WO2016090857A1 - 一种可降解的树脂组合物及使用它的预浸料、层压板、覆铜板及其降解方法 - Google Patents

一种可降解的树脂组合物及使用它的预浸料、层压板、覆铜板及其降解方法 Download PDF

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Publication number
WO2016090857A1
WO2016090857A1 PCT/CN2015/079967 CN2015079967W WO2016090857A1 WO 2016090857 A1 WO2016090857 A1 WO 2016090857A1 CN 2015079967 W CN2015079967 W CN 2015079967W WO 2016090857 A1 WO2016090857 A1 WO 2016090857A1
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group
alkylene
epoxy resin
curing agent
degradable
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English (en)
French (fr)
Inventor
邓华阳
黄增彪
刘潜发
杨中强
王鹏
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Shengyi Technology Co Ltd
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Shengyi Technology Co Ltd
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Priority to EP15868567.7A priority Critical patent/EP3231829B1/en
Priority to JP2017530038A priority patent/JP6438139B2/ja
Priority to US15/534,557 priority patent/US10400058B2/en
Publication of WO2016090857A1 publication Critical patent/WO2016090857A1/zh
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/66—Mercaptans
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/092—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/24—Di-epoxy compounds carbocyclic
    • C08G59/245—Di-epoxy compounds carbocyclic aromatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/56—Amines together with other curing agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C08J3/243—Two or more independent types of crosslinking for one or more polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
    • C08J11/16—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with inorganic material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
    • C08J11/18—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C08J2363/02—Polyglycidyl ethers of bis-phenols
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling

Definitions

  • the present invention relates to a resin composition, and more particularly to a degradable resin composition and a prepreg, a laminate, a copper clad laminate and a degradation method therewith.
  • CCL is the raw material for printed circuit boards (PCBs), which is the foundation of the electronics industry and an indispensable component of all types of electronic products.
  • PCBs printed circuit boards
  • the recovery of copper clad laminates or PCBs can be divided into chemical recovery methods and physical recovery methods according to the principle.
  • the main methods are direct burial method, incineration method, pickling and cracking, etc., but these methods have toxic substances released, easy Secondary pollution to the environment such as air or soil.
  • the best recycling method in the world is the physical method.
  • the first method is to pulverize the metal powder and the non-metal powder according to the specific gravity of the metal and the non-metal. In a closed system, the metal powder and the non-metal powder are separated by a fan. This pulverization is repeated several times, and the pulverized powder even needs to reach the micron level to ensure the separation of metal and non-metal. This method has high energy consumption and noise, high requirements on equipment and incomplete recovery.
  • CN 1483754 discloses a chemical recovery method for a thermosetting epoxy resin composite material, which is characterized in that the thermosetting epoxy resin is degraded by a strong nitric acid solution, the corrosion of the container is large, and the recycling efficiency is low.
  • CN 101519505 discloses a high temperature aqueous phase separation thermosetting epoxy resin or a composite material thereof, which uses heteropoly acid as a catalyst to catalyze the degradation of epoxy resin, which has a great influence on the performance of the recovered material.
  • CN 103249712 A describes the synthesis of degradable polyamines or polythiols which can be used to cure epoxy resins and can be used in the field of carbon fiber composites, but it is also required to be compounded if applied to the field of copper clad laminates.
  • the degradable polyamine in this patent has low curing activity.
  • a curing agent accelerator such as imidazole, which may cause the gelation time of the glue to be too long, which is not conducive to the process control of the copper clad laminate.
  • curing; and the degradable polythiol has high curing activity and poor latency, which is not conducive to the application in the copper clad laminate.
  • the present invention provides a degradable resin composition and a prepreg, a laminate, and a copper clad laminate using the same.
  • the invention adopts different active degradable amine curing agent and degradable thiol curing agent to carry out reasonable compounding, and the reaction activity of the resin composition is effectively controlled without adding a curing accelerator, so that it can be adapted Equipped with the manufacturing process of copper clad laminates, it can produce degraded copper clad laminates with excellent comprehensive performance.
  • a degradable resin composition comprising: an epoxy resin, a degradable amine curing agent, a degradable thiol curing agent, and an inorganic filler;
  • the degradable amine curing agent has the following structure:
  • the degradable thiol curing agent has the following structure:
  • R 1 and R 2 are independently selected from a hydrogen atom, an alkyl group, a cycloalkyl group, a heterocyclic group, a heterocycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, a heteroaryl group, an alkylalkyl group, an alkynyl group, Any one of an alkylene group, an alkylene hydrocarbon group, an alkenylene group, an alkylene heteroalkenylene group, an alkynylene group or an alkylene alkynylene group;
  • R 1 and R 2 may be the same or different
  • R 1 and R 2 may be in the same ring structure as the co-adjacent carbon atoms, or may not be in the same ring structure.
  • R 3 and R 4 are independently selected from the group consisting of an alkylene group, an alkylene hydrocarbon group, an alkenylene group, an alkylene alkenylene group, an alkylene heteroalkenylene group, an alkynylene group, a cycloalkylene group, an alkylene cycloalkylene group.
  • R 3 and R 4 may be the same or different.
  • the epoxy resin is selected from the group consisting of bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin, isocyanate modified epoxy resin, o-cresol Epoxy resin, naphthalene epoxy resin, alicyclic epoxy resin, resorcinol epoxy resin, polyethylene glycol epoxy resin, trifunctional epoxy resin, tetrafunctional epoxy resin, dicyclopentane Any one or a mixture of at least two of a diene epoxy resin or a novolac epoxy resin.
