Eb electron beam curing light composite resin and application thereof

Abstract

The invention relates to Eb electron beam curing light composite resin and application thereof. The Eb electron beam curing light composite resin comprises polyurethane acrylic resin, epoxy acrylic resin, acrylic resin and auxiliaries. Different acrylic resins are selected to be mixed, Eb electron beam curing is adopted, the double bond conversion efficiency of 100% is achieved, no small molecule residues exist, and various properties of the resin are perfectly achieved. The prepared composite material is excellent in various properties and has a good application prospect.

Description

Technical Field

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

[0002] At present, large industrial buildings with lightweight insulating roof structures pose challenges to traditional glass crystalline silicon photovoltaic (PV) systems due to insufficient load-bearing capacity. In the field of BIPV (building-integrated photovoltaics), the hidden danger of overweight components caused by double-sided glass has not been solved. Similarly, the share of electric vehicles (EVs) in the entire automotive market has been continuously rising. At present, VIPV (vehicle-integrated photovoltaics) allows electric vehicles to be charged during the day and off-grid periods; therefore, the generated electricity can be used to extend the driving range of electric vehicles and reduce the number of charging stations. However, most VIPV products are for panoramic photovoltaic roofs, with glass as the front panel material, and the mass exceeds 15 kg / m 2 . In this case, the glass-glass structure front panel is not suitable in this regard because the extensive use of glass will significantly increase the weight of the vehicle and pose safety problems.

[0003] Currently, there are already many front panel materials developed for lightweight components on the market. Chinese Patent CN115466565A prepared a front panel for encapsulating lightweight components by selecting polyurethane acrylate resin, monomers, initiators, and curing agents, coating the resin on the surface of fiberglass cloth, and using a two-step method of photocuring + thermal curing. Because polyurethane acrylate resin is introduced, the encapsulating front panel has excellent weather resistance and ultraviolet resistance, but its heat resistance is average. Moreover, the refractive index of the polyurethane acrylate resin system is generally below 1.47, while the refractive index of conventional electronic-grade fiberglass products is about 1.55. The mismatch in refractive indices between the two will result in a high haze, reduced light transmittance, and a risk of delamination after aging. If products made of low-dielectric fiberglass are selected, although the refractive index can match that of the resin, the light transmittance and haze will be improved to some extent, but the price is high and the strength of low-dielectric fiberglass products is poor, which will also affect subsequent use. Chinese Patent CN118048016B prepared a prepreg for a lightweight front panel by selecting epoxy resin and corresponding curing agents in the form of prepreg for curing. Due to the introduction of epoxy resin, this formulation has good heat resistance and mechanical strength. However, due to the benzene ring in pure epoxy resin, its thickness resistance and maximum light transmittance are limited, 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 formulation, high weather resistance, high heat resistance, and high hardness are achieved, and 100% double bond conversion efficiency is realized by using Eb electron beam curing, perfectly exerting the performance of the resin formulation and achieving excellent performance.

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

[0006] 55 - 75 parts of polyurethane acrylate resin;

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

[0008] 5 - 15 parts of acrylate resin;

[0009] 0.5 - 3 parts of additives; Among them, the additives include 0.1 - 0.2 wt% of defoamer, 1 - 1.5 wt% of ultraviolet absorber, 0.2 - 0.5 wt% of antioxidant and 0.2 - 0.3 wt% of wetting agent.

[0010] Preferably, the polyurethane acrylate resin is one or more of bifunctional aliphatic polyurethane acrylate resin, trifunctional aliphatic polyurethane acrylate resin, and polyfunctional polyurethane acrylate resin.

[0011] 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.

[0012] Preferably, the acrylate resin is one of bifunctional pure acrylate or polyfunctional pure acrylate.

[0013] Preferably, the defoamer is one or more of TEGO 2700, TEGO 5300, BYK 1788, BYK 055, Efka 2720.

[0014] Preferably, the ultraviolet absorber is one or more of Tinuvin 292, Tinuvin 400, Tinuvin 123, Tinuvin234, Tinuvin 1600 Tinuvin 770, Chiguard 5431, Chiguard 234.

[0015] Preferably, the antioxidant is one or more of CHINOX 1076, CHINOX 1790, CHINOX GM, CHINOX 168, Irganox 1010, Irganox 1098.

[0016] 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.

[0017] The present invention also provides an application of an Eb electron beam cured lightweight composite resin in preparing a lightweight component front plate.

[0018] Furthermore, the preparation steps include:

[0019] The resin is uniformly 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.

