CN104233788A - Finishing technology for yellowing prevention of silk fabric - Google Patents

Finishing technology for yellowing prevention of silk fabric Download PDF

Info

Publication number
CN104233788A
CN104233788A CN201410505960.3A CN201410505960A CN104233788A CN 104233788 A CN104233788 A CN 104233788A CN 201410505960 A CN201410505960 A CN 201410505960A CN 104233788 A CN104233788 A CN 104233788A
Authority
CN
China
Prior art keywords
silk
silk fabric
yellowing
fibroin
finishing
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
Application number
CN201410505960.3A
Other languages
Chinese (zh)
Other versions
CN104233788B (en
Inventor
周继东
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.)
Guangzhou DIKENI Investment and Development Co., Ltd.
Original Assignee
Suzhou Insilk Digital Textile Science and Technology Co Ltd
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 Suzhou Insilk Digital Textile Science and Technology Co Ltd filed Critical Suzhou Insilk Digital Textile Science and Technology Co Ltd
Priority to CN201410505960.3A priority Critical patent/CN104233788B/en
Publication of CN104233788A publication Critical patent/CN104233788A/en
Application granted granted Critical
Publication of CN104233788B publication Critical patent/CN104233788B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Landscapes

  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)

Abstract

The invention discloses a finishing technology for the yellowing prevention silk fabric, and belongs to the technical field of silk. The finishing technology comprises the following steps: dissolving waste silk by using a lithium bromide solution to prepare a silk fibroin solution; immersing silk fabric into the silk fibroin solution containing ethylene glycol diglycidyl ether, taking out the silk fabric, naturally curing, and then immersing the silk fabric into a titanium dioxide sol solution; performing heat treatment after twice immersing and twice rolling; washing and drying to obtain the silk fabric subjected to yellowing-prevention finishing. The finishing method is simple and convenient to operate, can protect silky luster of the silk fabric, and has outstanding advantages in anti-aging and yellowing prevention; the waste silk is used as a raw material, so that the finishing method is environment-friendly and conducive to resource regeneration; the silk fabric prepared by the finishing method is comfortable, safe, environment-friendly, healthy and fashionable.

