CN108129788A - Luminous sole and preparation method thereof and Luminous shoe - Google Patents
Luminous sole and preparation method thereof and Luminous shoe Download PDFInfo
- Publication number
- CN108129788A CN108129788A CN201711426733.1A CN201711426733A CN108129788A CN 108129788 A CN108129788 A CN 108129788A CN 201711426733 A CN201711426733 A CN 201711426733A CN 108129788 A CN108129788 A CN 108129788A
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- Prior art keywords
- luminous
- rare earth
- sole
- preparation
- luminescent layer
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
-
- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B13/00—Soles; Sole-and-heel integral units
- A43B13/02—Soles; Sole-and-heel integral units characterised by the material
- A43B13/04—Plastics, rubber or vulcanised fibre
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)
- Luminescent Compositions (AREA)
Abstract
The present invention provides a kind of Luminous sole and preparation method thereof and Luminous shoes.Luminous sole includes：Luminescent layer, luminescent layer include rare earth luminescent material and bottom material, and by weight percentage, rare earth luminescent material includes 20 40% rare earth luminous objects, 50 75% carriers and 5 15% auxiliary agents.The preparation method of Luminous sole includes the preparation of rare earth luminescent material and two steps of injection of luminescent layer.Luminous shoe includes Luminous sole and the vamp being connected with Luminous sole.Luminous sole prepared by the present invention is sustainable to shine that (light emission luminance is more than 10mcd/m2) reach 35 hours, light emission luminance decays to human eye observation lower limit (0.32mcd/m2) time more up to 30 hours or more, stable, the repeatable charge and discharge light of chemical property, so as to overcome Luminous shoe extinction uneven, the shortcomings of illumination effect slowly declines.
Description
Technical field
The present invention relates to sole and its preparation field more particularly to a kind of Luminous sole and preparation method thereof and Luminous shoes.
Background technology
Luminous shoes refer under conditions of rather dark, Luminous shoes energy self-luminescence.When people puts on Luminous shoe sub-line
When walking dim place, the continuous illumination of Luminous shoes allows the automobile of surrounding people and operation is easier to identify oneself, to avoid
It collides and traffic accident, improves safety during dim section walking；It can also be improved when children put on Luminous shoes
The strange heart and pleasant feeling.
There are mainly two types of the prior arts of Luminous shoes：The noctilucence Galaxy footwear of 1.NIKE, the footwear are using luminescent material
It is synthesized with rubber soles, have absorption and stores ultraviolet capability, in the luminous characteristic of dark；2. LED bulb built in sole and
Accumulator, can be by controlling switch to shine to realize after charging.Although both technologies can be realized luminous, there are some
Problem：The noctilucence Galaxy footwear of NIKE make sole using Rare-earth Long Persistence Luminescent Phosphor powder powder and material for sole of shoe, from preparation method point
Analysis, rare earth density itself is in 2.8-3.4g/cm3Left and right, and material for sole of shoe density maximum is rubber, rubber soles density
1.6g/cm3Left and right, so in mixed process, rare earth can be sunk to the bottom, it is impossible to which blanking synchronous with sole material, the sole made have suction
The situation that light is uneven or timeliness is short.On the other hand, although this method can absorb luminous energy and shine, the duration
Short, it is directly to be contacted with ground to be fabricated to sole, can wear sole in use, so that light efficiency can weaken or destroy photism
Can, the waste material after abrasion can also generate pollution.And for LED bulb built in sole and accumulator, the shape that can be switched after charging
Formula, which is realized, to shine, but can determine the photism of LED because the inside is related to power circuit arrangement and the factors such as service lifetime of accumulator
Energy.
In addition, one layer of luminescenjt powder of spraying on luminescenjt powder or leather is implanted into processing procedure is dyed also by cloth
It realizes and shines, vamp is prepared, but the light absorbent of vamp is easily being cleaned and lost in wearing process with this luminous cloths,
Cause the shortcomings of extinction is uneven, and illumination effect slowly declines.
Therefore, existing structure of Luminous shoe and preparation method thereof is needed to improve, to prepare a kind of luminous power by force and hold
Long Luminous sole and Luminous shoe.
Invention content
The purpose of the present invention is to provide a kind of Luminous soles and preparation method thereof, are shone with what the Luminous sole made
Footwear.
