CN117487498A - Adhesive for solar photovoltaic backboard and preparation method thereof - Google Patents

Adhesive for solar photovoltaic backboard and preparation method thereof Download PDF

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Publication number
CN117487498A
CN117487498A CN202311629601.4A CN202311629601A CN117487498A CN 117487498 A CN117487498 A CN 117487498A CN 202311629601 A CN202311629601 A CN 202311629601A CN 117487498 A CN117487498 A CN 117487498A
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China
Prior art keywords
adhesive
solar photovoltaic
parts
antioxidant
curing agent
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CN202311629601.4A
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Chinese (zh)
Inventor
陈建清
刘磊好
蔡建南
许建明
马爱斌
江静华
宋丹
王屹峰
沈海峰
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Changshu Friends Connector Technology Co ltd
Hohai University HHU
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Changshu Friends Connector Technology Co ltd
Hohai University HHU
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Application filed by Changshu Friends Connector Technology Co ltd, Hohai University HHU filed Critical Changshu Friends Connector Technology Co ltd
Priority to CN202311629601.4A priority Critical patent/CN117487498A/en
Publication of CN117487498A publication Critical patent/CN117487498A/en
Pending legal-status Critical Current

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    • 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
    • C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
    • C09J167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/14—Gas barrier composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/204—Applications use in electrical or conductive gadgets use in solar cells
    • 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

Abstract

The invention discloses an adhesive for a solar photovoltaic backboard and a preparation method thereof, and belongs to the technical field of adhesives. The adhesive for the solar photovoltaic backboard comprises the following components in parts by weight: 100 parts of polyester resin, 10-35 parts of polyethylene naphthalate, 4-5 parts of curing agent, 0.6-3.5 parts of plasticizer, 0.5-3.2 parts of heat stabilizer and 0.05-1 part of antioxidant. According to the invention, through blending of the polyester resin and the polyethylene naphthalate, the crosslinking density is improved, and the excellent peeling strength is ensured; and meanwhile, an isocyanate curing agent and other auxiliary agents are used as auxiliary agents, a crosslinked reticular structure is formed through curing, the advantages of each component are exerted, the ageing resistance, the thermal stability and the peeling strength of the adhesive are improved, and the adhesive for the photovoltaic backboard required in the market is satisfied. The adhesive has the highest peeling strength reaching 14.91N/cm, has good adhesive layer bonding performance after PCT aging, and can be better applied to solar photovoltaic backboard.

Description

Adhesive for solar photovoltaic backboard and preparation method thereof
Technical Field
The invention belongs to the technical field of adhesives, and particularly relates to an adhesive for a solar photovoltaic backboard and a preparation method thereof.
Background
Solar energy is used as a clean energy source with high efficiency, stability, environmental protection and rich reserves, and is the hottest research direction in the new energy field in recent years. The solar photovoltaic backboard has the main functions of protecting the solar cell module from being corroded by outdoor environmental factors, plays roles of insulation, weather resistance, protection, support and the like, and is a key packaging material for protecting the solar cell module from long-term outdoor use.
The back sheet is usually a composite type, as shown in fig. 1, and generally has a three-layer structure: the outer layer is a fluorine film (PVF/PVDF layer) and has good environmental erosion resistance, and the middle layer is a polyester film (PET layer) and plays a supporting role; the inner layer is an adhesive layer, and the adhesive layer bonds the three-layer film structure together to form the backboard. Generally, the solar back panel is required to be used outdoors for a long time of 25 years, but the longer the time is, the adhesive strength of the adhesive is reduced due to the fact that the adhesive is hydrolyzed or other environmental factors are caused, so that the film is separated, and the service life of the solar back panel is shortened.
Patent application CN 113046003A discloses an aqueous adhesive for composite solar cell back plates and a composite method. The adhesive property of the aqueous polyacrylic emulsion, the aqueous hydrolysis resistance agent and the polyisocyanate interaction is improved, the average adhesive property is only 6.42N/cm, the average peeling strength after 24 hours of water boiling is only 5.86N/cm, and the peeling strength needs to be further improved.
