorite is too low, the generation amount of chlorine dioxide is low, and the effective action maintaining time of the purifying agent is short; if the addition amount of sodium chlorite is too high, the concentration of chlorine dioxide is high, and the stimulation effect on human bodies can be generated. If the addition amount of the water-absorbing resin is too low, the gel amount is insufficient, and the sustained-release duration is short; if the addition amount of the water-absorbent resin is too high, the slow release rate is slow, and the purification effect is poor.
Compared with the prior art, the invention has the following advantages:
(1) the air purifying agent is safe, low in price and environment-friendly;
(2) the air purifying agent can slowly release chlorine dioxide gas, has long effective service life, controllable chlorine dioxide release flux and stable product performance;
(3) the air purifying agent has simple preparation process and is expected to be popularized and applied.
Detailed Description
The present invention will be described in detail with reference to specific examples. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
In the following examples, unless otherwise specified, all the conventional commercially available raw materials or conventional processing techniques in the art are indicated.
In the following examples, the process of measuring the slow release rate of the scavenger is specifically as follows:
the prepared accessory bag is covered on the gel and placed in a sealed container, an open bottle containing the same weight of moisture is placed in the sealed container, the released chlorine dioxide gas is collected by using a liquid-sealed gas absorber, and then the rate of the purifying agent releasing chlorine dioxide is measured by an iodometric method.
In the following examples, bromothymol blue indicator, alpha-naphtholphthalein indicator, used was purchased from alatin.
Example 1:
(1) dissolving 1 part of sodium carbonate, 12 parts of sodium chlorite and 1 part of sodium sulfate in 72 parts of water, dripping an alpha-naphthol phthalein indicator into the mixture to obtain red, and adding 10 parts of polyethylene glycol to prepare gel;
(2) uniformly mixing 2 parts of dried calcium chloride, 2 parts of calcium oxide, 2 parts of sodium dihydrogen phosphate and 2 parts of sodium bicarbonate, and sealing and packaging to form an auxiliary material bag;
(3) when in use, the auxiliary material bag is unsealed, the content of the auxiliary material bag is poured out and covered on the gel, the two materials react to release chlorine dioxide, and the chlorine dioxide is stably and slowly released in the gel. The slow release rate of 100g of the air purifying agent is 15-20mg/h, and the air purifying agent gradually turns colorless, which indicates that the reaction of the raw materials is finished.
Example 2:
(1) dissolving 1 part of sodium carbonate, 10 parts of sodium chlorite and 1 part of magnesium sulfate in 72 parts of water, dripping a bromothymol blue indicator into the mixture to form blue, and then adding 8 parts of sodium polyacrylate to prepare gel;
(2) uniformly mixing 2 parts of dried calcium chloride, 2 parts of calcium oxide, 2 parts of sodium dihydrogen phosphate and 2 parts of sodium bicarbonate, and sealing and packaging to form an auxiliary material bag;
(3) when the auxiliary material bag is used, the auxiliary material bag is unsealed, the content of the auxiliary material bag is poured out and covered on the gel, the two materials react to release chlorine dioxide, and the chlorine dioxide is stably and slowly released in the gel. The slow release rate of 100g of the air purifying agent is 14-16mg/h, and the blue color gradually changes into yellow color, which indicates that the raw material reaction is finished.
Example 3:
most of the same is true as in example 1, except that in this example, the polyethylene glycol is replaced with polyvinyl alcohol.
Example 4:
compared with example 1, most of the results are the same, except that in this example, the polyethylene glycol is changed to polyacrylamide.
Example 5:
most of the results were the same as in example 1, except that in this example, 12 parts of sodium chlorite was changed to 11 parts of sodium chlorite.
Example 6:
compared with the example 1, most of the results are the same, except that in the example, 8 parts of polyethylene glycol is changed into 9 parts of polyethylene glycol, the viscosity of the gel is improved, and the slow release rate of the prepared 100g of the air purifying agent is 14-15 mg/h.
Comparative example 1:
most of the results were the same as in example 1, except that in this comparative example, calcium chloride and calcium oxide were not added. The prepared purifying agent still has no obvious chlorine dioxide release detected after being placed for 24 hours, the sodium chlorite decomposition reaction is started slowly, and compared with the example 1, the result shows that the addition of the calcium chloride and the calcium oxide can quickly start the sodium chlorite decomposition reaction and increase the release rate of the chlorine dioxide.
Comparative example 2:
compared with the example 1, most of the purification agents are the same except that in the comparative example, 2 parts of calcium chloride and 2 parts of calcium oxide are changed into 4 parts of calcium chloride and 4 parts of calcium oxide, the prepared purifying agent has high speed of releasing chlorine dioxide, but has short duration and basically releases all chlorine dioxide within 48 hours.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.

