Eb electron beam curing light weight composite resin and its application

Abstract

The present application relates to a kind of Eb electron beam curing light composite resin and its application, including polyurethane acrylic resin, epoxy acrylic resin, acrylic resin, auxiliary.The present application selects different acrylic resin mixture, adopts Eb electron beam curing, reaches 100% double bond conversion efficiency, no small molecule residue, perfect realization the performance of resin.The performance of the composite material prepared is excellent, and has good application prospect.

Description

Technical Field

[0001] The present invention belongs to the technical field of lightweight components, and in particular relates to an Eb electron beam cured lightweight composite resin and application thereof. Background Art

[0002] At present, large industrial buildings with lightweight insulated roof structures pose a challenge to traditional glass crystalline silicon photovoltaic (PV) systems due to their insufficient load-bearing capacity. In the field of BIPV (building integrated photovoltaics), the hidden danger of double-sided glass causing excessive weight of components has not been solved. In the same situation, the share of electric vehicles (EVs) in the entire automotive market has been increasing. At this stage, VIPV (vehicle integrated photovoltaics) allows electric vehicles to be charged during the day and off-grid; therefore, the electricity generated can be used to extend the driving range of electric vehicles and reduce the number of charging stations / times. However, most VIPV products are aimed at panoramic photovoltaic roofs, with glass as the front panel material and a mass of more than 15kg / m 2 In this case, a glass-glass front structure is not suitable in this regard, as the extensive use of glass would significantly increase the weight of the vehicle and raise safety issues.

[0003] At present, there are many front panel materials developed for lightweight components on the market. Chinese patent CN115466565A selects polyurethane acrylic resin, monomer, initiator and curing agent, coats the resin on the surface of glass fiber cloth, and prepares a lightweight component packaging front panel through a two-step method of light curing + heat curing. The packaging front panel has excellent weather resistance and UV resistance due to the introduction of polyurethane acrylic resin, but its heat resistance is general, and the refractive index of the polyurethane acrylic resin system is generally below 1.47, while the refractive index of conventional electronic-grade glass fiber products is around 1.55. The mismatch between the refractive indices of the two will lead to high haze, reduced transmittance, and the risk of delamination after aging. If products made of low-dielectric glass fiber are selected, although the refractive index can match the resin, the transmittance and haze will be improved, but the price is high and the strength of low-dielectric glass fiber products is poor, which will also affect subsequent use. Chinese patent CN118048016B selects epoxy resin and corresponding curing agent in the form of prepreg to prepare lightweight front panel prepreg. Due to the introduction of epoxy resin, the formula has good heat resistance and mechanical strength. However, pure epoxy resin has limited thickness resistance and maximum light transmittance due to the presence of benzene rings, and there is also a risk of failure after aging. Summary of the Invention

[0004] The technical problem to be solved by the present invention is to provide an Eb electron beam cured lightweight composite resin and its application. By optimizing the resin formula, high weather resistance, high heat resistance, and high hardness are achieved, and Eb electron beam curing is used to achieve 100% double bond conversion efficiency, perfectly exerting the performance of the resin formula and achieving excellent performance.

[0005] The present invention provides an Eb electron beam cured lightweight composite resin, which comprises the following components in parts by mass:

[0006] Polyurethane acrylic resin 55-75 parts;

[0007] 15-35 parts of epoxy acrylic resin;

[0008] 5-15 parts of acrylic resin;

[0009] 0.5-3 parts of additives;

[0010] The auxiliary agent comprises 0.1-0.2 wt % of a defoamer, 1-1.5 wt % of an ultraviolet absorber, 0.2-0.5 wt % of an antioxidant and 0.2-0.3 wt % of a wetting agent.

[0011] Preferably, the polyurethane acrylic resin is one or more of a difunctional aliphatic polyurethane acrylic resin, a trifunctional aliphatic polyurethane acrylic resin, and a multifunctional polyurethane acrylic resin.

[0012] Preferably, the epoxy acrylate resin is one or more of bisphenol A epoxy acrylate, amine-modified epoxy acrylate, fatty acid-modified epoxy acrylate, and aliphatic epoxy acrylate.

[0013] Preferably, the acrylic resin is one of bifunctional pure acrylate or multifunctional pure acrylate.

[0014] Preferably, the defoaming agent is one or more of TEGO 2700, TEGO 5300, BYK 1788, BYK 055, and Efka 2720.

[0015] Preferably, the ultraviolet absorber is one or more of Tinuvin 292, Tinuvin 400, Tinuvin 123, Tinuvin 234, Tinuvin 1600, Tinuvin 770, Chiguard 5431, and Chiguard 234.

[0016] Preferably, the antioxidant is one or more of CHINOX 1076, CHINOX 1790, CHINOX GM, CHINOX 168, Irganox 1010, and Irganox 1098.

[0017] Preferably, the wetting agent is one of TEGO 432, TEGO 2300, TEGO 2100, TEGO 4100, TEGO 270, TEGO 245, BYK 333, BYK378, and BYK 3455.

[0018] The present invention also provides an application of an Eb electron beam cured lightweight composite resin in preparing a lightweight component front plate.

[0019] Furthermore, the preparation steps include:

[0020] The resin is evenly coated on the surface of the glass fiber cloth to obtain a prepreg composite material; the prepreg composite material is subjected to electron beam radiation curing by an Eb electron beam curing device to obtain a lightweight component front plate.

[0021] Preferably, the fiberglass cloth is one or more of EW100, EW160, EW200, EW300, EW400, EW500, EW600, EW700, EW800, EW900, and EW1000.

[0022] Preferably, the electron accelerator energy used in the electron beam radiation curing is 200-500 keV.

[0023] Beneficial effects

[0024] This invention combines a polyurethane acrylic resin (high weather resistance and toughness), a high-strength / high-thermal-stability epoxy acrylic resin (high strength / high thermal stability), and an acrylate (yellowing resistance) with electron beam curing (Eb). In the absence of monomers and initiators, it achieves 100% double bond conversion efficiency, a narrower molecular weight distribution, and higher molecular weight and crosslink density. This overcomes the low conversion efficiency, molecular weight, and crosslinking density that affect aging performance associated with traditional UV curing. The resulting lightweight module front panel is free of small molecule residues such as monomers, initiators, and various additives, exhibits excellent weather resistance, and has promising application prospects. DETAILED DESCRIPTION

[0025] Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiments are only used to illustrate the present invention and are not used in limiting the scope of the present invention.In addition, should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms fall equally within the scope limited by the appended claims of the application.

[0026] Example 1

[0027] The resin formula in this embodiment is, by weight, 55 parts of polyurethane acrylic resin, 35 parts of epoxy acrylic resin, 8 parts of acrylic resin, and 2 parts of auxiliary agent.

[0028] The polyurethane acrylic resin is B-205; the epoxy acrylic resin is ETERCURE 621-100; and the acrylic resin is ETERCURE 65350. The additives are 0.2 wt% of defoamer BYK 055, 1 wt% of UV absorber Tinuvin 400, 0.5 wt% of antioxidant CHINOX 1076, and 0.3 wt% of wetting agent TEGO 270.

[0029] The resin is evenly coated on the surface of the glass fiber cloth to obtain a prepreg composite material. The prepreg composite material is then electron beam cured using an Eb electron beam curing device to obtain a lightweight component front panel. The glass fiber cloth is EW100 and the electron accelerator energy is 200keV.

[0030] Example 2

[0031] The process was the same as in Example 1 except that the ratio of polyurethane acrylic resin was adjusted to 65 parts and epoxy acrylic resin was adjusted to 25 parts.

[0032] Example 3

[0033] The process was the same as in Example 1 except that the ratio of polyurethane acrylic resin was adjusted to 75 parts and epoxy acrylic resin was adjusted to 15 parts.

[0034] Example 4

[0035] The same procedures as in Example 1 were followed except that 30 parts of epoxy acrylic resin and 13 parts of acrylic resin were used.

[0036] Example 5

[0037] The same procedures as in Example 1 were followed except that 28w parts of epoxy acrylic resin and 15 parts of pure acrylic resin were used.

[0038] Example 6

[0039] The process is the same as that of Example 1 except that the polyurethane acrylic resin B-205 in Example 1 is replaced by ETERCURE 6157B-80.

[0040] Example 7

[0041] The method is the same as that of Example 1 except that the polyurethane acrylic resin B-205 in Example 1 is replaced by ETERCURE 6157B-80 and ETERCURE 6170 in a mass ratio of 3:1.

[0042] Example 8

[0043] The process is the same as that of Example 1 except that the polyurethane acrylic resin B-205 in Example 1 is replaced by CN980 NS.

[0044] Example 9

[0045] The process is the same as that of Example 1 except that the polyurethane acrylic resin B-205 in Example 1 is replaced by FSP 8060.

[0046] Example 10

[0047] The process is the same as that of Example 1 except that the epoxy acrylic resin ETERCURE 621-100 in Example 1 is replaced by EB 600.

[0048] Example 11

[0049] The process is the same as that of Example 1 except that the epoxy acrylic resin ETERCURE 621-100 in Example 1 is replaced by CN104 NS.

[0050] Example 12

[0051] The process is the same as that of Example 1 except that the epoxy acrylic resin ETERCURE 621-100 in Example 1 is replaced by CN 118.

[0052] Example 13

[0053] The process is the same as that of Example 1 except that the epoxy acrylic resin ETERCURE 621-100 in Example 1 is replaced by SD 7209.

[0054] Example 14

[0055] The process is the same as in Example 1 except that the acrylic resin ETERCURE 65350 is replaced by ETERCURE DR-A819.

[0056] Example 15

[0057] The process is the same as that of Example 1 except that the acrylic resin ETERCURE 65350 is replaced by GU 2600K.

[0058] Example 16

[0059] The process is the same as that of Example 1 except that the acrylic resin ETERCURE 65350 is replaced by SA 345.

[0060] Example 17

[0061] The preparation method is the same as that of Example 1, except that the auxiliary agents in Example 1 are replaced by 0.2 wt % of defoamer BYK 1788, 1 wt % of ultraviolet absorber Tinuvin 1600, 0.5 wt % of antioxidant CHINOX 168, and 0.3 wt % of wetting agent TEGO 4100.

[0062] Example 18

[0063] The preparation method is the same as that of Example 1 except that the auxiliary agents in Example 1 are replaced by 0.1 wt % of defoamer TEGO 2700, 1.5 wt % of ultraviolet absorber Chiguard 5431, 0.2 wt % of antioxidant CHINOX GM, and 0.2 wt % of wetting agent TEGO 270.

[0064] Example 19

[0065] Except that the glass fiber cloth in Example 1 is replaced by EW200, the rest is the same as Example 1.

[0066] Example 20

[0067] Except that the glass fiber cloth in Example 1 is replaced by EW500, the rest is the same as Example 1.

[0068] Example 21

[0069] Except that the energy of the electron accelerator in Example 1 is adjusted to 350 keV, the rest is the same as Example 1.

[0070] Example 22

[0071] Except that the energy of the electron accelerator in Example 1 is adjusted to 500 keV, the rest is the same as Example 1.

[0072] Comparative Example 1

[0073] The resin formula is polyurethane acrylic resin B-205 (100 wt %), the glass fiber cloth is EW100, the electron accelerator energy is 200 keV, and the rest is the same as in Example 1.

[0074] Comparative Example 2

[0075] The resin formula is epoxy acrylic resin ETERCURE 621-100 (100 wt %), the glass fiber cloth is EW100, the electron accelerator energy is 200 keV, and the rest is the same as in Example 1.

[0076] Comparative Example 3

[0077] The resin formula is acrylic resin ETERCURE 65350 (100 wt %), the glass fiber cloth is EW100, the electron accelerator energy is 200 keV, and the rest is the same as in Example 1.

[0078] Comparative Example 4

[0079] The resin formula in this comparative example is, by weight, 41 parts of polyurethane acrylic resin, 25 parts of epoxy acrylic resin, 5 parts of acrylic resin, 25 parts of isobornyl methacrylate, 2 parts of auxiliary agent, and 2 parts of initiator TPO.

[0080] The polyurethane acrylic resin is B-205; the epoxy acrylic resin is ETERCURE 621-100; and the acrylic resin is ETERCURE 65350. The additives are 0.2 wt% of defoamer BYK 055, 1 wt% of UV absorber Tinuvin 400, 0.5 wt% of antioxidant CHINOX 1076, and 0.3 wt% of wetting agent TEGO 270.

[0081] The resin is evenly coated on the surface of the fiberglass cloth to form a prepreg composite material. The prepreg composite material is then cured to form a lightweight component front panel. The fiberglass cloth is EW100, and the curing method is a UV-LED with a wavelength of 365nm.

[0082] Comparative Example 5

[0083] The resin formula in this comparative example is as follows, in parts by weight: 70 parts of polyurethane acrylic resin, 26 parts of isobornyl methacrylate, 2 parts of auxiliary agent, and 2 parts of initiator TPO.

