CN107841256B - PID (potential induced degradation) -resistant photovoltaic EVA (ethylene-vinyl acetate) packaging adhesive film and preparation method thereof - Google Patents
PID (potential induced degradation) -resistant photovoltaic EVA (ethylene-vinyl acetate) packaging adhesive film and preparation method thereof Download PDFInfo
- Publication number
- CN107841256B CN107841256B CN201610831415.2A CN201610831415A CN107841256B CN 107841256 B CN107841256 B CN 107841256B CN 201610831415 A CN201610831415 A CN 201610831415A CN 107841256 B CN107841256 B CN 107841256B
- Authority
- CN
- China
- Prior art keywords
- adhesive film
- eva
- pid
- eva adhesive
- equal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000002313 adhesive film Substances 0.000 title claims abstract description 75
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 title abstract description 107
- 239000005038 ethylene vinyl acetate Substances 0.000 title abstract description 107
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 title abstract description 107
- 230000015556 catabolic process Effects 0.000 title abstract description 9
- 238000006731 degradation reaction Methods 0.000 title abstract description 9
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 238000004806 packaging method and process Methods 0.000 title abstract description 6
- 230000032683 aging Effects 0.000 claims abstract description 18
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 15
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 9
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 9
- 238000004383 yellowing Methods 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 239000007822 coupling agent Substances 0.000 claims abstract description 8
- 229920005989 resin Polymers 0.000 claims description 33
- 239000011347 resin Substances 0.000 claims description 33
- 239000002516 radical scavenger Substances 0.000 claims description 14
- -1 xanthate ion Chemical class 0.000 claims description 13
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 12
- 229940116351 sebacate Drugs 0.000 claims description 8
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims description 5
- WYKYCHHWIJXDAO-UHFFFAOYSA-N tert-butyl 2-ethylhexaneperoxoate Chemical group CCCCC(CC)C(=O)OOC(C)(C)C WYKYCHHWIJXDAO-UHFFFAOYSA-N 0.000 claims description 5
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 claims description 4
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 claims description 4
- 239000012991 xanthate Substances 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- 238000003490 calendering Methods 0.000 claims description 2
- 239000000155 melt Substances 0.000 claims description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical group OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 2
- 239000002994 raw material Substances 0.000 abstract description 15
- 239000004611 light stabiliser Substances 0.000 abstract description 11
- 150000002500 ions Chemical class 0.000 description 18
- 230000002829 reductive effect Effects 0.000 description 14
- 238000004132 cross linking Methods 0.000 description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 238000009413 insulation Methods 0.000 description 5
- 238000005096 rolling process Methods 0.000 description 5
- 229910001415 sodium ion Inorganic materials 0.000 description 5
- 230000007547 defect Effects 0.000 description 4
- 230000004069 differentiation Effects 0.000 description 4
- 230000010354 integration Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000001186 cumulative effect Effects 0.000 description 3
- 239000008393 encapsulating agent Substances 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- BOXSVZNGTQTENJ-UHFFFAOYSA-L zinc dibutyldithiocarbamate Chemical group [Zn+2].CCCCN(C([S-])=S)CCCC.CCCCN(C([S-])=S)CCCC BOXSVZNGTQTENJ-UHFFFAOYSA-L 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000004659 dithiocarbamates Chemical class 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- CONMNFZLRNYHIQ-UHFFFAOYSA-N 3-methylbutoxymethanedithioic acid Chemical group CC(C)CCOC(S)=S CONMNFZLRNYHIQ-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 241000237858 Gastropoda Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical group CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003878 thermal aging Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/14—Peroxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/38—Thiocarbonic acids; Derivatives thereof, e.g. xanthates ; i.e. compounds containing -X-C(=X)- groups, X being oxygen or sulfur, at least one X being sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/39—Thiocarbamic acids; Derivatives thereof, e.g. dithiocarbamates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5425—Silicon-containing compounds containing oxygen containing at least one C=C bond
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/04—Homopolymers or copolymers of ethene
- C09J123/08—Copolymers of ethene
- C09J123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C09J123/0853—Vinylacetate
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention provides a PID (potential induced degradation) -resistant photovoltaic EVA (ethylene vinyl acetate) packaging adhesive film and a preparation method thereof, wherein the EVA adhesive film comprises the following raw materials in percentage by mass: 0.5-0.8% of main cross-linking agent, 0.4-0.6% of auxiliary cross-linking agent, 0.2-0.5% of light stabilizer, 0.3-1.2% of ion capturing agent, 0.1-0.5% of coupling agent and 0.1-0.5% of antioxidant. The volume resistivity of the EVA adhesive film prepared by the invention is more than or equal to 1016Omega cm, the shrinkage is controlled to be less than or equal to 0.5 percent, the damp-heat aging yellowing value is less than or equal to 2.5 after the test is carried out for 2000 hours under the conditions of the temperature of 85 ℃ and the relative humidity of 85 percent, the ultraviolet aging yellowing value is less than or equal to 2.5, the anti-PID adhesive film has good anti-PID performance, and the reliability and the stability of the adhesive film are good.
