WO2021026987A1 - 树脂组合物、预浸料及相关基板 - Google Patents

树脂组合物、预浸料及相关基板 Download PDF

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Publication number
WO2021026987A1
WO2021026987A1 PCT/CN2019/104828 CN2019104828W WO2021026987A1 WO 2021026987 A1 WO2021026987 A1 WO 2021026987A1 CN 2019104828 W CN2019104828 W CN 2019104828W WO 2021026987 A1 WO2021026987 A1 WO 2021026987A1
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Prior art keywords
resin composition
polyphenylene ether
parts
mass
prepreg
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PCT/CN2019/104828
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English (en)
French (fr)
Inventor
王宏远
张翼蓝
王和志
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瑞声声学科技(深圳)有限公司
瑞声科技（南京）有限公司
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Publication of WO2021026987A1 publication Critical patent/WO2021026987A1/zh

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    • 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
    • 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
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/285—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyethers
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
    • 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
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards
    • 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
    • C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08J2371/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08J2371/12—Polyphenylene oxides
    • 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
    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C08J2463/10—Epoxy resins modified by unsaturated compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/05—Polymer mixtures characterised by other features containing polymer components which can react with one another

Definitions

  • the present invention relates to the technical field of copper clad laminates, in particular to a resin composition and prepregs, laminates, copper clad laminates and printed circuit boards using the resin composition.
  • Polyphenylene ether has many excellent properties, such as high temperature resistance, water resistance and humidity resistance, excellent electrical properties and good dimensional stability. Among them, polyphenylene ether has a low dielectric constant Dk of an insulating material and a low dielectric loss factor Df. In terms of dielectric properties, in high-speed circuits, the relationship between the signal transmission rate and the dielectric constant Dk of the insulating material is that the lower the dielectric constant Dk of the insulating material, the faster the signal transmission rate. Therefore, in order to increase the signal transmission rate, it is necessary to develop a substrate with a low dielectric constant. As the signal rate increases, the signal loss in the substrate can no longer be ignored.
  • polyphenylene ether is an ideal resin for preparing high frequency copper clad laminate substrates.
  • Epoxy resin has a wide range of types, low price, excellent manufacturability, mechanical properties, dimensional stability and metal adhesion properties, and the epoxy group in its structure can undergo ring-opening polymerization under specific conditions to form heat resistance Good cured product.
  • Blending epoxy resin and polyphenylene ether can not only reduce the molding processability of the resin, improve the adhesion between the substrate and the copper foil (epoxy groups improve the adhesion), but also effectively reduce the cost of raw materials.
  • a single polyphenylene ether resin has a high melting point and a large melt viscosity, and it is difficult to meet the requirements of the processability and performance of the copper clad laminate material at the same time.
  • due to the large difference in chemical structure of epoxy resin and polyphenylene ether resin it is difficult to prepare homogeneous resin and cured product by blending the two separately, which cannot meet the basic requirements of substrate stability.
  • the purpose of the present invention is to provide a polyphenylene ether with high viscosity and good processability, good compatibility between polyphenylene ether and glycidyl ether, improved adhesion between polyphenylene ether and metal, and heat resistance Good, excellent dielectric properties and low cost resin composition and prepreg, laminate, copper clad laminate and printed circuit board using the resin composition.
  • the present invention provides a resin composition, which comprises the following components in parts by mass:
  • Reactive functional group-terminated modified polyphenylene ether copolymer 65 to 80 parts by mass; glycidyl ether having a reactive group capable of reacting with the reactive functional group-terminated modified polyphenylene ether copolymer, 20 to 35 Mass parts
  • Crosslinking agent with two or more epoxy groups, 5-25 parts by mass;
  • Free radical initiator 0-3 parts by mass
  • a catalyst or curing agent for epoxy groups 0-1.5 parts by mass.
  • the reactive functional group-terminated modified polyphenylene ether copolymer includes polyphenylene ether, and the molecular weight of the polyphenylene ether is 1000-3000.
