CN104231204B - A kind of TPUE used for solar batteries and preparation method thereof - Google Patents
A kind of TPUE used for solar batteries and preparation method thereof Download PDFInfo
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- CN104231204B CN104231204B CN201410477861.9A CN201410477861A CN104231204B CN 104231204 B CN104231204 B CN 104231204B CN 201410477861 A CN201410477861 A CN 201410477861A CN 104231204 B CN104231204 B CN 104231204B
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- tpue
- solar batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Abstract
The invention provides a kind of TPUE used for solar batteries, it is mainly prepared by the following raw material by weight：100 parts of PEPA, 60~90 parts of dicyclopentadiene phenol epoxy resin, aliphatic diisocyanate and diol chain-extension agent；Wherein, the ratio between amount of material of control OH groups and NCO group is 1:1.2~1.4；The weight average molecular weight for controlling PEPA is 10000~20000, and the molecular weight distribution (Mw/Mn) of control PEPA is 1~2.4.The TPU film obtained using the TPUE of the present invention has the advantages that high transparency, translucency are good, never xanthochromia, fusing point are high and adhesion strength is high compared with traditional eva film.In addition, when the film is used to make solar cell, it is not necessary to be crosslinked, the production process of solar cell can be accelerated.
Description
Technical field
The present invention relates to a kind of TPUE used for solar batteries and preparation method thereof.
Background technology
At present, the installed capacity of global solar facility is almost with Exponential growth, and exploitation generating efficiency and production efficiency are more
High solar cell module becomes particularly important.If silicon wafer is directly exposed in air, its opto-electronic conversion function will
Decay.Need to encapsulate silicon wafer using a kind of good glue-line of transparent, ageing-resistant, caking property for this, and with upper strata protective glass,
Lower floor protection materials TPT (polyvinyl fluoride composite membrane) bondings are integrated, and constitute solar module.
The most basic function of EVA adhesive film has been exactly the effect of being bonded and sealed, i.e., by silicon wafer and atmospheric isolation.At the same time,
The anti-reflection effect to glass can also be played, is conducive to the raising of photoelectric conversion efficiency of the solar battery.
Solar cell packaging EVA is, for base-material, to be aided with several modifications using EVA (vinyl acetate content is 30-33%)
Agent, film-type product is rolled into through film-forming apparatus.The product is heated during solar cell package, produces cross-linking reaction,
Belong to heat cured hot melt adhesive film.Glued membrane after solidification have at a relatively high light transmittance, adhesive strength, heat endurance, air-tightness and
Ageing-resistant performance.
Bayer Material Science company obtains important breakthrough in this regard in recent years.The said firm research staff succeed in developing one
Thermoplastic polyurethane is planted, trade name VISTA-SOLAR novel thin film is made using thermoplastic polyurethane, the sun is used as
Energy battery raw material replaces traditional eva film, not only makes the production of solar cell more convenient and convenient, also substantially increases
The generating efficiency of solar cell.
The content of the invention
In consideration of it, an object of the present invention is to provide a kind of TPUE used for solar batteries, make
The TPU film obtained with the TPUE of the present invention is compared with traditional eva film, with high transparency, printing opacity
Property it is good, never xanthochromia, fusing point be high and the high advantage of adhesion strength.In addition, when the film is used to make solar cell, it is not necessary to enter
Row crosslinking, can accelerate the production process of solar cell.
In order to achieve the above object, present invention employs following technical scheme：
A kind of TPU film used for solar batteries, it is mainly prepared by the following raw material by weight：
100 parts of PEPA
60~90 parts of dicyclopentadiene phenol epoxy resin
Aliphatic diisocyanate
Diol chain-extension agent；
Wherein, the ratio between amount of material of control-OH groups and-NCO group is 1:1.2~1.4；
The weight average molecular weight for controlling PEPA is 10000~20000, by the Weight-average molecular for controlling PEPA
Measure in the range of this, to make solidfied material that there is excellent adhesion strength, and suitable for coating.If weight average molecular weight is less than 10000,
Adhesion strength is too low, and weight average molecular weight is more than 20000, it is difficult to apply, and is difficult to prepare film, and preferably 12000~18000,
Further preferred 13000~17000.