Description
Technical Field
The invention belongs to the field of photovoltaic materials, relates to an EVA (ethylene vinyl acetate) adhesive film and a preparation method thereof, and particularly relates to a PID (potential induced degradation) -resistant photovoltaic EVA packaging adhesive film and a preparation method thereof.
Background
In 2013, quality problems of domestic and foreign power stations appear on a large scale after the photovoltaic power stations which are invested at early stage at home and abroad are continuously connected to the power generation and run for a period of time. Many power stations develop quality issues such as snails, Potential Induced Degradation (PID), etc. Some domestic power stations use poor EVA (Ethylene Vinyl Acetate) film, which causes the power stations to experience up to 60% attenuation when they are operated for about one year.
The formation mechanism of PID is closely related to the hydrolysis of EVA and sodium ion in glass. When water vapor enters the assembly through the sealed silica gel or the back plate, ester bonds in the EVA are decomposed in water to generate acetic acid capable of moving freely. After the acetic acid reacts with the alkali precipitated on the glass surface, sodium ions which can move freely are generated. The sodium ions move to the surface of the battery piece under the action of an external electric field to form leakage current. Under the action of leakage current, positively charged carriers pass through the glass and flow to the ground through the frame, so that negative charges are accumulated on the surface of the cell, and photoelectric carriers (holes) are attracted to flow to the surface of the N-type silicon to be gathered and not flow to the positive electrode (P electrode) as in a normal state. Thereby the PID effect of the output power attenuation due to the surface polarization occurs.
The current major basis for solving PID from encapsulating materials is to reduce hydrolysis of the EVA material and increase the insulation resistance of the EVA itself. Therefore, the volume resistivity is increased by reducing the content of VA (Vinyl Acetate) in the EVA adhesive film or properly changing the formula, so that the migration of sodium ions is hindered, and the PID attenuation is delayed.
CN105820764A discloses a photovoltaic packaging EVA composite adhesive film with PID resistance, which is prepared by selecting EVA resin with VA content of 20-26% and matching with other additives to make the adhesive film have PID resistance. The VA content is reduced, the PID attenuation can be relieved, but the polarity of the material is reduced, the peel strength is poor, and the crosslinking degree is reduced, so that the use risk of the EVA adhesive film is increased.
CN103756578A discloses a fluoride compound modified EVA encapsulant film, which has good hydrolysis resistance and insulation properties, and achieves the purpose of PID resistance, however, by increasing the insulation properties, i.e. increasing the volume resistivity of the EVA encapsulant film, although the PID can be well controlled in a short period, the hidden trouble of failure exists in a long period. Because the EVA film ages and degrades during use, the volume resistivity decreases over time, resulting in a failure to resist the PID effect.
Therefore, in the art, it is desirable to have an EVA adhesive film that is resistant to PID over a long period of time.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide an EVA (ethylene vinyl acetate) adhesive film and a preparation method thereof, and particularly provides a PID (potential induced degradation) -resistant photovoltaic EVA packaging adhesive film and a preparation method thereof. The EVA adhesive film disclosed by the invention has a long-term effective PID (proportion integration differentiation) resistant effect and is good in reliability and stability.
In order to achieve the purpose, the invention adopts the following technical scheme:
on one hand, the invention provides an EVA adhesive film, which is prepared from EVA resin and the following components in percentage by mass of the EVA resin:
in the invention, by adopting the ion capturing agent and selecting the components and the content of the EVA adhesive film, the EVA adhesive film overcomes the defects of reduced material polarity, poor peel strength, low crosslinking degree and crosslinking rate, easy aging and degradation and reduced volume resistivity, and can ensure the PID resistance of the EVA adhesive film for a long time.
