Photo-thermal dual-curing frame film as well as preparation method and application thereof

Abstract

The invention discloses a photo-thermal dual-curing frame film and a preparation method and application thereof, and relates to the technical field of frame films for film electrode preparation, and the photo-thermal dual-curing frame film comprises a release film layer, a photo-thermal dual-curing glue layer and a base material layer which are arranged in sequence; the photo-thermal dual-curing adhesive layer is prepared from acid modified polyolefin resin, liquid rubber, a reactive diluent, a first organic solvent, a photoinitiator, a photosensitizer and a cross-linking agent according to the weight ratio of 100: (20 to 50): (20 to 50): (10 to 30): (30 to 50): (0.5 to 3.0): (0.3 to 3.0). The problem that the CCM film and the frame film are prone to poor hot-pressing composition is solved, and meanwhile the problems that the membrane electrode production process is tedious and the processing efficiency is low are solved.

Description

Technical Field

[0001] This invention relates to the field of frame film technology for membrane electrode fabrication, specifically to a photothermal dual-curing frame film, its preparation method, and its application. Background Technology

[0002] A fuel cell is a power generation device that directly converts the chemical energy present in fuel and oxidant into electrical energy. Fuel cells have advantages such as zero emissions, no vibration or noise, good load response, and high reliability. Fuel cells can generally be classified into alkaline fuel cells, phosphoric acid fuel cells, molten carbonate fuel cells, solid oxide fuel cells, and proton exchange membrane fuel cells. Among them, proton exchange membrane fuel cells have high energy conversion efficiency, can start quickly at room temperature, have no water loss due to electrolysis, and have a long lifespan. Therefore, they have developed rapidly in recent years and are receiving increasing attention.

[0003] The core components of a proton exchange membrane fuel cell include a first catalyst layer, a proton exchange membrane, a second catalyst layer, an upper frame, a lower frame, and gas diffusion layers on both sides. The manufacturing process of the fuel cell membrane electrode typically includes catalyst slurry preparation, catalyst layer coating, frame bonding, gas diffusion layer coating, and gas diffusion layer bonding. The proton exchange membrane is very sensitive to temperature and humidity and is easily deformed with changes in ambient temperature and humidity. In addition to increasing the effective area of ​​the electrode and improving the membrane strength to stabilize the membrane electrode size, the frame can also prevent direct contact between the proton exchange membrane and the electrode plate, which could cause mechanical damage and affect the overall service life of the fuel cell. Therefore, an effectively bonded fuel cell membrane electrode frame can greatly improve the operational reliability and lifespan of the fuel cell.

[0004] In existing technologies, the blank areas and the periphery of the catalyst layer are typically designed to be bonded to the upper and lower frames, respectively. During the frame bonding process, air often exists between the upper and lower frames. The frame tape is usually made by using an airtight PEN or PI film as the base film and then coating one side with hot melt adhesive. Although this type of single-sided tape composite proton exchange membrane can support the frame, ordinary hot melt adhesive has poor temperature resistance and aging resistance. It is prone to delamination under long-term immersion in water and antifreeze, which can lead to product damage. In addition, hot melt adhesive products are not easy to align during the composite proton exchange membrane processing, resulting in poor hot-pressing bonding. Furthermore, the membrane electrode manufacturing process produced by this technology is cumbersome and inefficient, making it difficult to automate production. Summary of the Invention

[0005] The first technical problem to be solved by the present invention is to provide a photothermal dual-curing border film that has good temperature resistance and aging resistance, thereby improving the quality of the product, in order to address the shortcomings of the existing technology.

[0006] To solve the first technical problem mentioned above, the technical solution of the present invention is:

[0007] A photothermal dual-curing frame film includes a release film layer, a photothermal dual-curing adhesive layer, and a substrate layer arranged sequentially.

[0008] The photothermal dual-curing adhesive layer is composed of acid-modified polyolefin resin, liquid rubber, reactive diluent, first organic solvent, photoinitiator, photosensitizer and crosslinking agent in a weight ratio of 100:20~50:20~50:10~30:30~50:0.5~3.0:0.3~3.0.

[0009] Preferably, the release film layer is a mesh release film or a matte release film, and the thickness of the release film layer is 50-150 μm;

[0010] The substrate layer is one of PEN material, PI material, PPS material, and LCP material, and the thickness of the substrate layer is 16-200μm;

[0011] The thickness of the photothermal dual-curing adhesive layer is 10-80 μm.