Description

A kind of finishing technique of anti-yellowing of silk fabric
Technical field:
The present invention relates to silk technical field, relate in particular to a kind of finishing technique of anti-yellowing of silk fabric.
Background technology:
Containing a large amount of ultraviolet in sunlight, most ultraviolet can absorb by the ozone layer in air, only have the ultraviolet of about 10% to project on ground.Appropriate ultraviolet radiation is necessary to human body and plant growth, but excessive accept ultraviolet irradiation and can cause problems.
Silk is a kind of natural protein fibre, main containing fibroin, silk gum and other materials on a small quantity, can be there is yellowing in silk fiber under the factor effects such as light, heat, biology, its mechanical property, surface topography, aggregate structure, molecular mass etc. all create change, and the yellowing processes effect of its illumination to silk fabric is larger.
Usually in storage process, yellowing variable color in various degree can all be had, mainly because the amino acid residue such as the tryptophan in fibroin and TYR is oxidized and painted in atmosphere through the silk fabric of refining bleaching.The light yellowing of silk fabric is fibroin macromolecule generation photochemical reaction in essence, namely under light illumination, the temperature of silk fabric raises, and fibroin polymer segment energy of thermal motion increases, molecule segment easily easily ruptures, and cracking goes out the low molecule product of some yellow.Meanwhile, silk fabric surface and internal temperature raise, and produce internal stress, occur warpage and be full of cracks, humidity increases, and silk fiber occurs swelling, volume becomes large, and the intermolecular force of its aggregated structure changes, and change in various degree all occurs for the speed of yellowing and the mechanical strength of silk fiber.
Two kinds are had at present: a kind of is the silk fabric of yellowing is carried out bleaching to make it return to original whiteness, and another kind silk fabric is being carried out to anti-ultraviolet radiation treatment to prevent its yellowing to the yellowing-proof finish of silk fabric.The yellowing-proof finish of silk fabric has ultra-violet absorber, antioxidant, the agent of resin truth, wherein ultra-violet absorber optionally absorbs ultraviolet and is converted to harmless energy, the destruction of ultraviolet to silk can be reduced, the ultra-violet absorber decapacitation with industrial utility value absorbs outside the ultraviolet of specific wavelength, also have good photostability, usefulness is lasting, nontoxic washable.
Summary of the invention:
The object of this invention is to provide a kind of finishing technique of anti-yellowing of silk fabric, the method utilizes the fibroin ethylene glycol diglycidylether aqueous solution and fibroin Nano sol finishing agent, silk fabric is successively immersed in two kinds of solution, improve the anti-uv-ray of silk fabric, yellowing-proof finish is carried out to silk fabric.
Object of the present invention is achieved through the following technical solutions:
A finishing technique for the anti-yellowing of silk fabric, comprises the following steps:
(1) be dissolved in lithium-bromide solution by useless silk, 60-70 DEG C of process 2-3h, obtains silk fibroin protein solution;
(2) mixed with silk fibroin protein solution by the ethylene glycol diglycidylether aqueous solution, the obtained fibroin ethylene glycol diglycidylether aqueous solution, immerses silk fabric in solution, until after silk fabric drenched by dissolution homogeneity, take out and dry;
(3) presoma of titanium, glacial acetic acid, water are mixed, regulate pH value, be stirred to collosol state, then mix with silk fibroin protein solution, obtained fibroin Nano sol finishing agent;
(4) immersed by silk fabric in fibroin Nano sol finishing agent, two leachings two are heat-treated after rolling, and take out washing drying, obtain the silk fabric of anti-yellowing.
Preferred as technique scheme, the concentration of the silk fibroin protein solution described in step (1) is 2-10%.
Preferred as technique scheme, in the fibroin ethylene glycol diglycidylether aqueous solution described in step (2), the content of fibroin is 0.1%-2%, and the content of ethylene glycol diglycidylether is 1%-5%.
Preferred as technique scheme, the presoma of the titanium described in step (3) is butyl titanate.
Preferred as technique scheme, the pH value described in step (3) is 2-4.