In the invention, the mass percentage content of the EVA resin VA (vinyl acetate) is 28-33%, such as 28%, 29%, 30%, 31%, 32% or 33%; the melt index of the EVA resin is 22-28 g/10min, such as 22g/10min, 23g/10min, 24g/10min, 25g/10min, 26g/10min, 27g/10min or 28g/10 min. According to the invention, the VA content does not need to be specially reduced, and the VA content of 28-33% can be selected, so that the increase of the use risk of the EVA adhesive film caused by the defects of reduced material polarity, poor peeling strength, low crosslinking degree and rate and the like due to the reduction of the VA content is avoided, and the quality instability caused by the fluctuation of the VA content is prevented.
Preferably, the volume resistivity of the EVA resin is more than or equal to 1.0 x 1015Omega. cm, e.g. 1.0X 1015Ω.cm、3.0×1015Ω.cm、5.0×1015Ω.cm、8.0×1015Omega. cm or 1.0X 1016Omega, cm, etc
In the present invention, the amount of the primary crosslinking agent may be 0.5 to 0.8%, for example, 0.5%, 0.55%, 0.6%, 0.65%, 0.7%, 0.75%, or 0.8% by mass of the EVA resin. If the amount of the main crosslinking agent is too small, the crosslinking degree is deteriorated, the adhesion is deteriorated, and the aging resistance is also deteriorated; if the amount of the main crosslinking agent is too large, the production of the product is affected to some extent, and bubbles are generated during the production process.
Preferably, the primary crosslinking agent is tert-butyl peroxy-2-ethylhexanoate and/or 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane.
In the present invention, the amount of the co-crosslinking agent may be 0.4 to 0.6%, for example, 0.4%, 0.43%, 0.45%, 0.48%, 0.5%, 0.52%, 0.55%, 0.58%, or 0.6% by mass of the EVA resin. If the auxiliary crosslinking agent is too little, the crosslinking degree of the EVA is low, so that the product cannot obtain the due mechanical property, and if the auxiliary crosslinking agent is too much, molecules of the auxiliary crosslinking agent which do not participate in the crosslinking reaction remain in the EVA, so that the crosslinking rate of the EVA is influenced, and the EVA is difficult to produce smoothly.
Preferably, the auxiliary crosslinking agent is triallyl isocyanurate and/or trimethylolpropane trimethacrylate.
In the present invention, the amount of the light stabilizer may be 0.2 to 0.5%, for example, 0.2%, 0.23%, 0.25%, 0.28%, 0.3%, 0.34%, 0.38%, 0.4%, 0.43%, 0.45%, 0.48%, or 0.5% by mass of the EVA resin. When the amount of the light stabilizer is too small, the light stabilizing effect cannot be obtained, so that the EVA is easily aged under illumination, and when the amount of the light stabilizer is too large, the volume resistivity of the EVA is reduced, so that the insulation performance of the EVA is deteriorated.
Preferably, the light stabilizer is bis-2, 2,6, 6-tetramethylpiperidinol sebacate.
In the present invention, the amount of the ion scavenger may be 0.3 to 1.2% by mass, for example, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1% or 1.2% by mass of the EVA resin. If the amount of the ion scavenger is too small, the ion scavenger cannot play a role in blocking ions, and if the amount of the ion scavenger is too large, on one hand, the volume resistivity of the EVA is reduced, and on the other hand, since the scavenger is usually white or light yellow, the light transmittance of the EVA film is affected by too large amount of the scavenger.
Preferably, the ion scavenger is a xanthate and/or dithiocarbamate derivative.
Preferably, the xanthate ion scavenger is isoamyl xanthate.
Preferably, the dithiocarbamate derivative is zinc dibutyldithiocarbamate.
In the invention, the ion capturing agent can capture acetate ions generated by decomposition of EVA in water and sodium ions which are generated after reaction of acetic acid and alkali precipitated on the surface of glass and can move freely in time, so that the generation of PID (proportion integration differentiation) phenomenon is hindered, the ion capturing agent can continuously act, ions are captured for a long time, even if the EVA is subjected to photo-thermal aging and degradation and the volume resistivity is gradually reduced, the PID (proportion integration differentiation) resisting effect of the adhesive film cannot be influenced, and the adhesive film can play a specified function for a long time.