To achieve the above object, one of present invention provides a kind of Luminous sole, including：
Luminescent layer, luminescent layer include rare earth luminescent material and bottom material, and by weight percentage, rare earth luminescent material includes
The rare earth luminous objects of 20-40%, 50-75% carriers and 5-15% auxiliary agents.
The present invention provides the preparation method of Luminous sole, the injections of preparation and luminescent layer including rare earth luminescent material.
The present invention also provides a kind of Luminous shoe, the vamp being connected including Luminous sole and with Luminous sole.
The luminescent layer of Luminous sole of the present invention includes rare earth luminescent material and bottom material, by weight percentage, rare earth luminous
Material includes the rare earth luminous objects of 20-40%, 50-75% carriers and 5-15% auxiliary agents.The rare earth luminescent material and bottom material of luminescent layer
Between and the rare earth luminous object in rare earth luminescent material, carrier and auxiliary agent between can form good combination, avoid the occurrence of
The problem of rare earth luminous object generated due to rare earth luminous object is different from the density of carrier or bottom material is sunk to the bottom, and the luminescent layer formed
Durable, bottom material, carrier and auxiliary agent are very weak to the absorbability of light, and the rare earth luminous object in luminescent layer is made both easily to absorb light
Can make again the light sent out be not easy by carrier and auxiliary agent absorption, the bright position sent out, and it is sustainable shine (light emission luminance is more than
10mcd/m2) reach 3-5 hours, light emission luminance decays to human eye observation lower limit (0.32mcd/m2) time it is more reachable
30 hours or more, and chemical property is stablized, extinction, storage light, luminescence process may be repeated.
Specific embodiment
For the technology contents that the present invention will be described in detail, construction feature, it is described further below in conjunction with embodiment.
A kind of Luminous sole, including：Luminescent layer, luminescent layer include rare earth luminescent material and bottom material, by weight percentage,
Rare earth luminescent material includes the rare earth luminous objects of 20-40%, 50-75% carriers and 5-15% auxiliary agents, wherein, rare earth luminescent material:
Bottom material=(2-4): (8-6).
Preferably, auxiliary agent is modified one or more in compatilizer, stabilizer and diffusant, wherein TPE modifications selected from TPE
The weight ratio of compatilizer, stabilizer and diffusant is (0.5-5): (0.2-1): (0.2-1).TPE is modified compatilizer and plays load
Body and rare earth luminous object bonding effect, specifically, it is ethylene and octene copolymer that TPE, which is modified compatilizer,；Stabilizer can slow down
Reaction between rare earth luminous object, carrier and auxiliary agent keeps chemical balance, reduces surface tension, prevents light, thermal decomposition or oxidation
The effects that decomposition, specifically, stabilizer are a kind of liquid calcium zinc stabilizers；The effect of diffusant is to reduce to complete dispersion process institute
The time needed and energy stablize the surface nature of disperseed rare earth luminescent material, adjust the motility of pigment particles, specifically
It is inorganic diffusant, including calcium, magnesium, the carbonate of barium, phosphate or hydroxide.
Preferably, rare earth luminous object includes the luminescence rare earth of aluminate class, such as rare-earth-doped strontium aluminate (SrAl2O4, Eu2 +, Dy3+)。
Preferably, carrier and bottom material are substance of the same race, and include one kind in styrene block copolymer, polyurethane or two
Kind, styrene block copolymer and polyurethane are relatively transparent shoes materials and thermoplastic material, and density is small, to mitigating sole weight
It measures that helpful, rebound is high, effectively reduces road surface and ankle is impacted, effective protection ankle in walking improves the comfort of Luminous shoe
Can, hydrolysis and ageing properties, can digital preservation sole surface it is smooth, it is glossy.Wherein styrene block copolymer density≤
1.00g/cm3, elasticity >=55%, compressive deformation≤30%, hydrolysis is ageing-resistant, reduces to rare earth luminous object illumination effect
Inhibiting effect.
Preferably, further include the bottom for being fixed on luminescent layer side, bottom can be selected from rubber, polyaminoacid ester, ethylene-
Acetate copolymer, styrene block copolymer, polyurethane, preferably, bottom include styrene block copolymer, polyurethane
One or both of, bottom is contacted in the side of luminescent layer and with ground, and when walking avoids the friction on luminescent layer and ground.
The preparation method of Luminous sole includes the preparation of rare earth luminescent material and the injection of luminescent layer.If Luminous shoe further includes
The bottom of luminescent layer side is fixed on, preparation method further includes the injection of bottom.
The preparation of rare earth luminescent material includes raw material mixing processing successively, first time extrusion process, baking are handled, the
It is secondary to squeeze out simultaneously pelletizing processing.Rare earth luminescent material includes rare earth luminous object, carrier and auxiliary agent, at raw material mixing
After reason, first time extrusion process, baking processing and second of extrusion and pelletizing processing, between rare earth luminous object and carrier and auxiliary agent
Be uniformly mixed, rare earth luminous object is uniformly distributed in rare earth luminescent material, avoid because rare earth luminous object density be more than carrier and
Auxiliary agent and the rare earth luminous object that occurs sinks to the bottom phenomenon, with bottom material can synchronous blanking, the sole made has that extinction is uniform, photism
It can be good.
Preferably, first time extrusion process is that the mixture of the gained after raw material mixing processing is placed in extruder
It is interior, it through screw rod shearing and is squeezed out at 120-170 DEG C, mixture requires screw rod shearing stringent, and shearing dynamics cannot be too big, otherwise
Mixture easily breaks and influences performance, has a set of twin-screw to combine in the extruder prepared in rare earth luminescent material of the present invention,
Mixture can be sheared well and be allowed to mix evenly, destruction will not be generated to mixture by having.
Baking is that 10-90min is toasted at 40-80 DEG C, more preferably, is toasted 30 minutes with 50 DEG C in an oven, both makes water
Divide evaporation, and TPE is allowed to be modified compatilizer and is played a role, improve the com-patibilising effect between mixture each component, mixture is enable to reach
To good state, conducive to next processing.
Preferably, it is that gained mixture after toasted processing is placed in extruder that second, which squeezes out simultaneously pelletizing processing,
120-170 DEG C squeeze out solid tie rod, solid tie rod is cooled down after pelletizing.
A kind of Luminous shoe, the vamp being connected including Luminous sole and with Luminous sole, Luminous sole can pass through with vamp
Glue bonds or sews and connect.
Luminous sole below for the present invention and preparation method thereof is described in detail using embodiment.
Illustrate the component of Luminous sole in each embodiment first,
Embodiment 1
A kind of Luminous sole, including：
Bottom：Polyaminoacid ester,
Luminescent layer：Comprising 20wt% rare earth luminescent materials and 80wt% bottom materials, wherein, bottom material：Styrene block copolymer,
Rare earth luminescent material：20wt%Eu2+The SrAl of doping2O4, 75wt% styrene block copolymers, 2wt% ethylene
With octene copolymer, 2wt% liquid calcium zinc stabilizer and 1wt% magnesium carbonate.
Embodiment 2
A kind of Luminous sole, including：
Bottom：Polyaminoacid ester,
Luminescent layer：Comprising 30wt% rare earth luminescent materials and 70wt% bottom materials,
Wherein, bottom material：Styrene block copolymer,
Rare earth luminescent material：30wt%Eu2+The SrAl of doping2O4, 60wt% styrene block copolymers, 5 wt% ethylene
With octene copolymer, 2wt% liquid calcium zinc stabilizer and 3wt% calcium phosphate.
Embodiment 3
A kind of Luminous sole, including：
Bottom：Polyethylene vinyl acetate copolymer,
Luminescent layer：Comprising 40wt% rare earth luminescent materials and 60wt% bottom materials,
Wherein, bottom material：Styrene block copolymer,
Rare earth luminescent material：35wt%Dy3+The SrAl of doping2O4, 50wt% styrene block copolymers, 7 wt% ethylene
With octene copolymer, 3wt% liquid calcium zinc stabilizer and 5wt% barium hydroxides.
Comparative example 1
A kind of Luminous sole, including：
Bottom：Polyurethane,
Luminescent layer：Include 20wt%20wt%Eu2+The SrAl of doping2O4With 80wt% bottom materials, wherein, bottom material：Polyurethane.
Secondly, illustrate the preparation method of embodiment 1-3 Luminous soles：
1. the preparation of rare earth luminescent material
(1) raw material mixing is handled
It is poured into after rare earth luminescent material is weighed in formulation weight ratio in (band heating apparatus) batch mixer at a high speed, stirring 10
Minute, mixture is made to reach uniform,
(2) first time extrusion process
It is placed in obtained uniform mixture is handled through step (1) in double screw extruder, double screw extruder is in 120-
In the range of 170 DEG C set 10 sections, the corresponding temperature of 10 sections for 120 DEG C, 150 DEG C, 160 DEG C, 160 DEG C, 160 DEG C,
165 DEG C, 165 DEG C, 165 DEG C, 170 DEG C, 170 DEG C, mixture is constantly sheared by the screw rod of double screw extruder, rare earth luminous material
Mutual mechanism constantly occurs between material each component and twin-screw, is squeezed out from extruder after having sheared,
(3) baking is handled
It collects and handles the mixture squeezed out through step (2), in 50 DEG C of oven for baking 30 minutes, at this point, in baking process
Middle compatilizer plays a role, and the com-patibilising effect for making mixture each component is more preferable,
(4) simultaneously pelletizing processing is squeezed out second
Mixture after baking is poured into double screw extruder hopper, double screw extruder is in the range of 120-170 DEG C
Set 10 sections, the corresponding temperature of 10 sections for 120 DEG C, 150 DEG C, 160 DEG C, 160 DEG C, 160 DEG C, 165 DEG C, 165 DEG C,
165 DEG C, 170 DEG C, 170 DEG C, mixture is constantly sheared by the screw rod of double screw extruder, and mixture is extruded into solid gum
Item after supercooling sink cools down adhesive tape, is cut into cylindrical pellet with pelleter and rare earth luminescent material is made；
2nd, the injection of bottom and luminescent layer
Bottom raw material is put into injection molding machine, bottom is formed, then by rare earth luminescent material and bottom through injection molding machine injection mold
Material is put into injection molding machine, and the side of the bottom through injection molding machine injection mold forms luminescent layer, and injection machining parameter is as follows：
Temperature, pressure, speed, back pressure can be adjusted to occurrence by actual conditions according to range respective in table in table.
The preparation method of 1 Luminous sole of comparative example：
The injection of bottom and luminescent layer
Bottom raw material is put into injection molding machine, bottom is formed, then by rare earth luminous object and bottom material through injection molding machine injection mold
It is put into injection molding machine, the side of the bottom through injection molding machine injection mold forms luminescent layer, and injection machining parameter is as follows：
Temperature, pressure, speed, back pressure can be adjusted to occurrence by actual conditions according to range respective in table in table.
Luminous sole made from embodiment 1-3 and comparative example 1 is subjected to luminiferous inspection, Visual detection methods are as follows：
1.1 cut 70mm × 65mm specification sheet samples, can not such as get code test specification, can be actually big according to sample
It is small；
1.2 are placed on sample below shot-light, vertical range (50 ± 2) cm, Continuous irradiation 2h；
1.3 dark surrounds for the material after irradiation being placed in darkroom or being equal to darkroom (need to ensure the environment placed
In dark state)；
1.4 every 0.5h, the illumination effect for the sample that detects by an unaided eye in darkroom.
Note：1st, it is visually observed sample and shines judgement sample with luminous effect, otherwise without luminous effect.
2nd, the judgement of luminous effect must be judged by 3 people, take most judgement persons as final result.
Luminous sole made from embodiment 1-3 and comparative example 1 is subjected to luminiferous inspection, objective measure is as follows：
It is detected by illuminating meter, the light emission luminance of Luminous sole is judged according to instrument display brightness data.
Luminous sole carries out luminiferous inspection result such as following table made from embodiment 1-3 and comparative example 1：
The photism testing result of Examples 1 to 3 and comparative example 1 from upper table is it is found that the Luminous sole of Examples 1 to 3
After photism detects it is sustainable shine (light emission luminance be more than 10mcd/m2) reach 3-5 hours, light emission luminance decays to people's
Visually observe lower limit (0.32mcd/m2) time more up to 30 hours or more this as a result, Luminous sole because good with this
Luminescent properties, people put on the Luminous sole making Luminous shoe can allow surrounding people and operation the easier knowledge of automobile
Not, so as to avoid colliding and traffic accident, safety during dim section walking is improved, and Examples 1 to 3 is than comparison
The good luminous performance of example 1, this is because the rare earth luminescent material of luminescent layer is rare earth luminous object in comparative example 1, without carrier and
Auxiliary agent lacks the interaction of carrier and auxiliary agent and rare earth luminous object, this can both reduce the knot between rare earth luminous object and bottom material
With joint efforts, and rare earth luminous object can be allowed to sink to the bottom, the luminous layer defects of formation are more, of poor quality, reduce its luminescent properties.