The molecular weight distribution (Mw/Mn) for controlling PEPA is 1~2.4, by making molecular weight distribution be in foregoing model
In enclosing, can play simultaneously due to low molecular weight compositions the effect improved with the adaptation of base material and due to HMW into
The solidfied material divided is changed into the effect of high intensity, therefore strong as excellent, the initial bonding of the substrate bonding under wet heat condition
The high polyurethane film of degree.When molecular weight distribution (Mw/Mn) is less than 1, the initial adhesive strength reduction of polyurethane film, molecule
When amount distribution is more than 2.4, the adhesion strength of polyurethane film is equally reduced.
The weight average molecular weight for controlling dicyclopentadiene phenol epoxy resin is 500~800, preferably 600~800.
Dicyclopentadiene phenol epoxy resin be 60~90 parts, such as 61 parts, 62 parts, 63 parts, 64 parts, 65 parts, 66 parts, 67
Part, 68 parts, 69 parts, 70 parts, 71 parts, 72 parts, 73 parts, 74 parts, 75 parts, 76 parts, 77 parts, 78 parts, 79 parts, 80 parts, 81 parts, 82
Part, 83 parts, 84 parts, 85 parts, 86 parts, 87 parts, 88 parts or 89 parts, preferably 65~85 parts, further preferred 70~80 parts.
The ratio between amount of material of control-OH groups and-NCO group is 1:1.2~1.4, such as 1:1.21、1:1.22、1:
1.23、1:1.24、1:1.25、1:1.26、1:1.27、1:1.28、1:1.29、1:1.3、1:1.31、1:1.32、1:1.33、1:
1.34、1:1.35、1:1.36、1:1.37、1:1.38 or 1:1.39.
" mainly by " of the present invention, it is intended that it can also include other components, these other groups in addition to the component
Part assigns the polyurethane film different characteristics.In addition, " mainly by " of the present invention, may be replaced by closing
" being " of formula or " by ... constitute ".
For example, the raw material of the polyurethane film can also contain various additives, as concrete example, it can enumerate phosphorous
Fire retardant, antioxidant, heat stabilizer, hydrolysis-resisting agent, antistatic additive, pigment, colouring agent or lubricant etc..These various additives
It can be used alone, two kinds or two or more can also be used in mixed way.
The hydrolysis-resisting agent is selected from the mixture of three kinds of carbodiimides, epoxy resin and silane coupler, the matter of three
Amount is than being 1:2~3:4~5, such as 1:2.1:4.1、1:2.2:4.2、1:2.3:4.3、1:2.4:4.4、1:2.5:4.5、1:
2.6:4.6、1:2.7:4.7、1:2.8:4.8 or 1:2.9:4.9, preferably 1:2.2~2.8:4.2~4.8.
The raw material also includes light stabilizer or/and antioxidant；
Preferably, the light stabilizer is ultra-violet absorber or/and ultra-violet stabilizer.
The second object of the present invention is to provide a kind of TPUE used for solar batteries as described above
Preparation method, methods described comprises the following steps：
Each composition is mixed by formula ratio, thermoplastic polyurethane elastic used for solar batteries is obtained using prepolymer method
Body.
Compared with the prior art, the present invention has the advantages that：
The TPU film obtained using the TPUE of the present invention is compared with traditional eva film, with height
Transparent, translucency is good, never xanthochromia, fusing point be high and the high advantage of adhesion strength.In addition, the film is used to make solar cell
When, it is not necessary to it is crosslinked, the production process of solar cell can be accelerated.
Embodiment
Technical scheme is further illustrated below by embodiment.
Embodiment 1
A kind of TPUE used for solar batteries, it is mainly prepared into by the following raw material by weight
Arrive：
100 parts of PEPA
60 parts of dicyclopentadiene phenol epoxy resin
Aliphatic diisocyanate
Diol chain-extension agent；
Wherein, the ratio between amount of material of control-OH groups and-NCO group is 1:1.2；
The weight average molecular weight for controlling PEPA is 10000.