In the present invention, the amount of the coupling agent may be 0.1 to 0.5%, for example, 0.1%, 0.15%, 0.2%, 0.25%, 0.3%, 0.35%, 0.4%, 0.45%, or 0.5% by mass of the EVA resin. Too much coupling agent will delay the crosslinking time and increase the moisture absorption of EVA, resulting in reduced insulation performance. If the amount of the coupling agent is too small, the peel strength of EVA to glass or a backsheet is reduced.
Preferably, the coupling agent is gamma- (methacryloyloxy) propyltrimethoxysilane.
In the present invention, the amount of the antioxidant may be 0.1 to 0.5%, for example, 0.1%, 0.15%, 0.2%, 0.25%, 0.3%, 0.35%, 0.4%, 0.45%, or 0.5% by mass of the EVA resin. If the amount of the antioxidant is too small, the effect of resisting thermal-oxidative aging cannot be achieved, and if the amount of the antioxidant is too large, the stability and reliability of the EVA in long-term use are inevitably affected due to the high reactivity of the antioxidant.
Preferably, the antioxidant is pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ].
In the EVA adhesive film, the ion scavenger can act synergistically with the light stabilizer, so that the aging resistance of the EVA adhesive film is improved, the volume resistivity of the EVA adhesive film is increased, a better PID (proportion integration differentiation) resistance effect is achieved, and the reliability and the stability of the adhesive film are ensured.
On the other hand, the invention provides a preparation method of the EVA adhesive film, which comprises the following steps: mixing EVA resin, a main cross-linking agent, an auxiliary cross-linking agent, a light stabilizer, an ion capture agent, a coupling agent and an antioxidant, extruding by using an extruder, and calendering to form an adhesive film to obtain the EVA adhesive film.
Preferably, the extrusion is carried out at a barrel temperature of 70-90 deg.C, such as 70 deg.C, 73 deg.C, 75 deg.C, 78 deg.C, 80 deg.C, 82 deg.C, 85 deg.C, 88 deg.C or 90 deg.C.
The EVA adhesive film can be used as a photovoltaic packaging material and has good PID resistance.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the ion capturing agent is adopted, and the components and the content of the EVA adhesive film are selected, so that the EVA adhesive film overcomes the defects of reduced material polarity, poor peeling strength, low crosslinking degree and crosslinking rate, easiness in aging and degradation and reduced volume resistivity, the PID resistance of the EVA adhesive film can be ensured for a long time, the ion capturing agent and the light stabilizer are cooperated, the aging resistance of the EVA adhesive film is improved, the volume resistivity of the EVA adhesive film is increased, and the reliability and the stability of the adhesive film are ensured, wherein the volume resistivity of the EVA adhesive film prepared by the invention is more than or equal to 1016Omega cm, shrinkage rate controlled at 0.5% or less, damp-heat aging yellowing value of 2.5 or less after 2000 hr at 85 deg.C and 85% relative humidity, and ultraviolet aging cumulative irradiation amount up to 200KWh/m2And the yellowing value is less than or equal to 2.5, the film has good PID resistance, and the film has good reliability and stability.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
In this embodiment, the raw material for preparing the EVA adhesive film comprises EVA resin and the following components in percentage by mass of the EVA resin:
mixing EVA resin, tert-butyl peroxy-2-ethylhexanoate, triallyl isocyanurate, bis-2, 2,6, 6-tetramethylpiperidinol sebacate, isoamyl xanthogenate, gamma- (methacryloyloxy) propyltrimethoxysilane and tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, extruding and rolling to form an adhesive film, thereby obtaining the EVA adhesive film.
Example 2
In this embodiment, the EVA adhesive film includes EVA resin and the following components in percentage by mass of the EVA resin:
mixing EVA resin, 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane, trimethylolpropane trimethacrylate, sebacic acid bis-2, 2,6, 6-tetramethylpiperidinol ester, zinc dibutyl dithiocarbamate, gamma- (methacryloyloxy) propyl trimethoxy silane and tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, extruding by an extruder at the barrel temperature of 80 ℃, and rolling to form an adhesive film to obtain the EVA adhesive film.
Example 3
In this embodiment, the EVA adhesive film includes EVA resin and the following components in percentage by mass of the EVA resin:
mixing EVA resin, tert-butyl peroxy-2-ethylhexanoate, trimethylolpropane trimethacrylate, bis-2, 2,6, 6-tetramethylpiperidinol sebacate, isoamyl xanthogen acrylate, gamma- (methacryloyloxy) propyl trimethoxy silane and tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, extruding by using an extruder at the cylinder temperature of 70 ℃, and rolling to form an adhesive film to obtain the EVA adhesive film.
Example 4
In this embodiment, the EVA adhesive film includes EVA resin and the following components in percentage by mass of the EVA resin:
mixing EVA resin, 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane, triallyl isocyanurate, bis-2, 2,6, 6-tetramethylpiperidinol sebacate, isoamyl xanthogen allyl ester, gamma- (methacryloyloxy) propyl trimethoxy silane and tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, extruding the mixture at the barrel temperature of 90 ℃ by using an extruder, and rolling the mixture into an adhesive film to obtain the EVA adhesive film.
Example 5
In this embodiment, the EVA adhesive film includes EVA resin and the following components in percentage by mass of the EVA resin:
mixing EVA resin, tert-butyl peroxy-2-ethylhexanoate, triallyl isocyanurate, bis-2, 2,6, 6-tetramethylpiperidinol sebacate, zinc dibutyldithiocarbamate, gamma- (methacryloyloxy) propyltrimethoxysilane and tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, extruding the mixture by using an extruder at the barrel temperature of 80 ℃, and rolling the mixture into an adhesive film to obtain the EVA adhesive film.
Comparative example 1
The comparative example is different from example 1 only in that no ion scavenger is added to the raw materials for preparing the EVA adhesive film, and the other raw materials and the raw material usage amount are the same as example 1.
Comparative example 2
The comparative example is different from example 1 only in that no ion scavenger and light stabilizer are added to the raw materials for preparing the EVA adhesive film, and the other raw materials and the amounts of the raw materials are the same as those of example 1.
Comparative example 3
The comparative example is different from example 1 only in that no ion scavenger is added to the raw materials for preparing the EVA adhesive film, the dosage of the light stabilizer bis-2, 2,6, 6-tetramethylpiperidinol sebacate is 1.1%, and the other raw materials and the raw material dosage are the same as example 1.
Comparative example 4
The comparative example is different from example 1 only in that the light stabilizer bis-2, 2,6, 6-tetramethylpiperidinol sebacate is not added in the raw materials for preparing the EVA adhesive film, the dosage of the ion scavenger is 1.1 percent, and the other raw materials and the raw materials are the same as example 1.
The PID resistance of the EVA adhesive films prepared in the examples 1-5 and the comparative examples 1-4 is determined, wherein the volume resistivity and the shrinkage rate are tested according to GB/T29848-2013, and the humid and hot aging performance is tested by representing the humid and hot aging performance of the EVA adhesive films by the yellowing value of the EVA adhesive films after testing for 2000 hours at the temperature of 85 ℃ and the relative humidity of 85%; the cumulative irradiation amount of ultraviolet aging reaches 200KWh/m2Then, the ultraviolet aging performance of the EVA adhesive film is characterized by the yellowing value of the EVA adhesive film, and the result is shown in Table 1.
TABLE 1
From Table 1As a result, the volume resistivity of the EVA adhesive film prepared by the invention is more than or equal to 1016Omega cm, shrinkage rate less than or equal to 0.5%, and ultraviolet aging cumulative irradiation amount up to 200KWh/m after testing at 85 deg.C and 85% relative humidity for 2000 hr2And then, the ultraviolet aging yellowing value is less than or equal to 2.5, and the coating has good PID resistance and good reliability and stability.
The applicant states that the present invention is illustrated by the above examples to the anti-PID photovoltaic EVA encapsulant film and the preparation method thereof, but the present invention is not limited to the above examples, that is, the present invention is not limited to the above examples. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (8)
1. A wet heat aging yellowing value of less than or equal to 2.5, an ultraviolet aging yellowing value of less than or equal to 2.5, and a volume resistivity of more than or equal to 1016The EVA adhesive film of omega.cm is characterized in that the EVA adhesive film is prepared from EVA resin and the following components in percentage by mass:
2. the EVA adhesive film of claim 1, wherein the mass percentage of the EVA resin VA (vinyl acetate) is 28-33%, and the melt index of the EVA resin is 22-28 g/10 min.
