CN102194924B - Method for keeping long-time cohesive force between ethylene vinyl acetute (EVA) packaging adhesive film and glass panel dedicated to solar energy battery - Google Patents
Method for keeping long-time cohesive force between ethylene vinyl acetute (EVA) packaging adhesive film and glass panel dedicated to solar energy battery Download PDFInfo
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- CN102194924B CN102194924B CN201110083722A CN201110083722A CN102194924B CN 102194924 B CN102194924 B CN 102194924B CN 201110083722 A CN201110083722 A CN 201110083722A CN 201110083722 A CN201110083722 A CN 201110083722A CN 102194924 B CN102194924 B CN 102194924B
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Abstract
The invention provides a method for keeping long-time cohesive force between an ethylene vinyl acetate (EVA) packaging adhesive film and a glass panel dedicated to a solar energy battery, comprising the following steps: mixing a prehydrolyzed silane coupling agent, an EVA resin and other agents; and extruding and forming a film. Prehydrolysis realizes that an alcoxyl group in the silane coupling agent is transformed into hydroxide radical; under the condition of a lamination process of the solar energy battery, the alcoxyl group in the silane coupling agent can be rapidly condensed with the hydroxide radical on the surface of glass, thus a Si-O-Si covalent bond exists between the adhesive film and the glass surface; and the stable covalent bond ensures the long-time effective cohesive force of the EVA cohesive film and the glass surface under ultraviolet and high-temperature high-humidity condition.
Description
Technical field
The present invention relates to EVA glued membrane field, relate in particular to solar cell package EVA glued membrane.
Background technology
Solar cell is the device that solar energy is directly changed into electric energy, is a new and high technology of solar energy development, is a kind of novel special power supply.The principle of generating by solar is to utilize semi-conductive quantum effects such as silicon, directly converts sunlight into electric energy.The battery sheet directly is exposed in the atmosphere, and its opto-electronic conversion function can decay very soon, for the permanently effective need of work that guarantees solar cell encapsulates the battery sheet.The most common packaging technology is 5 layers of encapsulation, and light transmitting surface is a glass packaging.Usually with transmitance greater than 90% toughened glass; Be two-layer ethene-acetate ethylene copolymer (below be called EVA) glued membrane folder battery sheet then; Substrate is used composite plastic film, polyvinyl fluoride composite membrane (TPT) for example, and five layer materials add that behind the high temperature lamination aluminum alloy frame is sealed to form.
The EVA packaging adhesive film is the pith in the photovoltaic module, and it plays protection battery sheet, and the battery sheet, glass combines into an integral body effectively with backboard.The EVA glued membrane is heated to uniform temperature; Under molten condition, the crosslinking agent that wherein adds decomposes the generation free radical, causes the intermolecular combination of EVA; Make it and crystal silicon cell, glass, TPT backboard produce bonding and curing; Three kinds of materials consist of one, and EVA is no longer mobile in the assembly after the curing, and the battery sheet is no longer mobile.Because the solar cell long-term work is in the open-air atmosphere condition, the EVA glued membrane has added necessary antiager makes it can tolerate the erosion of different territorial environments and different weathers with ultraviolet absorber.It is the critical problem that guarantees the solar cell long-time stability that but the EVA glued membrane after solidifying keeps with glass and the permanently effective cohesive force of backboard.Usually in order to quicken to simulate the weather-proof ability of EVA glued membrane at solar module, we adopt temperature 85 degree, and humidity 85 degree (below be called " two 85 tests ") were realized in the short time simulating natural environment several years even the aging result of longer time.