  • the inorganic filler is silica, alumina, magnesia, aluminum hydroxide, magnesium hydroxide, boehmite, aluminum nitride, boron nitride, silicon carbide, titanium dioxide, kaolin, calcium carbonate or talc Any one or a mixture of at least two.
  • the ratio of the epoxy resin to the degradable curing agent, the ratio of the number of moles of epoxy groups in the epoxy resin to the total number of moles of active hydrogen in the degradable amine and the thiol curing agent is 0.8 to 1.2,
  • 0.83, 0.86, 0.89, 0.92, 0.95, 0.98, 1.01, 1.04, 1.07, 1.10, 1.13, 1.16 or 1.19 the number of moles of active hydrogen in the degradable amine curing agent and the active hydrogen mole in the degradable thiol curing agent
  • the ratio of the numbers is from 0.5 to 4.0, such as 0.9, 1.3, 1.7, 2.1, 2.5, 2.9, 3.3, 3.7 or 3.9, further preferably from 1.0 to 2.0.
  • the degradable amine curing agent is:
  • the degradable thiol curing agent is:
  • the inorganic filler is added in an amount of from 0 to 30 parts by weight, such as 4 parts by weight, 8 parts by weight, 12 parts by weight, 16 parts by weight, 20 parts by weight, based on 100 parts by weight of the resin composition containing the inorganic filler. Parts by weight or 28 parts by weight.
  • the resin composition may further contain various additives, and specific examples thereof include a flame retardant, an antioxidant, a heat stabilizer, an antistatic agent, an ultraviolet absorber, a pigment, a colorant, a lubricant, and the like. These various additives may be used singly or in combination of two or more kinds.
  • Another object of the present invention is to provide a resin glue obtained by dissolving or dispersing the resin composition as described above in a solvent.
  • the solvent in the present invention is not particularly limited, and specific examples thereof include alcohols such as methanol, ethanol, and butanol, ethyl cellosolve, butyl cellosolve, ethylene glycol-methyl ether, carbitol, and butyl.
  • Ethers such as carbitol, ketones such as acetone, methyl ethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and mesitylene; An ester such as ethyl acetate or ethyl acetate; a nitrogen-containing solvent such as N,N-dimethylformamide, N,N-dimethylacetamide or N-methyl-2-pyrrolidone. These solvents may be used alone or in combination of two or more.
  • aromatic hydrocarbon solvents such as toluene, xylene, and mesitylene, and acetone, methyl ethyl ketone, methyl ethyl ketone, and methyl group.
  • a ketone flux such as butyl ketone or cyclohexanone is used in combination.
  • a third object of the present invention is to provide a prepreg comprising a reinforcing material and a resin composition as described above attached to the reinforcing material by impregnation and drying.
  • a fourth object of the present invention is to provide a laminate comprising at least one prepreg as described above.
  • a fifth object of the present invention is to provide a copper clad laminate comprising at least one laminated prepreg as described above and laminated on one side of the laminated prepreg Or copper on both sides Foil.
  • the preparation method of the copper-clad laminate of the example row is as follows:
  • the glass fiber cloth is impregnated, baked to prepare a prepreg, and the prepreg is pressed against the copper foil to obtain an epoxy fiberglass cloth-based copper clad laminate.
  • a sixth object of the present invention is to provide a method for degrading a copper clad laminate, the method comprising the steps of:
  • the linear resin is a two-dimensional linear resin formed by breaking a chain of a three-dimensional network epoxy cured product.
  • the present invention has the following beneficial effects:
  • the invention adopts different active degradable amine curing agent and degradable thiol curing agent to carry out reasonable compounding, and the reaction activity of the resin composition is effectively controlled without adding a curing accelerator, so that it can be adapted With the manufacturing process of copper clad laminates, it is possible to produce a degradable copper clad laminate with excellent comprehensive performance. Moreover, the invention realizes green recycling of the copper clad laminate, and the manufacturing process is simple and controllable.
  • Degradable amine curing agent Prepared according to the method of CN 103249712 A.
  • Degradable thiol curing agent Prepared according to the method of CN 103249712 A.
  • Silicon micropowder DS1032, Lianyungang Donghai Silicon Micropowder Co., Ltd.
  • Degradable amine curing agent Prepared according to the method of CN 103249712 A.
  • Degradable thiol curing agent Prepared according to the method of CN 103249712 A.
  • Silicon micropowder DS1032, Lianyungang Donghai Silicon Micropowder Co., Ltd.
  • Degradable amine curing agent Prepared according to the method of CN 103249712 A.
  • Degradable thiol curing agent Prepared according to the method of CN 103249712 A.
  • Silicon micropowder DS1032, Lianyungang Donghai Silicon Micropowder Co., Ltd.
  • Degradable amine curing agent Prepared according to the method of CN 103249712 A.
  • Degradable thiol curing agent Prepared according to the method of CN 103249712 A.
  • Silicon micropowder DS1032, Lianyungang Donghai Silicon Micropowder Co., Ltd.
  • Degradable amine curing agent Prepared according to the method of CN 103249712 A.
  • Degradable thiol curing agent Prepared according to the method of CN 103249712 A.
  • Degradable amine curing agent Prepared according to the method of CN 103249712 A.
  • Degradable thiol curing agent Prepared according to the method of CN 103249712 A.
  • Silicon micropowder DS1032, Lianyungang Donghai Silicon Micropowder Co., Ltd.
  • amine curing agent Taking 125 parts of the above bisphenol A epoxy resin, 12.4 parts of the amine curing agent can be degraded, 26.1 parts of the thiol curing agent can be degraded, 40 parts of silicon micropowder, 100 parts of methyl ethyl ketone, and mixed to obtain a uniformly dispersed glue, and the glue is tested.
  • the gelation time (GT) was 220 s, and 2116 glass fiber cloth was immersed in the composition for sizing, and baked in an oven at 155 ° C for 5 minutes to prepare a prepreg.
  • Degradable amine curing agent Prepared according to the method of CN 103249712 A.
  • Degradable thiol curing agent Prepared according to the method of CN 103249712 A.
  • Silicon micropowder DS1032, Lianyungang Donghai Silicon Micropowder Co., Ltd.
  • Degradable amine curing agent Prepared according to the method of CN 103249712 A.
  • Degradable thiol curing agent Prepared according to the method of CN 103249712 A.
  • Silicon micropowder DS1032, Lianyungang Donghai Silicon Micropowder Co., Ltd.
  • Degradable amine curing agent Prepared according to the method of CN 103249712 A.
  • Degradable thiol curing agent Prepared according to the method of CN 103249712 A.
  • Silicon micropowder DS1032, Lianyungang Donghai Silicon Micropowder Co., Ltd.
  • Degradable amine curing agent Prepared according to the method of CN 103249712 A.
  • Silicon micropowder DS1032, Lianyungang Donghai Silicon Micropowder Co., Ltd.
  • Degradable thiol curing agent Prepared according to the method of CN 103249712 A.
  • Silicon micropowder DS1032, Lianyungang Donghai Silicon Micropowder Co., Ltd.
  • the gelation time (GT) of the test glue is For 45 s, 2116 glass fiber cloth was dipped into the composition for sizing, and baked in an oven at 155 ° C for 2 min to prepare a prepreg.
  • Both Examples 1-4 and Comparative Examples 1-2 employ the following method: the copper clad laminate obtained above is first etched away to obtain a recoverable copper recovery liquid, and the copper foil is etched.
  • the core plate is placed in an ethylene glycol solvent, adjusted to a pH of 4-6 with hydrochloric acid, and maintained at 100 ° C for 2 h.
  • the resin is completely degraded to obtain a glass fiber cloth and a degradation liquid, and the degradation liquid can be filtered to obtain a filler.
  • the remaining degradation solution is added with sodium hydroxide solution to adjust the pH value to 7.
  • the resin composition will precipitate, and the filter will be dried to obtain the line. Resin. Thereby recycling of all components in the copper clad laminate is achieved.
  • Tg glass transition temperature
  • peel strength peel strength
  • interlayer adhesion interlayer adhesion
  • solder dipping resistance solder dipping resistance