Patent application CN 112126403A discloses a bonding composition for solar back plates and an adhesive thereof. The polymer polyol, the chain extender and the heat stabilizer are used as raw materials to interact with the reagent, the peeling strength is high and reaches 6.9N/cm, the ageing performance is good, after PCT (PCT) accelerated ageing, part of experimental groups have wrinkling, but the comprehensive performance is far from enough, and the polyurethane belongs to the category of polyurethane.
Patent application CN 104877625A discloses an adhesive and a preparation method thereof. Hydroxyl polyester, hydroxyl polyethylene naphthalate and a precursor containing PVDF resin are used as synthetic resins, and fluororesin is used as a modifier to assist other auxiliary agents. The fluorine resin is modified by polyester or acrylic resin, and a C-F bond is introduced, so that the ageing resistance of the fluorine resin is greatly improved, and the fluorine resin can adapt to the use of the photovoltaic module under severe conditions. However, the solvent is easily hydrolyzed in a wet environment, so that the back plate is layered, and the peeling strength is reduced.
At present, a common bonding system is a polyurethane system, and polyester polyol is used as a raw material for synthesizing an adhesive. The adhesive of the composite backboard used in the market is mainly solvent polyurethane adhesive, and because of the solvent, the adhesive has high safety risks in use and storage and transportation, is easy to hydrolyze at high temperature and high humidity, reduces the adhesive strength, has poor weather resistance and needs to be further improved in comprehensive performance.
Disclosure of Invention
The invention aims to provide a solvent-free polyester adhesive with high peel strength and hydrolysis aging resistance and a preparation method thereof, aiming at the defect of insufficient comprehensive performance of the existing solar photovoltaic backboard adhesive.
The invention aims to change the new thought of developing the raw materials of the back plate adhesive, utilizes the polyester resin as the raw material, improves the crosslinking density by blending the polyester resin and the polyethylene naphthalate, ensures excellent peeling strength, simultaneously assisted by the isocyanate curing agent and other auxiliary agents, forms a crosslinked reticular structure after curing, simultaneously plays the advantages of each component, improves the ageing resistance, the thermal stability and the peeling strength of the adhesive, and meets the requirements of the adhesives for the photovoltaic back plate on the market. The prepared adhesive has the highest peeling strength reaching 14.91N/cm, and good adhesive layer bonding performance after PCT aging, and can be better applied to solar photovoltaic backboard.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the adhesive for the solar photovoltaic backboard comprises the following raw materials in parts by weight: 100 parts of polyester resin, 10-30 parts of polyethylene naphthalate, 4-5 parts of curing agent, 0.6-3.5 parts of plasticizer, 0.5-3.2 parts of heat stabilizer and 0.05-1 part of antioxidant.
Preferably, the solid content of the polyester resin is 40-60%, the acid value is less than 1mgKOH/g, the hydroxyl value is 17+/-3 mgKOH/g, and the viscosity is 400-600 mPa.s.
Preferably, the density of the polyethylene naphthalate is 1330kg/m3, and the viscosity is 200-300mPa.s.
Preferably, the curing agent is isocyanate curing agent selected from one or at least two of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, 1, 6-hexamethylene diisocyanate or hexamethylene diisocyanate.
Preferably, the plasticizer is selected from one or at least two of dibutyl phthalate (DBP), dioctyl phthalate (DOP), tricresyl phosphate, triphenyl phosphate or dioctyl sebacate.
Preferably, the heat stabilizer is selected from one or at least two of stannous octoate, dibutyl tin dilaurate and triethylenediamine.
Preferably, the antioxidant is a hindered amine or hindered phenol; further preferably, the antioxidant is any one or at least two of antioxidant 1010, antioxidant 1076, antioxidant 1790 and antioxidant BHT.
Preferably, the adhesive is used for compounding the solar photovoltaic backboard, and when the adhesive is compounded, the coating and sizing amount is 8 g/m2-10 g/m2, the dry film thickness is 7-9 um, the compounding temperature is 80-120 ℃, and the compounding pressure is 0.3-0.8 Mpa; after compounding, curing at 60 ℃ x 72 h.
The preparation method of the adhesive for the solar photovoltaic backboard comprises the following preparation steps:
(1) Preparation of the Mixed solution
Weighing polyester resin and polyethylene naphthalate according to a proportion, placing the polyester resin and the polyethylene naphthalate on an electric heating platform at 70-90 ℃, starting a stirrer, increasing the rotating speed to 3-5 Hz, sequentially weighing and adding a plasticizer, a heat stabilizer and an antioxidant, and stirring for 5-10 minutes to prepare a mixed solution;
(2) Preparation of adhesive for solar photovoltaic backboard
Adding an isocyanate curing agent into the mixed solution prepared in the step (1), continuously stirring for 5-10 minutes to prepare a glue solution, filtering the glue solution, ultrasonically degassing until no bubbles exist, and standing at room temperature to prepare the adhesive for the solar photovoltaic backboard.
The principle and the beneficial effects of the invention are as follows:
(1) The adhesive for the solar photovoltaic backboard is solvent-free, does not need to be dissolved by using a solvent, is simple to use, and is safe and environment-friendly. The invention solves the problems of high humidity, easy hydrolysis and low peeling strength of the traditional solvent polyurethane adhesive.
(2) According to the invention, polyethylene naphthalate (PEN) with little difference in compatibility with polyester resin is adopted to carry out blending modification on polyester, and because benzene ring is replaced by naphthalene ring in the molecular structure of PEN, the naphthalene ring has larger conjugated double bond than the benzene ring, has larger molecular rigidity and stronger activity, and compared with the polyester, PEN has more excellent mechanical properties such as heat resistance, tensile strength and the like, ultraviolet radiation resistance, organic solvent resistance, hydrolysis resistance and barrier property. PEN is added into the polyester resin, so that the peel strength and ageing resistance of the polyester resin are greatly improved.
(3) The polyester adhesive specially designed for the solar backboard composite does not need to add a solvent, is easy to process, is environment-friendly and economical, has high interlayer peeling strength, has ageing resistance and good heat resistance, has excellent barrier property, effectively prevents hydrolysis between backboard film structures, and prolongs the service life of the backboard of the solar photovoltaic module, and the peeling strength after ageing is higher than that of the traditional adhesive.
(4) The adhesive prepared by the invention can be used for producing solar photovoltaic backboard, and the obtained product is inspected, and under the condition of PCT aging for 96 hours, the adhesive layer is free from hydrolysis and layering, and has no shrinkage and yellowing.
Drawings
Fig. 1 is a schematic diagram of a solar photovoltaic backsheet structure.
Fig. 2 is a schematic diagram of experimental peel strength of 10 groups of adhesives for back sheets of solar photovoltaic modules according to the present invention.
Fig. 3 is a schematic diagram showing the hardness change of 10 groups of experiments of the adhesive for the back sheet of the solar photovoltaic module.
Wherein 1 is PVF/PVDF layer, 2 is adhesive layer, 3 is PET layer.
Detailed Description
The present invention will be specifically described by way of examples and comparative examples, and the following experimental examples are only for further illustration of the present invention, and the actual embodiments are not limited thereto. If one of ordinary skill in the art is informed by this disclosure, the structural mode and the embodiments similar to the technical scheme are not creatively designed without departing from the gist of the present invention, and all the structural modes and the embodiments belong to the protection scope of the present invention.
The invention discloses an adhesive for a solar photovoltaic backboard, which comprises the following raw materials in parts by weight: 100 parts of polyester resin, 10-30 parts of polyethylene naphthalate, 4-5 parts of curing agent, 0.6-3.5 parts of plasticizer, 0.5-3.2 parts of heat stabilizer and 0.05-1 part of antioxidant.
In some embodiments of the invention, the polyester resin is a matrix resin, liquid, non-hot melt adhesive, having a solids content of 40-60%, an acid value of less than 1mgKOH/g, a hydroxyl value of 17+ -3 mgKOH/g,400-600 mPa.s. The appearance is clear and transparent, is solvent-soluble, linear and thermoplastic high molecular polyester, has the characteristics of good leveling property, good flexibility, high toughness, high weather resistance and the like, and has good adhesion to PET and PVF/PVDF. Preferably selected from one or a mixture of both of 50085 and 50087 of Changxing chemical industry Co., ltd.
In some embodiments of the invention, the polyethylene naphthalate also belongs to the polyester family, has good compatibility with polyester resins, and has low crystallinity and good transparency. And has more excellent heat resistance, tensile strength and other mechanical properties, ultraviolet radiation resistance, hydrolysis resistance and barrier property than polyester PET. Preferably any one or a mixture of two of the TN8065 series from the company Jia Gui Plastic Co., dongguan.
In some embodiments of the present invention, the curing agent is an isocyanate-based curing agent selected from one or a mixture of at least two of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, 1, 6-hexamethylene diisocyanate, hexamethylene diisocyanate.
In some embodiments of the invention, the plasticizer is selected from one or a mixture of at least two of dibutyl phthalate (DBP), dioctyl phthalate (DOP), tricresyl phosphate, triphenyl phosphate, dioctyl sebacate.
Through researches, the addition of the plasticizer component can improve the impact toughness and the elongation at break of the polymer, reduce the forming temperature of the polymer and improve the flexibility and the bonding strength of the adhesive film.
In some embodiments of the invention, the heat stabilizer is selected from one or a mixture of at least two of stannous octoate, dibutyl tin dilaurate, triethylenediamine.
Through researches, the heat stabilizer can improve the heat stability of polyester resin, reduce the activation energy of reaction and initiate the crosslinking reaction of high polymer, thereby effectively enabling the combined system to fully react.
In some embodiments of the invention, the antioxidant is a hindered amine or hindered phenol. Preferably, the antioxidant is any one or a mixture of at least two of antioxidant 1010, antioxidant 1076, antioxidant 1790 or antioxidant BHT.
Through researches, the antioxidant can inhibit the oxidation process of the backboard adhesive, eliminate the rupture of chemical bonds of organic molecules under the action of heat, light or oxygen, generate active free radicals, prevent the chain reaction and further delay the aging process of the backboard.
The adhesive for the solar photovoltaic backboard is a solvent-free adhesive, does not need to be dissolved by using a solvent, is simple to use, is safe and environment-friendly, and solves the problems of high humidity, easy hydrolysis and low peeling strength of the traditional solvent type polyurethane adhesive.
The industrial solar photovoltaic backboard production composite process comprises the following steps: unreeling the base film, corona, coating, hot drying, compounding, reeling, curing and packaging.
Wherein, the base film is: PET film, PVF film or PVDF film.
Compounding process parameters: the coating sizing amount is 8-10 g/m < 2 >, the dry film thickness is 7-9 um, the compounding temperature is 80-120 ℃, and the compounding pressure is 0.3-0.8 Mpa; after compounding, curing at 60 ℃ x 72 h.
The adhesive prepared by the invention can be used for producing solar photovoltaic backboard, and the obtained product is inspected, and under the condition of PCT aging for 96 hours, the adhesive layer is free from hydrolysis and layering, and has no shrinkage and yellowing.
Example 1
Weighing 100 parts of polyester resin 50085 and 15 parts of polyethylene naphthalate TN8065S in a clean crucible according to a proportion, placing the mixture on an electric heating platform at 70 ℃, slowly starting a stirrer, increasing the rotating speed to 3 Hz, sequentially weighing and adding 0.6 part of tricresyl phosphate, 0.5 part of stannous octoate and 1790.1 parts of antioxidant, enabling the mixed solution to be transparent, slowly and uniformly adding 4 parts of isophorone diisocyanate curing agent, continuously stirring at the original speed for 8 minutes, filtering the obtained glue solution by a 300-mesh filter screen, performing ultrasonic deaeration until no bubble exists, and standing at room temperature to obtain the backboard adhesive.
Coating the prepared backboard adhesive on the surface of a PET film by using a coating rod, controlling the adhesive coating amount to be 8-10 g/m < 2 >, drying at 80-120 ℃ for 2 min, adhering the PVDF film and the PET coated with the backboard adhesive together by using a film laminating machine, and performing pressurization and paving by using an electric press, wherein the composite pressure is controlled to be 0.3-0.8 Mpa; after compounding, curing at 60 ℃ x 72 h.
The initial peel strength of the prepared backsheet after curing was comprehensively evaluated as 9.25N/cm.
Example 2
100 parts of polyester resin 50085 and 15 parts of polyethylene naphthalate TN8065S are weighed in a clean crucible according to a proportion, placed on an electric heating platform at 70 ℃, a stirrer is slowly started, the rotating speed is increased to 5 Hz, 1.2 parts of dioctyl phthalate, 1.05 parts of triethylenediamine and 0.1 part of antioxidant 1076 are sequentially weighed and added, the mixed solution is transparent, 4.5 parts of isophorone diisocyanate curing agent is slowly and uniformly added, the stirring is continuously carried out for 8 minutes at the original speed, the obtained glue solution is filtered by a 300-mesh filter screen, ultrasonic deaeration is carried out until no bubble exists, and the back plate adhesive is obtained after the room temperature is kept.
A back sheet was produced in the same manner as in example 1, and the initial peel strength after aging was evaluated comprehensively as 11.03. 11.03N/cm.
Example 3
100 parts of polyester resin 50085 and 15 parts of polyethylene naphthalate TN8065S are weighed in a clean crucible according to a proportion, placed on an electric heating platform at 90 ℃, a stirrer is slowly started, the rotating speed is increased to 5 Hz, 1.5 parts of dioctyl sebacate, 1.35 parts of stannous octoate and 0.1 part of antioxidant 1010 are sequentially weighed and added, the mixed solution is transparent, 5 parts of hexamethylene diisocyanate curing agent is slowly and uniformly added, the original stirring is continued for 8 minutes, the obtained glue solution is filtered by a 300-mesh filter screen, ultrasonic deaeration is carried out until no bubble exists, and the back plate adhesive is obtained after the room temperature is kept.
A back sheet was prepared in the same manner as in example 1, and the initial peel strength after curing was evaluated as 14.91N/cm.
Example 4
Weighing 100 parts of polyester resin 50087 and 20 parts of polyethylene naphthalate TN8065C in a clean crucible according to a proportion, placing the mixture on an electric heating platform at 80 ℃, slowly starting a stirrer, increasing the rotating speed to 4 Hz, sequentially weighing and adding 1.2 parts of tricresyl phosphate, 1.4 parts of dibutyl tin dilaurate and 0.1 part of antioxidant BHT, enabling the mixed solution to be transparent, slowly and uniformly adding 5 parts of 1, 6-hexamethylene diisocyanate curing agent, continuously stirring at the original speed for 8 minutes, filtering the obtained glue solution by using a 300-mesh filter screen, carrying out ultrasonic deaeration until no bubble exists, and standing at room temperature to obtain the backboard adhesive.
A back sheet was produced in the same manner as in example 1, and the initial peel strength after aging was evaluated comprehensively as 8.45. 8.45N/cm.
Example 5
Weighing 100 parts of polyester resin 50087 and 20 parts of polyethylene naphthalate TN8065C in a clean crucible according to a proportion, placing the mixture on an electric heating platform at 80 ℃, slowly starting a stirrer, increasing the rotating speed to 4 Hz, sequentially weighing 1.6 parts of dibutyl phthalate, 1.8 parts of stannous octoate and 0.1 part of antioxidant 1010, adding 4 parts of diphenylmethane diisocyanate curing agent into the mixed solution to form transparent color, continuously stirring at an original speed for 10 minutes, filtering the obtained glue solution by a 300-mesh filter screen, ultrasonically degassing until no bubble exists, and standing at room temperature to obtain the backboard adhesive.
A back sheet was produced in the same manner as in example 1, and the initial peel strength after aging was evaluated comprehensively as 7.49. 7.49N/cm.
Example 6
Weighing 100 parts of polyester resin 50087 and 20 parts of polyethylene naphthalate TN8065C in a clean crucible according to a proportion, placing the mixture on an electric heating platform at 80 ℃, slowly starting a stirrer, increasing the rotating speed to 4 Hz, sequentially weighing and adding 3.5 parts of tricresyl phosphate, 3.2 parts of triethylenediamine and 1790.1 parts of antioxidant, enabling the mixed solution to be transparent, slowly and uniformly adding 4.5 parts of toluene diisocyanate curing agent, continuously stirring at the original speed for 10 minutes, filtering the obtained glue solution by a 300-mesh filter screen, ultrasonically degassing until no bubble exists, and standing at room temperature to obtain the backboard adhesive.
A back sheet was produced in the same manner as in example 1, and the initial peel strength after aging was comprehensively evaluated as 5.95. 5.95N/cm.
