CN1051672C - Mosquito-expelling and mosquito preventing compound - Google Patents
Mosquito-expelling and mosquito preventing compound Download PDFInfo
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- CN1051672C CN1051672C CN93103627A CN93103627A CN1051672C CN 1051672 C CN1051672 C CN 1051672C CN 93103627 A CN93103627 A CN 93103627A CN 93103627 A CN93103627 A CN 93103627A CN 1051672 C CN1051672 C CN 1051672C
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Abstract
The present invention provides a novel mosquito expelling and preventing composition which mainly comprises a solid carrier capable of sublimating under normal temperature and an effective amount of mosquito expelling and preventing agent, and a proper amount of synergy auxiliary agent can also be added. The composition of the present invention has the main advantages of obvious effect on expelling and preventing mosquitoes, no need of open flame or electrical heating while in use, no abnormal smell and no pollution to the environment. The novel mosquito expelling and preventing composition is more suitable for use in primary fire and explosion prevention areas and carrying on a journey.
Description
The present invention relates to the repellent and the control of sanitary insect pest, relate in particular to repellent and control the more serious various mosquitoes of people and animals' harm.
The mosquito-proof product of mosquito repellent in the market mainly contains mosquito-repellent incense, electric mosquito repellent tablet, vaporizer mosquito liquid and, mosquito-proof water water funk as the mosquito of repellant etc.These products generally need allow effective ingredient evaporate with naked light, Electric heating, or directly are coated on people's the skin, just can reach mosquito repellent, mosquito-proof effect.
The present invention is a kind of novel normal temperature mosquito-proof composition of mosquito repellent of volatilization down, and it does not need to light, and does not need electrical heating, needn't be coated in to reach mosquito repellent, mosquito-proof effect on the skin yet.
The objective of the invention is to realize in the following manner, it is a kind of solid-state mosquito repellent, mosquito-proof composition, it is characterized in that it mainly comprises two compounds: the first kind is the solid carrier that can distil under a kind of normal temperature, and second class is killed or kill mosquito, the anophelifuge of repellent action for mosquito is had.
The solid carrier of mosquito repellent of the present invention, mosquito-proof composition can be selected from a kind of in the following material: metaformaldehyde, methyl carbamate, cyclododecane, tristane, to the solid matter that chlorodiphenyl, naphthalene, camphor etc. have sublimability wherein are best with the metaformaldehyde.Metaformaldehyde (claiming 1,3 again, the 5-trioxane) is white crystals, 64 ℃ of fusing points, and European patent EP 269,292 has disclosed the effect that metaformaldehyde has repellent ant and Lian.The embodiment of the invention proves: if when having the metaformaldehyde of higher concentration in the space, mosquito is also had certain knockdown effect, but under concentration usually, do not reach mosquito repellent, mosquito-proof effect.In the present invention, metaformaldehyde, can bring out second compounds among the present invention-kill mosquito, anophelifuge when it distils at normal temperatures together in fact mainly as a kind of effective carrier, thereby reaches mosquito repellent, mosquito-proof purpose.
Second compounds-kill mosquito in mosquito repellent of the present invention, the mosquito-proof composition, the scope of anophelifuge are wider, can be a kind of in pyrethroid insecticides, organophosphorus insecticide, carbamate pesticide or the mosquito repellant or several.Wherein pyrethroid insecticides comprises decis, cypermethrin, permethrin, tetramethrin, allethrin (EBT), alkynes valerate, Chinese and Western aerosol chrysanthemum ester, Chinese and Western mosquito-killing chrysanthemum ester, propine chrysanthemum ester (ETOC), methothrin, sumicidin etc.Organophosphorus insecticide comprises Folithion, dichlorvos (DDVP), chlopyrifos, parathion etc.; Carbamate pesticide comprises sevin, Ba Sha, unden etc.; And mosquito repellant N, toluamide between the N-diethyl (DETA) and repefral.
Mosquito repellent of the present invention, mosquito-proof composition can also comprise the 3rd compounds-builder, and this builder can be selected from a kind of in the following material or several: peppermint, diatomite, talcum powder, maltonic acid-delta-lactone and vitamin C etc.
