CN103923398A - Polypropylene composite granular material used for radiation crosslinking foaming and preparation technology for foamed plastic - Google Patents
Polypropylene composite granular material used for radiation crosslinking foaming and preparation technology for foamed plastic Download PDFInfo
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- CN103923398A CN103923398A CN201310014475.1A CN201310014475A CN103923398A CN 103923398 A CN103923398 A CN 103923398A CN 201310014475 A CN201310014475 A CN 201310014475A CN 103923398 A CN103923398 A CN 103923398A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
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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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
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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
- C08L2203/00—Applications
- C08L2203/14—Applications used for foams
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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
- 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
- C08L2205/24—Crystallisation aids
- C08L2205/242—Beta spherulite nucleating agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
- C08L2312/06—Crosslinking by radiation
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention relates to a polypropylene composite granular material used for radiation crosslinking foaming and a preparation technology for foamed plastic. The formula of the polypropylene composite granular material involves, by weight part, 100 of polypropylene, 0.1-10 of a beta nucleating agent, 0.2-10 of a cooling masterbatch, 0.1-5 of a crosslinking promoter, 0.2-3 of an antioxidant, 0.2-6 of an auxiliary antioxidant, and 1-15 of a foaming agent. The preparation technology includes: subjecting other additives except the foaming agent to blending modification with polypropylene in proportion at 160-230DEG C; then adding the foaming agent to undergo extrusion granulation at 100-160DEG C; extruding the obtained granules into continuous master slices at 110-160DEG C; subjecting the master slices to continuous radiation crosslinking at a dosage of 10-120kGy; and then preheating the master slices subjected to radiation crosslinking in a preheating zone at a temperature ranging from room temperature to 200DEG C, and then completing foaming molding in a foaming zone at 200-260DEG C. The polypropylene composite granular material has high melt strength and low processing temperature, and is suitable for continuous making of high foaming materials. The technology ensures uniform mixing of the foaming agent and no generation of micro-decomposition. The granular material has high physical and mechanical properties and heat resistance, the raw materials are common and have wide sources, and the cost is low. Being able to realize continuous granulation, extrusion and foaming, the polypropylene composite granular material is suitable for continuous industrial production application.
Description
Technical field
The invention belongs to polypropylene expanded raw material and produce porous plastics technical field, specifically a kind of radiation crosslinking foaming is with polypropylene composite materials pellet and prepare the technique of porous plastics.
Background technology
General purpose polypropylene material expandability is poor, and viscosity and the temperature range of its suitable foaming are narrower.Therefore,, for improving the expandable and processing stability of polypropylene material, should select to have the polypropylene material of higher melt intensity, and add other stablizer, to adapt to polypropylene expanded requirement.
Chinese patent CN101081914A provides a kind of method of preparing radiation crosslinking foaming polypropylene material.The method is taking the mixture of polypropylene and other olefin polymer (as LDPE, HDPE, LLDPE etc.) as matrix resin, add in addition additional crosslinker, whipping agent and other auxiliary agent, through mixing, blend moulding, radiation crosslinking and high temperature foaming, make radiation crosslinking foaming polypropylene material successively.
But the foam material that above-mentioned employing PE blending method is made, can not be called PP foam material on stricti jurise, the mixed elasticity of blending method foam material can be low, heatproof is low, does not possess the gesture that has of PP foam material, and abscess is at random large, foaming material performance is poor, does not also possess good forming ability.
Summary of the invention
The object of the present invention is to provide one to be applicable to? the polypropylene composite materials pellet of radiation crosslinking foaming.
Another object of the present invention is to provide a kind of radiation crosslinking foaming polypropylene composite materials pellet to prepare the technique of porous plastics.
Realize the object of the invention technical scheme and be Co-polypropylene resin taking high fondant-strength as matrix resin, add the auxiliary agents such as cooling masterbatch, nucleator, crosslinking sensitizer, oxidation inhibitor, by blend granulation, make a kind of radiation crosslinking, special polypropylene composite materials pellet of free foaming of can be used for.The polypropylene composite materials granular material formula of radiation crosslinking foaming is specifically taking acrylic resin as 100 parts of weighing scales:
100 parts of polypropylene
0.1 part ~ 10 parts of beta nucleaters
0.2 part ~ 10 parts of cooling masterbatch
0.1 part ~ 5 parts of crosslinking accelerators
0.2 part ~ 3 parts, oxidation inhibitor
0.2 part ~ 6 parts of auxiliary antioxidants
1 part ~ 15 parts of whipping agents.