[0084] The polyurethane acrylic resin is B-205; the additives are 0.2wt% defoamer BYK 055, 1wt% UV absorber Tinuvin 400, 0.5wt% antioxidant CHINOX 1076, and 0.3wt% wetting agent TEGO 270.

[0085] The resin is evenly coated on the surface of the fiberglass cloth to form a prepreg composite material. The prepreg composite material is then cured to form a lightweight component front panel. The fiberglass cloth is EW100, and the curing method is a UV-LED with a wavelength of 365nm.

[0086] The performance test methods of the lightweight composite materials of the embodiments and comparative examples are as follows:

[0087] Visible light transmittance: GB / T2410-2008;

[0088] Abrasion resistance ASTM D968;

[0089] Coating adhesion ISO 2409;

[0090] Yellowing value: GB / T 39822-2021;

[0091] Heat resistance: 165℃, 4h;

[0092] Tensile strength: ASTM3039;

[0093] DH test and UV aging test: IEC 61215-2-2021, where the DH test is the aging test hours at 85°C and 85% ambient humidity.

[0094] Table 1 Test results of lightweight component front plate

[0095] Serial number Initial composite material transmittance / % tensile strength Abrasion resistance / coating adhesion (0-5 levels) Transmittance / % and yellowing / △Yi after DH3000 DH3000 post tensile strength DH3000 post-wear resistance / coating adhesion Transmittance / % and yellowing / △Yi after UV aging 300Kwh Wear resistance / coating adhesion after UV aging 300Kwh Tensile strength after UV aging 300Kwh Transmittance after heat resistance / % and yellowing / △Yi Heat resistance and wear resistance / coating adhesion Tensile strength after heat resistance Comparative Example 1 90.05 375 1 87.32 / 2.66 288 2 86.33 / 3.44 3 307 87.44 / 3.44 2 344 Comparative Example 2 90.11 402 2 79.43 / 4.67 291 4 73.88 / 6.22 5 266 89.22 / 1.23 2 385 Comparative Example 3 90.25 288 3 65.75 / 5.44 98 5 72.42 / 5.22 5 97 88.44 / 1.45 5 144 Comparative Example 4 90.44 402 1 86.78 / 3.21 387 2 87.22 / 2.55 2 366 87.66 / 1.22 2 376 Comparative Example 5 90.66 422 1 85.45 / 4.24 376 2 86.77 / 3.22 3 365 88.22 / 2.55 2 386 Example 1 90.82 476 0 90.80 / 0.22 474 0 90.66 / 0.28 0 470 90.81 / 0.09 0 471 Example 2 90.22 468 0 90.15 / 0.33 467 0 90.17 / 0.32 0 464 90.22 / 0.08 0 466 Example 3 90.18 444 0 90.02 / 0.14 444 0 90.00 / 0.33 0 442 90.15 / 0.11 0 444 Example 4 91.03 439 0 90.66 / 0.37 432 0 90.66 / 0.28 0 432 91.01 / 0.08 0 434 Example 5 92.04 439 0 91.88 / 0.22 438 0 91.66 / 0.11 0 437 92.04 / 0.02 0 435 Example 6 91.99 455 0 91.76 / 0.32 455 0 91.45 / 0.34 0 452 91.93 / 0.11 0 452 Example 7 90.88 426 0 90.67 / 0.24 420 0 90.12 / 0.22 0 424 90.77 / 0.22 0 423 Example 8 91.00 438 0 90.77 / 0.19 433 0 90.44 / 0.22 0 432 90.92 / 0.21 0 436 Example 9 90.56 457 0 90.44 / 0.23 452 0 90.11 / 0.44 0 455 90.44 / 0.22 0 451 Example 10 90.78 411 0 90.71 / 0.33 405 0 90.55 / 0.35 0 408 90.76 / 0.04 0 410 Example 11 91.06 402 0 90.11 / 0.23 400 0 90.88 / 0.19 0 400 91.01 / 0.19 0 402 Example 12 91.55 433 0 90.88 / 0.41 429 0 91.04 / 0.19 0 428 91.44 / 0.10 0 433 Example 13 92.21 452 0 91.87 / 0.22 447 0 91.44 / 0.33 0 451 92.18 / 0.04 0 451 Example 14 91.97 476 0 91.44 / 0.34 472 0 91.44 / 0.22 0 472 91.88 / 0.11 0 472 Example 15 91.48 498 0 91.42 / 0.25 495 0 91.34 / 0.36 0 496 91.29 / 0.22 0 493 Example 16 90.88 411 0 90.14 / 0.33 408 0 90.45 / 0.33 0 406 90.75 / 0.17 0 408 Example 17 90.56 456 0 90.44 / 0.15 451 0 90.22 / 0.18 0 452 90.49 / 0.11 0 452 Example 18 90.44 421 0 90.12 / 0.28 420 0 90.18 / 0.23 0 420 90.39 / 0.18 0 420 Example 19 90.72 462 0 90.44 / 0.16 455 0 90.33 / 0.34 0 452 90.67 / 0.13 0 461 Example 20 91.32 476 0 90.98 / 0.33 475 0 90.99 / 0.28 0 472 91.28 / 0.13 0 474 Example 21 91.48 499 0 90.99 / 0.17 492 0 90.76 / 0.16 0 492 91.46 / 0.05 0 495 Example 22 90.66 476 0 90.44 / 0.19 472 0 90.42 / 0.34 0 473 90.65 / 0.05 0 472

