A resin composition for a degradable and recyclable low-loss white copper clad laminate, its preparation, application and recycling method

Abstract

The present invention belongs to the technical field of copper clad laminates, and particularly relates to a resin composition for a degradable and recyclable low-loss white copper clad laminate, which includes a degradable curing agent; the degradable curing agent includes one or more of degradable curing agents having the following structural formula; a preparation method of the resin composition for the degradable and recyclable low-loss white copper clad laminate is also provided, which includes the following steps: taking a degradable curing agent, an alicyclic epoxy resin, a polyphenylene ether resin, a hydrocarbon resin, a filler, a fluorescent whitening agent, and mixing them uniformly with a solvent to obtain the resin composition for the degradable and recyclable low-loss white copper clad laminate. The present invention provides a recovery method for a prepreg and a copper clad laminate prepared according to the resin composition for the degradable and recyclable low-loss white copper clad laminate. Compared with other degradable curing agents, the copper clad laminate prepared by the degradable curing agent of the present invention has two advantages: 1) shortening the degradation time by at least more than half, 2) enhancing the flame retardant performance.

Description

Technical Field

[0001] The present invention belongs to the technical field of copper clad laminates, and particularly relates to a resin composition for a degradable and recyclable low-loss white copper clad laminate, its preparation, application and recycling method. Background Art

[0002] Traditional PCB boards often use thermosetting resin materials, which are the most difficult to handle and recycle due to their insolubility and infusibility. Currently, the main recycling methods for PCBs include landfilling, mechanical methods, and chemical methods. The separation efficiency of landfilling and mechanical methods is low; among them, chemical methods include heat treatment methods, solvent methods, supercritical fluid methods, etc., which generally require high temperature and high pressure conditions or strongly corrosive liquids, with high energy consumption, high risk factors, and easy to cause secondary pollution. In the context of the increasingly severe current environmental situation, for the treatment and recycling of PCB waste, a method that is green and environmentally friendly, has high separation efficiency, high recycling value, appropriate cost, and is suitable for industrialization is needed, which requires the PCB board itself to have a degradable function.

[0003] Chinese Patent (CN 106750182 A) discloses adding non-degradable curing agents to a degradable curing agent system to co-cure epoxy resin. The prepared laminates and printed circuit boards can be recycled and degraded, but the process of the used degradable curing agent is complex, and the dielectric loss (at 1 GHz) of the board is as high as 0.016. It can be seen that its dielectric loss is even greater at 10 GHz, which cannot meet the application requirements of high-frequency and high-speed copper clad laminates. There is also a technology for preparing degradable resin materials using curing agents containing disulfide bonds, but the degradation efficiency is still at a relatively low level.

[0004] Currently, for white copper clad laminates and their PCB boards used for encapsulating light-emitting diodes (LEDs), alicyclic epoxy resins are the mainstream resin system. However, the laminated boards of this system have high heat resistance and excellent acid and alkali corrosion resistance, making the recycling of such waste boards more difficult and the degradation conditions more demanding. However, none of the above-mentioned curing agent application technologies are applied to alicyclic epoxy resins. With the high-frequency and high-speed development of 5G signal transmission and the high integration of electronic products driving the rapid development of the copper clad laminate industry, for low-dielectric-loss white resin compositions and their copper clad laminates, there is an urgent need to develop a curing agent that is more easily degradable and recyclable and can be applied to alicyclic epoxy resins to meet higher terminal application requirements. Summary of the Invention

[0005] In order to solve the above technical problems, the present invention provides the following technical solutions:

[0006] The present invention provides a resin composition for a degradable and recyclable low-loss white copper clad laminate, comprising a degradable curing agent; the degradable curing agent comprises one or more of the degradable curing agents having the following structural formulas:

[0007] Among them, R1 includes one of a hydrogen atom, an alkyl group, a cycloalkyl group, a heterocyclic group, a heterocycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aromatic group, a heteroaromatic group, a hydrocarbonoxyalkyl group, a hydrocarbonoxycycloalkyl group, a hydrocarbonoxyheterocyclic group, a hydrocarbonoxyheterocycloalkyl group, a hydrocarbonoxyalkenyl group, a hydrocarbonoxycycloalkenyl group, a hydrocarbonoxyaromatic group, a hydrocarbonoxyheteroaromatic group, a cycloalkanediyl-oxyalkyl group, a cycloalkanediyl-oxycycloalkyl group, a cycloalkanediyl-oxyheterocyclic group, a cycloalkanediyl-oxyheterocycloalkyl group, a cycloalkanediyl-oxyalkenyl group, a cycloalkanediyl-oxycycloalkenyl group, a cycloalkanediyl-oxyaromatic group, a cycloalkanediyl-oxyheteroaromatic group, a heterocycloalkanediyl-oxyalkyl group, a heterocycloalkanediyl-oxycycloalkyl group, a heterocycloalkanediyl-oxyheterocyclic group, a heterocycloalkanediyl-oxyheterocycloalkyl group, a heterocycloalkanediyl-oxyalkenyl group, a heterocycloalkanediyl-oxycycloalkenyl group, a heterocycloalkanediyl-oxyaromatic group, a heterocycloalkanediyl-oxyheteroaromatic group, an aromaticdiyl-oxyalkyl group, an aromaticdiyl-oxycycloalkyl group, an aromaticdiyl-oxyheterocyclic group, an aromaticdiyl-oxyheterocycloalkyl group, an aromaticdiyl-oxyalkenyl group, an aromaticdiyl-oxycycloalkenyl group, an aromaticdiyl-oxyaromatic group, an aromaticdiyl-oxyheteroaromatic group.

[0008] Furthermore, in the said structural formula, R2, R3, R4, R5, R6, and R7 are each independently selected from: including an alkylene group, an alkylene-heteroalkylene group, an alkenylene group, an alkenylene-heteroalkenylene group, an alkylene-heteroalkenylene group, an alkynylene group, a cycloalkanediyl group, an alkylene-cycloalkanediyl group, an alkylene-cycloalkanediyl-alkylene group, an alkenylene-cycloalkanediyl group, an alkenylene-cycloalkanediyl-alkenylene group, an alkylene-cycloalkanediyl-alkenylene group, an alkynylene-cycloalkanediyl group, an alkynylene-cycloalkanediyl-alkynylene group, a heterocycloalkanediyl group, an alkylene-heterocycloalkanediyl group, an alkylene-heterocycloalkanediyl-alkylene group, an alkenylene-heterocycloalkanediyl group, an alkenylene-heterocycloalkanediyl-alkenylene group, an alkylene-heterocycloalkanediyl-alkenylene group, an alkynylene-heterocycloalkanediyl group, an alkynylene-heterocycloalkanediyl-alkynylene group, a cycloalkenediyl group, an alkylene-cyclalkenediyl group, an alkylene-cyclalkenediyl-alkylene group, an alkenylene-cyclalkenediyl group, an alkenylene-cyclalkenediyl-alkenylene group, an alkylene-cyclalkenediyl-alkenylene group, an alkynylene-cyclalkenediyl group, an alkynylene-cyclalkenediyl-alkynylene group, a heterocyclalkenediyl group, an alkylene-heterocyclalkenediyl group, an alkylene-heterocyclalkenediyl-alkylene group, an alkenylene-heterocyclalkenediyl group, an alkenylene-heterocyclalkenediyl-alkenylene group, an alkylene-heterocyclalkenediyl-alkenylene group, an alkynylene-heterocyclalkenediyl group, an alkynylene-heterocyclalkenediyl-alkynylene group, an aromaticdiyl group, an alkylene-aromaticdiyl group, an alkylene-aromaticdiyl-alkylene group, an alkenylene-aromaticdiyl group, an alkenylene-aromaticdiyl-alkenylene group, an alkylene-aromaticdiyl-alkenylene group, an alkynylene-aromaticdiyl group, an alkynylene-aromaticdiyl-alkynylene group, a heteroaromaticdiyl group, an alkylene-heteroaromaticdiyl group, an alkylene-heteroaromaticdiyl-alkylene group, an alkenylene-heteroaromaticdiyl group, an alkenylene-heteroaromaticdiyl-alkenylene group, an alkylene-heteroaromaticdiyl-alkenylene group, an alkynylene-heteroaromaticdiyl group, an alkynylene-heteroaromaticdiyl-alkynylene group.

[0009] Furthermore, in the said structural formula, R2, R3, R4, R5, R6, and R7 can be the same.

[0010] Furthermore, in the said structural formula, R2, R3, R4, R5, R6, and R7 can be different.

[0011] As a preferred embodiment of the resin composition for a degradable and recyclable low-loss white copper clad laminate of the present invention, in the structural formula of the degradable curing agent, R1 includes an aryl group; R2 includes an arylene group; R3 includes an arylene group; R4 includes an arylene group; R5 includes an arylene group; R6 includes an arylene group; R7 includes an arylene group.

[0012] Further, the degradable curing agent includes a degradable curing agent having the following molecular structure:

[0013] .

[0014] Further, it further includes the following components: alicyclic epoxy resin, polyphenylene ether resin, hydrocarbon resin, filler, fluorescent brightening agent, solvent, initiator.

[0015] Further, it includes the following components in parts by mass: 10-20 parts of the degradable curing agent, 10-20 parts of the alicyclic epoxy resin, 20-35 parts of the hydrocarbon resin, 50-70 parts of the polyphenylene ether resin, 50-100 parts of the solvent, 10-100 parts of the filler, 0.1-10 parts of the fluorescent brightening agent, 0.01-5 parts of the initiator.

[0016] Further, the alicyclic epoxy resin includes one or more of alicyclic glycidyl ethers and alicyclic glycidyl esters; the polyphenylene ether resin includes one or more of acrylate-capped polyphenylene ether, methacrylate-capped polyphenylene ether, and styrene-capped polyphenylene ether; the hydrocarbon resin includes one or more of polybutadiene, polystyrene, polystyrene-butadiene, polyisobutylene, and polystyrene-isobutylene.

[0017] Further, in the above resin composition for a degradable and recyclable low-loss white copper clad laminate, the filler includes one or more of spherical silica, titanium dioxide, silica powder, alumina, boron nitride, and barium titanate;

[0018] The fluorescent brightening agent includes one or more of stilbene derivatives, phenylpyrazoline derivatives, benzimidazole derivatives, benzpyrazole derivatives, coumarin derivatives, or naphthalenedicarboximide derivatives;

[0019] The solvent includes one or more of acetone, butanone, cyclohexanone, methyl isobutyl ketone, toluene, xylene, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl sulfoxide.

[0020] The initiator includes one or more of benzoyl peroxide, di-tert-butyl peroxide, diisopropylbenzene peroxide, bis(tert-butylperoxy)cumene, and tert-butyl peroxybenzoate.

[0021] Furthermore, the resin composition for the degradable and recyclable low-loss white copper clad laminate described above is a glue solution, and the solid content of the glue solution is 45-80%.

[0022] Correspondingly, the present invention also provides a preparation method of the resin composition for the degradable and recyclable low-loss white copper clad laminate described above:

[0023] A. Add the solvent to the degradable curing agent and mix evenly to obtain a mixture m;

[0024] B. Add the hydrocarbon resin, the alicyclic epoxy resin, the polyphenylene ether resin, the filler and the fluorescent brightening agent to the mixture m and mix evenly to obtain a mixture n;

[0025] C. Add the initiator to the mixture n and mix evenly to obtain the resin composition for the degradable and recyclable low-loss white copper clad laminate.

[0026] Furthermore, in steps A, B, and C, the method of mixing evenly includes stirring.

[0027] Furthermore, in the preparation method of the resin composition for the degradable and recyclable low-loss white copper clad laminate: in step A, the rotation speed of the stirring includes 1500 revolutions per minute, and the stirring time includes 60-120 minutes; in step B, the rotation speed of the stirring includes 1800 revolutions per minute, and the stirring time includes 60 minutes; in step C, the rotation speed of the stirring includes 1800 revolutions per minute, and the stirring time includes 30 minutes.

[0028] Correspondingly, the present invention also provides an application of the resin composition for the degradable and recyclable low-loss white copper clad laminate described above, and the resin composition for the degradable and recyclable low-loss white copper clad laminate is used to prepare one or more of prepregs and copper clad laminates.

[0029] Furthermore, the prepreg is obtained by the following method: impregnating a reinforcing material with the resin composition for the degradable and recyclable low-loss white copper clad laminate and drying to obtain the prepreg; the drying method includes heating.

[0030] Furthermore, the copper clad laminate includes copper foil and the prepreg described above; the copper foil is disposed on at least one surface of the prepreg; the number of prepregs includes one or more.

[0031] Furthermore, the copper clad laminate is obtained by the following method: cutting the prepreg, covering both sides with copper foil, and laminating and then placing in a press for hot pressing and curing.

[0032] Further, in the preparation method of the above-mentioned prepreg, the heating temperature includes 140 to 200 °C, and the heating time includes 2 to 3 min.

[0033] Further, in the preparation method of the above-mentioned copper clad laminate, the pressure of the hot pressing and curing includes 2 to 6 Mpa, the temperature of the hot pressing and curing includes 150 to 200 °C, and the time of the hot pressing and curing includes 60 to 140 min.

[0034] Correspondingly, the present invention also provides a product obtained according to the above application, and the product includes one or more of prepregs and copper clad laminates.

[0035] Correspondingly, the present invention also provides a recycling method for the above product, including the following steps:

[0036] S1. Immerse the product in an acidic solvent, while heating and performing ultrasonic oscillation, and then filter to obtain a solid mixture a;

[0037] S2. Wash the solid mixture a with an alkaline solvent, and then filter to obtain a solid mixture b;

[0038] S3. Immerse the solid mixture b in a decomposing agent, while heating and performing ultrasonic oscillation, and then filter to obtain a remaining solid;

[0039] S4. Wash and dry the remaining solid to obtain recycled glass fibers;

[0040] The decomposing agent includes one or more of aqueous solutions of mercaptoethanol, mercaptopropanol, mercaptobutanol, and mercaptopentanol; in step S1, the heating temperature includes 60 to 100 °C; in step S3, the heating temperature includes 60 to 100 °C; when the product is a copper clad laminate, the copper foil is peeled off from the surface of the product before step S1.

[0041] Further, the concentration of the decomposing agent includes 10 wt% to 90 wt%.

[0042] Further, the preparation method of the degradable curing agent includes the following steps:

[0043] Step 1: Add methyltetrahydrofuran, hydroxybenzaldehyde, triethylamine, and dichlorophenylphosphine, stir and reflux for reaction, filter and pour into ice water to obtain crystals, and dry the crystals to obtain bis(4-formylphenyl)phenylphosphonate;

[0044] Step 2: Dissolve the bis(4-formylphenyl)phenylphosphonate obtained in Step 1 in ethyl acetate to obtain Solution 1, and dissolve 4,4'-dithiobis(aniline) in an ethanol solution to obtain Solution 2. After mixing Solution 1 and Solution 2, freeze it under a nitrogen atmosphere, wash it with ether after distillation to obtain the degradable curing agent.

[0045] Further, in the preparation method of the above-mentioned semi-cured sheet, the heating method includes baking; the heating temperature includes 150-200 °C, and the heating time includes 200-800 sec.

[0046] Further, in the above-mentioned recovery method:

[0047] In Step S1, the acidic solvent includes one or more of formic acid solution, acetic acid solution, propionic acid solution, sulfuric acid solution, hydrofluoric acid solution, trichloroacetic acid solution, hydrochloric acid solution, boric acid solution;

[0048] In Step S2, the basic solvent includes one or more of sodium hydroxide solution, potassium hydroxide solution, sodium carbonate solution or ammonia water solution.

[0049] Further, in the above-mentioned recovery method: In Step S1, ultrasonically oscillate until the sheet swells; in Step S2, wash until the pH value is neutral; in Step S3, the concentration of the decomposing agent includes 10-90 wt%; in Step S3, the heating and the ultrasonic oscillation end when the resin layer is completely dissolved; in Step S4, the washing includes washing with distilled water.

[0050] Further, in the above-mentioned recovery method, the filtration in Step S1, Step S2, and Step S3 all uses a 400-mesh filter screen.

[0051] Through a large number of experiments, the present invention has explored and developed a degradable curing agent with a molecular structure as shown in the structural formula, thereby preparing a degradable curing agent with better degradation efficiency, yield, etc., effectively solving the problem of difficult degradation of white copper clad laminates, and effectively solving the problem of relatively large dielectric loss. It has the advantages of meeting various LED performance indicators, excellent dielectric properties, easy recovery, mild and rapid degradation conditions, and the degradable recovery products can be reused, and can be applied to the manufacturing fields of degradable and recyclable LED white copper clad laminates and high-frequency and high-speed copper clad laminates.

[0052] Compared with the prior art, implementing the present invention has the following beneficial effects:

[0053] 1. The self-made degradable curing agent of the present invention contains chemical bonds such as disulfide bonds and Schiff base bonds that are easy to hydrolyze, and the degradable curing agent also contains elements with flame retardant effects.

[0054] 2. Compared with the white copper clad laminates prepared using other degradable curing agents, the white copper clad laminates prepared with the degradable curing agent of the present invention have two advantages: 1) The degradation time is shortened by at least more than half, and 2) The flame retardant performance is significantly enhanced.

[0055] 3. The degradable curing agent of the present invention is combined with alicyclic epoxy resin, polyphenylene ether resin, hydrocarbon resin, etc. to prepare a resin composition for degradable and recyclable low-loss white copper clad laminates, and a prepreg and a white copper clad laminate are prepared with this resin composition, solving the technical problem of difficult degradation of low-loss prepregs and white copper clad laminates.

[0056] 4. Compared with traditional white LED copper clad laminates, the copper clad laminates prepared with the resin composition for degradable and recyclable low-loss white copper clad laminates of the present invention have better degradation efficiency and higher recovery rate. On this premise, the flame retardant grade is also improved from V2 in the comparative example to V0 in the example.

[0057] 5. The recovery method of the white copper clad laminate of the present invention has advantages such as the recyclability of the recovered materials and a high recovery rate. Detailed Embodiments

[0058] To make the objectives, technical solutions, and advantages of the present invention clearer, the present invention will be further described in detail below in conjunction with specific embodiments.

[0059] Preparation Example of Degradable Curing Agent

[0060] Step 1: Take a three-necked round-bottom glass flask, first add 400 ml of methyltetrahydrofuran, then add 0.6 mol of hydroxybenzaldehyde, 0.5 mol of triethylamine, and 0.2 mol of dichlorophenylphosphine, stir and reflux for 10 hours, filter and pour into ice water to obtain a white crystalline solid, and obtain bis(4-formylphenyl)phenylphosphonate after drying.

[0061] Step 2: Dissolve the bis(4-formylphenyl)phenylphosphonate obtained in Step 1 in 200 mL of ethyl acetate. First, completely dissolve 0.21 mol of 4,4'-dithiobisbenzenamine (0.21 mol, 52.16 g) in 550 ml of ethanol solution, add it, and react for 4 hours at -10°C under a nitrogen atmosphere. After distillation, wash with ether to obtain a dark yellow powdery bis(4-(((4-((4-benzaldehyde)dithio)phenyl)imino)methyl)phenyl)phenylphosphonate, that is, curing agent D1, and the molecular structure is as follows.

[0062]

[0063] Preparation Example of Resin Composition

[0064] Take each example or comparative example as a group, and weigh each component of each group according to the dosage of the components in Table 1; at room temperature, take 100 parts by mass of methyl ethyl ketone as the solvent for each group, keep the rotation speed at 1500 revolutions per minute, and continuously stir for 60 minutes after adding the degradable curing agent; slowly add hydrocarbon resin, alicyclic epoxy resin, polyphenylene ether resin, filler and fluorescent brightener, and stir at a rotation speed of 1800 revolutions per minute for 60 minutes; add the initiator and continue stirring for 30 min to dissolve and mix each component evenly to obtain a glue solution (i.e., resin composition) with a solid content of about 66%.

[0065] Table 1 Dosage of each component of the resin composition (in parts by mass)

[0066]

[0067] In Table 1, the information of each component is as follows:

[0068] Alicyclic epoxy resin A1: (CE2021, Chengdu Keyi High Polymer Technology Co., Ltd.);

[0069] Alicyclic epoxy resin A2: (TTA3150, Jiangsu Taitel Co., Ltd.);

[0070] Polyphenylene ether resin B1: (SA9000, Sabic);

[0071] Polyphenylene ether resin B2: (OPE-2st 2200, Mitsubishi Gas Chemical Company, Inc.);

[0072] Hydrocarbon resin C1: butadiene homopolymer (Ricon130, Creavil, France);

[0073] Hydrocarbon resin C2: styrene-butadiene copolymer (Ricon100, Creavil, France);

[0074] Degradable curing agent D1: bis(4-(((4-((4-benzaldehyde)disulfanyl)phenyl)imino)methyl)phenyl)phenylphosphonate; D1 is prepared by the method of the preparation example of the degradable curing agent of the present invention;

[0075] Degradable curing agent D2: degradable isocyanate (Cleavamine, Adesso Advanced Materials Co., Ltd.);

[0076] Degradable curing agent D3: degradable amine curing agent (ACP-2004, Adesso Advanced Materials Co., Ltd.);

[0077] Degradable curing agent D4: 4,4'-dithiobis(aniline), Aladdin Scientific Reagents Co., Ltd.;

[0078] Degradable curing agent D5: Degradable imine curing agent (KT-22, Evonik Industries AG), and the curing agent D5 contains Schiff base bonds;

[0079] Filler E1: Titanium dioxide (TDE, Suzhou Jinyi New Materials Technology Co., Ltd.);

[0080] Filler E2: Spherical silica (Q103, Suzhou Jinyi New Materials Technology Co., Ltd.);

[0081] Fluorescent brightening agent: (OB-1, Shanghai Aladdin Biochemical Technology Co., Ltd.);

[0082] Initiator: Benzoyl peroxide (BPO, Hubei Xinghengye Co., Ltd.).

[0083] Semi-cured sheet preparation example

[0084] Taking each example or comparative example in Table 1 as a group, impregnate the resin composition prepared in the preparation example of the above resin composition into 2116 glass cloth, and then bake it in an oven at 171 °C for 2 - 3 min to obtain semi-cured sheets of each group respectively.

[0085] Copper clad laminate preparation example

[0086] Taking each example or comparative example in Table 1 as a group, take 6 semi-cured sheets prepared in the semi-cured sheet preparation example above for each group, stack them by group, cover both sides with copper foil (1Oz HTE copper foil), press them in a hot press at 2 - 6 Mpa and 170 °C for 60 min, and cool naturally to obtain copper clad laminates with a thickness of about 1.0 mm for each group respectively.

[0087] Effect example 1

[0088] Take the copper clad laminates obtained in the copper clad laminate preparation example (Examples 1, 2, 3 and Comparative Examples 1, 2, 3, 4, 5) and conduct performance tests respectively. The performance test methods of the copper clad laminates are as follows:

[0089] (1) Glass transition temperature (Tg): Tested by the DMA method, and tested according to the IPC-TM-650 2.4.24.2 method.

[0090] (2) Dielectric properties (Dk / Df): Tested according to the IPC-TM-650 2.5.5.9 method, and the frequency is 3 GHz.

[0091] (3) Flame retardancy: Tested by the IPC-TM-650 2.3.10 method.

[0092] (4)Water absorption rate: Samples with copper foils removed from both sides are steamed in a pressure cooker at 121 °C and 105 kPa for 1 hour, and the water absorption rate is calculated based on the weights before and after steaming.

[0093] Effect Example 2

[0094] Take each group of copper clad laminates (Examples 1, 2, 3 and Comparative Examples 1, 2, 3, 4, 5) prepared in the copper clad laminate preparation examples. First, peel the copper foil on the surface of the copper clad laminate samples, and then carry out degradation and recovery on the obtained copper clad laminates according to the following steps, and measure their respective degradation times and glass fiber recovery rates.

[0095] Step 1: Soak in hydrochloric acid and heat at 80 °C for 1 hour while ultrasonically vibrating until the plate swells, and filter using a 400-mesh filter screen;

[0096] Step 2: Wash with an aqueous sodium hydroxide solution until the pH value is neutral, and filter using a 400-mesh filter screen;

[0097] Step 3: Soak in 2-mercaptoethanol solvent, heat at 80 °C for 4 hours while ultrasonically vibrating until the resin layer is completely dissolved, and filter using a 400-mesh filter screen to obtain the remaining solid;

[0098] Step 4: Wash the remaining solid with distilled water and dry to obtain the recovered glass fiber.