Comparative example 1
This comparative example provides an adhesive for a backsheet of a photovoltaic module, which is basically the same as that of example 1 except that 20 parts of polyethylene naphthalate in the raw material is removed.
A back sheet was produced in the same manner as in example 1, and the initial peel strength after aging was comprehensively evaluated as 3.96N/cm.
Comparative example 2
This comparative example provides an adhesive for a back sheet of a photovoltaic module, which is basically the same as that of example 1 except that polyethylene naphthalate in the raw material is replaced with methyl silicone resin.
A back sheet was produced in the same manner as in example 1, and the initial peel strength after aging was comprehensively evaluated as 4.35N/cm.
Comparative example 3
This comparative example provides an adhesive for a back sheet of a photovoltaic module, which is basically the same as that of example 1 except that dioctyl sebacate as a plasticizer in the raw material is removed.
A back sheet was produced in the same manner as in example 1, and the initial peel strength after aging was comprehensively evaluated as 5.35. 5.35N/cm.
Comparative example 4
The preparation components of the photovoltaic module backboard adhesive are basically the same as those of the embodiment 1, and the difference is that ultrasonic defoaming in the preparation process is replaced by standing room temperature defoaming, and curing conditions in the backboard composite process are replaced by 40 ℃ and 36h.
A back sheet was produced in the same manner as in example 1, and the initial peel strength after aging was comprehensively evaluated as 2.25N/cm.
Standard or specific methods of testing:
after composite curing, the initial peel strength and the peel strength after PCT aging and the back sheet film peel condition of each of examples 1 to 6 and comparative examples 1 to 4 were tested, respectively, and the results are specifically shown in tables 1 and 2.
Peel strength test: the adhesive was tested with reference to GB/T2790-1995 180℃peel strength test method. After cutting the sample into bars of width 10.00 mm and length 200 mm, the test was performed at a peel speed of 130 mm/min.
Wet heat aging resistance test: PCT test is to test the peel strength of cured sample sheet after being placed for 96 hours at 121 ℃ under the pressure of 0.1Mpa, and test the flexible material to rigid material under the conditions of the peel speed of 130 mm/min and the spline width of 10 mm by referring to the method of the test method of 180 DEG peel strength of adhesive of national standard GB/T2790-1995.
And (3) testing the hardness of the adhesive film: and a pointer type Shore hardness tester is adopted for testing. The adhesive film is prepared on a high-temperature release film according to the formula, the film thickness is 1 mm, and the baking temperature is 60 ℃.
Table 1 peel strength evaluation table
Table 2 backboard film appearance evaluation chart
As can be seen from tables 1 and 2, the adhesive for a photovoltaic back sheet has very good peel strength, hydrolysis resistance and aging resistance. The peel strength after curing and after aging of the first four groups was greater than 8.4. 8.4N/cm and 7.0. 7.0N/cm, respectively, up to 14.91N/cm. The peel strength and the national standard of the adhesive for the common traditional solar photovoltaic backboard are far exceeded.
From examples 1-6 and comparative examples 1-4, the polyester resin PET and polyethylene naphthalate PEN are blended to obtain good effect because naphthalene ring replaces benzene ring in the molecular structure of the polyethylene naphthalate PEN, naphthalene ring has larger conjugated double bond than benzene ring, the crosslinking density of the adhesive is improved, and other auxiliary agents are added to ensure excellent ageing resistance and peeling strength.
Meanwhile, by the comparative example 3, it was found that the plasticizer used in the present invention also has a certain influence on the peel strength of the system, which is inferior to the effect of polyethylene naphthalate on the system.
The hardness of the adhesive is high, so that the adhesive has good heat resistance, the required curing time is short, and the introduction of PEN improves the heat resistance of the polyester adhesive through the hardness test of the adhesive film. Meanwhile, the appearance of the PCT is still good after aging, stripping and shrinkage and yellowing are not generated among adhesive layers, and the stability of the backboard is obviously higher.
According to the invention, through the selection of the component reagents and the optimization of the proportion of each component, the PET (polyethylene naphthalate) is adopted to blend and modify the PET of the polyester resin, and the prepared back plate adhesive has better expected effects on peeling strength, ageing resistance and other properties, and improves the comprehensive performance.