3. The EVA adhesive film of claim 1, wherein the EVA resin has a volume resistivity of 1.0 x 10 or more15Ω.cm。
4. The EVA adhesive film of claim 1, wherein the primary crosslinking agent is tert-butyl peroxy-2-ethylhexanoate and/or 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane.
5. The EVA adhesive film of claim 1, wherein the xanthate ion scavenger is allyl isoamyl xanthate.
6. The EVA adhesive film of claim 1, wherein the coupling agent is gamma- (methacryloyloxy) propyl trimethoxysilane.
7. The EVA adhesive film of claim 1, wherein the antioxidant is pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ].
8. The method for preparing the EVA adhesive film of any one of claims 1-7, wherein the method comprises: mixing EVA resin, a main cross-linking agent, triallyl isocyanurate and/or trimethylolpropane trimethacrylate, bis-2, 2,6, 6-tetramethylpiperidinol sebacate, a xanthate ion capture agent, a coupling agent and an antioxidant, extruding by using an extruder, and calendering to form an adhesive film to obtain the EVA adhesive film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610831415.2A CN107841256B (en) | 2016-09-19 | 2016-09-19 | PID (potential induced degradation) -resistant photovoltaic EVA (ethylene-vinyl acetate) packaging adhesive film and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610831415.2A CN107841256B (en) | 2016-09-19 | 2016-09-19 | PID (potential induced degradation) -resistant photovoltaic EVA (ethylene-vinyl acetate) packaging adhesive film and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107841256A CN107841256A (en) | 2018-03-27 |
| CN107841256B true CN107841256B (en) | 2020-11-10 |
Family
ID=61656616
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610831415.2A Active CN107841256B (en) | 2016-09-19 | 2016-09-19 | PID (potential induced degradation) -resistant photovoltaic EVA (ethylene-vinyl acetate) packaging adhesive film and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107841256B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112898920A (en) * | 2019-11-19 | 2021-06-04 | 杭州福斯特应用材料股份有限公司 | Composition for forming PID (potential induced degradation) resistant packaging adhesive film, PID resistant packaging adhesive film and solar module |
| CN111961422A (en) * | 2020-07-27 | 2020-11-20 | 苏州赛伍应用技术股份有限公司 | Multifunctional packaging adhesive film and preparation method thereof |
| CN112251166A (en) * | 2020-10-21 | 2021-01-22 | 苏州赛伍应用技术股份有限公司 | Packaging adhesive film with different pre-crosslinking degrees and preparation method thereof |
| CN114605927B (en) * | 2022-03-31 | 2023-08-11 | 江苏中来新材科技有限公司 | high-PID-resistance photovoltaic adhesive film, preparation method thereof and photovoltaic module |
| CN115537142A (en) * | 2022-08-30 | 2022-12-30 | 杭州师范大学 | Sodium ion barrier film and preparation method thereof |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102898840B (en) * | 2011-07-28 | 2015-07-08 | 北京科化新材料科技有限公司 | Insulating silicone rubber composition |
| CN102433077A (en) * | 2011-10-11 | 2012-05-02 | 宁波威克丽特功能塑料有限公司 | Ethylene vinyl acetate (EVA) adhesive film for solar cell and preparation method thereof |
| WO2013150730A1 (en) * | 2012-04-06 | 2013-10-10 | 三井化学東セロ株式会社 | Solar cell module |
| CN103254802B (en) * | 2013-03-19 | 2015-06-03 | 江苏鹿山光伏科技有限公司 | EVA packaging adhesive film for resisting potential-induced degradation of photovoltaic module |
| CN103756578A (en) * | 2014-01-09 | 2014-04-30 | 常州斯威克光伏新材料有限公司 | Fluorine compound-modified ethylene-vinyl acetate (EVA) packaging film and preparation method thereof |
| CN105038624B (en) * | 2015-08-05 | 2017-10-31 | 乐凯胶片股份有限公司 | A kind of photovoltaic EVA packaging adhesive films |
| CN105542671B (en) * | 2015-12-18 | 2018-09-21 | 广州市白云化工实业有限公司 | Photovoltaic module packaging adhesive film |
-
2016
- 2016-09-19 CN CN201610831415.2A patent/CN107841256B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN107841256A (en) | 2018-03-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107841256B (en) | PID (potential induced degradation) -resistant photovoltaic EVA (ethylene-vinyl acetate) packaging adhesive film and preparation method thereof | |