[0020] Preferably, the glass fiber cloth is one or more of EW100, EW160, EW200, EW300, EW400, EW500, EW600, EW700, EW800, EW900, and EW1000.

[0021] Preferably, the electron accelerator energy used in the electron beam radiation curing is 200-500 keV.

[0022] Beneficial Effects

[0023] The present invention selects polyurethane acrylic resin (high weather resistance / high toughness), high strength / high thermal stability epoxy acrylic resin (high strength / high thermal stability), and acrylate (yellowing resistance) to achieve 100% double bond conversion efficiency, narrower molecular weight distribution, higher molecular weight and cross-linking density in the absence of monomers and initiators through Eb electron beam curing, overcoming the problems of low conversion efficiency of traditional UV curing, low molecular weight and cross-linking degree affecting aging performance. The prepared lightweight component front plate has no small molecule residues such as monomers, initiators, and various additives, has excellent weather resistance, and has good application prospects. DETAILED DESCRIPTION

[0024] The present invention will be further described below in conjunction with specific embodiments. It should be understood that these embodiments are only used to illustrate the present invention and are not intended to limit the scope of the present invention. In addition, it 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 within the scope limited by the appended claims of the application equally.

[0025] Example 1

[0026] The resin formula in this embodiment is based on weight parts, 55 parts of polyurethane acrylic resin, 35 parts of epoxy acrylic resin, 8 parts of acrylic resin, and 2 parts of auxiliary agent.

[0027] The polyurethane acrylate resin is B-205; the epoxy acrylate resin is ETERCURE 621-100; the acrylate resin is ETERCURE 65350; the additives are 0.2 wt% defoamer BYK 055, 1 wt% ultraviolet absorber Tinuvin 400, 0.5 wt% antioxidant CHINOX 1076, and 0.3 wt% wetting agent TEGO 270.

[0028] The resin was uniformly coated on the surface of the fiberglass cloth to obtain a prepreg composite; the prepreg composite was subjected to electron beam radiation curing through an Eb electron beam curing device to obtain a front panel of a lightweight component. Among them, the fiberglass cloth was EW100 and the energy of the electron accelerator was 200 keV.

[0029] Example 2

[0030] Except that the proportion of the polyurethane acrylate resin in Example 1 was adjusted to 65 parts and the epoxy acrylate resin was 25 parts, the rest was the same as in Example 1.

[0031] Example 3

[0032] Except that the proportion of the polyurethane acrylate resin in Example 1 was adjusted to 75 parts and the epoxy acrylate resin was 15 parts, the rest was the same as in Example 1.

[0033] Example 4

[0034] Except that the epoxy acrylate resin in Example 1 was 30 parts and the acrylate resin was 13 parts, the rest was the same as in Example 1.

[0035] Example 5

[0036] Except that the epoxy acrylate resin in Example 1 was 28 w parts and the pure acrylate resin was 15 parts, the rest was the same as in Example 1.

[0037] Example 6

[0038] Except that the polyurethane acrylate resin B-205 in Example 1 was replaced with ETERCURE 6157B-80, the rest was the same as in Example 1.

[0039] Example 7

[0040] Except that the polyurethane acrylate resin B-205 in Example 1 was replaced with ETERCURE 6157B-80 and ETERCURE 6170 in a mass ratio of 3:1, the rest was the same as in Example 1.

[0041] Example 8

[0042] Except that the polyurethane acrylate resin B-205 in Example 1 was replaced with CN980 NS, the rest was the same as in Example 1.

[0043] Example 9

[0044] Except that the polyurethane acrylate resin B-205 in Example 1 was replaced with FSP 8060, the rest was the same as in Example 1.

[0045] Example 10

[0046] Except that the epoxy acrylate resin ETERCURE 621-100 in Example 1 was replaced with EB 600, the rest was the same as in Example 1.

[0047] Example 11

[0048] Except that the epoxy acrylate resin ETERCURE 621-100 in Example 1 was replaced with CN104 NS, the rest was the same as in Example 1.

[0049] Example 12

[0050] Except that the epoxy acrylate resin ETERCURE 621-100 in Example 1 was replaced with CN 118, the rest was the same as in Example 1.

[0051] Example 13

[0052] Except that the epoxy acrylate resin ETERCURE 621-100 in Example 1 was replaced with SD 7209, the rest was the same as in Example 1.

[0053] Example 14

[0054] Except that the acrylate resin ETERCURE 65350 in Example 1 was replaced with ETERCURE DR-A819, the rest was the same as in Example 1.

[0055] Example 15

[0056] Except that the acrylate resin ETERCURE 65350 in Example 1 was replaced with GU 2600K, the rest was the same as in Example 1.