Preferred as technique scheme, in the fibroin Nano sol finishing agent described in step (3), the content of fibroin is 0.2-2%.
Preferred as technique scheme, the pick-ups that two leachings two described in step (4) are rolled are 80%-90%.
Preferred as technique scheme, the heat-treat condition described in step (4) is 80 DEG C of preliminary drying 3-5min, 120-150 DEG C of heat treatment 3-5min.
Preferred as technique scheme, the method for the washing described in step (4) is for soaping.
Beneficial effect of the present invention is: it utilizes epoxy material solution and nanometer titanium dioxide titanium solution as yellowing-proof finish agent, the epoxy radicals that epoxy material possesses can play closed effect to causing the amino acid of yellowing, significant anti-yellowing effect can be played, nano titanium oxide can through visible ray, and reflection or ABSORPTION AND SCATTERING brachium are the ultraviolet light of 200-400nm, there is good shielding action to UVA and UVB, and there is excellent water dispersible, nonpoisonous and tasteless nonirritant.Yellowing finishing agent is mixed with a small amount of fibroin; can reach on the basis of anti-yellowing process; ensure the good characteristic that silk fabric is original; the method is simple to operation, can protect the silky luster of silk fabric, and has outstanding superiority in anti-yellowing is anti-aging; and utilize useless silk to be raw material; both environmental protection, is conducive to resource regeneration again, the silk fabric of preparation is comfortable, safety, environmental protection, health, fashion.
Detailed description of the invention:
In order to deepen the understanding of the present invention, below in conjunction with embodiment, the invention will be further described, and this embodiment only for explaining the present invention, does not form limiting the scope of the present invention.
Embodiment 1:
The silk that given up by 10g is dissolved in 100ml lithium-bromide solution, 60 DEG C of process 2h, obtain the silk fibroin protein solution that concentration is 10%, the ethylene glycol diglycidylether aqueous solution is mixed with silk fibroin protein solution, the obtained aqueous solution containing the fibroin of 2% and the ethylene glycol diglycidylether of 5%, silk fabric is immersed in solution, after being drenched by dissolution homogeneity to silk fabric, take out 30 DEG C of oven dry.
20ml butyl titanate, 40ml glacial acetic acid, 40ml water are mixed, regulate pH value to be 2, be stirred to sol-gel state, then mix with silk fibroin protein solution, the content of obtained fibroin is the fibroin Nano sol finishing agent of 2%, immersed by silk fabric in fibroin Nano sol finishing agent, after two leachings two are rolled, pick-up is 90%, 80 DEG C of preliminary drying 5min, 150 DEG C of heat treatment 3min, take out drying of soaping, obtain the silk fabric of anti-yellowing.
Irradiate 10h by being flat in Ultraviolet radiation case after the silk fabric water-wet of yellowing-proof finish, recording whiteness retention with Datacolor color matching instrument is 95.2%.
Embodiment 2:
The silk that given up by 2g is dissolved in 100ml lithium-bromide solution, 60 DEG C of process 2h, obtaining concentration is 2% silk fibroin protein solution, the ethylene glycol diglycidylether aqueous solution is mixed with silk fibroin protein solution, the obtained aqueous solution containing the fibroin of 0.1% and the ethylene glycol diglycidylether of 1%, silk fabric is immersed in solution, after being drenched by dissolution homogeneity to silk fabric, take out 30 DEG C of oven dry.
20ml butyl titanate, 60ml glacial acetic acid, 20ml water are mixed, regulate pH value to be 4, be stirred to sol-gel state, then mix with silk fibroin protein solution, the content of obtained fibroin is the fibroin Nano sol finishing agent of 0.2%, immersed by silk fabric in fibroin Nano sol finishing agent, after two leachings two are rolled, pick-up is 80%, 80 DEG C of preliminary drying 3min, 120 DEG C of heat treatment 5min, take out drying of soaping, obtain the silk fabric of anti-yellowing.
Irradiate 10h by being flat in Ultraviolet radiation case after the silk fabric water-wet of yellowing-proof finish, recording whiteness retention with Datacolor color matching instrument is 91.7%.
Embodiment 3:
The silk that given up by 5g is dissolved in 100ml lithium-bromide solution, 60 DEG C of process 3h, obtaining concentration is 5% silk fibroin protein solution, the ethylene glycol diglycidylether aqueous solution is mixed with silk fibroin protein solution, the obtained aqueous solution containing the fibroin of 0.5% and the ethylene glycol diglycidylether of 2%, silk fabric is immersed in solution, after being drenched by dissolution homogeneity to silk fabric, take out 30 DEG C of oven dry.
20ml butyl titanate, 40ml glacial acetic acid, 40ml water are mixed, regulate pH value to be 4, be stirred to sol-gel state, then mix with silk fibroin protein solution, the content of obtained fibroin is the fibroin Nano sol finishing agent of 0.5%, immersed by silk fabric in fibroin Nano sol finishing agent, after two leachings two are rolled, pick-up is 85%, 80 DEG C of preliminary drying 4min, 130 DEG C of heat treatment 4min, take out drying of soaping, obtain the silk fabric of anti-yellowing.
Irradiate 10h by being flat in Ultraviolet radiation case after the silk fabric water-wet of yellowing-proof finish, recording whiteness retention with Datacolor color matching instrument is 93.6%.
Embodiment 4:
The silk that given up by 10g is dissolved in 100ml lithium-bromide solution, 60 DEG C of process 2h, obtaining concentration is 10% silk fibroin protein solution, the ethylene glycol diglycidylether aqueous solution is mixed with silk fibroin protein solution, the obtained aqueous solution containing the fibroin of 1% and the ethylene glycol diglycidylether of 2%, silk fabric is immersed in solution, after being drenched by dissolution homogeneity to silk fabric, take out 30 DEG C of oven dry.
20ml butyl titanate, 60ml glacial acetic acid, 20ml water are mixed, regulate pH value to be 2, be stirred to sol-gel state, then mix with silk fibroin protein solution, the content of obtained fibroin is the fibroin Nano sol finishing agent of 0.3%, immersed by silk fabric in fibroin Nano sol finishing agent, after two leachings two are rolled, pick-up is 90%, 80 DEG C of preliminary drying 3min, 120 DEG C of heat treatment 4min, take out drying of soaping, obtain the silk fabric of anti-yellowing.
Irradiate 10h by being flat in Ultraviolet radiation case after the silk fabric water-wet of yellowing-proof finish, recording whiteness retention with Datacolor color matching instrument is 94.7%.
Embodiment 5:
The silk that given up by 6g is dissolved in 100ml lithium-bromide solution, 60 DEG C of process 2h, obtaining concentration is 6% silk fibroin protein solution, the ethylene glycol diglycidylether aqueous solution is mixed with silk fibroin protein solution, the obtained aqueous solution containing the fibroin of 1% and the ethylene glycol diglycidylether of 3%, silk fabric is immersed in solution, after being drenched by dissolution homogeneity to silk fabric, take out 30 DEG C of oven dry.
20ml butyl titanate, 40ml glacial acetic acid, 40ml water are mixed, regulate pH value to be 4, be stirred to sol-gel state, then mix with silk fibroin protein solution, the content of obtained fibroin is the fibroin Nano sol finishing agent of 1%, immersed by silk fabric in fibroin Nano sol finishing agent, after two leachings two are rolled, pick-up is 80%, 80 DEG C of preliminary drying 3-5min, 150 DEG C of heat treatment 5min, take out drying of soaping, obtain the silk fabric of anti-yellowing.
Irradiate 10h by being flat in Ultraviolet radiation case after the silk fabric water-wet of yellowing-proof finish, recording whiteness retention with Datacolor color matching instrument is 94.2%.
Embodiment 6:
The silk that given up by 2g is dissolved in 100ml lithium-bromide solution, 60 DEG C of process 2h, obtaining concentration is 2% silk fibroin protein solution, the ethylene glycol diglycidylether aqueous solution is mixed with silk fibroin protein solution, the obtained aqueous solution containing the fibroin of 0.5% and the ethylene glycol diglycidylether of 4%, silk fabric is immersed in solution, after being drenched by dissolution homogeneity to silk fabric, take out 30 DEG C of oven dry.
20ml butyl titanate, 60ml glacial acetic acid, 20ml water are mixed, regulate pH value to be 3, be stirred to sol-gel state, then mix with silk fibroin protein solution, the content of obtained fibroin is the fibroin Nano sol finishing agent of 0.2%, immersed by silk fabric in fibroin Nano sol finishing agent, after two leachings two are rolled, pick-up is 85%, 80 DEG C of preliminary drying 3min, 120 DEG C of heat treatment 3min, take out drying of soaping, obtain the silk fabric of anti-yellowing.
Irradiate 10h by being flat in Ultraviolet radiation case after the silk fabric water-wet of yellowing-proof finish, recording whiteness retention with Datacolor color matching instrument is 93.9%.

