CN102604046A - DMP-30 (dimethyl phthalate-30) closing method and application of DMP-30 in epoxy adhesive - Google Patents
DMP-30 (dimethyl phthalate-30) closing method and application of DMP-30 in epoxy adhesive Download PDFInfo
- Publication number
- CN102604046A CN102604046A CN2012100645801A CN201210064580A CN102604046A CN 102604046 A CN102604046 A CN 102604046A CN 2012100645801 A CN2012100645801 A CN 2012100645801A CN 201210064580 A CN201210064580 A CN 201210064580A CN 102604046 A CN102604046 A CN 102604046A
- Authority
- CN
- China
- Prior art keywords
- acid
- dmp
- enclosure method
- epoxy adhesive
- contain
- 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.)
- Granted
Links
- 0 C*c(cc1*C)cc(*(C)C)c1O Chemical compound C*c(cc1*C)cc(*(C)C)c1O 0.000 description 2
Abstract
The invention relates to a DMP-30 (dimethyl phthalate-30) closing method, which includes mixing, by weight, 60%-90% of DMP-30 and 10-40% of acidoid to disable the DMP-30 to open loops of epoxy perssad. The balance can be damaged by gently heating to start curing reaction in practical application of the DMP-30, so that the DMP-30 turns to be similar to a latency curing agent or curing catalyst. The invention further comprises epoxy adhesive containing the closed DMP-30, and the adhesive can be used for adhering only by gently heating.
Description
Technical field
The present invention relates to the enclosure method of a kind of DMP-30 and, be used for improving its stability, belong to the epoxyn field at epoxy adhesive in the application of epoxy adhesive.
Background technology
The DMP-30 structural formula is:
Its molecular formula: C15H27N3O, molecular weight: 265.40, CAS No.:90-72-2, title: 2,4,6-three (dimethylaminomethyl) phenol, English name: 2,4,6-tris (dimethylaminomethyl) phenol flash-point: 150 ℃; Proportion (25 ℃): 0.97, outward appearance is a light yellow transparent liquid, about 250 ℃ of boiling point has the amine stink, is soluble in organic solvent, is dissolved in cold water, is slightly soluble in hot water.
Mainly as epoxy curing agent, fast setting or temperature curing epoxy low resin coating serve as cast, sealing member etc. to DMP-30 at normal temperatures.DMP-30 can be separately as epoxy curing agent; Consumption to the bisphenol A epoxide resin of epoxy equivalent (weight) 185-195 is 10%, also can mix use with other epoxy hardener, rises to promote solidification; Can improve solidification rate, consumption is 0.1%-3% when doing promotor and using; Ambient cure consumption 10%-15% when being used for epoxy resin-liquid polysulfide system, consumption 6% is heating and curing.In general, DMP-30 uses separately and can give bonding system and sealing material particular performances, can reduce solidification value greatly as promotor use, improves curing efficiency, has purposes widely in epoxy resin gluing agent field.Its cured epoxy group open loop mechanism is following: at first be the N atom among the DMP-30; Owing to contain lone-pair electron; The nucleophilicity of its lone-pair electron is impelled the attack epoxide group; After epoxide group was opened, the negative oxygen ion of formation can further react with epoxide group, thereby realized the polymerizing curable of epoxy resin.See following reaction process:
DMP-30 generally is applied in and does the solidifying agent use in the two component epoxy glue, mainly is because its amido alkalescence is stronger, is easy to and the epoxide group ring-opening reaction; Therefore, can not use, even as promotor as latent curing agent; Can not make single-component epoxy glue, and, when two components use; It is short also to exist the running time, the phenomenon that gel is too fast, and this is the major defect during DMP-30 uses.
Summary of the invention
Technical problem to be solved by this invention provides the enclosure method of a kind of DMP-30; Be to keep latent to a certain extent with assurance DMP-30 through the pH value of interpolation acidic substance among the DMP-30 being controlled whole system; Overcome easily and ring-opening reaction takes place epoxide group at short notice; Cause in use, the running time is short, the defective that gel is too fast.