[0012] Preferably, the acid-modified polyolefin resin comprises a polyolefin resin, a second organic solvent, a modifier, and an initiator;

[0013] The preparation method of the acid-modified polyolefin resin includes the following steps:

[0014] The polyolefin resin and modifier are dissolved in the second organic solvent, and then an initiator is added. The reaction is carried out under nitrogen atmosphere at 140-160°C for 1-3 hours to obtain acid-modified polyolefin resin.

[0015] The weight ratio of polyolefin resin, second organic solvent, modifier and initiator is 100:300~500:5~15:0.6~1.2.

[0016] Preferably, the polyolefin resin is at least one of polyethylene, polypropylene, and propylene-α-olefin copolymer;

[0017] The second organic solvent is one or a mixture of two of ethyl acetate and toluene;

[0018] The initiator is a mixed solution of benzoyl peroxide and azobisisobutyronitrile, wherein the weight ratio of benzoyl peroxide to azobisisobutyronitrile is 3-4:1;

[0019] The modifier is at least one of free acid anhydrides and their substituted products, acrylates, vinyl esters, and styrene derivatives.

[0020] Preferably, the liquid rubber is a hydroxyl-terminated acrylate liquid rubber prepared by free radical polymerization using mercaptoethanol as a chain transfer agent, as disclosed in the literature "Synthesis and characterization of hydroxyl-terminated poly (butyl acrylate) liquid rubber" (Journal of Applied Polymer Science, 2012, 125 (3): 2120-2126).

[0021] Preferably, the first organic solvent is one or a mixture of two of ethyl acetate and toluene.

[0022] Preferably, the photoinitiator is prepared by mixing 1-hydroxycyclohexylbenzophenone and 2-hydroxy-2-methyl-1-phenylpropanone in a weight ratio of 1:3 to 5;

[0023] The photosensitizer is 9,10-dibutoxyanthracene;

[0024] The crosslinking agent is an acrylic polymer with epoxy groups.

[0025] Preferably, the reactive diluent is one or a mixture of two or more of the following: methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-heptyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, isooctyl methacrylate, nonyl methacrylate, isononyl methacrylate, decyl methacrylate, isodecanyl methacrylate, lauryl methacrylate, tridecyl methacrylate, 2-acryloyloxyethyl hexahydrophthalic acid ester, 2-acryloyloxyethyl-2-hydroxyethyl-phthalic acid ester, 2-hydroxypropyl acrylate, 2-hydroxyethyl acrylate, and 2-hydroxybutyl acrylate.

[0026] The second technical problem to be solved by the present invention is to provide a method for preparing a photothermal dual-curing frame film, which has good temperature resistance and aging resistance and high product quality, in order to address the shortcomings of the existing technology.

[0027] To solve the second technical problem mentioned above, the technical solution of the present invention is:

[0028] A method for preparing a photothermal dual-curing border film includes the following steps:

[0029] S1, Preparation of acid-modified polyolefin resin

[0030] Polyolefin resin, a second organic solvent, a modifier, and an initiator are added to a reaction vessel and reacted at 120-160 r / min and 140-160 °C for 1-3 h. The resulting reaction solution is cooled to 40 °C to obtain acid-modified polyolefin resin.

[0031] S2: Preparation of photothermal dual-curing hot melt adhesive

[0032] Add the acid-modified polyolefin resin, liquid rubber, reactive diluent, first organic solvent, photoinitiator, photosensitizer and crosslinking agent obtained in step S1 into the reactor, stir and mix evenly, and after standing, obtain photothermal dual-curing hot melt adhesive.

[0033] S3: Preparation of photothermal dual-curing type border film

[0034] The photothermal dual-curing hot melt adhesive obtained in step S2 is filtered, and then the photothermal dual-curing hot melt adhesive is coated onto the surface of the substrate layer using a doctor blade coater or a CED coater to form a photothermal dual-curing hot melt adhesive layer. After drying, a release film layer is attached to the surface of the photothermal dual-curing hot melt adhesive, and then it is rolled up to obtain a photothermal dual-curing frame film.

[0035] The third technical problem to be solved by the present invention is to provide a membrane electrode made using the photothermal dual-curing frame film of the present invention, which has high process efficiency, in order to address the shortcomings of the existing technology.

[0036] To solve the third technical problem mentioned above, the technical solution of the present invention is as follows:

[0037] A membrane electrode, the preparation method of which includes the following steps:

[0038] S4: Place the photothermal dual-curing frame film on the first and third rollers of the membrane electrode bonding equipment, place the CCM film on the second roller of the membrane electrode bonding equipment, and position the CCM film on the second roller between the photothermal dual-curing frame film on the first and third rollers.

[0039] S5: The photothermal dual-curing frame film on the first material roller is conveyed by the first conveying device, the first die-cutting device, and the first positioning device, and the photothermal dual-curing frame film on the first material roller is anoly bonded to the anode on one side of the CCM film.

[0040] S6: The photothermal dual-curing frame film on the third material roller is conveyed by the second conveying device, the second die-cutting device, and the second positioning device, and the photothermal dual-curing frame film on the third material roller is cathode bonded to the cathode on the other side of the CCM film.

[0041] S7: The CCM film and the photothermal dual-curing frame film bonded to the top and bottom sides are brought into the UV machine through the third conveying device. The photothermal dual-curing adhesive layer of the photothermal dual-curing frame film is fully cured and bonded to the CCM film by UV light irradiation, and then wound up by the take-up roller.

[0042] S8: The material wound in step S7 is cut into the required specifications and sizes using a die-cutting device to obtain the membrane electrode product.

[0043] Due to the adoption of the above technical solution, the beneficial effects of the present invention are:

[0044] 1. This invention provides a photothermal dual-curing hot melt adhesive layer on the surface of the substrate layer. When not exposed to UV light, this layer exhibits pressure sensitivity, facilitating bonding with the proton exchange membrane during membrane electrode assembly (MEA) production. Furthermore, when exposed to UV light, the adhesive layer demonstrates strong adhesion to the MEA, exhibiting excellent temperature and aging resistance. It is less prone to delamination even after prolonged immersion in water and antifreeze, ensuring product lifespan. Additionally, the photothermal dual-curing frame film, made from this adhesive layer, does not require heating or pressing as in traditional CCM processes when bonded to the CCM film. Therefore, preheating and rolling equipment is unnecessary. UV light irradiation ensures a firm bond between the frame film and CCM film, eliminating the need for subsequent hot-pressing equipment, thus shortening the process and improving efficiency.

[0045] 2. This invention improves the problem of poor hot-pressing bonding between CCM film and frame film, and at the same time solves the problems of complicated manufacturing process and low processing efficiency of film electrode. Attached Figure Description

[0046] Figure 1 This is a flowchart illustrating the fabrication process of the membrane electrode in Embodiment 7 of the present invention;

[0047] Among them, 1. First material roller; 2. Third material roller; 3. Second material roller; 4. First conveying device; 5. First die-cutting device; 6. First positioning device; 7. Anode bonding; 8. Second conveying device; 9. Second die-cutting device; 10. Second positioning device; 11. Cathode bonding; 12. Third conveying device; 13. UV machine; 14. Take-up roller. Detailed Implementation

[0048] The present invention will be further illustrated below with reference to the embodiments. Example 1

[0049] A photothermal dual-curing frame film includes a release film layer, a photothermal dual-curing adhesive layer, and a substrate layer arranged sequentially.

[0050] The photothermal dual-curing adhesive layer is composed of acid-modified polyolefin resin, liquid rubber, reactive diluent, first organic solvent, photoinitiator, photosensitizer and crosslinking agent in a weight ratio of 100:20:20:10:30:0.5:0.3.

[0051] The release film layer is a grid release film, and the thickness of the release film layer is 50 μm;

[0052] The substrate layer is made of PEN material, and the thickness of the substrate layer is 16 μm;

[0053] The thickness of the photothermal dual-curing adhesive layer is 10 μm.

[0054] The acid-modified polyolefin resin includes a polyolefin resin, a second organic solvent, a modifier, and an initiator;

[0055] The preparation method of the acid-modified polyolefin resin includes the following steps:

[0056] The polyolefin resin and modifier are dissolved in the second organic solvent, and then an initiator is added. The reaction is carried out under nitrogen conditions to obtain acid-modified polyolefin resin.

[0057] The weight ratio of polyolefin resin, second organic solvent, modifier and initiator is 100:300:5:0.6.

[0058] The polyolefin resin is polyethylene;

[0059] The second organic solvent is ethyl acetate;

[0060] The initiator is a mixed solution of benzoyl peroxide and azobisisobutyronitrile, wherein the weight ratio of benzoyl peroxide to azobisisobutyronitrile is 3:1;

[0061] The modifier is maleic anhydride.

[0062] The liquid rubber is a hydroxyl-terminated acrylate liquid rubber prepared by free radical polymerization using mercaptoethanol as a chain transfer agent. In this embodiment, the liquid rubber is Kuraray methacrylate type liquid rubber UC-102.