The weight percentage of kill mosquito in mosquito repellent of the present invention, the mosquito-proof composition, anophelifuge is 0.1-10%, is better with 0.1-6%; The weight percentage of carrier is 70-99.5%, is better with 79.00-99.50%; The weight percentage of builder is 0.4-20%.
Advantage of the present invention is significantly, and not only the mosquito-prevention mosquito-repellent effect is fairly obvious for the present composition, and does not need naked light or electrical heating when using, and free from extraneous odour is free from environmental pollution again, more needn't scruple to cause fire alarm and other trouble.Except being suitable for general indoor use, preferably in one-level fire prevention, explosion-proof area and portably use on the road.
The present invention is described in further detail by the following examples:
Embodiment 1-43
Solid carrier metaformaldehyde, various kill mosquito anophelifuge and builder are formed homogeneous compositions with Table I and the listed proportioning of Table II, strike out thick 0.5 centimetre with mould, the nahlock that φ is 3.0 centimetres, heavily about 6 grams, under 25 ℃ of room temperatures, the per minute volatile quantity is about the 10-12 milligram.
In 20 centimetres of φ, high 43 centimetres standard cylinder analyzer, put into 30-50 head 3-5 days the female mosquito of Culex pipiens pallens in back that sprouts wings.Put into mosquito repellent anophelifuge of the present invention in bottom centre then, about one minute, can observe mosquito and descend one after another, be parked in the container below, no longer circle in the air.The time of knocking down percentage and all knocking down with observed different time mosquito, the results are shown in Table III.
Table 1
| Embodiment | The dosage of metaformaldehyde, insecticide, repellant and builder (Wt%) | |||||||||
| Metaformaldehyde | EBT | Little western mosquito-killing chrysanthemum ester | Chinese and Western aerosol chrysanthemum ester | DDVP | Folithion | Ba Sha | DETA | Decis | Builder | |
| 1 | 100.00 | |||||||||
| 2 | 99.00 | 1.00 | ||||||||
| 3 | 99.00 | 0.30 | 0.30 | 0.40 | ||||||
| 4 | 98.50 | 0.30 | 0.30 | 0.40 | 0.50 | |||||
| 5 | 95.00 | 5.00 | ||||||||
| 6 | 85.00 | 5.00 | Diatomite 10.00 | |||||||
| 7 | 83.90 | 0.30 | 0.40 | 0.40 | 5.00 | Diatomite 10.00 | ||||
| 8 | 98.20 | 0.30 | 1.00 | 0.50 | ||||||
| 9 | 89.00 | 1.00 | Vitamin C 10.00 | |||||||
| 10 | 98.20 | 0.80 | 1.00 | |||||||
| 11 | 99.00 | 1.00 | ||||||||
| 12 | 88.20 | 0.30 | 0.50 | 1.00 | Peppermint 10.00 | |||||
| 13 | 98.00 | 0.50 | 0.50 | 1.00 | ||||||
| 14 | 88.00 | 0.50 | 0.50 | 1.00 | Vitamin C 9.00 peppermints 1.00 | |||||
| 15 | 99.10 | 0.40 | 0.50 | |||||||
| Embodiment | The dosage of metaformaldehyde, insecticide, repellant and builder (Wt%) | |||||||||
| Metaformaldehyde | EBT | The Chinese and Western mosquito-killing chrysanthemum ester | Chinese and Western aerosol chrysanthemum ester | DDVP | Folithion | Ba Sha | DETA | Decis | Builder | |