[0099] Method for measuring the glass fiber recovery rate: Weigh the total weight W of the recovered glass fiber 2 and take the ratio (unit: %) to the weight W of the glass fiber in the sample before recovery 1 .

[0100] Method for measuring the degradation time: Take the start time when the sample is completely dissolved as the starting time when the above-mentioned recovery step 1 begins, and take the time when the resin layer is completely dissolved in the above-mentioned recovery step 3 as the termination time when the sample is completely dissolved. The difference between the latter and the former is the time taken for the sample to be completely dissolved, denoted as the degradation time (unit: h).

[0101] The results of various tests on the copper clad laminates prepared in Examples 1 to 3 and Comparative Examples 1 to 5 in the above Effect Example 1 and Effect Example 2 are shown in Table 2.

[0102] Table 2 Performance test and recovery test results of each group of copper clad laminates

[0103]

[0104] From the main performance data of the copper clad laminates in Table 2, it can be seen that the performances of the copper clad laminates of Example 1, Example 2, and Example 3 all meet the requirements of IPC4101 / 126 and meet the usage requirements of ordinary FR-4 copper clad laminates.

[0105] The data analysis from Table 2 is as follows:

[0106] Compared with the resin compositions of Examples 1 to 3, after replacing the biodegradable curing agent (D1) of the present invention in the examples with the biodegradable cyanate curing agent (D2) of Comparative Example 1, the degradation time of the plate is significantly prolonged, the flame retardancy becomes poor, and the resin compositions of Examples 1 to 3 do not require the use of isocyanate. Therefore, compared with Comparative Example 1, the water absorption rate also has obvious advantages.

[0107] Compared with the resin compositions of Examples 1 to 3, after replacing the curing agent (D1) of the present invention in the examples with the biodegradable amine curing agent (D3) of Comparative Example 2, the flame retardancy of the plate becomes poor.

[0108] The resin composition of Comparative Example 3 uses the biodegradable cyanate (D2) of Comparative Example 1 and the biodegradable amine curing agent (D3) of Comparative Example 2 at the same time. The flame retardancy and biodegradability of the plate are not good, and it is basically equivalent to Comparative Example 1.

[0109] The resin composition of Comparative Example 4 uses 4,4'-dithiobis(aniline) as the curing agent (D4), and the resin composition of Comparative Example 5 uses a biodegradable imine curing agent as the curing agent (D5), while the resin compositions of Examples 1 to 3 use the self-made biodegradable curing agent (D1) of the present invention. It can be seen from the data in Table 2 that the degradation time of the plates in the examples is shortened by more than half compared with that of Comparative Example 4 or Comparative Example 5, and the degradation time of the plates in the examples is shortened by about 60% compared with that of Comparative Example 4; for the glass fiber recovery rate, the examples are all increased by 24% - 26% compared with Comparative Example 4 and increased by 21% - 23% compared with Comparative Example 5. The main reason is the combined action of multiple easily hydrolyzable bonds (disulfide bonds, Schiff base bonds) to achieve a synergistic degradation effect of 1 + 1 > 2.

[0110] In addition, the flame retardancy of the plates in Examples 1 to 3 all reaches the V0 grade, which is significantly improved compared with the V2 grade of the plates in Comparative Examples 1 to 5. It is speculated that this is related to the fact that the biodegradable curing agent used in the resin composition in the examples of the present invention contains phosphorus elements.

[0111] In summary, in the recovery test results of Examples 1 to 3, both the degradation time and the glass fiber recovery rate are significantly better than those of Comparative Examples 1 to 5, and the degradation time is shortened by half or more; in the performance test results of Examples 1 to 3, the flame retardancy is significantly better than that of Comparative Examples 1 to 5. Therefore, when using the biodegradable curing agent of the present invention and preparing resin compositions, prepregs and white copper clad laminates by the preparation method of the present invention, compared with the application of the biodegradable curing agent in the prior art to prepare white copper clad laminates, technical progress such as better flame retardancy of the plates, shorter degradation time and higher recovery rate is obtained.