  • the main structure of the polyphenylene ether is as shown in formula (1):
  • R1, R2, R3 and R4 are independent of each other; R1, R2, R3 and R4 are any one of H, alkyl and ester groups;
  • the end group structure of the polyphenylene ether is as (2):
  • X and R can be freely combined; X is any one of -C6H4-, -CH2-, -O- and -COO-; R is any one of -CH3, -C6H5 and H.
  • the polyphenylene ether includes at least one of acrylate-terminated polyphenylene ether and vinyl-terminated polyphenylene ether.
  • the structure of the glycidyl ether is as shown in formula (3):
  • Y is any one of -O-, -C6H4-, and -COO-; Z is (-CH2-) n , and n is a positive integer.
  • the crosslinking agent includes any one of triglycidyl isocyanurate, 1,4-cyclohexane tetraglycidyl ether and pentaerythritol glycidyl ether.
  • the free radical initiators include peroxide initiators, azo initiators and dicumin.
  • the catalyst or curing agent structure of the epoxy group does not contain an active hydrogen structure.
  • the catalyst or curing agent of the epoxy group is any one of 1-substituted imidazoles, esters and tertiary amines.
  • the present invention also provides a prepreg.
  • the prepreg comprises a substrate and the resin composition as described in any one of the above, which is attached to the substrate after being impregnated and dried.
  • the present invention also provides a laminated board, which comprises at least one laminated prepreg as described above.
  • the present invention also provides a copper clad laminate.
  • the copper clad laminate comprises at least one laminated prepreg as described above and copper laminated on one or both sides of the laminated prepreg. Foil.
  • the present invention also provides a printed circuit board, which includes at least one laminated prepreg as described above.
  • the resin composition of the present invention is based on the composition ratio and selection of glycidyl ether compounds having both epoxy groups and unsaturated double bonds as compatibilizers or the second resin component and polyphenylene ether. Blending and copolymerization to prepare a resin composition with good processability, excellent heat resistance and dielectric properties of the cured product, and relatively low cost, so that the resin composition of the present invention and the prepreg using the resin composition Materials, laminates, copper-clad laminates and printed circuit boards can improve the viscosity of polyphenylene ether and have good manufacturability, make the compatibility of polyphenylene ether and glycidyl ether good, and improve the adhesion between polyphenylene ether and metal. Relay, good heat resistance, excellent dielectric properties and low cost.
  • the present invention provides a resin composition, which comprises the following components in parts by mass:
  • Component (A) Modified polyphenylene ether copolymer terminated with reactive functional groups, 65 to 80 parts by mass;
  • Component (B) has a glycidyl ether with a reactive group capable of reacting with the modified polyphenylene ether copolymer terminated with the reactive functional group, 20 to 35 parts by mass;
  • Component (C) a crosslinking agent with two or more epoxy groups, 5-25 parts by mass;
  • Component (D) a catalyst for initiating olefin polymerization, 0-3 parts by mass, the catalyst is composed of at least one free radical initiator;
  • Component (E) epoxy group catalyst or curing agent 0-1.5 parts by mass.
  • each component is selected according to actual needs, for example, added according to the performance requirements of the resin composition.
  • the component (A) is less than 65 parts by mass, the heat resistance of the resin will be poor and the dielectric loss will increase; while if the component (A) is more than 80 parts by mass, the viscosity of the resin system will increase, the processability will be poor, and processing will be difficult.
  • Component (B) is mainly used to control the viscosity of the resin.
  • the content of component (B) increases, the resin manufacturability becomes better but the dielectric loss increases.
  • the content of component (B) is less than 20 parts, the resin system viscosity increases, and the manufacturability changes. difference;
  • component (C) If the content of component (C) is small, the heat resistance of the cured resin will be reduced, the volatile content of the resin will increase if the content is too much, the molding process will be worse, and the cured resin will easily produce defects;
  • Component (D) and component (E) are initiators or catalysts, the processing window is narrowed when the content is high, and the material molding cycle is long due to the low content.
  • Component (A) provides a host resin with high heat resistance and low dielectric properties.
  • the reactive functional group-terminated modified polyphenylene ether copolymer includes polyphenylene ether, and the molecular weight of the polyphenylene ether is 1000-3000.
  • the polyphenylene ether includes at least one of acrylate-terminated polyphenylene ether and vinyl-terminated polyphenylene ether.
  • the main structure of the polyphenylene ether is as shown in formula (1):
  • R1, R2, R3, and R4 are independent of each other.