EVA keeps and the cohesive force problem of glass in order to solve; Usually in the EVA resin, add the cohesive force that silane coupler improves EVA glued membrane and face glass; Wherein silane coupler gets organic group such as thiazolinyl and EVA copolymerization, and silane oxygen partly can be in the course of processing and glass surface hydroxyl hydrolytic condensation.But after we notice simple interpolation silane coupler in practical application; The initial adhesion power of EVA glued membrane and glass is more than 100N/cm behind the lamination; Decay is very big behind the two 85 hot and humid burn-in tests of process; 500 hours cohesive forces decay to 24N/cm under the condition of temperature 85 degree, humidity 85 degree, and cohesive force was merely 13N/cm in 1000 hours.The method of testing of cohesive force is a standard with GB/T 2790-1995 peeling strength test method.Wherein cause initial adhesion power big and the very fast reason of decay is that the EVA glued membrane is through the very strong non-bonding active force (like hydrogen bond action) of formation between high temperature lamination and the glass; But in ageing test; This hydrogen bond action power is dissociated under long-term hot and humid environment gradually, thereby forfeiture is to the cohesive force of glass.If the silane coupler that can make adding combines to form chemical bond Si-O-Si with the silicon hydroxyl of glass surface effectively, metastable chemical bond Si-O-Si then can effectively keep EVA glued membrane and glass surface cohesive force under hot and humid and strong ultraviolet environments.But under the laminating technology condition, unhydrolysed silane is difficult in the short time and the silicon hydroxyl hydrolytic condensation of glass surface.Therefore need be before lamination with silane hydrolyzate, a kind of method is with certain hour in the hot water of glued membrane immersion 90 degree that added silane coupler and extrusion modling, the alcoxyl functional group hydrolysis of silane coupler, then glued membrane is taken out dry; But this method can cause the loss of component in the glued membrane.Second method is before the extrusion modling of EVA glued membrane, to add hydrolytic condensation catalyst (for example organic tin salt); Can be in the silicon hydroxyl hydrolytic condensation of short time realization with glass surface; The shortcoming of this method is because silane coupler ratio in the EVA glued membrane of adding is very low, is difficult to realize point-to-point effective catalyzing hydrolysis condensation.Also having a kind of method relatively more commonly used is that silane coupler is mixed with rare ethanolic solution and hydrolysis, then this solution evenly is sprayed on the EVA glued membrane surface of extrusion modling, makes EVA glued membrane surface form very thin one deck silane coupler.Wherein a large amount of solvent evaporates can be brought very big potential safety hazard to production operation.
Summary of the invention
In order to address the above problem; The present invention provides a kind of method that in advance silane coupler is hydrolyzed; And the technology of direct and EVA master's micelle and the extrusion molding of auxiliary agent batch mixing; This technology can not cause the loss of component in the glued membrane and reduce a large amount of uses of dangerous organic solvent, and can behind EVA adhesive film compression technology, effectively improve and the long-term cohesive force of face glass.The process of this prehydrolysis can solve the problem that EVA glued membrane and face glass keep long-term cohesive force.
For reaching above purpose technical scheme of the present invention:
A kind of method that keeps long-term cohesive force between special-purpose EVA packaging adhesive film of solar cell and the face glass that makes comprises step and the step of EVA resin and silane coupled agent composition and face glass condensation of step, EVA resin and the silane coupled agent composition extrusion modling of silane coupler and EVA mixed with resin; Also comprise step before said silane coupler and the EVA mixed with resin step with silane coupler prehydrolysis.
Further, in the said step with silane coupler prehydrolysis, its prehydrolysis:
A. the mol ratio of the water in silane coupler and the solution is 1:3
B. hydrolysis temperature is 40 ℃-60 ℃,
C. reaction time is 20 minutes to 40 minutes,
D. hydrating solution pH value is 3-5.
Further, the above hydrolysis temperature is 45 ℃, and the pH value is 3.5, and said reaction time is 35 minutes.
Further, in the step of above-mentioned said silane coupler and EVA mixed with resin, said mixed method is that silane coupler after the prehydrolysis and EVA resin alloy is crosslinked.
Further, in the said step with silane coupler prehydrolysis, its prehydrolysis:
A. add ethanol in the hydrating solution, the mol ratio of the water in silane coupler and the solution is 1:3, and the water in the solution and the volume ratio of ethanol are 1:3,
B. hydrolysis temperature is 60 ℃-90 ℃,
C. reaction time is 60 minutes to 90 minutes,
D. hydrating solution pH value is 3-5.
Further, the above hydrolysis temperature is 65 ℃, and the pH value is 3.5, and said reaction time is 80 minutes.
Further, in the step of above-mentioned said silane coupler and EVA mixed with resin, said mixed method is that silane coupler after the prehydrolysis and EVA resin alloy is crosslinked.
Further, in the step of above-mentioned said silane coupler and EVA mixed with resin, said mixed method is for to be sprayed at the EVA resin surface with the silane coupler after the prehydrolysis.