Above disclosed is only the preferred embodiments of the present invention, it is impossible to the right model of the utility model is limited with this
It encloses, therefore equivalent variations made according to the claims of the present invention, belongs to the range that the utility model is covered.
Claims (10)
1. a kind of Luminous sole, including：
Luminescent layer, the luminescent layer include rare earth luminescent material and bottom material, which is characterized in that by weight percentage, described dilute
Native luminescent material includes the rare earth luminous objects of 20-40%, 50-75% carriers and 5-15% auxiliary agents.
2. Luminous sole according to claim 1, which is characterized in that the auxiliary agent is selected from TPE and is modified compatilizer, stabilizer
With it is one or more in diffusant.
3. Luminous sole according to claim 1, which is characterized in that the rare earth luminous object includes shining for aluminate class
Rare earth.
4. Luminous sole according to claim 1, which is characterized in that the carrier and the bottom material are substance of the same race, and
Include one or both of styrene block copolymer, polyurethane.
5. Luminous sole according to claim 1, which is characterized in that further include the bottom for being fixed on the luminescent layer side
Layer, the bottom include one or both of styrene block copolymer, polyurethane.
6. according to the preparation method of any Luminous soles of claim 1-5, which is characterized in that including described rare earth luminous
The preparation of material and the injection of the luminescent layer.
7. the preparation method of Luminous sole according to claim 6, which is characterized in that the preparation of the rare earth luminescent material
Include raw material mixing processing successively, first time extrusion process, baking processing, squeeze out simultaneously pelletizing processing for second.
8. the preparation method of Luminous sole according to claim 7, which is characterized in that the first time extrusion process be by
The mixture of gained is placed in extruder after raw material mixing processing, through screw rod shearing and is squeezed out at 120-170 DEG C.
9. the preparation method of Luminous sole according to claim 7, which is characterized in that at second of extrusion and pelletizing
Reason be by through the baking processing after gained mixture be placed in the extruder, 120-170 DEG C squeeze out solid tie rod, by institute
State pelletizing after solid tie rod cools down.
10. a kind of Luminous shoe, which is characterized in that shine including the Luminous sole as described in claim 1-5 is any and with described
The vamp that sole is connected.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711426733.1A CN108129788A (en) | 2017-12-25 | 2017-12-25 | Luminous sole and preparation method thereof and Luminous shoe |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711426733.1A CN108129788A (en) | 2017-12-25 | 2017-12-25 | Luminous sole and preparation method thereof and Luminous shoe |
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| Publication Number | Publication Date |
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| CN108129788A true CN108129788A (en) | 2018-06-08 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201711426733.1A Pending CN108129788A (en) | 2017-12-25 | 2017-12-25 | Luminous sole and preparation method thereof and Luminous shoe |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5716723A (en) * | 1996-03-07 | 1998-02-10 | Van Cleef; James Gresham | Glow in the dark shoe sole |
| JP2010031114A (en) * | 2008-07-28 | 2010-02-12 | Hayakawa Rubber Co Ltd | Phosphorescent rubber composition |
| CN102408700A (en) * | 2011-09-13 | 2012-04-11 | 暨南大学 | Preparation method of long-afterglow luminescent plastics |
| CN105602140A (en) * | 2016-01-21 | 2016-05-25 | 苏州市景荣科技有限公司 | Preparation method of luminous composite for sole material |
-
2017
- 2017-12-25 CN CN201711426733.1A patent/CN108129788A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5716723A (en) * | 1996-03-07 | 1998-02-10 | Van Cleef; James Gresham | Glow in the dark shoe sole |
| JP2010031114A (en) * | 2008-07-28 | 2010-02-12 | Hayakawa Rubber Co Ltd | Phosphorescent rubber composition |
| CN102408700A (en) * | 2011-09-13 | 2012-04-11 | 暨南大学 | Preparation method of long-afterglow luminescent plastics |
| CN105602140A (en) * | 2016-01-21 | 2016-05-25 | 苏州市景荣科技有限公司 | Preparation method of luminous composite for sole material |
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Effective date of registration: 20190611 Address after: 523000 XiaCao Industrial Zone, Wangniudun Town, Dongguan City, Guangdong Province Applicant after: Dongguan Xingmao Rubber and Plastic Technology Co., Ltd. Address before: 342300 No. 2 Dagong Road, Yinkeng Town, Yudu County, Ganzhou City, Jiangxi Province Applicant before: Lai Jiacai |
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