| WO2021238116A1 (en) | Anti-pid poe adhesive film specifically for photovoltaic double-glass assembly packaging and preparation method therefor | |
| JP6555730B2 (en) | Anti-reflective polyolefin solar cell module sealing adhesive film and method for producing the same | |
| WO2018121656A1 (en) | White polyolefin packaging film and preparation method therefor | |
| DE112009001580B4 (en) | Ethylene copolymer composition, film for sealing a solar cell element and their use | |
| CN103756579A (en) | EVA (Ethylene Vinyl-Acetate) packaging glue film with high gas-water barrier property and preparation method thereof | |
| CN104861886A (en) | EVA adhesive film for encapsulating solar cell and preparing process of EVA adhesive film | |
| CN104449436B (en) | A kind of solar components encapsulation EVA adhesive film of high steam oxygen-barrier property and preparation method thereof | |
| CN114605927B (en) | high-PID-resistance photovoltaic adhesive film, preparation method thereof and photovoltaic module | |
| CN108997957A (en) | A kind of white EVA packaging adhesive film and preparation method thereof | |
| CN116535996B (en) | Water vapor barrier type anti-aging white EVA packaging adhesive film and preparation process thereof | |
| CN114854331B (en) | Ultraviolet cut-off type EVA photovoltaic adhesive film, preparation method thereof and photovoltaic module | |
| KR20140072934A (en) | Encapsulation composition for a solarcell and preparing process fo the sheet using the same | |
| CN104449435A (en) | High-ultraviolet barrier property EVA adhesive film for solar module packaging and preparing method of high-ultraviolet barrier property EVA adhesive film | |
| CN104022175B (en) | Fluorescence fluoro-containing copolymer film used for encapsulation of solar battery and preparation method thereof | |
| CN115895100B (en) | Gain casting film, preparation method and application thereof | |
| CN108395855A (en) | A kind of special encapsulating material of solar cell and preparation method thereof | |
| JP2016117897A (en) | Co-crosslinking agent system for encapsulation film containing urea compound | |
| CN104212050A (en) | Polyethylene-fiber-modified EVA (Ethylene Vinyl Acetate) packaging adhesive film | |
| CN114686143A (en) | EVA adhesive film for solar cell packaging and preparation process thereof | |
| CN111394016B (en) | Silane crosslinking type POE adhesive film and preparation method and application thereof | |
| CN113185935A (en) | Irradiation crosslinking modified EVA optical adhesive and preparation method thereof | |
| CN103725211B (en) | EVA film encapsulated in solar battery and preparation method of EVA film | |
| KR101993994B1 (en) | ethylene vinyl acetate copolymer composite for solar cell encapsulant and solar cell encapsulant thereby | |
| CN117866544A (en) | PID-resistant EVA packaging adhesive film and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| CB02 | Change of applicant information |
Address after: 215129 Suzhou high tech Zone, Jiangsu Province, Lu Shan Road, No. 199, No. Applicant after: CSI SOLAR POWER GROUP Co.,Ltd. Applicant after: CHANGSHU TEGU NEW MATERIAL TECHNOLOGY Co.,Ltd. Address before: 215011 Suzhou high tech Industrial Development Zone, Jiangsu, Lu Shan Road, No. 199 Applicant before: CSI SOLAR POWER (CHINA) Inc. Applicant before: CHANGSHU TEGU NEW MATERIAL TECHNOLOGY Co.,Ltd. |
|
| CB02 | Change of applicant information | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 215129 199 deer Road, Suzhou hi tech Development Zone, Jiangsu, Suzhou Patentee after: Atlas sunshine Power Group Co.,Ltd. Patentee after: CHANGSHU TEGU NEW MATERIAL TECHNOLOGY Co.,Ltd. Address before: 215129 199 deer Road, Suzhou hi tech Development Zone, Jiangsu, Suzhou Patentee before: CSI SOLAR POWER GROUP Co.,Ltd. Patentee before: CHANGSHU TEGU NEW MATERIAL TECHNOLOGY Co.,Ltd. |
|
| CP01 | Change in the name or title of a patent holder |