[0063] The first organic solvent is ethyl acetate.

[0064] The photoinitiator is prepared by mixing 1-hydroxycyclohexylbenzophenone and 2-hydroxy-2-methyl-1-phenylpropanone in a weight ratio of 1:3;

[0065] The photosensitizer is a 9,10-dibutoxyanthracene material, specifically an ANTHRACURE™ product;

[0066] The crosslinking agent is an acrylic polymer with epoxy groups, specifically a product of the MARPROOF.G series from Nippon Oil Co., Ltd.

[0067] The reactive diluent is methyl methacrylate. Example 2

[0068] A photothermal dual-curing frame film includes a release film layer, a photothermal dual-curing adhesive layer, and a substrate layer arranged sequentially.

[0069] The photothermal dual-curing adhesive layer is composed of acid-modified polyolefin resin, liquid rubber, reactive diluent, first organic solvent, photoinitiator, photosensitizer and crosslinking agent in a weight ratio of 100:30:30:20:40:1.0:1.0.

[0070] The release film layer is a grid release film, and the thickness of the release film layer is 100μm;

[0071] The substrate layer is made of PI material, and the thickness of the substrate layer is 50 μm;

[0072] The thickness of the photothermal dual-curing adhesive layer is 20 μm.

[0073] The acid-modified polyolefin resin includes a polyolefin resin, a second organic solvent, a modifier, and an initiator;

[0074] The preparation method of the acid-modified polyolefin resin includes the following steps:

[0075] The polyolefin resin and modifier are dissolved in the second organic solvent, and then an initiator is added. The reaction is carried out under nitrogen conditions to obtain acid-modified polyolefin resin.

[0076] The weight ratio of polyolefin resin, second organic solvent, modifier and initiator is 100:350:8:0.8.

[0077] The polyolefin resin is polypropylene;

[0078] The second organic solvent is toluene;

[0079] The initiator is a mixed solution of benzoyl peroxide and azobisisobutyronitrile, wherein the weight ratio of benzoyl peroxide to azobisisobutyronitrile is 4:1;

[0080] The modifier is isooctyl acrylate.

[0081] The liquid rubber is a hydroxyl-terminated acrylate liquid rubber prepared by free radical polymerization using mercaptoethanol as a chain transfer agent. In this embodiment, the liquid rubber is Kuraray methacrylate type liquid rubber UC-102.

[0082] The first organic solvent is toluene.

[0083] The photoinitiator is prepared by mixing 1-hydroxycyclohexylbenzophenone and 2-hydroxy-2-methyl-1-phenylpropanone in a weight ratio of 1:4;

[0084] The photosensitizer is a 9,10-dibutoxyanthracene material, specifically an ANTHRACURE™ product;

[0085] The crosslinking agent is an acrylic polymer with epoxy groups, specifically a product of the MARPROOF.G series from Nippon Oil Co., Ltd.

[0086] The reactive diluent is a mixture of ethyl methacrylate, n-propyl methacrylate, and n-heptyl methacrylate, wherein the mass ratio of ethyl methacrylate, n-propyl methacrylate, and n-heptyl methacrylate is 1:2:1. Example 3

[0087] A photothermal dual-curing frame film includes a release film layer, a photothermal dual-curing adhesive layer, and a substrate layer arranged sequentially.

[0088] The photothermal dual-curing adhesive layer is composed of acid-modified polyolefin resin, liquid rubber, reactive diluent, first organic solvent, photoinitiator, photosensitizer and crosslinking agent in a weight ratio of 100:40:35:25:45:2.0:1.8.

[0089] The release film layer is a matte release film, and the thickness of the release film layer is 75 μm;

[0090] The substrate layer is made of PPS material, and the thickness of the substrate layer is 125 μm;

[0091] The thickness of the photothermal dual-curing adhesive layer is 50 μm.

[0092] The acid-modified polyolefin resin includes a polyolefin resin, a second organic solvent, a modifier, and an initiator;

[0093] The preparation method of the acid-modified polyolefin resin includes the following steps:

[0094] The polyolefin resin and modifier are dissolved in the second organic solvent, and then an initiator is added. The reaction is carried out under nitrogen conditions to obtain acid-modified polyolefin resin.

[0095] The weight ratio of polyolefin resin, second organic solvent, modifier and initiator is 100:400:10:1.0.