The technical scheme that the present invention solves the problems of the technologies described above is following: a kind of DMP-30 enclosure method is mixed and made into by 60%～90% (weight percent) DMP-30,10%～40% (weight percent) acidic substance.
In the wherein said acidic substance hydrogen cation and said in the following reaction process of nitrogen-atoms cohesive process:
The invention has the beneficial effects as follows: the hydrogen cation that utilization acid provides combines with the nitrogen-atoms among the DMP-30; Form a kind of weak acid state; Perhaps utilize the lone-pair electron of nitrogen-atoms among the lewis acidic electron pairing ability complexing DMP-30, thereby make DMP-30 lose open loop ability epoxide group, and in practical application; Only need low-grade fever to destroy this balance; Just can start curing reaction, thereby make DMP-30 become a kind of similar latent curing agent, perhaps curing catalyst; Therefore having formed one type has the same low-temperature curing performance of similar two component epoxy sizing agent, has the novel epoxy sizing agent system of the same easy processing property of single-component epoxy sizing agent simultaneously.
On the basis of technique scheme, the present invention can also do following improvement.
Add acidic substance in the said DMP-30 enclosure method and make the pH value in the mixed system be controlled at 7-12, preferred PH is 7-10.
Adopt the beneficial effect of above-mentioned further scheme to be: to combine with nitrogen-atoms among the DMP-30 to guarantee to provide enough hydrogen cations.
Further, said acidic substance comprise mineral acid, and organic acid does not contain carboxyl in Lewis acid or the organism but shows the tart material.
Further, described mineral acid is a nitric acid, phosphoric acid, sulfuric acid, hydrochloric acid, hydrofluoric acid, hydrochloric acid, hydroiodic acid HI, Hydrogen bromide, hypochlorous acid, perchloric acid, bromic acid, a kind of or any several kinds mixture in the acid iodide etc.
Further, not containing carboxyl in the said organism but showing the tart material is barbituric acid, phenylethyl barbituric acid.
Further, said organic acid is C
1-C
90Longer chain fatty acid, contain the aromatic acid of benzene ring structure, contain the organic acid of alicyclic structure, contain a kind of or any several kinds mixture in organic acid of not comprising key etc.
Further, said Lewis acid comprises group of the lanthanides, and actinium series is so subgroup element and the 3rd main group etc. contain the compound of the element of unsaturated unoccupied orbital.
Further, the said compound that contains the element of unsaturated unoccupied orbital is an aluminum chloride, zinc chloride.
The present invention also provides a kind of epoxy adhesive; It is characterized in that; The material that comprises following weight percent: according to the DMP-30 5～38% after the sealing of above-mentioned DMP-30 enclosure method preparation, epoxy resin 30～60%, thinner 1～5%, filler 30～60%, coupling agent 0～1%.
Embodiment
Below principle of the present invention and characteristic are described, institute gives an actual example and only is used to explain the present invention, is not to be used to limit scope of the present invention.
Embodiment 1
Accurately take by weighing each raw material by following weight percent, DMP-30 consumption 90%, phosphorous acid 10%.Simple physical through the two is mixed, and after mixing, the mixture pH value of formation is 7.1, and it is subsequent use that the mixture room temperature keeps.Its application at epoxy adhesive is made up of following each raw material: the DMP-30 38% after 828EL epoxy resin 30%, tertiary butyl carbonic ether glycidyl ether thinner 2%, Nanjing Hua Yuan silicon powder NF110 consumption 30%, the sealing.Above-mentioned each component is added in the duplicate rows star dynamic mixing stirrer successively, be evacuated to vacuum tightness and be-0.08～-0.05MPa, stirred 2 hours in 500 rev/mins, stirring gets final product.