Claims (10)

1. The double-solid slow-release air purifying agent is characterized by comprising gel and an auxiliary material bag which acts with the gel and enables the gel to release chlorine dioxide, wherein the gel comprises the following raw materials in parts by weight: 1 part of sodium carbonate, 10-12 parts of sodium chlorite, 1 part of sulfate, 72 parts of water and 8-10 parts of water-absorbing resin; the auxiliary material bag comprises the following raw materials in parts by weight: 2 parts of calcium chloride, 2 parts of calcium oxide, 2 parts of sodium dihydrogen phosphate and 2 parts of sodium bicarbonate.
2. The dual-solid slow-release air purifying agent according to claim 1, wherein the sulfate is sodium sulfate or magnesium sulfate.
3. The dual-solid slow-release air purifying agent as claimed in claim 1, wherein the water-absorbent resin is polyethylene glycol, sodium polyacrylate, polyvinyl alcohol or polyacrylamide.
4. The dual-solid slow-release air purifying agent as claimed in claim 1, wherein the preparation process of the gel comprises the following steps:
and (3) dispersing sodium carbonate, sodium chlorite and sulfate in water, and then mixing with water absorption resin to obtain the gel.
5. The double-solid slow-release air purifying agent according to claim 4, wherein the mass ratio of the sodium carbonate to the sodium chlorite to the sulfate to the water-absorbent resin is 1: 10: 1: 72: 8.
6. the dual-solid slow-release air purifying agent according to claim 4, wherein the raw material of the gel further comprises an indicator for indicating the reaction speed and the utilization degree of the raw material.
7. The dual-solid slow-release air purifying agent as claimed in claim 6, wherein sodium carbonate, sodium chlorite and sulfate are dispersed in water, indicator is added dropwise, and the mixture is mixed with water-absorbent resin to obtain gel.
8. The dual-solid slow-release air purifying agent according to claim 6, wherein the indicator is bromothymol blue indicator or alpha-naphthol phthalein indicator.
9. The dual-solid slow-release air purifying agent according to claim 1, wherein the preparation process of the auxiliary material bag comprises the following steps:
and (3) uniformly mixing calcium chloride, calcium oxide, sodium dihydrogen phosphate and sodium bicarbonate, and hermetically packaging to obtain the auxiliary material bag.
10. The dual-solid slow-release air purifying agent according to claim 1, wherein when the purifying agent is used, the auxiliary material bag is unsealed, the contents of the auxiliary material bag are poured out and covered on the gel, and the gel slowly releases chlorine dioxide.
CN202111411965.6A 2021-11-25 2021-11-25 Double-solid slow-release air purifying agent Pending CN114052042A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111411965.6A CN114052042A (en) 2021-11-25 2021-11-25 Double-solid slow-release air purifying agent

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111411965.6A CN114052042A (en) 2021-11-25 2021-11-25 Double-solid slow-release air purifying agent

Publications (1)

Publication Number Publication Date
CN114052042A true CN114052042A (en) 2022-02-18

Family

ID=80276144

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111411965.6A Pending CN114052042A (en) 2021-11-25 2021-11-25 Double-solid slow-release air purifying agent

Country Status (1)

Country Link
CN (1) CN114052042A (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108079359A (en) * 2017-12-22 2018-05-29 浙江惠普科技发展有限公司 A kind of steam atomization air purification bag
CN110433623A (en) * 2019-07-25 2019-11-12 苏州拜革环能科技有限公司 A kind of changeable colour slow-release disinfection bactericidal purifying material
CN112826357A (en) * 2021-02-26 2021-05-25 华侨大学 Chlorine dioxide sustained-release gel device for toilet and sterilization toilet lid thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108079359A (en) * 2017-12-22 2018-05-29 浙江惠普科技发展有限公司 A kind of steam atomization air purification bag
CN110433623A (en) * 2019-07-25 2019-11-12 苏州拜革环能科技有限公司 A kind of changeable colour slow-release disinfection bactericidal purifying material
CN112826357A (en) * 2021-02-26 2021-05-25 华侨大学 Chlorine dioxide sustained-release gel device for toilet and sterilization toilet lid thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
李振华，伏宏彬，郑光洪，: "《染整专业英语》", 30 November 2005, 中国纺织出版社 *
菅田田，张钦发，刘悦悦，莫宜澄: "二氧化氯缓释剂的研究及应用进展", 《食品工业》 *
贵州省化工情报中心站编: "《贵州省化工产品手册》", 30 September 1988, 贵州省化工厅信息处 *

Similar Documents

Publication Publication Date Title
CN111602669B (en) Solid chlorine dioxide slow-release agent
JPS59132937A (en) Deodorant
CN111713490B (en) Chlorine dioxide disinfection gel and preparation method thereof
US8048201B2 (en) Oxygen scavenger and a method for scavenging oxygen
CN111296428A (en) Long-term slow-release chlorine dioxide solid material
CN111264519A (en) Solid chlorine dioxide slow-release material and preparation method thereof
CN110384105A (en) A kind of controllable sustained-release disinfection and sterilization scavenging material
CN110898246A (en) Gel powder capable of purifying air and preparation method thereof
CN105688646A (en) Air purification elimination agent
JPS6359338A (en) Ozone removing agent
US5360574A (en) Gel-form deodorant composition containing chloride dioxide
CN113662004A (en) Slow-release chlorine dioxide disinfection card using zeolite as carrier
CN104432407B (en) A kind of moisture film oxygen absorbent and preparation method thereof
CN113663510A (en) Indoor deodorant after decoration and preparation method thereof
CN114052042A (en) Double-solid slow-release air purifying agent
CN105010389B (en) A kind of slow released ClO 2 pulvis and preparation method thereof
CN114146209A (en) Solid slow-release air purifying agent and preparation method thereof
CN111701439A (en) Formaldehyde-removing color-changing gel with visual perception and preparation method thereof
CN110585467A (en) Air purification gel composition and preparation method thereof
JPH0365239A (en) Deodorizing agent
CN104174268A (en) Aromatic air purification powder
AU2020338368A1 (en) Solid material for purifying air and preparation method and use thereof
CN111567518A (en) Gel-like sodium hypochlorite disinfectant and preparation method and application thereof
CN115363024B (en) Preparation method of slow-release type immobilized chlorine dioxide air purifying agent
JPS63258644A (en) Deodorizer

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination