High-toughness photocurable coating

Abstract

The present invention provides a high-toughness photocurable coating, which comprises the following components in parts by weight: 60-85 parts of an acrylate monomer; 8-25 parts of a polyurethane acrylate resin; 2-8 parts of a compound A; 1-5 parts of a photo-initiator; 0.1-0.8 parts of a wetting agent; 0.1-0.8 parts of a defoaming agent; and 0.5-2 parts of a pigment. The requirements of a battery for an adhesive property, the resistance to bending and cracking and the adhesive force can be satisfied.

Description

High-toughness photocuring coating

[0001] Cross-reference to related applications

[0002] The present application claims priority to Chinese Patent Application No. 202410448743.9, filed on April 15, 2024, the contents of which are incorporated herein by reference. TECHNICAL FIELD

[0003] The present application belongs to the technical field of new energy automobile batteries, in particular to battery insulation materials, and specifically to high-toughness photocuring coating. BACKGROUND

[0004] New energy vehicles use unconventional vehicle fuels as power sources, and have made unprecedented breakthroughs in terms of types, technology, and market share. New energy vehicles that use non-petroleum fuels usually use batteries as energy storage power sources.

[0005] In order to ensure good bonding performance and insulation performance of the square shell battery, some manufacturers currently use photocuring coating solutions. Compared with other photocuring coatings, the photocuring coating of the present application has better bonding performance, bending cracking resistance, and adhesion on the basis of ensuring excellent insulation performance.

[0006] SUMMARY

[0007] The purpose of the present application is to overcome at least one of the disadvantages of the prior art, and to provide a photocuring coating that meets the bonding performance requirements of batteries.

[0008] To solve the above technical problems, the present application provides a high-toughness photocuring coating, which comprises the following components by weight:

[0009] The preparation method of the compound A comprises the following steps:

[0010] (1) Compound B is added to toluene, and after azeotropic dehydration under nitrogen, it is cooled to 80-100°C, chloroplatinic acid is added, and a mixture of compound C and toluene is added dropwise, and stirred to obtain compound D; the azeotropic dehydration time is 1-3 hours, preferably 2 hours, the cooling temperature is preferably 90°C, the dropwise addition time of compound C is preferably controlled to be 2 hours; the stirring reaction temperature is 100-110°C, preferably 105°C, and the stirring reaction time is 5-7 hours, preferably 6 hours;

[0011] The structural formula of compound B is: The structural formula of compound C is: The structural formula of compound D is: wherein n = 10-30;

[0012] (2) adding compound D into toluene, adding concentrated sulfuric acid, increasing temperature and adding acrylic acid, after the reaction, increasing temperature to 110-130°C, preferably 120°C, increasing temperature to 120°C for 10 minutes; acrylic acid dropping time is controlled in 1-3 hours, preferably 2 hours; using cooling reflux device to collect water produced in the reaction, continuing to react until no water is produced after the completion of acrylic acid dropping, which is considered as the end of this reaction; obtaining intermediate E, decreasing temperature to 100-120°C, preferably 110°C, continuing to add mixture of dibenzoyl peroxide, vinyl phosphonic acid and toluene into the reaction solution, adding time is controlled in 1-3 hours, preferably 2 hours, continuing to react at 110°C for 1 hour, distilling toluene under reduced pressure to obtain the compound A;

[0013] The structural formula of intermediate E is: wherein n=10-30.

[0014] Preferably, the polyurethane acrylic resin is selected from one or both of aliphatic polyurethane acrylate resin and aromatic polyurethane acrylate resin, the resin viscosity is 10000-80000 cps@60°C, the elongation is 20-150%, and the functionality is 2-6. Preferably, the aliphatic polyurethane acrylate resin has a viscosity of 20000-60000 cps@60°C, an elongation of 20-50%, and a functionality of 2.

[0015] Preferably, the acrylate monomer comprises 5-20 parts of a first acrylate monomer, 10-40 parts of a second acrylate monomer, 10-40 parts of a third acrylate monomer, 3-20 parts of a fourth acrylate monomer, and 3-10 parts of a fifth acrylate monomer.

[0016] The first acrylate monomer is selected from one or both of tricyclodecane dimethanol diacrylate (TCDDA) and ethoxylated trimethylolpropane trimethacrylate (TMP9EOTMA), preferably tricyclodecane dimethanol diacrylate (TCDDA).

[0017] The second acrylate monomer is selected from one or both of dicyclopentadiene acrylate (DCPA), cyclotrimethylolpropane formal acrylate (DTFA), isobornyl methacrylate (IBOMA) and isobornyl acrylate (IBOA), preferably dicyclopentadiene acrylate (DCPA).

[0018] The third acrylate monomer is selected from one or two of dicyclopentenyl ethoxylate acrylate (DCPEA), dicyclopentenyl ethoxylate methacrylate (DCPEA), and dicyclopentanemethacrylate (HDCPMA), preferably dicyclopentenyl ethoxylate acrylate (DCPEA);

[0019] The fourth acrylate monomer is selected from one or two of lauryl acrylate (LA), stearyl acrylate (SA), octadecyl to docosyl acrylate (BEA), lauryl methacrylate (LMA), and 2-ethylhexyl methacrylate, preferably lauryl acrylate (LA);

[0020] The fifth acrylate monomer is selected from one or two of 1,6-hexanediol diacrylate (HDDA), ethoxylated 1,6-hexanediol diacrylate (HD2EODA), dipropylene glycol diacrylate (DPGDA), tripropylene glycol diacrylate (TPGDA), neopentyl glycol diacrylate (NPGDA), propoxylated neopentyl glycol diacrylate (NPG2PODA), ethylene glycol dimethacrylate (EGDMA), triethylene glycol dimethacrylate (3EGDMA), and diethylene glycol dimethacrylate (DEGDMA).

[0021] Preferably, the acrylate monomers consist of tricyclodecanedimethanol diacrylate, dicyclopentadiene acrylate, dicyclopentenyl ethoxylate acrylate, lauryl acrylate, 1,6-hexanediol diacrylate.

[0022] Preferably, the photoinitiator is selected from an α-cleavage radical photoinitiator or a hydrogen abstraction radical photoinitiator. Among them, the α-cleavage radical photoinitiator (Type I) is one or two of benzoin derivatives, benzil ketals, α-α dialkoxyacetophenone, α-hydroxyalkyl phenone, α-aminoalkyl phenone, and acylphosphine oxide. Preferably, the photoinitiator is selected from acylphosphine oxide.

[0023] Preferably, the wetting agent is a silicone-based wetting agent, and the defoaming agent is a silicone-free defoaming polymer mixture.

[0024] Preferably, the pigment is ink blue. BRIEF DESCRIPTION OF DRAWINGS

[0025] Figure 1 is the H-NMR spectrum of compound A.

[0026] Figure 2 is the H-NMR spectrum of compound D.

[0027] Figure 3 is the H-NMR spectrum of compound E. DETAILED DESCRIPTION

[0028] In order to make the technical means, creative features, purposes and effects of the present application easy to understand, the present application is further described below in combination with specific examples.

[0029] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs, and the materials referred to in this disclosure are incorporated by reference.

[0030] The experimental methods in the following examples are all conventional methods unless otherwise specified. The instruments and equipment used in the following examples are all conventional laboratory instruments and equipment unless otherwise specified. The test materials used in the following examples are all commercially available from conventional biochemical reagent stores unless otherwise specified.

[0031] The photocurable coating of the present application uses a compound A having a polyunsaturated double bond and a polyphosphonic acid group. The polyunsaturated double bond of the compound A enables the compound A to effectively participate in the photocuring reaction, and after photocuring, the compound A and the main body are completely reacted and effectively combined together. The polyphosphonic acid group of the compound A can be completely reacted with the metal substrate to ensure good shear strength, and the polysiloxane structure of the compound A can realize spatial rotation. Compared with the known silane coupling agent such as vinyl silane and the vinyl organic acid such as vinyl phosphonic acid, the photocurable coating has excellent toughness, thereby achieving excellent bending resistance.

[0032] The photocurable coating of the present application significantly improves the bending resistance under the premise of meeting the shear strength and adhesion performance.

[0033] Example 1

[0034] Preparation of compound A

[0035] (1) Preparation of compound D

[0036] A compound B (commercial product, magnolol) 100 g with the structural formula was added to 400 g of toluene, and was subjected to azeotropic dehydration under nitrogen for 2 hours, and then was cooled to 90℃, 1.0 g of chloroplatinic acid was added, and was dropped into a mixture of 107 g of a compound C (commercial product, Si-H containing dimethyl siloxane, n = 10-30) with 428 g of toluene, and then was stirred at 105℃ for 6 hours to obtain a compound D (n = 10-30) with the structural formula The hydrogen spectrum of the compound D is shown in FIG. 3.

[0037] (2) Preparation of compound A

[0038] ​0.2 mol of compound D was added in 600 g of toluene solution, 15 g of concentrated sulfuric acid was added, the temperature was slowly increased to 120°C, the stirring paddle was used to stir at 80 RPM, the temperature was increased to 120°C for 10 minutes, and the addition of acrylic acid was started. The total amount of acrylic acid was 0.8 mol, which was slowly added dropwise over 2 hours. The water produced in the reaction was collected using a cooling reflux device. After the addition of acrylic acid was completed, the reaction was continued until no water was produced, which was considered the end of this reaction. The product was mainly intermediate E, and its hydrogen spectrum is shown in Figure 4, and the structural formula is:

[0039] After the temperature was reduced to 110°C and stabilized for 10 minutes, 15 g of dibenzoyl peroxide, 1.2 mol of vinyl phosphonic acid, and 30 g of toluene were slowly added dropwise to the solution, and the total time was controlled at 2 hours. After the addition was completed, the reaction was continued at 110°C for one hour. Toluene was distilled off under reduced pressure to obtain compound A. The H-NMR spectrum of compound A is shown in Figure 1.

[0040] Example 2:

[0041] This example 2 provides a high-toughness photocurable coating, which consists of the following components by weight parts:

[0042] Tricyclodecane dimethanol diacrylate (TCDDA) 10 parts, dicyclopentadiene acrylate (DCPA) 30 parts, dicyclopentadiene oxyethyl acrylate (DCPEA) 25 parts, lauric acid acrylate (LA) 10 parts, 1,6-hexanediol diacrylate (HDDA) 5 parts, polyurethane acrylate resin 13 parts, compound A 3 parts, phenyl bis(2,4,6-trimethylbenzoyl) phosphine oxide 1.8 parts, silicone wetting agent 1.0 part, non-silicone defoaming polymer defoamer 0.3 part, ink blue pigment 0.9 part.

[0043] The preparation process is to add polyurethane acrylic resin 15.9 parts into the stirred kettle, heat to 50°C, stir for 10 minutes, then slowly add the mixture of tricyclodecane dimethylol diacrylate (TCDDA) 10 parts, dicyclopentadiene acrylate (DCPA) 30.3 parts, dicyclopentadiene oxyethyl acrylate (DCPEA) 25 parts, compound A 3 parts and lauric acid acrylate (LA) 10 parts into the stirred kettle within 30 minutes, cool to room temperature after the addition is completed, then slowly add the mixture of 1,6-hexanediol diacrylate (HDDA) 2.5 parts, phenyl bis(2,4,6-trimethylbenzoyl) phosphine oxide 1.8 parts, silicone wetting agent 0.3 parts, non-silicone defoaming polymer defoaming agent 0.3 parts into the stirred kettle within 30 minutes, stir for 10 minutes after the addition is completed, again slowly add the mixture of 1,6-hexanediol diacrylate (HDDA) 2.5 parts and ink blue pigment 0.9 parts into the stirred kettle within 10 minutes, stir for 30 minutes after vacuuming to a vacuum degree of not less than -0.8 bar, and the coating preparation is completed. The stirring speed is controlled to be 300 rpm during the whole preparation process.

[0044] Example 3

[0045] This example 3 provides a high-toughness photocurable coating, which consists of the following components by weight parts:

[0046] Tricyclodecane dimethylol diacrylate (TCDDA) 10 parts, dicyclopentadiene acrylate (DCPA) 30 parts, dicyclopentadiene oxyethyl acrylate (DCPEA) 21 parts, lauric acid acrylate (LA) 10 parts, 1,6-hexanediol diacrylate (HDDA) 5 parts, polyurethane acrylate resin 16 parts, compound A 5 parts, phenyl bis(2,4,6-trimethylbenzoyl) phosphine oxide 1.8 parts, silicone wetting agent 0.3 parts, non-silicone defoaming polymer defoaming agent 0.3 parts, ink blue pigment 0.6 parts.

[0047] The whole preparation process is the same as example 2, and the feeding sequence is to add polyurethane acrylic resin first, then add the mixture of acrylic monomer and compound A, then add the mixture of acrylic monomer, curing agent and additive, and finally add the mixture of acrylic monomer and pigment.

[0048] Example 4

[0049] This example 4 provides a high-toughness photocurable coating, which consists of the following components by weight parts:

[0050] Tricyclodecane dimethanol diacrylate (TCDDA) 10 parts, dicyclopentadiene acrylate (DCPA) 30 parts, dicyclopentadiene oxyethyl acrylate (DCPEA) 22 parts, lauryl acrylate (LA) 10 parts, 1,6-hexanediol diacrylate (HDDA) 4 parts, polyurethane acrylate resin 13 parts, Compound A 8 parts, phenyl bis(2,4,6-trimethylbenzoyl) phosphine oxide 1.8 parts, silicone wetting agent 0.3 parts, non-silicone defoamer 0.3 parts, ink blue pigment 0.6 parts.

[0051] The entire preparation process is the same as Example 2, and the order of addition is to add the polyurethane acrylate resin first, then add the mixture of acrylate monomers and Compound A, then add the mixture of acrylate monomers, curing agent and additives, and finally add the mixture of acrylate monomers and pigments.

[0052] Comparative Example 1

[0053] Tricyclodecane dimethanol diacrylate (TCDDA) 10 parts, dicyclopentadiene acrylate (DCPA) 30 parts, dicyclopentadiene oxyethyl acrylate (DCPEA) 25 parts, LA (dodecyl acrylate) 10 parts, 1,6-hexanediol diacrylate (HDDA) 5 parts, polyurethane acrylate resin 13 parts, phenyl bis(2,4,6-trimethylbenzoyl) phosphine oxide 1.8 parts, vinyl trimethoxysilane 3 parts, silicone wetting agent 1.0 parts, non-silicone defoamer 0.3 parts, ink blue pigment 0.9 parts.

[0054] The entire preparation process is the same as Example 2, and the order of addition is to add the polyurethane acrylate resin first, then add the mixture of acrylate monomers and Compound A, then add the mixture of acrylate monomers, curing agent and additives, and finally add the mixture of acrylate monomers and pigments.

[0055] Comparative Example 2

[0056] Tricyclodecane dimethanol diacrylate (TCDDA) 10 parts, dicyclopentadiene acrylate (DCPA) 30 parts, dicyclopentadiene oxyethyl acrylate (DCPEA) 25 parts, LA (dodecyl acrylate) 10 parts, 1,6-hexanediol diacrylate (HDDA) 5 parts, polyurethane acrylate resin 13 parts, phenyl bis(2,4,6-trimethylbenzoyl) phosphine oxide 1.8 parts, vinyl trimethoxysilane 3 parts, silicone wetting agent 1.0 parts, non-silicone defoamer 0.3 parts, ink blue pigment 0.9 parts.

[0057] The entire preparation process is the same as Example 2, and the order of addition is to add the polyurethane acrylate resin first, then add the mixture of acrylate monomers and Compound A, then add the mixture of acrylate monomers, curing agent and additives, and finally add the mixture of acrylate monomers and pigments.

[0058] The high-toughness photocuring coating obtained from the embodiments 2 to 4 and the comparative examples 1 to 2 of the present application is subjected to performance test, mainly including shear strength test, adhesion test, insulation withstand voltage test, bending resistance test, and the results are shown in Table 1 below.

[0059] The specific method of shear strength test refers to the standard of GB / T 7124-2008 Adhesives - Determination of shear strength (rigid material to rigid material), and the bonding of the cured coating uses the structural adhesive with shear strength greater than 20 MPa sold in the market. The specific method of adhesion test refers to GBT9286-1998 Scratch test of paint and varnish films. The specific method of insulation withstand voltage test refers to GB / T 1408.1-2016 Electrical strength test methods for solid insulating materials; insulation resistance: DC 1500V 60s insulation resistance ≥ 500MΩ, withstand voltage: DC 6000V 60s leakage current ≤ 0.1mA. The specific method of bending resistance test is as follows: a cylindrical shaft bending tester is equipped with a φ32mm shaft rod, which is inserted into the test piece after the tester is placed, so that the coating to be tested faces away from the shaft rod and is perpendicular to the shaft rod and in contact with the shaft rod; the tester is operated at a stable speed within 1-2s to bend the test piece by 180°; the tester is restored, and the test piece is taken out to check the appearance of the coating under sufficient light. The preparation process of the sample is as follows: a laser is used to process an aluminum plate with the required size, and the roughness Rz of the aluminum plate after processing is not less than 8, then the photocuring coating is sprayed or printed on the surface of the aluminum plate, the coating thickness is 100-120 microns, and the coating is cured by using an electrodeless lamp, and the curing energy is not less than 6000mj / cm 2 .