Embodiment 2
Accurately take by weighing each raw material by following weight percent, DMP-30 consumption 80%, Hydrocerol A 20%.Simple physical through the two is mixed, and after mixing, the mixture pH value of formation is 9.8, and it is subsequent use that the mixture room temperature keeps.Its application at epoxy adhesive is made up of following each raw material: the DMP-30 15% after E51 epoxy resin 25%, H8 thinner 5%, 600 order silicon powder fillers 54%, KH560 coupling agent 1%, the sealing.Above-mentioned each component is added in the duplicate rows star dynamic mixing stirrer successively, be evacuated to vacuum tightness and be-0.08～-0.05MPa, stirred 2 hours in 500 rev/mins, stirring gets final product.
Embodiment 3
Accurately take by weighing each raw material by following weight percent, DMP-30 consumption 60%, oleic acid 40%.Simple physical through the two is mixed, and after mixing, the mixture pH value of formation is 8.3, and it is subsequent use that the mixture room temperature keeps.Its application at epoxy adhesive is made up of following each raw material: the DMP-30 25% after 8240 epoxy resin 44%, 1,4 butyleneglycol glycidyl ether thinner 1%, 600 order silicon powder fillers 29%, KH560 coupling agent 1%, the sealing.Above-mentioned each component is added in the duplicate rows star dynamic mixing stirrer successively, be evacuated to vacuum tightness and be-0.08～-0.05MPa, stirred 2 hours in 500 rev/mins, stir.
Embodiment 4
Accurately take by weighing each raw material by following weight percent, DMP-30 consumption 60%, aluminum chloride 40%.Simple physical through the two is mixed, and after mixing, the mixture pH value of formation is 9.9, and it is subsequent use that the mixture room temperature keeps.Its application at epoxy adhesive is made up of following each raw material: the DMP-30 25% after E44 epoxy resin 50%, Ex10 thinner 5%, 201 spherical powder fillers 19%, KH560 coupling agent 1%, the sealing.Above-mentioned each component is added in the duplicate rows star dynamic mixing stirrer successively, be evacuated to vacuum tightness and be-0.08～-0.05MPa, stirred 2 hours in 500 rev/mins, stirring gets final product.
Embodiment 5
Accurately take by weighing each raw material by following weight percent, DMP-30 consumption 85%, barbituric acid 15%.Simple physical through the two is mixed, and after mixing, the mixture pH value of formation is 8.6, and it is subsequent use that the mixture room temperature keeps.Its application at epoxy adhesive is made up of following each raw material: the DMP-30 15% after 862 epoxy resin 49%, N10 thinner 1%, 1250 order silicon powder fillers 34%, KH560 coupling agent 1%, the sealing.Above-mentioned each component is added in the duplicate rows star dynamic mixing stirrer successively, be evacuated to vacuum tightness and be-0.08～-0.05MPa, stirred 2 hours in 500 rev/mins, stir.
Embodiment 6
Accurately take by weighing each raw material by following weight percent, DMP-30 consumption 80%, barbituric acid 10%, oleic acid 10%.Simple physical through the two is mixed, and after mixing, the mixture pH value of formation is 8.8, and it is subsequent use that the mixture room temperature keeps.Its application at epoxy adhesive is made up of following each raw material: the DMP-30 15% after 4901E epoxy resin 30%, N10 thinner 5%, NF110 filler 49%, KH560 coupling agent 1%, the sealing.Above-mentioned each component is added in the duplicate rows star dynamic mixing stirrer successively, be evacuated to vacuum tightness and be-0.08～-0.05MPa, stirred 2 hours in 500 rev/mins, stirring gets final product.
Embodiment 7
Accurately take by weighing each raw material by following weight percent, DMP-30 consumption 75%, barbituric acid 15%, Hydrocerol A 10%.Simple physical through the two is mixed, and after mixing, the mixture pH value of formation is 8.2, and it is subsequent use that the mixture room temperature keeps.Its application at epoxy adhesive is made up of following each raw material: the DMP-30 5% after 133L polyurethane modified epoxy resin 35%, DER732 thinner 1%, 101 spherical powder fillers 59%, the sealing.Above-mentioned each component is added in the duplicate rows star dynamic mixing stirrer successively, be evacuated to vacuum tightness and be-0.08～-0.05MPa, stirred 2 hours in 500 rev/mins, stir.