[0057] Example 16

[0058] Except that the acrylate resin ETERCURE 65350 in Example 1 was replaced with SA 345, the rest was the same as in Example 1.

[0059] Example 17

[0060] Except that the additives in Example 1 were replaced with 0.2 wt% defoamer BYK 1788, 1 wt% ultraviolet absorber Tinuvin 1600, 0.5 wt% antioxidant CHINOX 168, and 0.3 wt% wetting agent TEGO 4100, the rest was the same as in Example 1.

[0061] Example 18

[0062] Except that the additives in Example 1 were replaced with 0.1 wt% defoamer TEGO 2700, 1.5 wt% ultraviolet absorber Chiguard 5431, 0.2 wt% antioxidant CHINOX GM, and 0.2 wt% wetting agent TEGO 270, the rest was the same as in Example 1.

[0063] Example 19

[0064] Except that the fiberglass cloth in Example 1 was replaced with EW200, the rest was the same as in Example 1.

[0065] Example 20

[0066] Except that the fiberglass cloth in Example 1 was replaced with EW500, the rest was the same as in Example 1.

[0067] Example 21

[0068] Except that the energy of the electron accelerator in Example 1 was adjusted to 350 keV, the rest was the same as in Example 1.

[0069] Example 22

[0070] Except that the energy of the electron accelerator in Example 1 was adjusted to 500 keV, the rest was the same as in Example 1.

[0071] Comparative Example 1

[0072] The resin formulation was polyurethane acrylate resin B-205 (100 wt%), the fiberglass cloth was EW100, the energy of the electron accelerator was 200 keV, and the rest was the same as in Example 1.

[0073] Comparative Example 2

[0074] The resin formulation was epoxy acrylate resin ETERCURE 621-100 (100 wt%), the fiberglass cloth was EW100, the energy of the electron accelerator was 200 keV, and the rest was the same as in Example 1.

[0075] Comparative Example 3

[0076] The resin formulation is acrylic resin ETERCURE 65350 (100 wt%), the fiberglass cloth is EW100, the energy of the electron accelerator is 200 keV, and the rest is the same as in Example 1.

[0077] Comparative Example 4

[0078] In this comparative example, the resin formulation is by weight parts: 41 parts of polyurethane acrylate resin, 25 parts of epoxy acrylate resin, 5 parts of acrylic resin, 25 parts of isobornyl methacrylate, 2 parts of additives, and 2 parts of initiator TPO.

[0079] The polyurethane acrylate resin is B-205; the epoxy acrylate resin is ETERCURE 621-100; the acrylic resin is ETERCURE 65350; the additives are 0.2 wt% defoamer BYK 055, 1 wt% ultraviolet absorber Tinuvin 400, 0.5 wt% antioxidant CHINOX 1076, and 0.3 wt% wetting agent TEGO 270.

[0080] The resin was uniformly coated on the surface of the fiberglass cloth to obtain a prepreg composite; the prepreg composite was cured to obtain the front panel of the lightweight component. Among them, the fiberglass cloth is EW100, and the curing method is selected as a light curing device with a wavelength of UV-LED and 365 nm for curing.

[0081] Comparative Example 5

[0082] In this comparative example, the resin formulation is by weight parts: 70 parts of polyurethane acrylate resin, 26 parts of isobornyl methacrylate, 2 parts of additives, and 2 parts of initiator TPO.

[0083] The polyurethane acrylate resin is B-205; the additives are 0.2 wt% defoamer BYK 055, 1 wt% ultraviolet absorber Tinuvin 400, 0.5 wt% antioxidant CHINOX 1076, and 0.3 wt% wetting agent TEGO 270.

[0084] The resin was uniformly coated on the surface of the fiberglass cloth to obtain a prepreg composite; the prepreg composite was cured to obtain the front panel of the lightweight component. Among them, the fiberglass cloth is EW100, and the curing method is selected as a light curing device with a wavelength of UV-LED and 365 nm for curing.

[0085] The performance test methods for the lightweight composites of the examples and comparative examples are as follows:

[0086] Visible light transmittance: GB / T2410-2008;

[0087] Abrasion resistance: ASTM D968;

[0088] Coating adhesion: ISO 2409;

[0089] Yellowing value: GB / T 39822-2021;

[0090] Heat resistance: 165°C, 4h;

[0091] Tensile strength: ASTM3039;

[0092] DH test and UV aging test: IEC 61215-2-2021, where the DH test is the number of hours of aging test under the conditions of 85°C and 85% ambient humidity.