| 16 | 79.10 | 0.40 | 0.50 | Talcum powder 20.00 | ||||||
| 17 | 79.00 | 0.25 | 0.25 | 0.50 | Vitamin C 20.00 | |||||
| 18 | 99.29 | 0.20 | 0.50 | 0.01 | ||||||
| 19 | 98.80 | 0.40 | 0.50 | 0.30 | ||||||
| 20 | 99.05 | 0.50 | 0.05 | Peppermint 0.40 | ||||||
| 21 | 89.50 | 0.50 | Maltonic acid-delta-lactone 10.0 | |||||||
| 22 | 89.15 | 0.30 | 0.50 | 0.05 | Maltonic acid-delta-lactone 10.00 | |||||
| 23 | 99.50 | 0.50 | ||||||||
| 24 | 89.50 | 0.50 | Maltonic acid δ lactone 10.00 | |||||||
| 25 | 89.20 | 0.50 | 0.30 | Maltonic acid-delta-lactone 10.00 | ||||||
| 26 | 99.00 | 0.50 | 0.50 | |||||||
| 27 | 99.00 | 0.50 | 0.50 | |||||||
| 28 | 99.00 | 0.50 | 0.50 | |||||||
| 29 | 89.60 | 0.20 | 0.20 | Maltonic acid δ lactone 10.00 | ||||||
| Embodiment | The dosage of metaformaldehyde, insecticide, repellant and builder (Wt%) | |||||||||
| Metaformaldehyde | EBT | The Chinese and Western mosquito-killing chrysanthemum ester | Chinese and Western aerosol chrysanthemum ester | DDVP | Folithion | Ba Sha | DETA | Decis | Builder | |
| 30 | 89.20 | 0.40 | 0.40 | Maltonic acid-δ lactone 10.00 | ||||||
| 31 | 89.20 | 0.40 | 0.40 | Maltonic acid-δ lactone 10.00 | ||||||
| 32 | 79.00 | 0.30 | 0.30 | 0.40 | Maltonic acid-delta-lactone 20.00 | |||||
| 33 | 89.80 | 0.10 | 0.10 | Maltonic acid-delta-lactone 10.00 | ||||||
| 34 | 89.60 | 0.20 | 0.20 | Maltonic acid-δ lactone 10.00 | ||||||
| 35 | 89.60 | 0.20 | 0.20 | D gluconic acid-δ lactone 10.00 | ||||||
| 36 | 89.50 | 0.20 | 0.10 | 0.20 | D glucono-10.00 | |||||
| 44 | 95.00 | 5.00 | ||||||||
| Embodiment | The dosage of metaformaldehyde, insecticide, repellant and builder (Wt%) | |||||||||
| Metaformaldehyde | EBT | The Chinese and Western mosquito-killing chrysanthemum ester | Chinese and Western aerosol chrysanthemum ester | DDVP | Folithion | Ba Sha | DETA | Decis | Builder | |
| 45 | 97.00 | 3.00 | ||||||||
| 46 | 96.00 | 2.00 | 2.00 | |||||||
| 47 | 96.00 | 2.00 | 2.00 | |||||||
| 48 | 97.50 | 0.50 | 0.50 | 0.50 | Peppermint 1.00 | |||||
Table II
| Numbering | The dosage of metaformaldehyde, insecticide, repellant and builder (Wt%) | |||||||||||
| Metaformaldehyde | EBT | Chinese and Western aerosol chrysanthemum ester | Ba Sha | Unden | Chlopyrifos | Tetramethrin | Propine chrysanthemum ester (ETOC) | Permethrin | Cypermethrin | Methothrin | Builder | |
| 37 | 89.90 | 0.05 | 0.05 | Maltonic acid-delta-lactone 10 | ||||||||
| 38 | 99.50 | 0.50 | ||||||||||
| 39 | 89.10 | 0.20 | 0.20 | 0.50 | Maltonic acid-delta-lactone 10 | |||||||
| 40 | 89.40 | 0.20 | 0.20 | 0.20 | Maltonic acid-delta-lactone 10 | |||||||
| 41 | 89.65 | 0.10 | 0.10 | 0.10 | 0.05 | Maltonic acid-delta-lactone 10 | ||||||
| 42 | 89.40 | 0.20 | 0.10 | 0.20 | 0.10 | Maltonic acid-delta-lactone 10 | ||||||
| 43 | 89.60 | 0.10 | 0.10 | 0.10 | 0.05 | 0.05 | Maltonic acid-delta-lactone 10 | |||||
Table III
| Embodiment | The rate of knockdown of different time (%) | |||||||||||||||||
| 5’ | 10’ | 15’ | 20’ | 25’ | 30’ | 35’ | 40’ | 45’ | 50’ | 55’ | 60’ | 65’ | 70’ | 80’ | 90’ | 100’ | ||
| 1 | 14.3 | 20.0 | 25.7 | 34.3 | 48.6 | 51.3 (120’) | ||||||||||||