Through following experimental test closed performance of the present invention and at the application performance of epoxy adhesive.Closed performance is in order to improve the stability of epoxy adhesive, therefore, characterizes through observing the sizing agent viscosity change, and the hardness after the application of epoxy adhesive is solidified through it, tensile strength, shearing resistance characterizes.
The viscosity of test example 1 epoxy adhesive changes performance test
The viscosity test embodiment is undertaken by following method: sample and the existing common bi-component epoxy adhesive of embodiment 1-5 are measured viscosity under 25 ℃ of conditions; Be placed on sample in 25 ℃ of thermostat containers then and preserved 4 hours; Take out the back and measure viscosity, characterize stability of sample through the viscosity change situation.
Concrete data are seen table 1.
Test example 2 hardness Shore test
Hardness test: test according to GB/T 531-1999
The hardness test embodiment is undertaken by following method: with the sample of embodiment 1-5 and existing common bi-component epoxy adhesive 60 ℃ solidify 180min after, according to the GB/T 531-1999 hardness of specimen respectively.
Concrete data are seen table 2.
The test of test example 3 tensile strengths
Tensile strength test: test according to GB/T528-1998
Tensile strength test implementation scheme is undertaken by following method: with the sample of embodiment 1-5 and existing common bi-component epoxy adhesive 60 ℃ solidify 180min after, according to the GB/T528-1998 tensile strength of specimen respectively.
Concrete data are seen table 3.
The test of test example 4 shearing resistances
Shearing resistance test: test according to GB/T7124-1986
Shearing resistance test implementation scheme is undertaken by following method: with the sample of embodiment 1-5 and existing common bi-component epoxy adhesive 60 ℃ solidify 180min after, according to the GB/T7124-1986 shearing resistance of specimen respectively.
Concrete data are seen table 4.
Table 1 embodiment 1-7 and common bi-component epoxy adhesive viscosity contrast test result
Table 2 embodiment 1-7 and common bi-component epoxy adhesive Shore hardness contrast test result
| Sample | Shore hardness D performance test |
| The sample of embodiment 1 | 82 |
| The sample of embodiment 2 | 83 |
| The sample of embodiment 3 | 83 |
| The sample of embodiment 4 | 83 |
| The sample of embodiment 5 | 82 |
| The sample of embodiment 6 | 84 |
| The sample of embodiment 7 | 80 |
| Comparative example's sample | 80 |
Table 3 embodiment 1-7 and common bi-component epoxy adhesive tensile strength contrast test result
| Sample | Tensile strength performance test (Mpa) |
| The sample of embodiment 1 | ?34.3 |
| The sample of embodiment 2 | ?32.9 |
| The sample of embodiment 3 | 32.8 |
| The sample of embodiment 4 | 34.5 |
| The sample of embodiment 5 | 34.2 |
| The sample of embodiment 6 | 30.4 |
| The sample of embodiment 7 | 29.2 |
| Comparative example's sample | 30.3 |
Table 4 embodiment 1-7 and common bi-component epoxy adhesive shearing resistance contrast test result
| Sample | Shearing resistance performance test (Mpa) |
| The sample of embodiment 1 | ?13.3 |
| The sample of embodiment 2 | ?12.9 |
| The sample of embodiment 3 | ?12.8 |
| The sample of embodiment 4 | ?13.5 |
| The sample of embodiment 5 | ?13.2 |
| The sample of embodiment 6 | ?12.4 |
| The sample of embodiment 7 | ?12.1 |
| Comparative example's sample | ?12.5 |
From above data analysis; The embodiment stability of sample is higher than common double component epoxy sizing agent far away; Mechanical properties such as hardness, tensile strength, shearing resistance, contrast with comparative example result; Each item index is relatively more consistent, explains through the DMP-30 solidifying agent behind the sealing treatment and does not lose reactive behavior.On the whole, explaining when sealing DMP-30 of the present invention is applied to epoxy adhesive that do not lose under the prerequisite of its mechanical property in assurance, stability has increased significantly, is the method for one type of novel raising epoxy adhesive stability.