Advantage of the present invention and beneficial effect:
A kind of method that keeps long-term cohesive force between special-purpose EVA packaging adhesive film of solar cell and the face glass that makes provided by the invention; Before silane coupler mixes with the EVA resin, silane coupler is carried out prehydrolysis; Make the silane coupler hydrolysis form the silicon hydroxyl; Mix extrusion modling with the EVA resin then.The organic group part is combined closely with the EVA resin in the silane coupler under the laminating technology condition; Silicon hydroxylic moiety in the silane coupler can with the quick condensation of the hydroxyl of glass surface, the stable Si-O-Si covalent bond under hot and humid and strong ultraviolet environments of formation can effectively guarantee the long-term cohesive force of EVA glued membrane and glass surface.
Description of drawings
Fig. 1. conventional process flow figure.
Fig. 2. a kind of solar cell provided by the invention and face glass keep the process chart of long-term cohesive force.
Fig. 3. a kind of solar cell provided by the invention and face glass keep the prehydrolysis process chart of embodiment 1 in the technology of long-term cohesive force.
Fig. 4. a kind of solar cell provided by the invention and face glass keep laminating technology chemical reaction sketch map in the technology of long-term cohesive force.
Fig. 5. a kind of solar cell provided by the invention and face glass keep the prehydrolysis process chart of embodiment 2 in the technology of long-term cohesive force.
Fig. 6. process the infrared spectrogram of EVA glued membrane after the direct blend of the unhydrolysed silane coupler of traditional handicraft.
Fig. 7. a kind of solar cell provided by the invention and face glass keep in the technology of long-term cohesive force the infrared spectrogram of EVA glued membrane after the prehydrolysis technology.
Fig. 8. a kind of solar cell provided by the invention and face glass keep two 85 test data tables in the technology of long-term cohesive force.
Embodiment
As shown in Figure 1, in the traditional handicraft, directly silane coupler and EVA resin are carried out mixed film forming, through with the laminating technology of face glass and TPT backboard after, decay very fast through its long-term cohesive force of " two 85 " burn-in test.A kind of method that makes solar cell and face glass keep cohesive force for a long time provided by the invention is at first carried out prehydrolysis to silane coupler, and then mixes with the EVA resin.
In order to make the object of the invention, technical scheme and advantage clearer,, the present invention is carried out specifying among the embodiment below in conjunction with accompanying drawing and embodiment.Should be appreciated that specific embodiment described herein only in order to explanation the present invention, and be not used in qualification the present invention.
Embodiment 1.
As shown in Figure 2; A kind of method that keeps long-term cohesive force between special-purpose EVA packaging adhesive film of solar cell and the face glass that makes provided by the invention, comprise silane coupler and EVA mixed with resin step, extrusion modling step and with the step of face glass condensation.
Before silane coupler and EVA mixed with resin step,, and reaction is controlled at hydrolysing step with silane coupler prehydrolysis.As shown in Figure 3, the process of prehydrolysis be with in the silane coupler-Si-OR
1The chemical bond hydrolysis becomes-the Si-OH chemical bond, and its reaction equation is:
RSi(OR
1)
3+3H
2O→RSi(OH)
3+3R
1OH
Wherein R is an organo-functional group, normally vinyl, amino, epoxy radicals, methacryloxypropyl or urea groups; R
1Be hydrolyzable groups, be generally methoxyl group, ethyoxyl, acetoxyl group etc., generate silanol SiOH during these group hydrolysis.
Said step with silane coupler prehydrolysis is to carry out under the acid condition of 3-5 in the pH value, and first-selected pH value is 3.5.Acid reagent can adopt hydrochloric acid or acetic acid.
The mol ratio of the water in said silane coupler and the solution is 1:3, and reaction temperature is 40 ℃-60 ℃, so that reaction is controlled at hydrolysing step; Reaction time and reaction temperature are inversely proportional to; The low then reaction time of temperature is long relatively, the temperature height then the reaction time short relatively, the reaction time is generally at 20-40 minute; First-selected temperature is 45 ℃, and the time is 35 minutes.
Like Fig. 3, shown in Figure 4; To pass through silane coupler and EVA resin and other auxiliary agent blend after the said method prehydrolysis; And then the process screw rod is extruded the stretching film forming; Peroxide under the laminating technology condition in the EVA resin causes copolymerzation with cross-linking, and the quick condensation reaction of silicon hydroxyl of silicon hydroxyl in the silane coupler and glass surface forms the Si-O-Si covalence key.