Component and the weight percent of above-mentioned formula optimization are as follows:
100 parts of polypropylene
0.2 part ~ 5 parts of beta nucleaters
0.5 part ~ 4 parts of cooling masterbatch
1 part ~ 3 parts of crosslinking accelerators
0.5 part ~ 1.5 parts, oxidation inhibitor
1 part ~ 3 parts of auxiliary antioxidants
5 parts ~ 10 parts of whipping agents.
Acrylic resin in above-mentioned is the Co-polypropylene resin of high fondant-strength, and melting index is 0.1 ~ 10g/10min, is preferably 0.2 ~ 3g/min.
Nucleator in above-mentioned is beta nucleater, adds minimum quantity to start to work, and add-on is too high, can bring unnecessary cost to increase.
Cooling masterbatch add-on in above-mentioned is different and different with polypropylene mobility, melt strength variation and the purity of cooling masterbatch own, taking polypropylene as 100 parts of weighing scales, is generally 0.2 ~ 10%.
Other auxiliary agent (crosslinking accelerator, oxidation inhibitor, auxiliary antioxidant etc.) in above-mentioned adds minimum quantity to start to work, and add-on is too high, can bring unnecessary cost to increase.
The additional proportion of the whipping agent in above-mentioned is decided by final foamed products foam expansion, and taking polypropylene+polyethylene as 100 parts of weighing scales, general additional proportion is 1 ~ 15%, can make expansion ratio and be the series product of 2 ~ 30 times.
Other additive in above-mentioned can comprise polyethylene wax, colour batch, fire retardant, but is not limited to above-mentioned additive.
Above-mentioned radiation crosslinking foaming is prepared the technique of porous plastics with polypropylene composite materials pellet, comprise following operation steps:
(1) first cooling masterbatch, nucleator, oxidation inhibitor, auxiliary antioxidant, crosslinking sensitizer and other auxiliary agent except whipping agent are carried out to blending and modifying with polypropylene in proportion, processing temperature is 160 ~ 230 DEG C;
(2) add whipping agent to carry out extruding pelletization, processing temperature is 100 ~ 160 DEG C again;
(2) pellet of gained is extruded into continuous master slice, extrusion temperature is 110 ~ 160 DEG C; Master slice is carried out to continuous gamma radiation and be cross-linked, radiation dose is 10 ~ 120kGy; First the preheating zone preheating in room temperature ~ 200 DEG C by the master slice after radiation crosslinking, then complete foaming the foaming zone of 200 ~ 260 DEG C;
Radiation crosslinking foaming of the present invention has the following advantages with polypropylene composite materials pellet tool:
A) use nucleator, cooling masterbatch, oxidation inhibitor, auxiliary antioxidant to carry out blending and modifying granulation to polypropylene, can change polyacrylic mobility, reduce high temperature ageing, improve its melt strength, reduce processing temperature, made it to become the raw material that is suitable for making continuously high-foaming material;
B) adopt mixing, the extrusion pelletization technology of substep, during with whipping agent granulation, prilling temperature scope is 100 ~ 160 DEG C, can guarantee that whipping agent mixes, but not produce differential solution, and final production goes out continuous foamed products;
C) pp material used is the common raw material of selling on market, has greatly increased raw material sources, has reduced production cost;
D) utilize the radiating crosslinked polypropylene porous plastics that the present invention produces to have than the better physical and mechanical properties of other foamed polyolefine plastic and thermotolerance.
Radiation crosslinking foaming of the present invention is prepared the technique of porous plastics with polypropylene composite materials pellet, due to can serialization granulation, extrude and foam, be applicable to the continuous production application of actual industrialization.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated, and following embodiment is only for technical scheme of the present invention is described, but to not restriction of the present invention.
embodiment 1
Radiation crosslinking foaming of the present invention polypropylene composite materials pellet, the proportioning components of expansion ratio 3.8 is for taking weight part: acrylic resin is 2 parts of 100 parts, 2 parts of masterbatch of PP100 cooling, 0.4 part of TMPTMA11 part of beta nucleater, 0100.5 part of DLTP1 part AC whipping agent.
The technological operation step of specifically preparing porous plastics is as follows:
(1) first cooling masterbatch, nucleator, oxidation inhibitor, auxiliary antioxidant, crosslinking sensitizer and other auxiliary agent except whipping agent are carried out to blending and modifying with polypropylene in proportion, processing temperature is 160 ~ 230 DEG C;
(2) add whipping agent to carry out extruding pelletization, processing temperature is 100 ~ 160 DEG C again;
(3) pellet of gained is extruded into continuous master slice, extrusion temperature is 110 ~ 160 DEG C; Master slice is carried out to continuous gamma radiation and be cross-linked, radiation dose is 10 ~ 120kGy; First the preheating zone preheating in room temperature ~ 200 DEG C by the master slice after radiation crosslinking, then complete foaming the foaming zone of 200 ~ 260 DEG C.
embodiment 2
Radiation crosslinking foaming of the present invention polypropylene composite materials pellet, the proportioning components of expansion ratio 10 is for taking weight part: acrylic resin is 5 parts of 100 parts, 2 parts of masterbatch of PP100 cooling, 0.4 part of TMPTMA11 part of beta nucleater, 0100.5 part of DLTP1 part AC whipping agent.