[0096] The polyolefin resin is a propylene-α-olefin copolymer;

[0097] The second organic solvent is a mixed solution of ethyl acetate and toluene, with a volume ratio of ethyl acetate to toluene of 1:2;

[0098] The initiator is a mixed solution of benzoyl peroxide and azobisisobutyronitrile, wherein the weight ratio of benzoyl peroxide to azobisisobutyronitrile is 3.5:1;

[0099] The modifier is butyl acrylate.

[0100] The liquid rubber is a hydroxyl-terminated acrylate liquid rubber prepared by free radical polymerization using mercaptoethanol as a chain transfer agent. In this embodiment, the liquid rubber is Kuraray methacrylate type liquid rubber UC-203.

[0101] The first organic solvent is a mixed solution of ethyl acetate and toluene, wherein the volume ratio of ethyl acetate to toluene is 1:2.

[0102] The photoinitiator is prepared by mixing 1-hydroxycyclohexylbenzophenone and 2-hydroxy-2-methyl-1-phenylpropanone in a weight ratio of 1:3;

[0103] The photosensitizer is a 9,10-dibutoxyanthracene material, specifically an ANTHRACURE™ product;

[0104] The crosslinking agent is an acrylic polymer with epoxy groups, specifically a product of the MARPROOF.G series from Nippon Oil Co., Ltd.

[0105] The active diluent is a mixture of 2-ethylhexyl methacrylate, n-octyl methacrylate, isooctyl methacrylate, nonyl methacrylate, isononyl methacrylate, decyl methacrylate, isodecyl methacrylate, lauryl methacrylate, and tridecyl methacrylate, wherein the mass ratio of 2-ethylhexyl methacrylate, n-octyl methacrylate, isooctyl methacrylate, nonyl methacrylate, isononyl methacrylate, decyl methacrylate, isodecyl methacrylate, lauryl methacrylate, and tridecyl methacrylate is 1:1:1:3:1:2:1:2:1. Example 4

[0106] A photothermal dual-curing frame film includes a release film layer, a photothermal dual-curing adhesive layer, and a substrate layer arranged sequentially.

[0107] The photothermal dual-curing adhesive layer is composed of acid-modified polyolefin resin, liquid rubber, reactive diluent, first organic solvent, photoinitiator, photosensitizer and crosslinking agent in a weight ratio of 100:45:38:28:40:2.5:2.0.

[0108] The release film layer is a matte release film, and the thickness of the release film layer is 100μm;

[0109] The substrate layer is made of LCP material, and the thickness of the substrate layer is 120 μm;

[0110] The thickness of the photothermal dual-curing adhesive layer is 80 μm.

[0111] The acid-modified polyolefin resin includes a polyolefin resin, a second organic solvent, a modifier, and an initiator;

[0112] The preparation method of the acid-modified polyolefin resin includes the following steps:

[0113] The polyolefin resin and modifier are dissolved in the second organic solvent, and then an initiator is added. The reaction is carried out under nitrogen conditions to obtain acid-modified polyolefin resin.

[0114] The weight ratio of polyolefin resin, second organic solvent, modifier and initiator is 100:450:12:1.1.

[0115] The polyolefin resin is a mixture of polyethylene and polypropylene, wherein the mass ratio of polyethylene to polypropylene is 1:1;

[0116] The second organic solvent is ethyl acetate and toluene, wherein the volume ratio of ethyl acetate to toluene is 1:3;

[0117] The initiator is a mixed solution of benzoyl peroxide and azobisisobutyronitrile, wherein the weight ratio of benzoyl peroxide to azobisisobutyronitrile is 4:1;

[0118] The modifier is a mixture of methyl methacrylate and vinyl acetate, wherein the mass ratio of methyl methacrylate to vinyl acetate is 1:1.

[0119] The liquid rubber is a hydroxyl-terminated acrylate liquid rubber prepared by free radical polymerization using mercaptoethanol as a chain transfer agent. In this embodiment, the liquid rubber is Kuraray methacrylate type liquid rubber UC-203.

[0120] The first organic solvent is a mixed solution of ethyl acetate and toluene, wherein the volume ratio of ethyl acetate to toluene is 3:2.

[0121] The photoinitiator is prepared by mixing 1-hydroxycyclohexylbenzophenone and 2-hydroxy-2-methyl-1-phenylpropanone in a weight ratio of 1:4;

[0122] The photosensitizer is a 9,10-dibutoxyanthracene material, specifically an ANTHRACURE™ product;

[0123] The crosslinking agent is an acrylic polymer with epoxy groups, specifically a product of the MARPROOF.G series from Nippon Oil Co., Ltd.