| 2 | 6.7 | 60.0 | 100.0 | |||||||||||||||
| 3 | 20.7 | 69.0 | 89.1 | 100.0 | ||||||||||||||
| 4 | 6.5 | 58.1 | 83.9 | 96.8 | 100 (57’) | |||||||||||||
| 5 | 14.3 | 28.6 | 82.1 | 100 (68’) | ||||||||||||||
| 6 | 12.5 | 46.9 | 75.0 | 100 (130’) | ||||||||||||||
| 7 | 6.0 | 45.4 | 75.8 | 90.9 | 94.0 | 100 | ||||||||||||
| 8 | 12.2 | 34.1 | 68.3 | 95.1 | 100 | |||||||||||||
| 9 | 5.7 | 17.1 | 25.7 | 45.7 | 77.1 | 100 | ||||||||||||
| 10 | 7.9 | 63.2 | 84.2 | 94.7 | 100 | |||||||||||||
| 11 | 9.4 | 21.9 | 46.9 | 84.4 | 93.8 | 100 | ||||||||||||
| 12 | 21.6 | 35.1 | 81.1 | 94.6 | 100 | |||||||||||||
| 13 | 5.1 | 35.9 | 92.3 | 97.4 | 100 | |||||||||||||
| 14 | 7.5 | 40.0 | 45.0 | 90.0 | 95.0 | 100 (52’) | ||||||||||||
| 15 | 5.7 | 15.4 | 55.7 | 96.0 | 100 | |||||||||||||
| Embodiment | The rate of knockdown of different time (%) | |||||||||||||||||
| 5’ | 10’ | 15’ | 20’ | 25’ | 30’ | 35’ | 40’ | 45’ | 50’ | 55’ | 60’ | 65’ | 70’ | 80’ | 90’ | 100’ | ||
| 16 | 5.7 | 34.6 | 80.7 | 96.0 | 100 | |||||||||||||
| 17 | 11.7 | 66.7 | 98.2 | 100 | ||||||||||||||
| 18 | 9.3 | 75.0 | 100 | |||||||||||||||
| 19 | 9.3 | 78.1 | 100 | |||||||||||||||
| 20 | 2.9 | 14.7 | 20.6 | 73.5 | 100 | |||||||||||||
| 21 | 11.8 | 38.2 | 55.1 | 73.5 | 91.2 | 100 | ||||||||||||
| 22 | 7.7 | 15.4 | 25.6 | 46.2 | 61.5 | 92.3 | 100 | |||||||||||
| 23 | 11.1 | 22.2 | 44.4 | 68.9 | 75.6 | 80.0 | 82.2 | 91.1 | 100 | |||||||||
| 24 | 5.5 | 16.7 | 27.8 | 50.0 | 66.7 | 72.2 | 86.1 | 94.4 | 100 | |||||||||
| 25 | 12.8 | 30.8 | 46.2 | 64.1 | 74.4 | 97.4 | 100 | |||||||||||
| 26 | 18.2 | 24.2 | 36.4 | 42.4 | 60.6 | 84.8 | 100 | |||||||||||
| 27 | 7.2 | 11.9 | 31.0 | 42.9 | 76.2 | 90.5 | 1.00 | |||||||||||
| 28 | 16.2 | 27.0 | 29.7 | 43.2 | 64.9 | 86.5 | 97.3 | 100 | ||||||||||
| 29 | 25.0 | 57.1 | 71.4 | 82.1 | 92.9 | 100 | ||||||||||||
| 30 | 23.1 | 38.5 | 50.0 | 61.5 | 92.3 | 100 | ||||||||||||
| 31 | 15.6 | 31.3 | 50.0 | 62.5 | 75.0 | 78.1 | 90.6 | 100 | ||||||||||
| 32 | 8.6 | 17.1 | 20.0 | 22.8 | 57.1 | 77.1 | 80.1 | 100 | ||||||||||
| 33 | 23.5 | 50.0 | 67.6 | 79.4 | 88.2 | 94.1 | 100 | |||||||||||
| 34 | 12.9 | 35.5 | 51.6 | 74.2 | 87.1 | 93.5 | 100 | |||||||||||
| 35 | 10.3 | 31.0 | 31.0 | 48.3 | 65.5 | 82.8 | 93.1 | 100 | ||||||||||
| 36 | 35.7 | 53.6 | 67.9 | 71.4 | 78.6 | 85.7 | 92.9 | 100 | ||||||||||
| 37 | 10.5 | 18.4 | 39.5 | 47.4 | 71.1 | 89.5 | 100 | |||||||||||
| Embodiment | The rate of knockdown of different time (%) | |||||||||||||||||
| 5’ | 10’ | 15’ | 20’ | 25’ | 30’ | 35’ | 40’ | 45’ | 50’ | 55’ | 60’ | 65’ | 70’ | 80’ | 90’ | 100’ | ||
| 38 | 18.4 | 26.3 | 26.3 | 42.1 | 57.3 | 78.9 | 89.5 | 94.7 | 100 | |||||||||
| 39 | 6.0 | 12.1 | 18.2 | 27.3 | 33.3 | 48.5 | 75.8 | 87.9 | 100 | |||||||||
| 40 | 23.1 | 30.1 | 46.2 | 79.5 | 100 | |||||||||||||
| 41 | 10.5 | 26.3 | 42.1 | 47.4 | 57.9 | 65.8 | 78.9 | 92.1 | 100 | |||||||||
| 42 | 7.7 | 20.5 | 28.2 | 33.3 | 46.2 | 56.4 | 74.4 | 89.7 | 100 | |||||||||
| 43 | 26.2 | 38.1 | 64.3 | 71.4 | 78.6 | 92.8 | 100 | |||||||||||
| 44 | 100 (360’) | |||||||||||||||||