  • Interlayer adhesion a small knife is used to peel the sample from the 2 layers of bonding sheets by about 20 mm. The sample is clamped on the test fixture, and the upper and lower ends are fixed to keep the sample in a vertical state at a speed of 50 mm/min. Apply tension in the direction, separate the sample with the axe blade, separate at least 50mm, read the data, and the test result can be obtained;
  • the equivalent ratio of epoxy group to active hydrogen should also be controlled within a reasonable range, otherwise the copper clad laminate may be incompletely cured or the curing agent may remain, thereby affecting the performance of the copper clad laminate.
  • the reaction activity is moderate, the process control is simple, and the prepared copper clad laminate has good comprehensive performance, and can realize effective and green recycling.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Epoxy Resins (AREA)
  • Laminated Bodies (AREA)
  • Reinforced Plastic Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Processing Of Solid Wastes (AREA)
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Abstract

本发明涉及一种树脂组合物以及使用它的预浸料、层压板、覆铜板及其降解方法。该树脂组合物包括：环氧树脂、可降解胺固化剂、可降解硫醇固化剂以及无机填料。使用其制作的覆铜板，包括数张叠合的预浸料，及设于叠合后的预浸料一侧或两侧的铜箔，每一预浸料包括增强材料及通过含浸干燥之后附着在增强材料上的树脂组合物。本发明采用可降解胺固化剂与可降解硫醇固化剂复配，得到反应速率可调控的固化体系，便于覆铜板制造过程中的工艺控制，制得的覆铜板综合性能佳，可完全降解，并实现各有效组份的回收再利用。

Description

一种可降解的树脂组合物及使用它的预浸料、层压板、覆铜板及其降解方法 技术领域
本发明涉及一种树脂组合物，尤其涉及一种可降解的树脂组合物以及使用它的预浸料、层压板、覆铜板及其降解方法。
背景技术
覆铜板是印制电路板(PCB)的原材料，PCB是电子工业的基础，是各类电子产品不可或缺的重要元器件。随着电子产品的升级和换代更新，废弃的PCB越来越多，这些废旧的PCB在自然条件下，其中的有害成分可以通过水、大气、土壤进入环境，给环境造成潜在的、长期的危害，而且这些危害具有不可恢复性，因此，必须对其进行科学合理的回收，废旧PCB的回收逐渐成为一个新兴的产业。
目前，覆铜板或PCB的回收按照原理来分可以分为化学回收法和物理回收法，主要方法有直接掩埋法、焚烧法、酸洗和裂解等方法，但这些方法都有有毒物质释放，易对空气或土壤等环境造成二次污染。目前国际上推行最佳回收方法为物理方法，既采用先粉碎后根据金属和非金属的比重不一样，在密闭的系统中用风机鼓风将金属粉末和非金属粉末进行分离，这种方法要求对此多次粉碎，粉碎后的粉末甚至要达到微米级才能确保金属和非金属的分离，此方法能耗和噪音大，对设备要求高且回收不完全。
CN 1483754公开了一种热固性环氧树脂复合材料的化学回收方法，其是采用强硝酸溶液降解热固性环氧树脂，对容器的腐蚀大，且回收效益低。CN 101519505公开了一种高温水相分离热固性环氧树脂或其复合材料的方法，其是使用杂多酸作为催化剂催化环氧树脂降解，对回收物的性能影响大。
对于可降解的环氧固化体系虽然有报道，但在覆铜板中的应用却未见报道。CN 103249712 A介绍了合成可降解的聚胺或聚硫醇，可以用来固化环氧树脂，并可用在碳纤维复合材料领域，但若应用到覆铜板领域还需要进行相关复配。该专利中的可降解的聚胺固化活性低，为了不影响其降解性能，还不能添加咪唑类等固化剂促进剂，故会导致胶水的凝胶化时间过长，不利于覆铜板的工艺控制和固化；而可降解的聚硫醇类固化活性高，潜伏性差，也不利于在覆铜板中的应用。
发明内容
针对已有技术的问题，本发明的目的在提供一种可降解的树脂组合物及使用它的预浸料、层压板以及覆铜板。本发明采用不同活性的可降解胺固化剂和可降解硫醇固化剂进行合理的复配，在不添加固化促进剂的条件下，使得树脂组合物的反应活性得到了有效控制，使其能适配于覆铜板的制造工艺，制得综合性能优异的可将降解覆铜板。
为了达到上述目的，本发明采用了如下技术方案：
一种可降解树脂组合物，其包括：环氧树脂、可降解胺固化剂、可降解硫醇固化剂以及无机填料；
其中，所述可降解胺固化剂具有如下结构：
Figure PCTCN2015079967-appb-000001
所述可降解硫醇固化剂具有如下结构：
Figure PCTCN2015079967-appb-000002