Embodiment 2.
A kind of method that keeps long-term cohesive force between special-purpose EVA packaging adhesive film of solar cell and the face glass that makes provided by the invention, comprise silane coupler and EVA mixed with resin step, extrusion modling step and with the step of face glass condensation.
Before silane coupler and EVA mixed with resin step, with silane coupler prehydrolysis, control is reflected at hydrolysing step.As shown in Figure 5, the process of prehydrolysis be with in the silane coupler-Si-OR
1The chemical bond hydrolysis becomes-the Si-OH chemical bond, and its reaction equation is:
RSi(OR
1)
3+3H
2O→RSi(OH)
3+3R
1OH
Wherein R is an organo-functional group, and normally vinyl, pi-allyl, amino, epoxy radicals, methacryloxypropyl, sulfydryl or urea groups can react with resin, and these reactive groups can combine with the organic substance reaction; R
1Be hydrolyzable groups, be generally methoxyl group, ethyoxyl, acetoxyl group etc., generate silanol SiOH during these group hydrolysis.
Said step with silane coupler prehydrolysis is to carry out under the acid condition of 3-5 in the pH value, and first-selected pH value is 3.5, and sour reagent can adopt volatile acid such as hydrochloric acid, acetic acid.
Add ethanol in the hydrating solution, the water volume ratio in ethanol and the solution is 3:1, and the mol ratio of the water in silane coupler and the solution is 1:3; Reaction temperature is controlled at 50 ℃-80 ℃, and reaction temperature was controlled at 30-90 minute, and reaction temperature and reaction time are inversely proportional to; The reaction temperature height then the reaction time short relatively; The low then reaction time of reaction temperature is long relatively, and first-selected reaction temperature is 65 ℃, and the reaction time is 80 minutes.
Like Fig. 4, shown in Figure 5; To pass through silane coupler and EVA resin and other auxiliary agent blend after the said method prehydrolysis; And then the process screw rod is extruded the stretching film forming; Perhaps the silane coupler after the above-mentioned prehydrolysis evenly is sprayed at the EVA glued membrane surface of extruding the stretching film forming through screw rod; Under the laminating technology condition, cause copolymerzation with cross-linking through the peroxide in the EVA resin, the quick condensation reaction of silicon hydroxyl of silicon hydroxyl in the silane coupler and glass surface forms the Si-O-Si covalence key.
Prehydrolysis makes that silane coupler in the EVA glued membrane is that form with the silicon hydroxyl exists; Like Fig. 6 and Fig. 7 middle infrared spectrum (instrument model: Nicolet 5700 Fourier infrared spectrographs; Detect foundation: GB/T 6040-2002 infrared spectrum analysis general rule): no matter be blending technology (Fig. 7 solid line) or spraying coating process (Fig. 7 dotted line); EVA glued membrane behind the hydrolysis process infrared absorption peak of obvious Si-OH occurred at 3209 cm-1 and 1580 cm-1, and does not have not observe (Fig. 6) in the EVA glued membrane infrared spectrum of hydrolysis process.Silicon hydroxyl in the silane coupler under the laminating technology condition can with the quick condensation reaction of silicon hydroxyl of glass surface, and the formation of Si-O-Si covalent bond guarantees the permanently effective cohesive force of EVA glued membrane and glass surface.
Result behind two 85 burn-in tests has also confirmed this point.As shown in Figure 8; Through 85 ℃ of excess temperatures, the hydrothermal aging of humidity 85 after 500 hours with the cohesive force of glass at 54N/cm, through 1000 hours; Still can reach 50N/cm (detecting instrument: universal tensile testing machine, detection foundation: peeling strength test GB/T 2790-1995) with glassy bond power
Claims (1)
1. one kind makes the method that keeps long-term cohesive force between special-purpose EVA packaging adhesive film of solar cell and the face glass, comprises step and the step of EVA resin and silane coupled agent composition and face glass condensation of step, EVA resin and the silane coupled agent composition extrusion modling of silane coupler and EVA mixed with resin; It is characterized in that: also comprise step before said silane coupler and the EVA mixed with resin step silane coupler prehydrolysis; In the step of said silane coupler and EVA mixed with resin, said mixed method is that silane coupler after the prehydrolysis and EVA resin alloy is crosslinked;
In the said step with silane coupler prehydrolysis, its prehydrolysis:
A. the mol ratio of the water in silane coupler and the solution is 1:3,
B. hydrolysis temperature is 40 ℃-60 ℃,
C. reaction time is 20 minutes to 40 minutes,
D. hydrating solution pH value is 3-5.
2. a kind of method that keeps long-term cohesive force between special-purpose EVA packaging adhesive film of solar cell and the face glass that makes according to claim 1 is characterized in that said hydrolysis temperature is 45 ℃, and the pH value is 3.5.