[0124] The reactive diluent is a mixture of 2-acryloyloxyethyl hexahydrophthalic acid ester, 2-acryloyloxyethyl-2-hydroxyethyl-phthalic acid ester, 2-hydroxypropyl acrylate, 2-hydroxyethyl acrylate, and 2-hydroxybutyl acrylate, wherein the mass ratio of 2-acryloyloxyethyl hexahydrophthalic acid ester, 2-acryloyloxyethyl-2-hydroxyethyl-phthalic acid ester, 2-hydroxypropyl acrylate, 2-hydroxyethyl acrylate, and 2-hydroxybutyl acrylate is 1:2:2:1:1. Example 5

[0125] A photothermal dual-curing frame film includes a release film layer, a photothermal dual-curing adhesive layer, and a substrate layer arranged sequentially.

[0126] The photothermal dual-curing adhesive layer is composed of acid-modified polyolefin resin, liquid rubber, reactive diluent, first organic solvent, photoinitiator, photosensitizer and crosslinking agent in a weight ratio of 100:50:50:30:50:3.0:3.0.

[0127] The release film layer is a grid release film, and the thickness of the release film layer is 150 μm;

[0128] The substrate layer is made of PEN material, and the thickness of the substrate layer is 188 μm;

[0129] The thickness of the photothermal dual-curing adhesive layer is 40 μm.

[0130] The acid-modified polyolefin resin includes a polyolefin resin, a second organic solvent, a modifier, and an initiator;

[0131] The preparation method of the acid-modified polyolefin resin includes the following steps:

[0132] The polyolefin resin and modifier are dissolved in the second organic solvent, and then an initiator is added. The reaction is carried out under nitrogen conditions to obtain acid-modified polyolefin resin.

[0133] The weight ratio of polyolefin resin, second organic solvent, modifier and initiator is 100:500:15:1.2.

[0134] The polyolefin resin is a mixture of polyethylene, polypropylene and propylene-α-olefin copolymer, wherein the mass ratio of polyethylene, polypropylene and propylene-α-olefin copolymer is 1:2:1;

[0135] The second organic solvent is ethyl acetate;

[0136] The initiator is a mixed solution of benzoyl peroxide and azobisisobutyronitrile, wherein the weight ratio of benzoyl peroxide to azobisisobutyronitrile is 3:1;

[0137] The modifier is a styrene-acrylonitrile copolymer.

[0138] The liquid rubber is a hydroxyl-terminated acrylate liquid rubber prepared by free radical polymerization using mercaptoethanol as a chain transfer agent. In this embodiment, the liquid rubber is Kuraray methacrylate type liquid rubber UC-102.

[0139] The first organic solvent is ethyl acetate.

[0140] The photoinitiator is prepared by mixing 1-hydroxycyclohexylbenzophenone and 2-hydroxy-2-methyl-1-phenylpropanone in a weight ratio of 1:5;

[0141] The photosensitizer is a 9,10-dibutoxyanthracene material, specifically an ANTHRACURE™ product;

[0142] The crosslinking agent is an acrylic polymer with epoxy groups, specifically a product of the MARPROOF.G series from Nippon Oil Co., Ltd.

[0143] The reactive diluent is a mixture of methyl methacrylate and 2-hydroxybutyl acrylate, wherein the mass ratio of methyl methacrylate to 2-hydroxybutyl acrylate is 1:1. Example 6

[0144] The preparation method of the photothermal dual-curing border film in Examples 1-5 includes the following steps:

[0145] S1, Preparation of acid-modified polyolefin resin

[0146] Polyolefin resin, a second organic solvent, a modifier, and an initiator are added to a reaction vessel and reacted at 120-160 r / min and 140-160 °C for 1-3 h. The resulting reaction solution is cooled to 40 °C to obtain acid-modified polyolefin resin.

[0147] S2: Preparation of photothermal dual-curing hot melt adhesive

[0148] Add the acid-modified polyolefin resin, liquid rubber, reactive diluent, first organic solvent, photoinitiator, photosensitizer and crosslinking agent obtained in step S1 into the reactor, stir and mix evenly, and after standing, obtain photothermal dual-curing hot melt adhesive.