[0112] The above-disclosed are only the preferred embodiments of the present invention, and the scope of the rights of the present invention cannot be limited by this. Therefore, equivalent changes made according to the claims of the present invention still fall within the scope covered by the present invention.

Claims

1. An application of a degradable and recyclable resin composition, characterized in that: The invention is applied to reduce the dielectric loss of degradable white copper-clad laminates; the components of the degradable recycling resin composition include a degradable curing agent, alicyclic epoxy resin, polyphenylene ether resin, hydrocarbon resin, and an initiator; the degradable curing agent includes one or more degradable curing agents having the following structural formula: Wherein, R1 is an aromatic group, and R2, R3, R4, R5, R6, and R7 are each an aromatic support group; The mass ratio of the degradable curing agent, the alicyclic epoxy resin, the hydrocarbon resin, and the polyphenylene ether resin includes 10 to 20 parts: 10 to 20 parts: 20 to 35 parts: 50 to 70 parts; The polyphenylene ether resin includes one or more of acrylate-terminated polyphenylene ether, methacrylate-terminated polyphenylene ether and styrene-terminated polyphenylene ether; the hydrocarbon resin includes one or more of polybutadiene, polystyrene, polystyrene-butadiene, polyisobutadiene and polystyrene-isobutadiene.

2. The use of the degradable and recyclable resin composition according to claim 1, characterized in that: The degradable curing agent includes a degradable curing agent having the following molecular structure: 。 3. The use of the degradable and recyclable resin composition according to claim 1, characterized in that: The degradable and recyclable resin composition further comprises the following components: filler, fluorescent brightener and solvent.

4. The use of the degradable and recyclable resin composition as claimed in claim 3, characterized in that: The degradable and recyclable resin composition comprises the following components in parts by mass: 10 to 20 parts of the degradable curing agent, 10 to 20 parts of the alicyclic epoxy resin, 20 to 35 parts of the hydrocarbon resin, 50 to 70 parts of the polyphenylene ether resin, 50 to 100 parts of the solvent, 10 to 100 parts of the filler, 0.1 to 10 parts of the fluorescent whitening agent, and 0.01 to 5 parts of the initiator.

5. The use of the degradable and recyclable resin composition as claimed in claim 3, characterized in that: The alicyclic epoxy resin includes one or more of alicyclic glycidyl ether and alicyclic glycidyl ester.

6. The use of the degradable and recyclable resin composition as claimed in claim 3, characterized in that: The preparation method of the degradable and recyclable resin composition comprises the following steps: A, adding the solvent to the degradable curing agent, and mixing them evenly to obtain a mixture m; B. Adding the hydrocarbon resin, the alicyclic epoxy resin, the polyphenylene ether resin, the filler and the fluorescent brightener into the mixture m, and mixing them evenly to obtain a mixture n; C. Add the initiator into the mixture n, and mix them evenly to obtain the biodegradable and recyclable resin composition.

7. The use of the degradable and recyclable resin composition according to any one of claims 1 to 6, characterized in that: The degradable and recyclable resin composition is used for preparing one or more of a prepreg and a copper-clad laminate.

8. A product obtained by the application according to claim 7, characterized in that: The product includes one or more of a prepreg and a copper clad laminate.

9. A method for recycling the product according to claim 8, characterized in that: The steps include: S1, soaking the product in an acidic solvent, heating and ultrasonically shaking at the same time, filtering to obtain a solid mixture a; S2, washing the solid mixture a with an alkaline solvent, filtering, and obtaining a solid mixture b; S3, soaking the solid mixture b in a decomposing agent, heating and ultrasonically vibrating at the same time, filtering to obtain a residual solid; S4, washing and drying the remaining solid to obtain recycled glass fiber; The decomposition agent includes one or more of a mercaptoethanol aqueous solution, a mercaptopropanol aqueous solution, a mercaptobutanol aqueous solution, and a mercaptopentanol aqueous solution; in step S1, the heating temperature includes 60 to 100° C.; in step S3, the heating temperature includes 60 to 100° C.; when the product is a copper clad laminate, the copper foil is peeled off from the surface of the product before step S1.

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