3. a kind of silane coupler method for hydrolysis according to claim 2 is characterized in that said reaction time is 35 minutes.
4. one kind makes the method that keeps long-term cohesive force between special-purpose EVA packaging adhesive film of solar cell and the face glass, comprises step and the step of EVA resin and silane coupled agent composition and face glass condensation of step, EVA resin and the silane coupled agent composition extrusion modling of silane coupler and EVA mixed with resin; It is characterized in that: also comprise step before said silane coupler and the EVA mixed with resin step silane coupler prehydrolysis; In the step of said silane coupler and EVA mixed with resin, said mixed method is that silane coupler after the prehydrolysis and EVA resin alloy is crosslinked; In the said step with silane coupler prehydrolysis, its prehydrolysis:
A. add ethanol in the hydrating solution, the mol ratio of the water in silane coupler and the solution is 1:3, and the water in the solution and the volume ratio of ethanol are 1:3,
B. hydrolysis temperature is 60 ℃-90 ℃,
C. reaction time is 60 minutes to 90 minutes,
D. hydrating solution pH value is 3-5.
5. a kind of method that keeps long-term cohesive force between special-purpose EVA packaging adhesive film of solar cell and the face glass that makes according to claim 4 is characterized in that said hydrolysis temperature is 65 ℃, and the pH value is 3.5.
6. a kind of method that keeps long-term cohesive force between special-purpose EVA packaging adhesive film of solar cell and the face glass that makes according to claim 5 is characterized in that said reaction time is 80 minutes.
7. a kind of method that keeps long-term cohesive force between special-purpose EVA packaging adhesive film of solar cell and the face glass that makes according to claim 4; It is characterized in that: in the step of said silane coupler and EVA mixed with resin, said mixed method is for to be sprayed at the EVA resin surface with the silane coupler after the prehydrolysis.
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| CN201110083722A CN102194924B (en) | 2011-04-02 | 2011-04-02 | Method for keeping long-time cohesive force between ethylene vinyl acetute (EVA) packaging adhesive film and glass panel dedicated to solar energy battery |
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| CN105176427A (en) * | 2015-08-31 | 2015-12-23 | 江苏斯威克新材料有限公司 | Method for making special solar cell EVA packaging glue film and glass panel maintain long-term adhesion |
| CN106753204B (en) * | 2016-12-30 | 2020-10-30 | 广州市白云化工实业有限公司 | Two-component silicone structural sealant and preparation method thereof |
| CN109087964A (en) * | 2018-07-24 | 2018-12-25 | 合肥华盖光伏科技有限公司 | A kind of preparation method of photovoltaic module back side performance protective film |
| CN113670815B (en) * | 2021-10-22 | 2022-02-18 | 南京日托光伏新能源有限公司 | Tensile test method for solder paste and core plate of MWT component |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009115566A2 (en) * | 2008-03-20 | 2009-09-24 | Epg (Engineered Nanoproducts Germany) Ag | Siloxane composite-based light-weight optical lenses |
| CN101747478A (en) * | 2008-12-17 | 2010-06-23 | 中国科学院大连化学物理研究所 | 'One-pot' preparation of organic-inorganic hybridization porous monolithic material |
| CN101885945A (en) * | 2010-07-02 | 2010-11-17 | 浙江大学 | Silanization processing method for metal surface and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009115566A2 (en) * | 2008-03-20 | 2009-09-24 | Epg (Engineered Nanoproducts Germany) Ag | Siloxane composite-based light-weight optical lenses |
| CN101747478A (en) * | 2008-12-17 | 2010-06-23 | 中国科学院大连化学物理研究所 | 'One-pot' preparation of organic-inorganic hybridization porous monolithic material |
| CN101885945A (en) * | 2010-07-02 | 2010-11-17 | 浙江大学 | Silanization processing method for metal surface and application thereof |
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