[0149] S3: Preparation of photothermal dual-curing type border film

[0150] The photothermal dual-curing hot melt adhesive obtained in step S2 is filtered, and then the photothermal dual-curing hot melt adhesive is coated onto the surface of the substrate layer using a doctor blade coater or a CED coater to form a photothermal dual-curing hot melt adhesive layer. After drying, a release film layer is attached to the surface of the photothermal dual-curing hot melt adhesive, and then it is rolled up to obtain a photothermal dual-curing frame film. Example 7

[0151] A membrane electrode, the preparation method of which includes the following steps:

[0152] S4: Place the photothermal dual-curing frame film on the first roller 1 and the third roller of the membrane electrode bonding equipment, place the CCM film on the second roller 3 of the membrane electrode bonding equipment, and make the CCM film on the second roller located between the photothermal dual-curing frame film of the first roller and the third roller.

[0153] S5: The photothermal double-cured frame film on the first material roller is conveyed by the first conveying device 4, the first die-cutting device 5, and the first positioning device 6, and the photothermal double-cured frame film on the first material roller is anoly bonded to the anode on one side of the CCM film.

[0154] S6: The photothermal double-cured frame film on the third material roller is conveyed by the second conveying device 8, the second die-cutting device 9, and the second positioning device 10, and the photothermal double-cured frame film on the third material roller is cathode bonded to the cathode on the other side of the CCM film 11.

[0155] S7: The CCM film and the photothermal double-curing frame film bonded to the upper and lower sides are brought into the UV machine 13 through the third conveying device 12. By UV light irradiation, the photothermal double-curing adhesive layer of the photothermal double-curing frame film is fully cured and bonded to the CCM film, and then wound up by the take-up roller 14.

[0156] S8: The material wound in step S7 is cut into the required specifications and sizes using a die-cutting device to obtain the membrane electrode product.

[0157] Chemical resistance tests (resistance to acid in the working environment of fuel cells) were conducted on the photothermal dual-curing frame films of Examples 1-5 after photothermal curing.

[0158] Test method:

[0159] The border membrane sample was immersed in a 0.5 mol / L H2SO4 solution (simulating the acidic environment of a fuel cell) at 95℃ for 500 h. After removal, the mass change rate and tensile strength retention rate were measured.

[0160] Test metrics:

[0161] Mass change rate (required ≤ ±3%, to avoid swelling or dissolution)

[0162] Tensile strength retention rate (≥80% required to ensure stable mechanical properties)

[0163] The test results are shown in the table below:

[0164]

[0165] The photothermal dual-curing frame films from Examples 1-5 were respectively operated according to Example 7, and the airtightness of the resulting membrane electrode products was tested.

[0166] Test method:

[0167] Using an airtightness testing device, the membrane electrode assembly was formed into a single-cell simulation device. Nitrogen gas at 0.3 MPa was introduced, and the contact points between the frame membrane, the proton exchange membrane, and the electrode plates were tested. The leakage rate was determined by the soap bubble method or a gas flow meter.

[0168] Test metric: Leakage rate (requirement ≤ 1×10⁻⁶) -6 (Pa·m³ / s)

[0169] Test results:

[0170]

[0171] It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Furthermore, it should be understood that after reading the teachings of this invention, those skilled in the art can make various alterations or modifications to the invention, and these equivalent forms also fall within the scope defined by the appended claims.

Claims

1. A photothermal dual-curing type frame film, characterized in that: It includes a release film layer, a photothermal dual-curing adhesive layer, and a substrate layer arranged sequentially; The photothermal dual-curing adhesive layer is composed of acid-modified polyolefin resin, liquid rubber, reactive diluent, first organic solvent, photoinitiator, photosensitizer and crosslinking agent in a weight ratio of 100:20~50:20~50:10~30:30~50:0.5~3.0:0.3~3.

0.

2. The photothermal dual-curing frame film as described in claim 1, characterized in that: The release film layer is a mesh release film or a matte release film, and the thickness of the release film layer is 50-150μm; The substrate layer is one of PEN material, PI material, PPS material, and LCP material, and the thickness of the substrate layer is 16-200μm; The thickness of the photothermal dual-curing adhesive layer is 10-80 μm.

3. The photothermal dual-curing frame film as described in claim 1, characterized in that: The acid-modified polyolefin resin includes a polyolefin resin, a second organic solvent, a modifier, and an initiator; The preparation method of the acid-modified polyolefin resin includes the following steps: The polyolefin resin and modifier are dissolved in the second organic solvent, and then an initiator is added. The reaction is carried out under nitrogen atmosphere at 140-160°C for 1-3 hours to obtain acid-modified polyolefin resin. The weight ratio of polyolefin resin, second organic solvent, modifier and initiator is 100:300~500:5~15:0.6~1.