其中：
R1和R2独立地选自氢原子、烷基、环烷基、杂环基、杂环烷基、烯基、环烯基、芳香基、杂芳香基、烷杂烷基、炔基、亚烃基、亚烃杂亚烃基、亚烯基、亚烃杂亚烯基、亚炔基或亚烃杂亚炔基中的任意一种；
R1和R2可以相同，也可以不同；
R1和R2可以与共同相邻的碳原子在同一个环结构中，也可以不在同一个环结构中。
R3和R4独立地选自亚烃基、亚烃杂亚烃基、亚烯基、亚烯杂亚烯基、亚烃杂亚烯基、亚炔基、环烷撑基、亚烃环烷撑基、亚烃环烷撑亚烃基、亚烯环烷撑基、亚烯环烷撑亚烯基、亚烃环烷撑亚烯基、亚炔环烷撑基、亚炔环烷撑亚炔基、杂环烷撑基、亚烃杂环烷撑基、亚烃杂环烷亚烃基、亚烯杂环烷撑基、亚烯杂环烷亚烯基、亚烃杂环烷亚烯基、亚炔杂环烷撑基、亚炔杂环烷亚炔基、环烯撑基、亚烃环烯撑基、亚烃环烯撑亚烃基、亚烯环烯撑基、亚烯环烯撑亚烯基、亚烃环烯撑亚烯基、亚炔环烯撑基、亚炔环烯撑亚炔基、杂环烯撑基、亚烃杂环烯撑基、亚烃杂环烯亚烃基、亚烯杂环烯撑基、亚烯杂环烯亚烯基、亚烃杂环烯亚烯基、亚炔杂环烯撑基、亚炔杂环烯亚炔基、芳香撑基、亚烃芳香撑基、亚烃芳香撑亚烃基、亚烯芳香撑基、亚烯芳香撑亚烯基、亚烃芳香撑亚烯基、亚炔芳香撑基、亚炔芳香撑亚炔基、杂芳香撑基、亚烃杂芳香撑基、亚烃杂芳香撑亚烃基、亚烯杂芳香撑基、亚烯杂芳香撑亚烯基、亚烃杂芳香撑亚烯基、亚炔杂芳香撑基、亚炔杂芳香撑亚炔基、1，4-烷基取代哌嗪、羰基或硫 代羰基中的任意一种；
R3和R4可以相同，也可以不同。
优选地，环氧树脂选自双酚A型环氧树脂、双酚F型环氧树脂、双酚S型环氧树脂、联苯型环氧树脂、异氰酸酯改性环氧树脂、邻甲酚类环氧树脂、萘类环氧树脂、脂环族类环氧树脂、间苯二酚型环氧树脂、聚乙二醇型环氧树脂、三官能团环氧树脂、四官能团环氧树脂、双环戊二烯类环氧树脂或酚醛型环氧树脂中的任意一种或者至少两种的混合物。
优选地，所述无机填料为二氧化硅、氧化铝、氧化镁、氢氧化铝、氢氧化镁、勃姆石、氮化铝、氮化硼、碳化硅、二氧化钛、高岭土、碳酸钙或滑石粉中的任意一种或者至少两种的混合物。
优选地，所述环氧树脂与可降解固化剂的比值，环氧树脂中的环氧基摩尔数与可降解胺及硫醇固化剂中的总的活泼氢摩尔数的比值为0.8～1.2，例如0.83、0.86、0.89、0.92、0.95、0.98、1.01、1.04、1.07、1.10、1.13、1.16或1.19，可降解胺固化剂中活泼氢的摩尔数与可降解硫醇固化剂中的活泼氢摩尔数之比为0.5～4.0，例如0.9、1.3、1.7、2.1、2.5、2.9、3.3、3.7或3.9，进一步优选1.0～2.0。
优选地，所述可降解胺固化剂为：
Figure PCTCN2015079967-appb-000003
所述可降解硫醇固化剂为：
Figure PCTCN2015079967-appb-000004
以包含无机填料的树脂组合物为100重量份计，所述无机填料的添加量为0-30重量份，例如4重量份、8重量份、12重量份、16重量份、20重量份、24 重量份或28重量份。
本发明所述的“包括”，意指其除所述组份外，还可以包括其他组份，这些其他组份赋予所述树脂组合物不同的特性。除此之外，本发明所述的“包括”，还可以替换为封闭式的“为”或“由……组成”。
例如，所述树脂组合物还可以含有各种添加剂，作为具体例，可以举出阻燃剂、抗氧剂、热稳定剂、抗静电剂、紫外线吸收剂、颜料、着色剂或润滑剂等。这些各种添加剂可以单独使用，也可以两种或者两种以上混合使用。
本发明的目的之二在于提供一种树脂胶液，其是将如上所述的树脂组合物溶解或分散在溶剂中得到。
作为本发明中的溶剂，没有特别限定，作为具体例，可以举出甲醇、乙醇、丁醇等醇类，乙基溶纤剂、丁基溶纤剂、乙二醇-甲醚、卡必醇、丁基卡必醇等醚类，丙酮、丁酮、甲基乙基甲酮、甲基异丁基甲酮、环己酮等酮类，甲苯、二甲苯、均三甲苯等芳香族烃类，乙氧基乙基乙酸酯、醋酸乙酯等酯类，N，N-二甲基甲酰胺、N，N-二甲基乙酰胺、N-甲基-2-吡咯烷酮等含氮类溶剂。上述溶剂可以单独使用一种，也可以两种或者两种以上混合使用，优选甲苯、二甲苯、均三甲苯等芳香族烃类溶剂与丙酮、丁酮、甲基乙基甲酮、甲基异丁基甲酮、环己酮等酮类熔剂混合使用。
本发明的目的之三在于提供一种预浸料，其包括增强材料及通过含浸干燥后附着在增强材料上的如上所述的树脂组合物。
本发明的目的之四在于提供一种层压板，所述层压板含有至少一张如上所述的预浸料。
本发明的目的之五在于提供一种覆铜箔层压板，所述覆铜箔层压板包括至少一张叠合的如上所述的预浸料及压覆在叠合后的预浸料的一侧或两侧的铜 箔。
示例行的覆铜箔层压板的制备方法为：
通过溶剂将所述树脂组合物溶解后，浸润玻纤布，烘烤制成预浸料，再将预浸料与铜箔压合，即制得环氧玻纤布基覆铜板。
本发明的目的之六在于提供一种覆铜箔层压板的降解方法，所述方法包括以下步骤：
(1)将覆铜箔层压板蚀刻掉铜箔，得到铜的回收液；
(2)将蚀刻后铜箔后的芯板置于有机溶剂中，用盐酸调节pH值为4～6，在100-140℃，保持2～4h，树脂完全降解，得到增强材料和降解液，对降解液进行过滤分离，得到无机填料和树脂溶液；
(3)用氢氧化钠或氢氧化钾调节树脂溶液的pH值为6-8，树脂析出，过滤干燥后，得到线性树脂。
线性树脂为三维网状的环氧固化物断链后形成的二维线性树脂。
通过上述方法实现了对覆铜箔层压板中的有效组分的高效、绿色的回收再利用。
与已有技术相比，本发明具有如下有益效果：
本发明采用不同活性的可降解胺固化剂和可降解硫醇固化剂进行合理的复配，在不添加固化促进剂的条件下，使得树脂组合物的反应活性得到了有效控制，使其能适配于覆铜板的制造工艺，能制得综合性能优异的可将降解覆铜板。并且，本发明实现了对覆铜板的绿色回收，制造工艺简便可控。
具体实施方式
下面通过具体实施方式来进一步说明本发明的技术方案。
实施例1
双酚A环氧树脂，DER530，环氧当量为430g/mol，DOW CHEMICAL
可降解胺固化剂按照CN 103249712 A的方法制得。
可降解硫醇固化剂
Figure PCTCN2015079967-appb-000006
按照CN 103249712 A的方法制得。
硅微粉，DS1032，连云港东海硅微粉有限公司
丁酮，兰州石化有限公司
取上述双酚A环氧树脂125份，可降解胺固化剂10份，可降解硫醇固化剂21份，硅微粉60份，丁酮133.3份，混合得到分散均匀的胶液，测试胶液的凝胶化时间(GT)为225s，将2116玻璃纤维布浸入到组合物中进行上胶，在155℃烘箱中，烘烤3min，制得预浸料。
再将数张上述预浸料叠合，上下各配1张35μm电解铜箔，在真空压机中按照既定程序，在180℃、压力35kgf/cm2的条件下热压90min，制成厚度为0.6mm的双面覆铜板。
实施例2
双酚A环氧树脂，DER530，环氧当量为430g/mol，DOW CHEMICAL
可降解胺固化剂
Figure PCTCN2015079967-appb-000007
按照CN 103249712 A的方法制得。
可降解硫醇固化剂
Figure PCTCN2015079967-appb-000008
按照CN 103249712 A的方法制得。
硅微粉，DS1032，连云港东海硅微粉有限公司
丁酮，兰州石化有限公司
取上述双酚A环氧树脂125份，可降解胺固化剂4份，可降解硫醇固化剂33份，硅微粉60份，丁酮133.3份，混合得到分散均匀的胶液，测试胶液的凝胶化时间(GT)为105s，将2116玻璃纤维布浸入到组合物中进行上胶，在155℃烘箱中，烘烤4min，制得预浸料。
再将数张上述预浸料叠合，上下各配1张35μm电解铜箔，在真空压机中按照既定程序，在180℃、压力35kgf/cm2的条件下热压90min，制成厚度为0.6mm的双面覆铜板。
实施例3
双酚A环氧树脂，DER530，环氧当量为430g/mol，DOW CHEMICAL
可降解胺固化剂
Figure PCTCN2015079967-appb-000009
按照CN 103249712 A的方法制得。
可降解硫醇固化剂
Figure PCTCN2015079967-appb-000010
按照CN 103249712 A的方法制得。
硅微粉，DS1032，连云港东海硅微粉有限公司
丁酮，兰州石化有限公司
取上述双酚A环氧树脂125份，可降解胺固化剂15.9份，可降解硫醇固化剂8.2份，硅微粉60份，丁酮133.3份，混合得到分散均匀的胶液，测试胶液的凝胶化时间(GT)为420s，将2116玻璃纤维布浸入到组合物中进行上胶，在155℃烘箱中，烘烤5min，制得预浸料。
再将数张上述预浸料叠合，上下各配1张35μm电解铜箔，在真空压机中按照既定程序，在180℃、压力35kgf/cm2的条件下热压90min，制成厚度为0.6mm的双面覆铜板。
实施例4
邻甲酚酚醛环氧树脂，EPON164，环氧当量为225g/mol，MOMENTIVE
可降解胺固化剂
Figure PCTCN2015079967-appb-000011
按照CN 103249712 A的方法制得。
可降解硫醇固化剂
Figure PCTCN2015079967-appb-000012
按照CN 103249712 A的方法制得。
硅微粉，DS1032，连云港东海硅微粉有限公司
丁酮，兰州石化有限公司
取上述邻甲酚酚醛环氧树脂100份，可降解胺固化剂15.2份，可降解硫醇固化剂31.5份，硅微粉60份，丁酮133.3份，混合得到分散均匀的胶液，测试胶液的凝胶化时间(GT)为230s，将2116玻璃纤维布浸入到组合物中进行上胶，在155℃烘箱中，烘烤8min，制得预浸料。
再将数张上述预浸料叠合，上下各配1张35μm电解铜箔，在真空压机中按照既定程序，在180℃、压力35kgf/cm2的条件下热压90min，制成厚度为0.6mm的双面覆铜板。
实施例5
双酚A环氧树脂，DER530，环氧当量为430g/mol，DOW CHEMICAL
可降解胺固化剂
Figure PCTCN2015079967-appb-000013
按照CN 103249712 A的方法制得。
可降解硫醇固化剂按照CN 103249712 A的方法制得。
丁酮，兰州石化有限公司
取上述双酚A环氧树脂125份，可降解胺固化剂10份，可降解硫醇固化剂21份，丁酮72份，混合得到分散均匀的胶液，测试胶液的凝胶化时间(GT)为245s，将2116玻璃纤维布浸入到组合物中进行上胶，在155℃烘箱中，烘烤5min，制得预浸料。
再将数张上述预浸料叠合，上下各配1张35μm电解铜箔，在真空压机中按照既定程序，在180℃、压力35kgf/cm2的条件下热压90min，制成厚度为0.6mm的双面覆铜板。
实施例6
双酚A环氧树脂，DER530，环氧当量为430g/mol，DOW CHEMICAL
可降解胺固化剂
Figure PCTCN2015079967-appb-000015
按照CN 103249712 A的方法制得。
可降解硫醇固化剂
Figure PCTCN2015079967-appb-000016
按照CN 103249712 A的方法制得。
硅微粉，DS1032，连云港东海硅微粉有限公司
丁酮，兰州石化有限公司
取上述双酚A环氧树脂125份，可降解胺固化剂12.4份，可降解硫醇固化剂26.1份，硅微粉40份，丁酮100份，混合得到分散均匀的胶液，测试胶液的凝胶化时间(GT)为220s，将2116玻璃纤维布浸入到组合物中进行上胶，在155℃烘箱中，烘烤5min，制得预浸料。
再将数张上述预浸料叠合，上下各配1张35μm电解铜箔，在真空压机中按照既定程序，在180℃、压力35kgf/cm2的条件下热压90min，制成厚度为0.6mm的双面覆铜板。
实施例7
双酚A环氧树脂，DER530，环氧当量为430g/mol，DOW CHEMICAL
可降解胺固化剂
Figure PCTCN2015079967-appb-000017
按照CN 103249712 A的方法制得。
可降解硫醇固化剂
Figure PCTCN2015079967-appb-000018
按照CN 103249712 A的方法制得。
硅微粉，DS1032，连云港东海硅微粉有限公司
丁酮，兰州石化有限公司
取上述双酚A环氧树脂125份，可降解胺固化剂8.3份，可降解硫醇固化剂17.4份，硅微粉55份，丁酮100份，混合得到分散均匀的胶液，测试胶液的凝胶化时间(GT)为265s，将2116玻璃纤维布浸入到组合物中进行上胶，在155℃烘箱中，烘烤5min，制得预浸料。
再将数张上述预浸料叠合，上下各配1张35μm电解铜箔，在真空压机中按照既定程序，在180℃、压力35kgf/cm2的条件下热压90min，制成厚度为 0.6mm的双面覆铜板。
实施例8
双酚A环氧树脂，DER530，环氧当量为430g/mol，DOW CHEMICAL
可降解胺固化剂
Figure PCTCN2015079967-appb-000019
按照CN 103249712 A的方法制得。
可降解硫醇固化剂
Figure PCTCN2015079967-appb-000020
按照CN 103249712 A的方法制得。
硅微粉，DS1032，连云港东海硅微粉有限公司
丁酮，兰州石化有限公司
取上述双酚A环氧树脂125份，可降解胺固化剂20份，可降解硫醇固化剂21份，硅微粉60份，丁酮133.3份，混合得到分散均匀的胶液，测试胶液的凝胶化时间(GT)为330s，将2116玻璃纤维布浸入到组合物中进行上胶，在155℃烘箱中，烘烤3min，制得预浸料。
再将数张上述预浸料叠合，上下各配1张35μm电解铜箔，在真空压机中按照既定程序，在180℃、压力35kgf/cm2的条件下热压90min，制成厚度为0.6mm的双面覆铜板。
实施例9
双酚A环氧树脂，DER530，环氧当量为430g/mol，DOW CHEMICAL
可降解胺固化剂
Figure PCTCN2015079967-appb-000021
按照CN 103249712 A的方法制得。
可降解硫醇固化剂
Figure PCTCN2015079967-appb-000022
按照CN 103249712 A的方法制得。
硅微粉，DS1032，连云港东海硅微粉有限公司
丁酮，兰州石化有限公司
取上述双酚A环氧树脂125份，可降解胺固化剂20份，可降解硫醇固化剂26份，硅微粉60份，丁酮133.3份，混合得到分散均匀的胶液，测试胶液的凝胶化时间(GT)为330s，将2116玻璃纤维布浸入到组合物中进行上胶，在155℃烘箱中，烘烤3min，制得预浸料。
再将数张上述预浸料叠合，上下各配1张35μm电解铜箔，在真空压机中按照既定程序，在180℃、压力35kgf/cm2的条件下热压90min，制成厚度为0.6mm的双面覆铜板。
比较例1
双酚A环氧树脂，DER530，环氧当量为430g/mol，DOW CHEMICAL
可降解胺固化剂
Figure PCTCN2015079967-appb-000023
按照CN 103249712 A的方法制得。
硅微粉，DS1032，连云港东海硅微粉有限公司
丁酮，兰州石化有限公司
取上述双酚A环氧树脂100份，可降解胺固化剂16份，硅微粉60份，丁酮133.3份，混合得到分散均匀的胶液，测试胶液的凝胶化时间(GT)为大于1000s，将2116玻璃纤维布浸入到组合物中进行上胶，在155℃烘箱中，烘烤 15min，制得预浸料。
再将数张上述预浸料叠合，上下各配1张35μm电解铜箔，在真空压机中按照既定程序，在180℃、压力35kgf/cm2的条件下热压90min，制成厚度为0.6mm的双面覆铜板。
比较例2
双酚A环氧树脂，DER530，环氧当量为430g/mol，DOW CHEMICAL
可降解硫醇固化剂
Figure PCTCN2015079967-appb-000024
按照CN 103249712 A的方法制得。
硅微粉，DS1032，连云港东海硅微粉有限公司
丁酮，兰州石化有限公司
取上述双酚A环氧树脂100份，可降解硫醇固化剂33.4份，硅微粉60份，丁酮133.3份，混合得到分散均匀的胶液，测试胶液的凝胶化时间(GT)为45s，将2116玻璃纤维布浸入到组合物中进行上胶，在155℃烘箱中，烘烤2min，制得预浸料。
再将数张上述预浸料叠合，上下各配1张35μm电解铜箔，在真空压机中按照既定程序，在180℃、压力35kgf/cm2的条件下热压90min，制成厚度为0.6mm的双面覆铜板。
覆铜板的降解与回收方法实施例1-4和比较例1-2都是采用如下方法：将上述制得的覆铜板，先蚀刻掉铜箔，得到可回收的铜回收液，将蚀刻铜箔后的芯板置于乙二醇溶剂中，用盐酸调节pH值为4-6，在100℃，保持2h，树脂完全降解，得到玻璃纤维布和降解液，过滤降解液便可得到填料，往剩下的降解液中滴加氢氧化钠溶液调节pH值为7，树脂组合物便会析出，过滤干燥便得到线 性树脂。从而实现了覆铜板中所有组份的回收。
针对上述制作的覆铜板，测试其玻璃化转变温度(Tg)、剥离强度、层间粘合力和耐浸焊性等性能。测试结果如下表1和表2。
表1
Figure PCTCN2015079967-appb-000025
表2
Figure PCTCN2015079967-appb-000026
Figure PCTCN2015079967-appb-000027
以上性能测试方法如下：
Tg：GBT 19466.2-2004；
层间粘合力：有小刀将试样剥起2层粘结片约20mm，将试样夹持在测试夹具上，上下两端固定，使试样保持垂直状态，以50mm/min的速度在垂直方向施加拉力，以斧刃分离试样，至少分离50mm，读取数据，即可得到测试结果；
耐浸焊：GB/T 4722-92；
剥离强度：测试使用IPC-TM-650 2.4.8方法；
可降解性：采用如实施例和比较例所述的方法。
通过实施例和对比例可知，单独使用可降解胺作为环氧树脂的固化剂，其反应活性低，凝胶化时间过长，不利于覆铜板制造过程中的工艺控制，覆铜板的性能不佳；单独使用可降解硫醇作为环氧树脂的固化剂，其反应活性高，凝胶化时间过短，同样不利于覆铜板制造过程中的工艺控制，所制得的覆铜板性能不佳。环氧基与活泼氢的当量比也需控制在合理的范围内，否则会导致覆铜板固化不完全或固化剂残留，从而影响覆铜板的性能。通过对可降解胺和硫醇固化剂进行合理复配，反应活性适中，工艺控制简便，所制得的覆铜板综合性能佳，能实现有效、绿色环保回收。
申请人声明，本发明通过上述实施例来说明本发明的详细方法，但本发明 并不局限于上述详细方法，即不意味着本发明必须依赖上述详细方法才能实施。所属技术领域的技术人员应该明了，对本发明的任何改进，对本发明产品各原料的等效替换及辅助成分的添加、具体方式的选择等，均落在本发明的保护范围和公开范围之内。

Claims (10)

  1. 一种可降解树脂组合物，其特征在于，所述树脂组合物包括：环氧树脂、可降解胺固化剂、可降解硫醇固化剂以及无机填料；
    其中，所述可降解胺固化剂具有如下结构：
    Figure PCTCN2015079967-appb-100001
    所述可降解硫醇固化剂具有如下结构：
    Figure PCTCN2015079967-appb-100002
    其中：
    R1和R2独立地选自氢原子、烷基、环烷基、杂环基、杂环烷基、烯基、环烯基、芳香基、杂芳香基、烷杂烷基、炔基、亚烃基、亚烃杂亚烃基、亚烯基、亚烃杂亚烯基、亚炔基或亚烃杂亚炔基中的任意一种；
    R3和R4独立地选自亚烃基、亚烃杂亚烃基、亚烯基、亚烯杂亚烯基、亚烃杂亚烯基、亚炔基、环烷撑基、亚烃环烷撑基、亚烃环烷撑亚烃基、亚烯环烷撑基、亚烯环烷撑亚烯基、亚烃环烷撑亚烯基、亚炔环烷撑基、亚炔环烷撑亚炔基、杂环烷撑基、亚烃杂环烷撑基、亚烃杂环烷亚烃基、亚烯杂环烷撑基、亚烯杂环烷亚烯基、亚烃杂环烷亚烯基、亚炔杂环烷撑基、亚炔杂环烷亚炔基、环烯撑基、亚烃环烯撑基、亚烃环烯撑亚烃基、亚烯环烯撑基、亚烯环烯撑亚烯基、亚烃环烯撑亚烯基、亚炔环烯撑基、亚炔环烯撑亚炔基、杂环烯撑基、亚烃杂环烯撑基、亚烃杂环烯亚烃基、亚烯杂环烯撑基、亚烯杂环烯亚烯基、亚烃杂环烯亚烯基、亚炔杂环烯撑基、亚炔杂环烯亚炔基、芳香撑基、亚烃芳香撑基、亚烃芳香撑亚烃基、亚烯芳香撑基、亚烯芳香撑亚烯基、亚烃芳香撑 亚烯基、亚炔芳香撑基、亚炔芳香撑亚炔基、杂芳香撑基、亚烃杂芳香撑基、亚烃杂芳香撑亚烃基、亚烯杂芳香撑基、亚烯杂芳香撑亚烯基、亚烃杂芳香撑亚烯基、亚炔杂芳香撑基、亚炔杂芳香撑亚炔基、1，4-烷基取代哌嗪、羰基或硫代羰基中的任意一种。
  2. 如权利要求1所述的树脂组合物，其特征在于，环氧树脂选自双酚A型环氧树脂、双酚F型环氧树脂、双酚S型环氧树脂、联苯型环氧树脂、异氰酸酯改性环氧树脂、邻甲酚类环氧树脂、萘类环氧树脂、脂环族类环氧树脂、间苯二酚型环氧树脂、聚乙二醇型环氧树脂、三官能团环氧树脂、四官能团环氧树脂、双环戊二烯类环氧树脂或酚醛型环氧树脂中的任意一种或者至少两种的混合物。
  3. 如权利要求1或2所述的树脂组合物，其特征在于，所述无机填料为二氧化硅、氧化铝、氧化镁、氢氧化铝、氢氧化镁、勃姆石、氮化铝、氮化硼、碳化硅、二氧化钛、高岭土、碳酸钙或滑石粉中的任意一种或者至少两种的混合物。
  4. 如权利要求1-3之一所述的树脂组合物，其特征在于，环氧树脂中的环氧基摩尔数与可降解胺及硫醇固化剂中的总的活泼氢摩尔数的比值为0.8～1.2，可降解胺固化剂中活泼氢的摩尔数与可降解硫醇固化剂中的活泼氢摩尔数之比为0.5～4.0，进一步优选1.0～2.0；
    优选地，所述可降解胺固化剂为：
    Figure PCTCN2015079967-appb-100003
    所述可降解硫醇固化剂为：
    Figure PCTCN2015079967-appb-100004
  5. 如权利要求1-4之一所述的树脂组合物，其特征在于，以包含无机填料的树脂组合物为100重量份计，所述无机填料的添加量为0-30重量份。
  6. 一种树脂胶液，其特征在于，其是将如权利要求1-5之一所述的树脂组合物溶解或分散在溶剂中得到。
  7. 一种预浸料，其特征在于，其包括增强材料及通过含浸干燥后附着在增强材料上的如权利要求1-5之一所述的树脂组合物。
  8. 一种层压板，其特征在于，所述层压板含有至少一张如权利要求7所述的预浸料。
  9. 一种覆铜箔层压板，其特征在于，所述覆铜箔层压板包括至少一张叠合的如权利要求7所述的预浸料及压覆在叠合后的预浸料的一侧或两侧的铜箔。
  10. 一种如权利要求9所述的覆铜箔层压板的降解方法，其特征在于，所述方法包括以下步骤：
    (1)将覆铜箔层压板蚀刻掉铜箔，得到铜的回收液；
    (2)将蚀刻铜箔后的芯板置于有机溶剂中，用盐酸调节pH值为4～6，在100-140℃下保持2～4h，树脂完全降解，得到增强材料和降解液，对降解液进行过滤分离，得到无机填料和树脂溶液；
    (3)用氢氧化钠或氢氧化钾调节树脂溶液的pH值为6-8，树脂析出，过滤干燥后，得到线性树脂。
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EP3231829A1 (en) 2017-10-18
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US20170321001A1 (en) 2017-11-09

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