The molecular weight distribution (Mw/Mn) for controlling PEPA is 1.
The weight average molecular weight for controlling dicyclopentadiene phenol epoxy resin is 500.
Method for preparing thermoplastic polyurethane elastomer used for solar batteries as described above, methods described includes following step
Suddenly：
Each composition is mixed by formula ratio, thermoplastic polyurethane elastic used for solar batteries is obtained using prepolymer method
Body.
Embodiment 2
A kind of TPU film used for solar batteries, it is mainly prepared by the following raw material by weight：
100 parts of PEPA
90 parts of dicyclopentadiene phenol epoxy resin
Aliphatic diisocyanate
Diol chain-extension agent；
Wherein, the ratio between amount of material of control-OH groups and-NCO group is 1:1.4；
The weight average molecular weight for controlling PEPA is 20000.
The molecular weight distribution (Mw/Mn) for controlling PEPA is 2.4.
The weight average molecular weight for controlling dicyclopentadiene phenol epoxy resin is 800.
Method for preparing thermoplastic polyurethane elastomer used for solar batteries as described above, methods described includes following step
Suddenly：
Each composition is mixed by formula ratio, thermoplastic polyurethane elastic used for solar batteries is obtained using prepolymer method
Body.
Embodiment 3
A kind of TPUE used for solar batteries, it is mainly prepared into by the following raw material by weight
Arrive：
100 parts of PEPA
70 parts of dicyclopentadiene phenol epoxy resin
Aliphatic diisocyanate
Diol chain-extension agent；
Wherein, the ratio between amount of material of control-OH groups and-NCO group is 1:1.3；
The weight average molecular weight for controlling PEPA is 12000.
The molecular weight distribution (Mw/Mn) for controlling PEPA is 2.
The weight average molecular weight for controlling dicyclopentadiene phenol epoxy resin is 600.
The raw material of the polyurethane also contains hydrolysis-resisting agent, the hydrolysis-resisting agent be selected from carbodiimides, epoxy resin and
The mixture that three kinds of silane coupler, the mass ratio of three is 1:2:4.
Method for preparing thermoplastic polyurethane elastomer used for solar batteries as described above, methods described includes following step
Suddenly：
Each composition is mixed by formula ratio, thermoplastic polyurethane elastic used for solar batteries is obtained using prepolymer method
Body.
Embodiment 4
A kind of TPUE used for solar batteries, it is mainly prepared into by the following raw material by weight
Arrive：
100 parts of PEPA
75 parts of dicyclopentadiene phenol epoxy resin
Aliphatic diisocyanate
Diol chain-extension agent；
Wherein, the ratio between amount of material of control-OH groups and-NCO group is 1:1.25.
The weight average molecular weight for controlling PEPA is 17000.
The molecular weight distribution (Mw/Mn) for controlling PEPA is 1.5.
The weight average molecular weight for controlling dicyclopentadiene phenol epoxy resin is 700.
The raw material of the polyurethane also contains hydrolysis-resisting agent, the hydrolysis-resisting agent be selected from carbodiimides, epoxy resin and
The mixture that three kinds of silane coupler, the mass ratio of three is 1:3:5.
Method for preparing thermoplastic polyurethane elastomer used for solar batteries as described above, methods described includes following step
Suddenly：
Each composition is mixed by formula ratio, thermoplastic polyurethane elastic used for solar batteries is obtained using prepolymer method
Body.
Embodiment 5
A kind of TPUE used for solar batteries, it is mainly prepared into by the following raw material by weight
Arrive：
100 parts of PEPA
75 parts of dicyclopentadiene phenol epoxy resin
Aliphatic diisocyanate
Diol chain-extension agent；
Wherein, the ratio between amount of material of-OH groups and-NCO group is 1 in control PEPA:1.25.
The weight average molecular weight for controlling PEPA is 17000.
The molecular weight distribution (Mw/Mn) for controlling PEPA is 1.5.
The weight average molecular weight for controlling dicyclopentadiene phenol epoxy resin is 700.
The raw material of the polyurethane also contains hydrolysis-resisting agent, the hydrolysis-resisting agent be selected from carbodiimides, epoxy resin and
The mixture that three kinds of silane coupler, the mass ratio of three is 1:3:5.