The above is merely preferred embodiment of the present invention, and is in order to restriction the present invention, not all within spirit of the present invention and principle, any modification of being done, is equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (9)
1. a DMP-30 enclosure method is characterized in that, is mixed and made into by 60%～90% (weight percent) DMP-30,10%～40% (weight percent) acidic substance.
2. according to the said DMP-30 enclosure method of claim 1, it is characterized in that the pH value of said mixed system is controlled to be 7-10.
3. according to claim 1 or 2 said DMP-30 enclosure methods, it is characterized in that said acidic substance comprise mineral acid, organic acid does not contain carboxyl in Lewis acid or the organism but shows the tart material.
4. according to the said DMP-30 enclosure method of claim 3, it is characterized in that described mineral acid is a nitric acid, phosphoric acid, sulfuric acid, hydrochloric acid, hydrofluoric acid, hydrochloric acid, hydroiodic acid HI, Hydrogen bromide, hypochlorous acid, perchloric acid, bromic acid, a kind of or any several kinds mixture in the acid iodide.
5. according to the said DMP-30 enclosure method of claim 3, it is characterized in that, do not contain carboxyl in the said organism but the material that shows acid performance is a barbituric acid, phenylethyl barbituric acid.
6. according to the said DMP-30 enclosure method of claim 3, it is characterized in that said organic acid is C
1-C
90Longer chain fatty acid, contain the aromatic acid of benzene ring structure, contain the organic acid of alicyclic structure, contain a kind of or any several kinds mixture in the organic acid that does not comprise key.
7. according to the said DMP-30 enclosure method of claim 3, it is characterized in that said Lewis acid comprises group of the lanthanides, actinium series, the compound of the element that contains unsaturated unoccupied orbital of all subgroup elements and the 3rd main group.
8. according to the said DMP-30 enclosure method of claim 7, it is characterized in that the said compound that contains the element of unsaturated unoccupied orbital is an aluminum chloride, zinc chloride.
9. epoxy adhesive; It is characterized in that; The material that comprises following weight percent: according to the DMP-30 5～38% after the sealing of the said DMP-30 enclosure method preparation of claim 1 to 8, epoxy resin 30～60%, thinner 1～5%, filler 30～60%, coupling agent 0～1%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210064580.1A CN102604046B (en) | 2012-03-13 | 2012-03-13 | DMP-30 (dimethyl phthalate-30) closing method and application of DMP-30 in epoxy adhesive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210064580.1A CN102604046B (en) | 2012-03-13 | 2012-03-13 | DMP-30 (dimethyl phthalate-30) closing method and application of DMP-30 in epoxy adhesive |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102604046A true CN102604046A (en) | 2012-07-25 |
| CN102604046B CN102604046B (en) | 2014-09-24 |
Family
ID=46521858
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210064580.1A Expired - Fee Related CN102604046B (en) | 2012-03-13 | 2012-03-13 | DMP-30 (dimethyl phthalate-30) closing method and application of DMP-30 in epoxy adhesive |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102604046B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103204756A (en) * | 2012-10-16 | 2013-07-17 | 湖北航天化学技术研究所 | High temperature-resistant solid propellant for oilfield fracturing |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4042031A (en) * | 1975-11-13 | 1977-08-16 | Shell Oil Company | Plugging subterranean earth formations with aqueous epoxy emulsions containing fine solid particles |
| CN1346375A (en) * | 1999-12-14 | 2002-04-24 | 三井化学株式会社 | Sealing agent for liquid-crystal display, cell, composition for sealing agent for liquid-crystal display cell, and liquid-crystal display element |
| CN102153977A (en) * | 2011-03-11 | 2011-08-17 | 中南林业科技大学 | Anti-seepage leak-stopping epoxy adhesive and preparation method thereof |