Claims (9)

1. a finishing technique for the anti-yellowing of silk fabric, is characterized in that comprising the following steps:
(1) be dissolved in lithium-bromide solution by useless silk, 60-70 DEG C of process 2-3h, obtains silk fibroin protein solution;
(2) mixed with silk fibroin protein solution by the ethylene glycol diglycidylether aqueous solution, the obtained fibroin ethylene glycol diglycidylether aqueous solution, immerses silk fabric in solution, until after silk fabric drenched by dissolution homogeneity, take out and dry;
(3) presoma of titanium, glacial acetic acid, water are mixed, regulate pH value, be stirred to collosol state, then mix with silk fibroin protein solution, obtained fibroin Nano sol finishing agent;
(4) immersed by silk fabric in fibroin Nano sol finishing agent, two leachings two are heat-treated after rolling, and take out washing drying, obtain the silk fabric of anti-yellowing.
2. the finishing technique of the anti-yellowing of a kind of silk fabric according to claim 1, is characterized in that: the concentration of the silk fibroin protein solution described in step (1) is 2-10%.
3. the finishing technique of the anti-yellowing of a kind of silk fabric according to claim 1, it is characterized in that: in the fibroin ethylene glycol diglycidylether aqueous solution described in step (2), the content of fibroin is 0.1%-2%, the content of ethylene glycol diglycidylether is 1%-5%.
4. the finishing technique of the anti-yellowing of a kind of silk fabric according to claim 1, is characterized in that: the presoma of the titanium described in step (3) is butyl titanate.
5. the finishing technique of the anti-yellowing of a kind of silk fabric according to claim 1, is characterized in that: the pH value described in step (3) is 2-4.
6. the finishing technique of the anti-yellowing of a kind of silk fabric according to claim 1, is characterized in that: in the fibroin Nano sol finishing agent described in step (3), the content of fibroin is 0.2-2%.
7. the finishing technique of the anti-yellowing of a kind of silk fabric according to claim 1, is characterized in that: the pick-up that two leachings two described in step (4) are rolled is 80%-90%.
8. the finishing technique of the anti-yellowing of a kind of silk fabric according to claim 1, is characterized in that: the heat-treat condition described in step (4) is 80 DEG C of preliminary drying 3-5min, 120-150 DEG C of heat treatment 3-5min.
9. the finishing technique of the anti-yellowing of a kind of silk fabric according to claim 1, is characterized in that: the method for the washing described in step (4) is for soaping.
CN201410505960.3A 2014-09-28 2014-09-28 A kind of finishing technique of the anti-yellowing of silk fabric Expired - Fee Related CN104233788B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410505960.3A CN104233788B (en) 2014-09-28 2014-09-28 A kind of finishing technique of the anti-yellowing of silk fabric

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410505960.3A CN104233788B (en) 2014-09-28 2014-09-28 A kind of finishing technique of the anti-yellowing of silk fabric

Publications (2)

Publication Number Publication Date
CN104233788A true CN104233788A (en) 2014-12-24
CN104233788B CN104233788B (en) 2016-06-08

Family

ID=52222633

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410505960.3A Expired - Fee Related CN104233788B (en) 2014-09-28 2014-09-28 A kind of finishing technique of the anti-yellowing of silk fabric

Country Status (1)

Country Link
CN (1) CN104233788B (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106758228A (en) * 2016-11-24 2017-05-31 江苏爱西施科技服务咨询股份有限公司 A kind of anti-ultraviolet dressing liquid of raising textile containing modified sericin and preparation method thereof
CN107287904A (en) * 2017-06-26 2017-10-24 苏州威尔德工贸有限公司 A kind of yellowing-proof finish method of real silk fabric
CN109989264A (en) * 2019-02-28 2019-07-09 常州琨瑶纺织品有限公司 A kind of preparation method of fabric finishing agent
CN111172740A (en) * 2020-03-05 2020-05-19 南通大学 Anti-yellowing antibacterial real silk fabric and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101187164A (en) * 2007-11-28 2008-05-28 南通大学 Anti-creasing anti-bacterial anti-violet composite function silk fabric and its preparation method
CN101617866A (en) * 2009-08-10 2010-01-06 浙江理工大学 Fabricating method of anti-bacteria health knitting clothes
CN102002854A (en) * 2010-12-06 2011-04-06 中原工学院 Multifunctional textile finishing agent, preparation method thereof and cotton textile finishing method

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101187164A (en) * 2007-11-28 2008-05-28 南通大学 Anti-creasing anti-bacterial anti-violet composite function silk fabric and its preparation method
CN101617866A (en) * 2009-08-10 2010-01-06 浙江理工大学 Fabricating method of anti-bacteria health knitting clothes
CN102002854A (en) * 2010-12-06 2011-04-06 中原工学院 Multifunctional textile finishing agent, preparation method thereof and cotton textile finishing method