Method for preparing thermoplastic polyurethane elastomer used for solar batteries as described above, methods described includes following step
Suddenly：
Each composition is mixed by formula ratio, thermoplastic polyurethane elastic used for solar batteries is obtained using prepolymer method
Body.
Comparative example 1
Remaining is same as Example 1, except the ratio between amount of material of control-OH groups and-NCO group is 1:1.05.
Comparative example 2
Remaining is same as Example 1, except the ratio between amount of material of control-OH groups and-NCO group is 1:1.5.
Comparative example 3
Remaining is same as Example 1, except the weight average molecular weight for controlling PEPA is 30000.
Comparative example 4
Remaining is same as Example 1, except the molecular weight distribution (Mw/Mn) of control control PEPA is 2.6.
Comparative example 5
Remaining is same as Example 1, except the weight average molecular weight for controlling dicyclopentadiene phenol epoxy resin is 400.
Comparative example 6
Remaining is same as Example 1, except the weight average molecular weight for controlling dicyclopentadiene phenol epoxy resin is 900.
Comparative example 7
Comparative example 7 is the A of CN 103492444 embodiment 1.
Comparative example 8
Comparative example 8 is the A of CN 103339214 embodiment 1.
Evaluate the making of sample
Using the PET film of 125 μ m-thicks (" X10S " of Dongli Ltd.'s manufacture) as base material, by above-described embodiment and right
In ratio the polyurethane film of gained fit 25 μ m-thicks fluorine film " AFLEX25PW " of manufacture (Asahi Glass Co., Ltd) and obtain
To laminated film.It is cured 72 hours at 50 DEG C, obtains evaluating sample.
Composite membrane after maturation process is carried out in splitting test, embodiment 1~4, splitting power is in 9N/cm
More than, and in comparative example 1~8, splitting power is 7~8N/cm.
Hydrothermal aging (DH) 2000h, wet jelly (HF) 20 circulations, accelerated hydrothermal agings are carried out to the composite membrane after curing
(105 DEG C, 100%RH, 192h) and UV 60kWh burin-in process.Splitting test is carried out to the composite membrane through burin-in process,
In embodiment 1~4, splitting power is in more than 8N/cm, and in comparative example 1~8, splitting power is 5~6N/cm.
In addition, the light transmittance of the TPU film obtained using the TPUE of embodiment 1~4 can reach
98% and more than, 165~175 DEG C, far above the light transmittance 85~90% of comparative example 1~4,130~140 DEG C of fusing point, with height
The good advantage of fusing point, high transparency and translucency.
Applicant states that the present invention illustrates the method detailed of the present invention, but not office of the invention by above-described embodiment
It is limited to above-mentioned method detailed, that is, does not mean that the present invention has to rely on above-mentioned method detailed and could implemented.Art
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention
Addition, selection of concrete mode etc., within the scope of all falling within protection scope of the present invention and being open.
Claims (11)
1. a kind of TPUE used for solar batteries, it is mainly prepared by the following raw material by weight：
100 parts of PEPA
60~90 parts of dicyclopentadiene phenol epoxy resin
Aliphatic diisocyanate
Diol chain-extension agent；
Wherein, the ratio between amount of material of-OH groups and-NCO group is 1 in control PEPA:1.2~1.4；
The weight average molecular weight for controlling PEPA is 10000~20000, controls the molecular weight distribution (Mw/ of PEPA
Mn it is) 1~2.4；
The weight average molecular weight for controlling dicyclopentadiene phenol epoxy resin is 500~800.
2. TPUE used for solar batteries as claimed in claim 1, it is characterised in that control polyester polyols
The weight average molecular weight of alcohol is 12000~18000.
3. TPUE used for solar batteries as claimed in claim 1 or 2, it is characterised in that control polyester
The weight average molecular weight of polyalcohol is 13000~17000.
4. TPUE used for solar batteries as claimed in claim 1 or 2, it is characterised in that control is bicyclic
The weight average molecular weight of pentadiene phenol-type epoxy resin is 600~800.