The technological operation step of specifically preparing porous plastics is as follows:
(1) first cooling masterbatch, nucleator, oxidation inhibitor, auxiliary antioxidant, crosslinking sensitizer and other auxiliary agent except whipping agent are carried out to blending and modifying with polypropylene in proportion, processing temperature is 160 ~ 230 DEG C;
(2) add whipping agent to carry out extruding pelletization, processing temperature is 100 ~ 160 DEG C again;
(3) pellet of gained is extruded into continuous master slice, extrusion temperature is 110 ~ 160 DEG C; Master slice is carried out to continuous gamma radiation and be cross-linked, radiation dose is 10 ~ 120kGy; First the preheating zone preheating in room temperature ~ 200 DEG C by the master slice after radiation crosslinking, then complete foaming the foaming zone of 200 ~ 260 DEG C.
embodiment 3
Radiation crosslinking foaming of the present invention polypropylene composite materials pellet, the proportioning components of expansion ratio 19 is for taking weight part: acrylic resin is 10 parts of 100 parts, 2 parts of masterbatch of PP100 cooling, 0.4 part of TMPTMA11 part of beta nucleater, 0100.5 part of DLTP1 part AC whipping agent.
The technological operation step of specifically preparing porous plastics is as follows:
(1) first cooling masterbatch, nucleator, oxidation inhibitor, auxiliary antioxidant, crosslinking sensitizer and other auxiliary agent except whipping agent are carried out to blending and modifying with polypropylene in proportion, processing temperature is 160 ~ 230 DEG C;
(2) add whipping agent to carry out extruding pelletization, processing temperature is 100 ~ 160 DEG C again;
(3) pellet of gained is extruded into continuous master slice, extrusion temperature is 110 ~ 160 DEG C; Master slice is carried out to continuous gamma radiation and be cross-linked, radiation dose is 10 ~ 120kGy; First the preheating zone preheating in room temperature ~ 200 DEG C by the master slice after radiation crosslinking, then complete foaming the foaming zone of 200 ~ 260 DEG C.
embodiment 4
Radiation crosslinking foaming of the present invention polypropylene composite materials pellet, expansion ratio 28.8 is taking weight part: acrylic resin is 100 parts, 2 parts of masterbatch of PP100 cooling, 0.4 part of TMPTMA11 part of beta nucleater, 0100.5 part of DLTP1 part AC whipping agent 15.
The technological operation step of specifically preparing porous plastics is as follows:
(1) first cooling masterbatch, nucleator, oxidation inhibitor, auxiliary antioxidant, crosslinking sensitizer and other auxiliary agent except whipping agent are carried out to blending and modifying with polypropylene in proportion, processing temperature is 160 ~ 230 DEG C;
(2) add whipping agent to carry out extruding pelletization, processing temperature is 100 ~ 160 DEG C again;
(3) pellet of gained is extruded into continuous master slice, extrusion temperature is 110 ~ 160 DEG C; Master slice is carried out to continuous gamma radiation and be cross-linked, radiation dose is 10 ~ 120kGy; First the preheating zone preheating in room temperature ~ 200 DEG C by the master slice after radiation crosslinking, then complete foaming the foaming zone of 200 ~ 260 DEG C.
Claims (5)
1. the polypropylene composite materials pellet that radiation crosslinking foaming is used, is characterized in that composition and proportioning are weight part meter: 100 parts of polypropylene,
0.1 part ~ 10 parts of beta nucleaters
0.2 part ~ 10 parts of cooling masterbatch
0.1 part ~ 5 parts of crosslinking accelerators
0.2 part ~ 3 parts, oxidation inhibitor
0.2 part ~ 6 parts of auxiliary antioxidants
1 part ~ 15 parts of whipping agents
The polypropylene composite materials pellet that radiation crosslinking foaming as claimed in claim 1 is used, is characterized in that composition and proportioning are weight part meter:
100 parts of polypropylene
0.2 part ~ 5 parts of beta nucleaters
0.5 part ~ 4 parts of cooling masterbatch
1 part ~ 3 parts of crosslinking accelerators
0.5 part ~ 1.5 parts, oxidation inhibitor
1 part ~ 3 parts of auxiliary antioxidants
1 part ~ 15 parts of whipping agents
The polypropylene composite materials pellet that radiation crosslinking foaming as described in claim 1 or 2 is used, is characterized in that: the Co-polypropylene resin that described acrylic resin is high fondant-strength, melting index is 0.1 ~ 10g/10min.