[0060] Table 1 test results

[0061] As can be seen from the above, the photocuring coating of the present application significantly improves the shear strength, adhesion performance and bending resistance performance while meeting the insulation withstand voltage requirement.

[0062] In this specification, the present application has been described with reference to its specific embodiments. However, it is obvious that various modifications and changes can be made without departing from the spirit and scope of the present application. Therefore, the specification should be considered as illustrative rather than limiting.

Claims

1. A high-toughness photocurable coating, characterized by, By weight parts, the following components are included: The preparation method of the compound A comprises the following steps: (1) compound B is added into toluene, and then dehydrated under the condition of nitrogen, and then cooled to 80-100 DEG C, and then chloroplatinic acid is added, and then compound C and toluene are added dropwise, and then stirred to obtain compound D; wherein the compound B has the structural formula: The structural formula of compound C is: The structural formula of compound D is: Wherein n=10-30; (2) compound D is added into toluene, and then concentrated sulfuric acid is added, and then heated, and then acrylic acid is added, and then cooled to 100-120 DEG C, and then the mixture of dibenzoyl peroxide, vinyl phosphonic acid and toluene is added into the reaction solution, and then distilled under reduced pressure to obtain the compound A; The structural formula of intermediate E is: Wherein n=10-30.

2. The high-toughness photocurable coating according to claim 1, characterized in that, The polyurethane acrylic resin is selected from one or both of aliphatic polyurethane acrylate resin and aromatic polyurethane acrylate resin, and the resin viscosity is 10000-80000 cps at 60 DEG C, the elongation rate is 20-150%, and the functionality is 2-6.

3. The high-toughness photocurable coating of claim 1, wherein, The acrylic monomer comprises 5-20 parts of the first acrylic monomer, 10-40 parts of the second acrylic monomer, 10-40 parts of the third acrylic monomer, 3-20 parts of the fourth acrylic monomer and 3-10 parts of the fifth acrylic monomer. The first acrylic monomer is selected from one or both of tricyclodecane dimethanol diacrylate and ethoxylated trimethylolpropane trimethacrylate. The second acrylic monomer is selected from one or both of dicyclopentadiene acrylate, cyclotrimethylolpropane formal acrylate, isobornyl methacrylate and isobornyl acrylate. The third acrylic monomer is selected from one or both of dicyclopentenyl ethoxylate acrylate, dicyclopentenyl ethoxylate methacrylate and dicyclopentane methacrylate. The fourth acrylic monomer is selected from one or both of lauryl acrylate, stearyl acrylate, octadecyl to docosyl acrylate, lauryl methacrylate and 2-ethylhexyl methacrylate. The fifth acrylic monomer is selected from one or both of 1,6-hexanediol diacrylate, ethoxylated 1,6-hexanediol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate, propoxylated neopentyl glycol diacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate and diethylene glycol dimethacrylate.

4. The high-toughness photocurable coating of claim 1, wherein, The acrylic monomer is composed of tricyclodecane dimethanol diacrylate, dicyclopentadiene acrylate, dicyclopentenyl ethoxylate acrylate, lauryl acrylate and 1,6-hexanediol diacrylate.

5. The high-toughness photocurable coating of claim 1, wherein, The photoinitiator is selected from an α-cleavage type free radical photoinitiator or a hydrogen elimination type free radical photoinitiator.

6. The high-toughness photocurable coating of claim 1, wherein, The photoinitiator is selected from an acyl phosphine oxide type.

7. The high-toughness photocurable coating of claim 1, wherein, The wetting agent is a silicone type wetting agent, and the defoaming agent is a defoaming polymer mixture without silicone.

8. The high-toughness photocurable coating of claim 1, wherein, The pigment is ink blue.

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