| 45 | 100 (180’) | |||||||||||||||||
| 46 | 12.1 | 100 (135’) | ||||||||||||||||
| 47 | 12.5 | 100 (150’) | ||||||||||||||||
| 48 | 8.1 | 24.3 | 35.1 | 81.0 | ||||||||||||||
Can know that from the listed data of Table III the carrier metaformaldehyde of seeing the present composition itself also has the effect of knocking down mosquito; After adding small amount of insecticide or repellant in the metaformaldehyde, the rate of knockdown of mosquito has improved greatly; In mosquitocide and the repellant, has mosquito-proof preferably effect with DDVP; But the effect of many numbering prescriptions has surpassed the prescription that adds DDVP separately, illustrates that the various compositions of the present invention all have effect significantly mosquito-proof, mosquito repellent.
Can see from the foregoing description 36: in standard testing tube of the present invention, the present composition is to the killing time of 50(KT50) (Kt of mosquito
50) the shortest be 9 minutes, near the level of general dish mosquito-repellent incense.
Embodiment 44-48
Proportioning according to Table I embodiment 44,45,46,47,48 is formed homogeneous compositions, and (preparation method is with other embodiment among the embodiment 1-43) simulate repellency test with small white mouse in 70 * 70 * 70 centimetres square glass test box.Test and put into specimen earlier in preceding 10 minutes, yet put into 50 female mosquitoes and shave off one of the small white mouse of belly wool, the belly of small white mouse up, four-footed binds and is fixed on the plank with restricting; For bite by mosquitos.The mosquito that all are put in process of the test all rests on the test tank wall, and none is sucked blood.
Embodiment 49:
Proportioning according to Table I embodiment 9 is formed homogeneous compositions, in 2.0 * 2.0 * 2.8 meters cell, put into 100 of above-mentioned composition 50 grams of the present invention and female Culex pipiens pallens adults, after 20 minutes, during the mosquito overwhelming majority stays and is parked in, on the wall of below, the personnel of sitting quietly in the chamber are had no attacking ability.Therefore, mosquito-proof, the repelling effect of the present composition are tangible.
Claims (8)
1. solid-state composition is characterized in that it mainly comprises:
(1) the solid carrier metaformaldehyde that can distil under a kind of normal temperature;
(2) expelling parasite of effective dose, insecticide, described expelling parasite, insecticide are selected from a kind of or several pyrethroid insecticideses, organophosphorus insecticide, carbamate pesticide or mosquito repellant, must be two or more for wherein pyrethroid insecticides.
2. solid-state composition according to claim 1, its feature is that also pyrethroid insecticides wherein is selected from: decis, cypermethrin, permethrin, tetramethrin, allethrin, Chinese and Western aerosol chrysanthemum ester, Chinese and Western mosquito-killing chrysanthemum ester, propine chrysanthemum ester or methothrin.