2.

4. The photothermal dual-curing frame film as described in claim 3, characterized in that: The polyolefin resin is at least one of polyethylene, polypropylene, and propylene-α-olefin copolymer; The second organic solvent is one or a mixture of two of ethyl acetate and toluene; The initiator is a mixed solution of benzoyl peroxide and azobisisobutyronitrile, wherein the weight ratio of benzoyl peroxide to azobisisobutyronitrile is 3-4:1; The modifier is at least one of free acid anhydrides and their substituted products, acrylates, vinyl esters, and styrene derivatives.

5. The photothermal dual-curing frame film as described in claim 1, characterized in that: The liquid rubber is a hydroxyl-terminated acrylate liquid rubber prepared by free radical polymerization using mercaptoethanol as a chain transfer agent.

6. The photothermal dual-curing frame film as described in claim 1, characterized in that: The first organic solvent is one or a mixture of two of ethyl acetate and toluene.

7. The photothermal dual-curing border film as described in claim 1, characterized in that: The photoinitiator is prepared by mixing 1-hydroxycyclohexylbenzophenone and 2-hydroxy-2-methyl-1-phenylpropanone in a weight ratio of 1:3 to 5. The photosensitizer is 9,10-dibutoxyanthracene; The crosslinking agent is an acrylic polymer with epoxy groups.

8. The photothermal dual-curing frame film as described in claim 1, characterized in that: The active diluent is one or a mixture of two or more of the following: methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-heptyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, isooctyl methacrylate, nonyl methacrylate, isononyl methacrylate, decyl methacrylate, isodecyl methacrylate, lauryl methacrylate, tridecyl methacrylate, 2-acryloyloxyethyl hexahydrophthalic acid ester, 2-acryloyloxyethyl-2-hydroxyethyl-phthalic acid ester, 2-hydroxypropyl acrylate, 2-hydroxyethyl acrylate, and 2-hydroxybutyl acrylate.

9. A method for preparing a photothermal dual-curing border film as described in any one of claims 1-8, characterized in that, Includes the following steps: S1, Preparation of acid-modified polyolefin resin Polyolefin resin, a second organic solvent, a modifier, and an initiator are added to a reaction vessel and reacted at 120-160 r / min and 140-160 °C for 1-3 h. The resulting reaction solution is cooled to 40 °C to obtain acid-modified polyolefin resin. S2: Preparation of photothermal dual-curing hot melt adhesive Add the acid-modified polyolefin resin, liquid rubber, reactive diluent, first organic solvent, photoinitiator, photosensitizer and crosslinking agent obtained in step S1 into the reactor, stir and mix evenly, and after standing, obtain photothermal dual-curing hot melt adhesive. S3: Preparation of photothermal dual-curing type border film The photothermal dual-curing hot melt adhesive obtained in step S2 is filtered, and then the photothermal dual-curing hot melt adhesive is coated onto the surface of the substrate layer using a doctor blade coater or a CED coater to form a photothermal dual-curing hot melt adhesive layer. After drying, a release film layer is attached to the surface of the photothermal dual-curing hot melt adhesive, and then it is rolled up to obtain a photothermal dual-curing frame film.

10. A membrane electrode, characterized in that: The photothermal dual-curing border film according to any one of claims 1-8, wherein the method for preparing the film electrode comprises the following steps: S4: Place the photothermal dual-curing frame film on the first and third rollers of the membrane electrode bonding equipment, place the CCM film on the second roller of the membrane electrode bonding equipment, and position the CCM film on the second roller between the photothermal dual-curing frame film on the first and third rollers. S5: The photothermal dual-curing frame film on the first material roller is conveyed by the first conveying device, the first die-cutting device, and the first positioning device, and the photothermal dual-curing frame film on the first material roller is anoly bonded to the anode on one side of the CCM film. S6: The photothermal dual-curing frame film on the third material roller is conveyed by the second conveying device, the second die-cutting device, and the second positioning device, and the photothermal dual-curing frame film on the third material roller is cathode bonded to the cathode on the other side of the CCM film. S7: The CCM film and the photothermal dual-curing frame film bonded to the top and bottom sides are brought into the UV machine through the third conveying device. The photothermal dual-curing adhesive layer of the photothermal dual-curing frame film is fully cured and bonded to the CCM film by UV light irradiation, and then wound up by the take-up roller. S8: The material wound in step S7 is cut into the required specifications and sizes using a die-cutting device to obtain the membrane electrode product.

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