Dual-curing high-adhesive-force and high-chemical-resistance three-proofing adhesive and preparation method thereof

Abstract

The invention discloses a dual-cured three-proofing adhesive with high adhesive force and high chemical resistance and a preparation method of the dual-cured three-proofing adhesive. The dual-cured three-proofing adhesive comprises 35-45 parts of dual-cured resin, 15-25 parts of acrylic resin, 12-20 parts of a diluent, 1-5 parts of a photoinitiator, 0.1-5 parts of a defoaming agent, 0.1-3 parts of a wetting agent and 0.1-3 parts of a coupling agent. According to the three-proofing adhesive, the polyester glycol and the polybutylene chain segment are introduced into the dual-curing resin, so that the adhesive force and chemical resistance of a system are greatly improved, the problems of insufficient adhesive force and chemical resistance in the prior art are solved in cooperation with the effects of the components such as the acrylic resin and the diluent, and meanwhile, the UV and moisture dual-curing effect is met.

Description

Technical Field

[0001] The present invention relates to the technical field of photocurable materials, and particularly relates to a dual-curing three-proof glue with high adhesion and high chemical resistance and a preparation method thereof. Background Art

[0002] Three-proof glue, also known as electrical protection glue, is a protective coating designed specifically to protect electronic circuit boards and components from environmental damage. It can effectively resist the erosion of natural factors such as moisture, dust, and mildew, and improve the service life and reliability of products.

[0003] Most of the existing three-proof glues contain organic solvents and pollute the environment. With the improvement of environmental protection requirements, strict restrictions on volatile solvents have been imposed at home and abroad. Although "three-proof glues" without solvents have emerged on the market, the requirements for adhesion and chemical resistance are becoming more and more stringent. Developing a new type of environmentally friendly solvent-free high-performance "three-proof glue" to replace the current solvent-based products has become an urgent requirement in the market.

[0004] In the prior art, a low-viscosity solvent-free silicone three-proof glue is disclosed, which comprises the following raw materials in parts by weight: 90-110 parts of vinyl silicone oil, 20-50 parts of long-chain alkyl-modified vinyl silicone oil, 10-30 parts of vinyl MQ resin, 10-30 parts of hydrogen-containing silicone oil, 0.2-1 part of tackifier, 0.1-0.5 part of catalyst, and 0.01-0.1 part of inhibitor. The vinyl silicone oil is end-vinyl silicone oil, and the viscosity of the end-vinyl silicone oil is 50-200 cps. By using low-viscosity end-vinyl silicone oil to reduce the viscosity of the silicone three-proof glue, it is beneficial to evenly coat the colloid on the surface of the circuit board. The low-viscosity end-vinyl silicone oil has a low surface tension and can form a thin film on the surface of the substrate to improve the curing efficiency of the silicone rubber, but it still has problems of insufficient adhesion and chemical resistance. Summary of the Invention

[0005] In order to overcome the deficiencies of the prior art and solve the problems of insufficient adhesion and chemical resistance in the prior art, one of the purposes of the present invention is to provide a dual-curing three-proof glue with high adhesion and high chemical resistance to solve the above-mentioned traditional technical problems.

[0006] Another purpose of the present invention is to provide a preparation method of the above-mentioned dual-curing three-proof glue with high adhesion and high chemical resistance.

[0007] One of the purposes of the present invention is realized by adopting the following technical scheme:

[0008] A dual-curing three-proof glue with high adhesion and high chemical resistance, comprising the following components in parts by weight:

[0009] 35 - 45 parts of dual - curing resin, 15 - 25 parts of acrylic resin, 15 - 40 parts of diluent, 1 - 5 parts of photo - initiator, 0.1 - 5 parts of defoamer, 0.1 - 3 parts of wetting agent, 0.1 - 3 parts of coupling agent;

[0010] Among them, the preparation of the dual - curing resin includes the following steps:

[0011] S1: Mix 1 mol of IPDI (isophorone diisocyanate) and 2 mol of polyester diol, then add inhibitor and catalyst, and react at 70 - 80 °C for 1.5 h - 2 h to obtain the first reaction solution;

[0012] S2: Add 2 mol of IPDI to the first reaction solution and react for 1.5 h - 2 h to obtain the second reaction solution;

[0013] S3: Add 2 mol of hydroxyl - terminated hydrogenated polybutadiene to the second reaction solution, test the NCO content every 20 min, and stop heating when the NCO content is 11 wt% - 13 wt% to obtain the product.

[0014] In the present invention, by introducing polyester diol and polybutene segments into the dual - curing resin, the adhesion and chemical resistance of the system are greatly improved. Then, with the cooperation of components such as acrylic resin, diluent, photo - initiator, defoamer, wetting agent, coupling agent, etc., the problems of insufficient adhesion and chemical resistance in the prior art are solved, and the dual curing effects of UV and moisture are satisfied simultaneously.

[0015] In the present invention, the weight parts of the dual - curing resin can be 35 parts, 38 parts, 40 parts, 42 parts, 45 parts, etc.

[0016] The weight parts of the acrylic resin can be 15 parts, 18 parts, 20 parts, 22 parts, 25 parts, etc.

[0017] The weight parts of the diluent can be 15 parts, 18 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, etc.

[0018] The weight parts of the photo - initiator can be 1 part, 2 parts, 3 parts, 4 parts, 5 parts, etc.

[0019] The weight parts of the defoamer can be 0.1 part, 0.5 part, 0.8 part, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, etc.

[0020] The weight parts of the wetting agent can be 0.1 part, 0.5 part, 0.8 part, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, etc.

[0021] The weight parts of the coupling agent can be 0.1 part, 0.5 part, 0.8 part, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, etc.

[0022] The following are the preferred technical solutions of the present invention, but do not limit the technical solutions provided by the present invention. Through the following preferred technical solutions, the purpose and beneficial effects of the present invention can be better achieved and realized.

[0023] Further, the polyester diol is one or more of polyethylene glycol adipate, poly-1,4-butylene glycol adipate, and polycarbonate diol.

[0024] Further, the polymerization inhibitor is one or more of hydroquinone, p-methoxyphenol, 2,5-di-tert-butylhydroquinone, and 2-tert-butylhydroquinone. Among them, the addition amount of the polymerization inhibitor is 0.01 - 1 mol.

[0025] Further, the catalyst is dimethylaminoethyl methacrylate, and the addition amount of the catalyst is 0.01 - 1 mol.

[0026] Further, the preparation of the acrylic resin includes the following steps:

[0027] Mix 1 mol of IPDI and 2 mol of polyether diol, add the polymerization inhibitor and the catalyst, react at 70 - 80 °C for 1.5 h - 2 h, then add 2 mol of IPDI and react for 1.5 h - 2 h. Then, add 2 mol of HEMA (2-hydroxyethyl methacrylate) and react for 1.5 h - 2 h to obtain it.

[0028] Among them, the polyether diol is one or more of polyethylene glycol and polypropylene glycol.

[0029] The polymerization inhibitor is one or more of hydroquinone, p-methoxyphenol, 2,5-di-tert-butylhydroquinone, and 2-tert-butylhydroquinone. Among them, the addition amount of the polymerization inhibitor is 0.01 - 1 mol.

[0030] The catalyst is dimethylaminoethyl methacrylate, and the addition amount of the catalyst is 0.01 - 1 mol.

[0031] Further, the diluent is one or more of isobornyl acrylate and tetrahydrofurfuryl acrylate.

[0032] Further, the photoinitiator is one or more of photoinitiator 184 and photoinitiator TMO.

[0033] Furthermore, the defoaming agent is a mixture of one or more of BYK-333, BYK-051, BYK-066N, KSZ-169A, Silok 8244, Silok 4084, and AKN-3003.

[0034] Furthermore, the wetting agent is leveling agent BYK333; and the coupling agent is coupling agent KH570.

[0035] The second object of the present invention is achieved by adopting the following technical solution:

[0036] A method for preparing a dual-cured high-adhesion, high-chemical-resistant three-proof adhesive comprises the following steps:

[0037] Put dual-cure resin, acrylic resin, diluent, photoinitiator, defoamer, wetting agent and coupling agent into a stirring device and stir evenly to obtain the product.

[0038] Compared with the prior art, the present invention has the following beneficial effects:

[0039] The dual-cured high-adhesion, high-chemical-resistant triple-proof adhesive of the present invention introduces polyester diol and polybutene segments into the dual-cured resin to greatly improve the adhesion and chemical resistance of the system, and then cooperates with the effects of acrylic resin, diluent, photoinitiator, defoamer, wetting agent, coupling agent and other ingredients to solve the problems of insufficient adhesion and chemical resistance of the prior art, while meeting the dual curing effects of UV and moisture. DETAILED DESCRIPTION

[0040] The present invention is further described below in conjunction with specific implementation methods. It should be noted that, under the premise of no conflict, the various embodiments or technical features described below can be arbitrarily combined to form a new embodiment.

[0041] The sources of some components in the embodiments and comparative examples are as follows:

[0042] Diluent: Isobornyl acrylate was purchased from Jinan Jingyu Chemical Co., Ltd., and tetrahydrofuran acrylate was purchased from Hubei Shineng Chemical Technology Co., Ltd.;

[0043] Photoinitiator: Photoinitiator 184 was purchased from Nantong Runfeng Petrochemical Co., Ltd., and photoinitiator TMO was purchased from Binzhou Shuangfeng Chemical Co., Ltd.;

[0044] Defoaming agent: BYK-333, purchased from Yinhuang (Shanghai) Industrial Co., Ltd.

[0045] In the following examples, the preparation of the dual-cure resin comprises the following steps:

[0046] S1: 1 mol IPDI and 2 mol polyester diol are mixed, and then an inhibitor and a catalyst are added, and the mixture is reacted at 70-80° C. for 2 h to obtain a first reaction solution;

[0047] S2: Add 2 mol IPDI to the first reaction solution and react for 2 h to obtain a second reaction solution;

[0048] S3: Add 2 mol of hydroxyl hydrogenated polybutadiene to the second reaction liquid, test the NCO content every 20 minutes, and stop heating when the NCO content is 11wt%-13wt%.

[0049] Among them, IPDI: purchased from Jinan Linyan Mandy New Materials Co., Ltd.;

[0050] Polyester diol: poly 1,4-butylene glycol adipate, purchased from Wuhan Lanabai Pharmaceutical Chemical Co., Ltd.;

[0051] Catalyst: hydroquinone, purchased from Jinan Century Tongda Chemical Co., Ltd.;

[0052] Inhibitor: dimethylaminoethyl methacrylate, purchased from Jinan Kaichuang Chemical Co., Ltd.;

[0053] Hydroxylated hydrogenated polybutadiene: purchased from Jining Sunbright Biotechnology Co., Ltd.

[0054] The preparation of acrylic resin comprises the following steps:

[0055] Mix 1 mol IPDI and 2 mol polyether diol, add inhibitor and catalyst, react at 70-80°C for 2 hours, then add 2 mol IPDI, react for 2 hours, then add 2 mol HEMA, react for 2 hours to obtain the product.

[0056] Among them, IPDI: purchased from Jinan Linyan Mandy New Materials Co., Ltd.;

[0057] Polyether diol: polyethylene glycol, purchased from Hai'an Petrochemical Plant, Jiangsu Province;

[0058] Catalyst: hydroquinone, purchased from Jinan Century Tongda Chemical Co., Ltd.;

[0059] Inhibitor: dimethylaminoethyl methacrylate, purchased from Jinan Kaichuang Chemical Co., Ltd.;

[0060] The three-proof glue includes the following steps:

[0061] Put dual-cure resin, acrylic resin, diluent, photoinitiator, defoamer, wetting agent and coupling agent into a stirring device and stir evenly to obtain the product.

[0062] Example 1

[0063] A three-proof glue comprises the following components in parts by weight:

[0064] 40 parts of dual-curing resin, 20 parts of acrylic resin, 17 parts of isobornyl acrylate, 17 parts of tetrahydrofurfuryl acrylate, 2 parts of photoinitiator 184, 1 part of photoinitiator TMO, 1 part of defoamer, 1 part of wetting agent, 1 part of coupling agent.

[0065] Example 2

[0066] A three-proof glue comprises the following components in parts by weight:

[0067] 40 parts of dual-curing resin, 15 parts of acrylic resin, 17 parts of isobornyl acrylate, 17 parts of tetrahydrofurfuryl acrylate, 2 parts of photoinitiator 184, 1 part of photoinitiator TMO, 1 part of defoamer, 1 part of wetting agent, 1 part of coupling agent.

[0068] Example 3

[0069] A three-proof glue comprises the following components in parts by weight:

[0070] 40 parts of dual-curing resin, 25 parts of acrylic resin, 17 parts of isobornyl acrylate, 17 parts of tetrahydrofurfuryl acrylate, 2 parts of photoinitiator 184, 1 part of photoinitiator TMO, 1 part of defoamer, 1 part of wetting agent, 1 part of coupling agent.

[0071] Example 4

[0072] A three-proof glue comprises the following components in parts by weight:

[0073] 35 parts of dual-curing resin, 20 parts of acrylic resin, 17 parts of isobornyl acrylate, 17 parts of tetrahydrofurfuryl acrylate, 2 parts of photoinitiator 184, 1 part of photoinitiator TMO, 1 part of defoamer, 1 part of wetting agent, 1 part of coupling agent.

[0074] Example 5

[0075] A three-proof glue comprises the following components in parts by weight:

[0076] 45 parts of dual-curing resin, 20 parts of acrylic resin, 17 parts of isobornyl acrylate, 17 parts of tetrahydrofurfuryl acrylate, 2 parts of photoinitiator 184, 1 part of photoinitiator TMO, 1 part of defoamer, 1 part of wetting agent, 1 part of coupling agent.

[0077] The comparative examples are as follows:

[0078] In Comparative Example 1, the amount of the dual-curing resin was increased and the amount of the acrylic resin was decreased so that the total amount of the two was the same, i.e., 50 parts of the dual-curing resin, 10 parts of the acrylic resin, 17 parts of isobornyl acrylate, 17 parts of tetrahydrofurfuryl acrylate, 2 parts of photoinitiator 184, 1 part of photoinitiator TMO, 1 part of defoamer, 1 part of wetting agent, and 1 part of coupling agent.

[0079] The requirements for other components and the preparation method were the same as those of the components and the preparation method in Example 1.

[0080] In Comparative Example 2, the acrylic resin was not contained, but the amount of the dual-curing resin was increased so that the total amount of the two was the same, i.e., 60 parts of the dual-curing resin, 17 parts of isobornyl acrylate, 17 parts of tetrahydrofurfuryl acrylate, 2 parts of photoinitiator 184, 1 part of photoinitiator TMO, 1 part of defoamer, 1 part of wetting agent, and 1 part of coupling agent.

[0081] The requirements for other components and the preparation method were the same as those of the components and the preparation method in Example 1.

[0082] Performance Test

[0083] 1. Test objects: Examples 1-5 and Comparative Examples 1-2.

[0084] 2. In the detection, for viscosity test: a cone-plate viscometer was used, the 1# rotor was used, and the test was carried out three times at 60 rpm and the average value was obtained; for adhesion test: the 3M tape cross-cut test was used; for surface drying: the needle-pricking method was used; for salt spray resistance: the test was carried out in accordance with GB / T 10125-2021.

[0085] 3. The test results are shown in Table 1 below.

[0086] Table 1

[0087] Project Surface Drying Moisture Curing Time (H) Adhesion Viscosity (cps) Salt Spray Resistance (H) Example 1 Excellent 5B 48 160 678 Example 2 Excellent 5B 41 158 654 Example 3 Excellent 5B 50 165 664 Example 4 Excellent 5B 45 152 615 Example 5 Excellent 5B 53 168 688 Comparative Example 1 Excellent 5B 48 180 672 Comparative Example 2 Poor 4B 64 220 336

[0088] The above-mentioned embodiments are only the preferred embodiments of the present invention, and the scope of protection of the present invention cannot be limited thereby. Any non-substantial changes and substitutions made by those skilled in the art based on the present invention fall within the scope of protection required by the present invention.

Claims

1. A dual-cured high-adhesion, high-chemical-resistant three-proof adhesive, characterized in that: The composition comprises the following components in parts by weight: Dual-curing resin 35-45 parts, acrylic resin 15-25 parts, diluent 15-40 parts, photoinitiator 1-5 parts, defoamer 0.1-5 parts, wetting agent 0.1-3 parts, coupling agent 0.1-3 parts; The preparation of the dual-curing resin includes the following steps: S1: 1 mol IPDI and 2 mol polyester diol are mixed, and then an inhibitor and a catalyst are added, and the mixture is reacted at 70-80° C. for 1.5 h-2 h to obtain a first reaction solution; S2: Add 2 mol IPDI to the first reaction solution and react for 1.5 h-2 h to obtain a second reaction solution; S3: Add 2 mol of hydroxyl hydrogenated polybutadiene to the second reaction liquid, test the NCO content every 20 minutes, and stop heating when the NCO content is 11wt%-13wt%.

2. The dual-cured high-adhesion, high-chemical-resistant conformal adhesive according to claim 1, characterized in that: The polyester diol is one or more of polyethylene glycol adipate, poly 1,4-butylene glycol adipate, and polycarbonate diol.

3. The dual-cured high-adhesion, high-chemical-resistant conformal adhesive according to claim 1, characterized in that: The polymerization inhibitor is one or more of hydroquinone, p-hydroxyanisole, 2,5-di-tert-butylhydroquinone, and 2-tert-butylhydroquinone; and the catalyst is dimethylaminoethyl methacrylate.

4. The dual-cured high-adhesion, high-chemical-resistant conformal adhesive according to claim 1, characterized in that: The preparation of the acrylic resin comprises the following steps: Mix 1 mol IPDI and 2 mol polyether diol, add inhibitor and catalyst, react at 70-80°C for 1.5h-2h, then add 2 mol IPDI, react for 1.5h-2h, then add 2 mol HEMA, react for 1.5h-2h to obtain the product.

5. The dual-cured high-adhesion, high-chemical-resistant conformal adhesive according to claim 4, characterized in that: The polyether diol is one or more of polyethylene glycol and polypropylene glycol.

6. The dual-cured high-adhesion, high-chemical-resistant conformal adhesive according to claim 1, characterized in that: The diluent is one or more of isobornyl acrylate and tetrahydrofuran acrylate.

7. The dual-cured high-adhesion, high-chemical-resistant conformal adhesive according to claim 1, characterized in that: The photoinitiator is one or more of photoinitiator 184 and photoinitiator TMO.

8. The dual-cured high-adhesion, high-chemical-resistant conformal adhesive according to claim 1, characterized in that: The defoamer is a mixture of one or more of BYK-333, BYK-051, BYK-066N, KSZ-169A, Silok8244, Silok 4084 and AKN-3003.

9. The dual-cured high-adhesion, high-chemical-resistant conformal adhesive according to claim 1, characterized in that: The wetting agent is leveling agent BYK333; the coupling agent is coupling agent KH570.

10. A method for preparing a dual-cured high-adhesion, high-chemical-resistant conformal adhesive as claimed in any one of claims 1 to 9, characterized in that: The steps include: Put dual-cure resin, acrylic resin, diluent, photoinitiator, defoamer, wetting agent and coupling agent into a stirring device, stir evenly to obtain the product.