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
范雪荣等: ""真丝织物的泛黄和防泛黄整理"", 《印染助剂》, vol. 13, no. 5, 20 October 1996 (1996-10-20) *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106758228A (en) * 2016-11-24 2017-05-31 江苏爱西施科技服务咨询股份有限公司 A kind of anti-ultraviolet dressing liquid of raising textile containing modified sericin and preparation method thereof
CN107287904A (en) * 2017-06-26 2017-10-24 苏州威尔德工贸有限公司 A kind of yellowing-proof finish method of real silk fabric
CN109989264A (en) * 2019-02-28 2019-07-09 常州琨瑶纺织品有限公司 A kind of preparation method of fabric finishing agent
CN111172740A (en) * 2020-03-05 2020-05-19 南通大学 Anti-yellowing antibacterial real silk fabric and preparation method thereof

Also Published As

Publication number Publication date
CN104233788B (en) 2016-06-08

Similar Documents

Publication Publication Date Title
CN104233788B (en) A kind of finishing technique of the anti-yellowing of silk fabric
CN107142546B (en) The compound polyester functional fibre of a kind of far infrared, antibacterial mite-removing and its manufacturing method
CN103432008B (en) Formed konjak mask and preparation method thereof
CN110774680B (en) High-skin-affinity antibacterial fabric and preparation method thereof
CN102276734B (en) Formaldehyde absorptive reagent capable of improving bonding strength of urea resins as well as preparation method and application thereof
CN103131233B (en) Ultraviolet screening agent and preparation method and application thereof
CN107974828A (en) A kind of preparation method of the special antibacterial wool fiber of wool cap
CN110820324A (en) Preparation method and application of biomass ultraviolet absorbent
CN106752100A (en) Modified morphology controllable nano-calcium carbonate powder of a kind of compound alkali lignin APEO activating agent and preparation method thereof
CN115040424A (en) Zinc oxide quantum dot coating, coating strategy, product and application
CN103882711A (en) Silk wrinkle-resistant finishing method
CN105040415A (en) Nano-antibacterial fabric
CN108018613B (en) Preparation method of photo-sterilization, self-cleaning and far-infrared composite nano particles and multifunctional fibers thereof
CN106337280B (en) A kind of cotton fabric uvioresistant Ecological station agent and its preparation and method for sorting
CN105441600B (en) Chrome-free tanning agent process for tanning in a kind of leather production
CN108532289B (en) Multifunctional fibroin fiber finishing agent, multifunctional fibroin fiber, preparation process and application thereof
CN104403249A (en) Preparation method of antibacterial super absorbent resin
CN109023922A (en) The preparation method of graphene composite material
CN109015982B (en) Preparation method for constructing super-hydrophobic layer on surface of bamboo/wood by utilizing geothermal water
CN108642919B (en) Special high-temperature leveling agent for superfine fiber fabric
CN109603792A (en) A kind of light urges the preparation method of scavenging material
CN104947409A (en) Production technology of nano coffee bamboo charcoal fiber fabric
CN104164783A (en) Preparation method for environment-friendly and anti-sunburn textile
CN110258108B (en) Crease-resistant finishing method for cotton fabric
CN106833310A (en) A kind of weaving face fabric of UV resistance

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C41 Transfer of patent application or patent right or utility model
CB03 Change of inventor or designer information

Inventor after: Zheng Xuefen

Inventor before: Zhou Jidong

COR Change of bibliographic data
TA01 Transfer of patent application right

Effective date of registration: 20160506

Address after: 510820, No. 93, west one hundred and fifteen, Huadu Avenue, Huadu Town, Huadu District, Guangdong, Guangzhou

Applicant after: Guangzhou DIKENI Investment and Development Co., Ltd.

Address before: 215000 Taishan road Jiangsu city Suzhou province high tech Zone No. 2 (Canton Technology Park test center A area 101, Room 201)

Applicant before: SUZHOU INSILK DIGITAL TEXTILE SCIENCE & TECHNOLOGY CO., LTD.

C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20160608

Termination date: 20160928