The above examples and comparative examples are only for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the present invention and to implement the same, not to limit the scope of the present invention. All equivalent changes or modifications made in accordance with the spirit of the present invention should be construed to be included in the scope of the present invention.

Claims (10)

1. An adhesive for a solar photovoltaic backboard is characterized in that: the material is prepared from the following raw materials in parts by weight:
100 parts of polyester resin
10-30 parts of polyethylene naphthalate
4-5 parts of curing agent
0.6-3.5 parts of plasticizer
0.5 to 3.2 parts of heat stabilizer
0.05-1 part of antioxidant.
2. The adhesive for a solar photovoltaic backsheet according to claim 1, wherein: the solid content of the polyester resin is 40-60%, the acid value is less than 1mgKOH/g, the hydroxyl value is 17+/-3 mgKOH/g, and the viscosity is 400-600 mPa.s.
3. The adhesive for a solar photovoltaic backsheet according to claim 1, wherein: the density of the polyethylene naphthalate is 1330kg/m 3 Viscosity 200-300mPa.s.
4. The adhesive for a solar photovoltaic backsheet according to claim 1, wherein: the curing agent is isocyanate curing agent, and is selected from one or at least two of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, 1, 6-hexamethylene diisocyanate and hexamethylene diisocyanate.
5. The adhesive for a solar photovoltaic backsheet according to claim 1, wherein: the plasticizer is selected from one or at least two of dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, triphenyl phosphate and dioctyl sebacate.
6. The adhesive for a solar photovoltaic backsheet according to claim 1, wherein: the heat stabilizer is selected from one or at least two of stannous octoate, dibutyl tin dilaurate and triethylenediamine.
7. The adhesive for a solar photovoltaic backsheet according to claim 1, wherein: the antioxidant is hindered amine or hindered phenol, and is selected from one or at least two of antioxidant 1010, antioxidant 1076, antioxidant 1790 and antioxidant BHT.
8. The adhesive for a solar photovoltaic backsheet according to any one of claims 1 to 7, wherein: the adhesive is used for the composite solar photovoltaic backboard, and the coating and sizing amount is 8 g/m during composite use 2 -10 g/m 2 The dry film thickness is 7-9 um, the compounding temperature is 80-120 ℃, and the compounding pressure is 0.3-0.8 Mpa; after compounding, curing at 60 ℃ x 72 h.
9. A method for preparing the adhesive for the solar photovoltaic back sheet according to claim 1, which is characterized in that: the preparation method comprises the following steps:
(1) Preparation of the Mixed solution
Weighing polyester resin and polyethylene naphthalate according to a proportion, placing the polyester resin and the polyethylene naphthalate on an electric heating platform at 70-90 ℃, starting a stirrer, increasing the rotating speed to 3-5 Hz, sequentially weighing and adding a plasticizer, a heat stabilizer and an antioxidant, and stirring for 5-10 minutes to prepare a mixed solution;
(2) Preparation of adhesive for solar photovoltaic backboard
Adding an isocyanate curing agent into the mixed solution prepared in the step (1), continuously stirring for 5-10 minutes to prepare a glue solution, filtering the glue solution, ultrasonically degassing until no bubbles exist, and standing at room temperature to prepare the adhesive for the solar photovoltaic backboard.
10. The method according to claim 9, wherein: the solid content of the polyester resin is 40-60%, the acid value is less than 1mgKOH/g, the hydroxyl value is 17+/-3 mgKOH/g, and the viscosity is 400-600 mPa.s; the density of the polyethylene naphthalate is 1330kg/m 3 Viscosity 200-300mpa.s;
the plasticizer is selected from one or at least two of dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, triphenyl phosphate and dioctyl sebacate;
the heat stabilizer is selected from one or at least two of stannous octoate, dibutyl tin dilaurate and triethylenediamine;
the antioxidant is hindered amine or hindered phenol, and is selected from one or at least two of antioxidant 1010, antioxidant 1076, antioxidant 1790 and antioxidant BHT;
the curing agent is isocyanate curing agent, and is selected from one or at least two of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, 1, 6-hexamethylene diisocyanate and hexamethylene diisocyanate.
CN202311629601.4A 2023-12-01 2023-12-01 Adhesive for solar photovoltaic backboard and preparation method thereof Pending CN117487498A (en)

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