[0093] Table 1 Test results of the front panel of the lightweight component

[0094] Serial number Initial light transmittance of composite material / % Tensile strength Wear resistance / Coating adhesion (0 - 5 levels) Light transmittance / % and yellowing / △Yi after DH3000 Tensile strength after DH3000 Wear resistance / Coating adhesion after DH3000 Light transmittance / % and yellowing / △Yi after 300Kwh of UV aging Wear resistance / Coating adhesion after 300Kwh of UV aging Tensile strength after 300Kwh of UV aging Light transmittance / % and yellowing / △Yi after heat resistance Wear resistance / Coating adhesion after heat resistance 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

[0095] As can be seen from the above table, the front panels of the lightweight components prepared in Examples 1-22 have excellent performance, and all performances remain stable after severe damp heat aging, wet UV aging, and heat resistance tests, indicating that by regulating the resin formula and through Eb electron beam curing, small molecule residues can be eliminated, achieving 100% double bond conversion efficiency and greatly improving the performance of the composite material.

[0096] Comparative Examples 1-3 are composite materials prepared by electron beam curing with a single resin formula, which can only maintain a certain performance of a single resin, such as the weather resistance of aliphatic polyurethane acrylate and the strength of epoxy acrylate, but the overall performance decays greatly after aging. Comparative Examples 4-5 are mixed resin formulas cured by conventional UV-LED. Because conventional UV curing requires the addition of monomers and has a low conversion efficiency, small molecule substances precipitate on the surface of the composite material after aging, the bonding force between the glass fiber and the resin becomes poor, and various performances decline.

[0097] For those skilled in the art, it is obvious that the present invention is not limited to the details of the above exemplary embodiments, and the present invention can be implemented in other specific forms without departing from the spirit or basic characteristics of the present invention. Therefore, from any point of view, the embodiments should be regarded as exemplary and non-limiting. The scope of the present invention is defined by the appended claims rather than the above description. Therefore, all changes falling within the meaning and scope of the equivalent elements of the claims are intended to be included in the present invention.

[0098] In addition, it should be understood that although this specification is described according to embodiments, not every embodiment only contains an independent technical solution. This narrative way of the specification is only for clarity. Those skilled in the art should regard the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

Claims

1. An Eb electron beam cured lightweight composite resin, characterized in that: By mass parts, it includes the following components: 55 - 75 parts of polyurethane acrylate resin; 15 - 35 parts of epoxy acrylate resin; 5 - 15 parts of acrylate resin; 0.5 - 3 parts of additives; Among them, the additives include 0.1 - 0.2 wt% of defoamer, 1 - 1.5 wt% of ultraviolet absorber, 0.2 - 0.5 wt% of antioxidant, and 0.2 - 0.3 wt% of wetting agent.

2. The Eb electron beam cured lightweight composite resin according to claim 1, characterized in that: The polyurethane acrylate resin is one or several of bifunctional aliphatic polyurethane acrylate resin, trifunctional aliphatic polyurethane acrylate resin, and polyfunctional polyurethane acrylate resin.

3. The Eb electron beam cured lightweight composite resin according to claim 1, characterized in that: The epoxy acrylate resin is one or several of bisphenol A epoxy acrylate, amine - modified epoxy acrylate, fatty acid - modified epoxy acrylate, and aliphatic epoxy acrylate.

4. The Eb electron beam cured lightweight composite resin according to claim 1, characterized in that: The acrylate resin is one of bifunctional pure acrylate or polyfunctional pure acrylate.

5. The Eb electron beam cured lightweight composite resin according to claim 1, characterized in that: The defoamer is one or several of TEGO 2700, TEGO 5300, BYK 1788, BYK 055, Efka 2720.

6. The Eb electron beam cured lightweight composite resin according to claim 1, characterized in that: The ultraviolet absorber is one or several of Tinuvin 292, Tinuvin 400, Tinuvin 123, Tinuvin 234, Tinuvin 1600, Tinuvin 770, Chiguard 5431, Chiguard 234; the antioxidant is one or several of CHINOX 1076, CHINOX1790, CHINOX GM, CHINOX 168, Irganox 1010, Irganox 1098.

7. 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, BYK3455.

8. Application of an Eb electron beam cured lightweight composite resin as claimed in claim 1 in the preparation of a front panel of a lightweight component.

9. The application according to claim 8, characterized in that: The preparation steps include: Uniformly coat the resin on the surface of the fiberglass cloth to obtain a prepreg composite material; irradiate and cure the prepreg composite material through an Eb electron beam curing device to obtain the front panel of the lightweight component.