3. solid-state composition as claimed in claim 1, its feature is that also wherein organophosphorus insecticide is selected from: Folithion, dichlorvos or chlopyrifos.
4. solid-state composition as claimed in claim 1 is characterized in that carbamate pesticide wherein is selected from: Ba Sha, unden etc.
5. as the described solid-state composition of claim 1-4, it is characterized in that it also comprises builder.
6. solid-state composition as claimed in claim 5, its feature are that also described builder can be selected from a kind of in the following material or several: peppermint, maltonic acid-delta-lactone, vitamin C etc.
7. solid-state composition as claimed in claim 6 is characterized in that wherein
The content of expelling parasite, insecticide (Wt%) is 0.10-6.00%
The content of carrier (Wt%) is 79.00-99.50%
The content of builder (Wt%) is 0.40-20.00%
8. as the purposes of solid-state composition as described in the claim 1-7, it is characterized in that it is used to mosquito repellent or mosquito-proof.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93103627A CN1051672C (en) | 1993-03-27 | 1993-03-27 | Mosquito-expelling and mosquito preventing compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93103627A CN1051672C (en) | 1993-03-27 | 1993-03-27 | Mosquito-expelling and mosquito preventing compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1075844A CN1075844A (en) | 1993-09-08 |
| CN1051672C true CN1051672C (en) | 2000-04-26 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN93103627A Expired - Lifetime CN1051672C (en) | 1993-03-27 | 1993-03-27 | Mosquito-expelling and mosquito preventing compound |
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| CN (1) | CN1051672C (en) |
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| ES2643140T3 (en) * | 2005-12-22 | 2017-11-21 | Oakwood Laboratories L.L.C. | Sublimable slow release delivery system and procedure for carrying it out |
| CN104126603B (en) * | 2009-06-05 | 2016-06-15 | 江苏扬农化工股份有限公司 | A kind of the method for control of Pest control repellant and insect |
| CN102771500A (en) * | 2012-07-09 | 2012-11-14 | 江苏碧松照明电气有限公司 | Insecticide cream |
| CN105230649A (en) * | 2015-09-09 | 2016-01-13 | 广州立白企业集团有限公司 | Pest repellent tablet with long-acting release of pyrethroid under heating |
| CN105369610A (en) * | 2015-12-14 | 2016-03-02 | 然晟(上海)实业发展有限公司 | Anti-mosquito and washable fabric and preparation method and application thereof |
| CN106137855A (en) * | 2016-08-17 | 2016-11-23 | 朱维 | A kind of natural infant mosquito-driving liquid containing Thallus Porphyrae extract |
| CN109736090A (en) * | 2019-01-21 | 2019-05-10 | 天津永阔国际贸易有限公司 | A kind of finishing fluid and application method for mosquito fabric |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87104588A (en) * | 1987-06-30 | 1988-03-16 | 上海市金山县东风涂料厂 | Slow-releasing agent for killing larvel mosquito |
| EP0269292A1 (en) * | 1986-11-04 | 1988-06-01 | Mitsubishi Gas Chemical Company, Inc. | Insect-proofing agent and insect proofing method |
| JPH09195669A (en) * | 1996-01-19 | 1997-07-29 | Hitachi Constr Mach Co Ltd | Shield drilling machine |
| JP3146139B2 (en) * | 1995-09-05 | 2001-03-12 | 丸尾カルシウム株式会社 | Plastic additive for light diffusion and plastic composition for light diffusion |
-
1993
- 1993-03-27 CN CN93103627A patent/CN1051672C/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0269292A1 (en) * | 1986-11-04 | 1988-06-01 | Mitsubishi Gas Chemical Company, Inc. | Insect-proofing agent and insect proofing method |
| CN87104588A (en) * | 1987-06-30 | 1988-03-16 | 上海市金山县东风涂料厂 | Slow-releasing agent for killing larvel mosquito |
| JP3146139B2 (en) * | 1995-09-05 | 2001-03-12 | 丸尾カルシウム株式会社 | Plastic additive for light diffusion and plastic composition for light diffusion |
| JPH09195669A (en) * | 1996-01-19 | 1997-07-29 | Hitachi Constr Mach Co Ltd | Shield drilling machine |
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| CN1075844A (en) | 1993-09-08 |
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