5. TPUE used for solar batteries as claimed in claim 1 or 2, it is characterised in that bicyclic penta 2
The content of alkene phenol-type epoxy resin is 65~85 parts.
6. TPUE used for solar batteries as claimed in claim 1 or 2, it is characterised in that bicyclic penta 2
The content of alkene phenol-type epoxy resin is 70~80 parts.
7. TPUE used for solar batteries as claimed in claim 1 or 2, it is characterised in that the raw material
Also include hydrolysis-resisting agent, the hydrolysis-resisting agent is selected from the mixture of three kinds of carbodiimides, epoxy resin and silane coupler, three
The mass ratio of person is 1:2~3:4~5.
8. TPUE used for solar batteries as claimed in claim 1 or 2, it is characterised in that the raw material
Also include hydrolysis-resisting agent, the hydrolysis-resisting agent is selected from the mixture of three kinds of carbodiimides, epoxy resin and silane coupler, three
The mass ratio of person is 1:2.2~2.8:4.2~4.8.
9. TPUE used for solar batteries as claimed in claim 1 or 2, it is characterised in that the raw material
Also include light stabilizer or/and antioxidant.
10. TPUE used for solar batteries as claimed in claim 9, it is characterised in that the light is stable
Agent is ultra-violet absorber or/and ultra-violet stabilizer.
11. a kind of method for preparing thermoplastic polyurethane elastomer used for solar batteries as described in one of claim 1-10,
Methods described comprises the following steps：
Each composition is mixed by formula ratio, TPUE used for solar batteries is obtained using prepolymer method.
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| CN201410477861.9A CN104231204B (en) | 2014-09-18 | 2014-09-18 | A kind of TPUE used for solar batteries and preparation method thereof |
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| CN201410477861.9A CN104231204B (en) | 2014-09-18 | 2014-09-18 | A kind of TPUE used for solar batteries and preparation method thereof |
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| CN104231204B true CN104231204B (en) | 2017-08-29 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107118731A (en) * | 2017-06-26 | 2017-09-01 | 张兆民 | Solar monocrystalline silicon slice adhesive |
| JP7184615B2 (en) * | 2018-11-30 | 2022-12-06 | 株式会社ダイセル | Polyurethane |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6515048B1 (en) * | 1998-12-07 | 2003-02-04 | Firma Carl Freudenberg | Adhesive powder |
| CN102838725A (en) * | 2011-06-22 | 2012-12-26 | 中国石油化工股份有限公司 | Preparation method of phenol-dicyclopentadiene epoxy resin |
| CN103819893A (en) * | 2014-02-26 | 2014-05-28 | 程六秀 | Flame-retardant antistatic IPN elastomer and preparation method thereof |
| CN104017167A (en) * | 2014-06-13 | 2014-09-03 | 奥斯汀新材料（张家港）有限公司 | Preparation method of heat-resistant polyester plastic polyurethane elastomer |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5761207B2 (en) * | 2011-02-04 | 2015-08-12 | 東洋インキＳｃホールディングス株式会社 | Polyurethane adhesive, adhesive for solar cell protective sheet, and back surface protective sheet for solar cell |
| JP5413704B1 (en) * | 2012-04-19 | 2014-02-12 | Ｄｉｃ株式会社 | Resin composition, two-component laminate adhesive, laminated film, and solar cell backsheet |
-
2014
- 2014-09-18 CN CN201410477861.9A patent/CN104231204B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6515048B1 (en) * | 1998-12-07 | 2003-02-04 | Firma Carl Freudenberg | Adhesive powder |
| CN102838725A (en) * | 2011-06-22 | 2012-12-26 | 中国石油化工股份有限公司 | Preparation method of phenol-dicyclopentadiene epoxy resin |
| CN103819893A (en) * | 2014-02-26 | 2014-05-28 | 程六秀 | Flame-retardant antistatic IPN elastomer and preparation method thereof |
| CN104017167A (en) * | 2014-06-13 | 2014-09-03 | 奥斯汀新材料（张家港）有限公司 | Preparation method of heat-resistant polyester plastic polyurethane elastomer |
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