2. the polypropylene composite materials pellet that the radiation crosslinking foaming as described in claim 2 is used, is characterized in that: the Co-polypropylene resin that described acrylic resin is high fondant-strength, melting index is 0.2 ~ 3g/min.
3. the polypropylene composite materials pellet that radiation crosslinking foaming as claimed in claim 3 is used, is characterized in that: described cooling masterbatch is 0.2 part ~ 10 parts.
4. the polypropylene composite materials pellet that the radiation crosslinking foaming as described in claim 4 is used, is characterized in that: other described additive is polyethylene wax, colour batch, fire retardant.
5. above-mentioned radiation crosslinking foaming is prepared the technique of porous plastics with polypropylene composite materials pellet, comprises following operation steps:
(1) first cooling masterbatch, nucleator, oxidation inhibitor, auxiliary antioxidant, crosslinking sensitizer and other auxiliary agent except whipping agent are carried out to blending and modifying with polypropylene in proportion, processing temperature is 160 DEG C ~ 230 DEG C; Or 160 DEG C ~ 190 DEG C
(2) add whipping agent to carry out extruding pelletization, processing temperature is 100 DEG C ~ 160 DEG C again; Or 120 DEG C ~ 150 DEG C
(2) pellet of gained is extruded into continuous master slice, extrusion temperature is 110 DEG C ~ 160 DEG C; Or 130 DEG C ~ 160 DEG C that master slice is carried out to continuous gamma radiation is crosslinked, radiation dose is 10 ~ 120kGy; First the preheating zone preheating 40 DEG C ~ 150 DEG C of room temperatures by the master slice after radiation crosslinking, then complete foaming the foaming zone of 200 DEG C ~ 260 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310014475.1A CN103923398A (en) | 2013-01-15 | 2013-01-15 | Polypropylene composite granular material used for radiation crosslinking foaming and preparation technology for foamed plastic |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310014475.1A CN103923398A (en) | 2013-01-15 | 2013-01-15 | Polypropylene composite granular material used for radiation crosslinking foaming and preparation technology for foamed plastic |
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| CN103923398A true CN103923398A (en) | 2014-07-16 |
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| CN201310014475.1A Pending CN103923398A (en) | 2013-01-15 | 2013-01-15 | Polypropylene composite granular material used for radiation crosslinking foaming and preparation technology for foamed plastic |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110557950A (en) * | 2018-03-30 | 2019-12-10 | 积水化学工业株式会社 | Polyolefin resin foam, process for producing polyolefin resin foam, and molded article |
| CN111438958A (en) * | 2020-03-17 | 2020-07-24 | 启东纽昇塑胶科技有限公司 | Production method of polypropylene foam material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1346843A (en) * | 2000-10-11 | 2002-05-01 | 中国石油化工股份有限公司 | Radiation cross-linked and foamed polypropylene material and its preparing process |
| CN101081914A (en) * | 2007-07-06 | 2007-12-05 | 天津市润生塑胶制品有限公司 | Polypropylene expanded material and method for manufacturing same |
| CN102311584A (en) * | 2011-07-26 | 2012-01-11 | 成都市新津事丰医疗器械有限公司 | Medical polypropylene material |
-
2013
- 2013-01-15 CN CN201310014475.1A patent/CN103923398A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1346843A (en) * | 2000-10-11 | 2002-05-01 | 中国石油化工股份有限公司 | Radiation cross-linked and foamed polypropylene material and its preparing process |
| CN101081914A (en) * | 2007-07-06 | 2007-12-05 | 天津市润生塑胶制品有限公司 | Polypropylene expanded material and method for manufacturing same |
| CN102311584A (en) * | 2011-07-26 | 2012-01-11 | 成都市新津事丰医疗器械有限公司 | Medical polypropylene material |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110557950A (en) * | 2018-03-30 | 2019-12-10 | 积水化学工业株式会社 | Polyolefin resin foam, process for producing polyolefin resin foam, and molded article |
| CN111438958A (en) * | 2020-03-17 | 2020-07-24 | 启东纽昇塑胶科技有限公司 | Production method of polypropylene foam material |
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Address after: 321100, 1, Baisha mountain, Yunshan street, Jinhua, Zhejiang, Lanxi Applicant after: ZHEJIANG JIAOLIAN IRRADIATED MATERIALS CO., LTD. Address before: 321100, 1, Baisha mountain, Yunshan street, Jinhua, Zhejiang, Lanxi Applicant before: ZHEJIANG JIAOLIAN IRRADIATED MATERIALS CO., LTD. |
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Application publication date: 20140716 |