[0096] It can be seen from the above table that the lightweight component front plates prepared in Examples 1-22 have excellent performance, and the various properties remain stable after rigorous moisture and heat aging, wet UV aging, and heat resistance tests, indicating that by regulating the resin formula and using Eb electron beam curing, small molecule residues can be eliminated, 100% double bond conversion efficiency can be achieved, and the performance of the composite material can be greatly improved.

[0097] Comparative Examples 1-3 are composite materials prepared using electron beam curing with single resin formulations. While these materials maintain only a single property of the individual resins, such as the weather resistance of aliphatic polyurethane acrylates and the strength of epoxy acrylates, their overall performance degrades significantly after aging. Comparative Examples 4-5 are mixed resin formulations cured using conventional UV-LEDs. Because conventional UV curing requires monomer addition and has low conversion efficiency, small molecules precipitate on the composite material's surface after aging, weakening the bond between the glass fiber and the resin and causing a decline in overall performance.

[0098] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above and that the invention can be embodied in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as illustrative and non-restrictive, and the scope of the invention is defined by the appended claims rather than the foregoing description, and it is intended that all variations that come within the meaning and range of equivalents of the claims be embraced therein.

[0099] In addition, it should be understood that although this specification is described in terms of implementation methods, not every implementation method contains only one independent technical solution. This narrative method of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each embodiment can also be appropriately combined to form other implementation methods that can be understood by those skilled in the art.

Claims

1. An Eb electron beam cured lightweight composite resin, characterized by: By mass, it is composed of the following components: Polyurethane acrylic resin 55-75 parts; 15-35 parts of epoxy acrylic resin; 5-15 parts of acrylic resin; 0.5-3 parts of additives; The polyurethane acrylic resin is one or more of B-205, ETERCURE 6157B-80, ETERCURE 6170, CN980 NS, and FSP8060; the epoxy acrylic resin is one or more of bisphenol A epoxy acrylate, amine-modified epoxy acrylate, fatty acid-modified epoxy acrylate, and aliphatic epoxy acrylate; the acrylic resin is a multifunctional pure acrylate; and the auxiliary agent includes one or more of a defoaming agent, an ultraviolet absorber, an antioxidant, and a wetting agent.

2. The Eb electron beam-cured lightweight composite resin according to claim 1, characterized in that: The defoaming agent is one or more of TEGO 2700, TEGO 5300, BYK 1788, BYK 055, and Efka 2720.

3. The Eb electron beam cured lightweight composite resin according to claim 1, characterized in that: The ultraviolet absorber is one or more of Tinuvin 292, Tinuvin 400, Tinuvin 123, Tinuvin 234, Tinuvin 1600, Tinuvin 770, Chiguard 5431, and Chiguard 234; and the antioxidant is one or more of CHINOX 1076, CHINOX 1790, CHINOX GM, CHINOX 168, Irganox 1010, and Irganox 1098.

4. The Eb electron beam-cured lightweight composite resin according to claim 1, characterized in that: The wetting agent is one of TEGO 432, TEGO 2300, TEGO 2100, TEGO 4100, TEGO 270, TEGO 245, BYK 333, BYK378, and BYK3455.

5. Use of the Eb electron beam cured lightweight composite resin according to claim 1 in preparing a lightweight component front plate.

6. The use according to claim 5, characterized in that: The preparation steps include: The resin is evenly coated on the surface of the glass fiber cloth to obtain a prepreg composite material; the prepreg composite material is subjected to electron beam radiation curing by an Eb electron beam curing device to obtain a lightweight component front plate.