-
2012
- 2012-03-13 CN CN201210064580.1A patent/CN102604046B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4042031A (en) * | 1975-11-13 | 1977-08-16 | Shell Oil Company | Plugging subterranean earth formations with aqueous epoxy emulsions containing fine solid particles |
| CN1346375A (en) * | 1999-12-14 | 2002-04-24 | 三井化学株式会社 | Sealing agent for liquid-crystal display, cell, composition for sealing agent for liquid-crystal display cell, and liquid-crystal display element |
| CN102153977A (en) * | 2011-03-11 | 2011-08-17 | 中南林业科技大学 | Anti-seepage leak-stopping epoxy adhesive and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| 《复合材料学报》 20070430 杨娇萍等 "2 ,4 ,6-三(二甲胺基甲基)苯酚有机改性蒙脱土" 50-54 1-2 第24卷, 第2期 * |
| 《环氧树脂生产与应用》 20010630 王德中等 环氧树脂生产与应用 化学工业出版社材料科学与工程出版中心 225-226 1-9 , 第2版 * |
| 杨娇萍等: ""2 ,4 ,6-三(二甲胺基甲基)苯酚有机改性蒙脱土"", 《复合材料学报》 * |
| 王德中等: "《环氧树脂生产与应用》", 30 June 2001, 化学工业出版社材料科学与工程出版中心 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103204756A (en) * | 2012-10-16 | 2013-07-17 | 湖北航天化学技术研究所 | High temperature-resistant solid propellant for oilfield fracturing |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102604046B (en) | 2014-09-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US20120029115A1 (en) | Room-temperature curable epoxy structural adhesive composition and preparation method thereof | |
| CN101215453B (en) | Adhesive for middle-temperature solidifying epoxy pre-dipping material and preparation method thereof | |
| CN104673161B (en) | A kind of flexibilized epoxies loss circulation material and preparation method and application | |
| CN102115655B (en) | Single component flexible epoxy sealant | |
| CN102453458B (en) | Nano rubber modified room temperature cured high temperature resistant structure adhesive | |
| CN104449508A (en) | Flexible epoxy structural adhesive and preparation method thereof | |
| CN103980463A (en) | Epoxy resin solvent-free low temperature curing agent, preparation method and application thereof | |
| CN102070874B (en) | High-permeability and high-strength epoxy grouting material, preparation method thereof and application thereof | |
| CN113429856B (en) | Low-temperature-resistant polymer cement waterproof coating and preparation method thereof | |
| CN109825163B (en) | High-permeability epoxy waterproof anticorrosive paint and preparation method thereof | |
| CN106010406A (en) | Modified epoxy resin anchor adhesive with high strength and toughness | |
| CN102329586B (en) | Epoxy structure adhesive for rotor blades and preparation method thereof | |
| CN110105709A (en) | The method of toughening agent modified epoxy resin toughness | |
| CN102276797B (en) | Epoxy resin composition with excellent temperature cycle performance and preparation method thereof | |
| CN105199081A (en) | Curing agent for epoxy resin and epoxy adhesive used at ultralow temperature | |
| CN101585958B (en) | Composition and method for preparing artificial gem | |
| CN105385109B (en) | A kind of composition epoxy resin and its purposes in dipping coil is prepared | |
| CN102604046B (en) | DMP-30 (dimethyl phthalate-30) closing method and application of DMP-30 in epoxy adhesive | |
| CN103554842A (en) | Novel shrinkage-free epoxy grouting material and preparation method thereof | |
| CN103254863B (en) | Latent single-component LCD (liquid crystal display) packaging adhesive | |
| CN104497273A (en) | High-modulus epoxy resin composition and preparation method thereof | |
| CN101831044A (en) | Method for preparing biphenyl thermotropic liquid crystal polyurethane | |
| CN105622899A (en) | Modified polyether amine curing agent and preparation method and application thereof | |
| CN103435781B (en) | A kind of epoxy curing agent and preparation method thereof and application | |
| CN112094629B (en) | Plugging agent suitable for fractured oil reservoir |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140924 Termination date: 20150313 |
|
| EXPY | Termination of patent right or utility model |