  • R1, R2, R3, and R4 are any one of H, an alkyl group, and an ester group.
  • the end group structure of the polyphenylene ether is as (2):
  • X is any one of -C6H4-, -CH2-, -O-, and -COO-;
  • R is any one of -CH3, -C6H5, and H.
  • Component (B) reduces the viscosity of the blend system, increases the compatibility between the polyphenylene ether and the epoxy resin, and improves the adhesion between the metal and the substrate material.
  • Y is any one of -O-, -C6H4- and -COO-.
  • Z is (-CH2-) n , and n is an integer.
  • the number of CH2 in Z is small, the cured product is brittle, and the high number is low reactivity.
  • the crosslinking agent includes any one of triglycidyl isocyanurate, 1,4-cyclohexane tetraglycidyl ether and pentaerythritol glycidyl ether.
  • the free radical initiators include peroxide initiators, azo initiators and dicumin,
  • the catalyst or curing agent structure of the epoxy group does not contain an active hydrogen structure.
  • the catalyst or curing agent of the epoxy group is any one of 1-substituted imidazoles, esters and tertiary amines.
  • the present invention also provides a prepreg.
  • the prepreg comprises a substrate and the resin composition as described in any one of the above, which is attached to the substrate after being impregnated and dried.
  • the present invention also provides a laminated board, which comprises at least one laminated prepreg as described above.
  • the present invention also provides a copper clad laminate.
  • the copper clad laminate comprises at least one laminated prepreg as described above and copper laminated on one or both sides of the laminated prepreg. Foil.
  • the present invention also provides a printed circuit board, which includes at least one laminated prepreg as described above.
  • Polyphenylene ether is methyl acrylate or vinyl terminated polyphenylene ether
  • the structure of the polyphenylene ether is as shown in formula (4):
  • the end group structure of the polyphenylene ether is as shown in formula (5):
  • the acrylate-terminated polyphenylene ether is Sabic product SA9000
  • the vinyl-terminated polyphenylene ether is Mitsubishi product OPE-1st.
  • Glycidyl ether is 1-allyloxy-2,3-propylene oxide.
  • the crosslinking agent is triglycidyl isocyanurate.
  • the catalyst is tert-butyl peroxybenzoate.
  • the structure of the catalyst is as formula (8):
  • the curing agent is N,N-dimethylbenzylamine.
  • the structure of the curing agent is as formula (9):
  • the present invention provides the following 4 sets of specific examples and 1 set of specific comparative examples for illustration, see Table 1 for details:
  • Component (E) is a catalyst for epoxy resin compound, and its function is similar to component (D), it is used to catalyze the polymer reaction of epoxy resin, and component (D) is used to catalyze the polymerization reaction of polyphenylene ether.
  • the resin composition includes: 70 parts by mass of acrylate-terminated polyphenylene ether, 30 parts by mass of 1-allyloxy-2,3-propylene oxide, 1 part by mass of tert-butyl peroxybenzoate, and 0.3 parts by mass of N,N-dimethylbenzylamine.
  • the resin composition includes: 70 parts by mass of acrylate-terminated polyphenylene ether, 30 parts by mass of 1-allyloxy-2,3-propylene oxide, and 20 parts by mass of triglycidyl isocyanurate , 1 part by mass of tert-butyl peroxybenzoate and 0.3 parts by mass of N,N-dimethylbenzylamine.
  • the resin composition comprises: 80 parts by mass of acrylate-terminated polyphenylene ether, 30 parts by mass of 1-allyloxy-2,3-propylene oxide, and 20 parts by mass of triglycidyl isocyanurate , 1 part by mass of tert-butyl peroxybenzoate and 0.3 parts by mass of N,N-dimethylbenzylamine.
  • the resin composition includes: 70 parts by mass of vinyl-terminated polyphenylene ether, 30 parts by mass of 1-allyloxy-2,3-propylene oxide, and 20 parts by mass of triglycidyl isocyanurate , 1 part by mass of tert-butyl peroxybenzoate and 0.3 parts by mass of N,N-dimethylbenzylamine.
  • the resin composition includes 70 parts by mass of acrylate-terminated polyphenylene ether, 1 part by mass of tert-butyl peroxybenzoate, and 30 parts by mass of styrene butadiene resin.
  • the dielectric constant DK is the ability of a material to store electrostatic energy (charge) in an electric field.
  • the lower the dielectric constant the lower the ability to store charges and the faster the signal transmission speed.
  • the dielectric constant Dk of Example 2-4 is close to that of Example 1 or Comparative Example 1, the heat resistance Tg is significantly higher than that of Example 1, the peel strength is significantly better than that of Comparative Example 1, and the cost is significantly lower than that of Comparative Example 1. It shows that the resin composition of the present invention has excellent dielectric properties. If it is used to prepare copper clad laminates, it can exhibit good signal transmission performance.
  • Dielectric loss Df refers to the phenomenon that the material itself heats up due to the consumption of part of the electrical energy in the alternating electric field.
  • the field of high-frequency copper clad laminates requires the dielectric loss Df of the matrix resin to be less than 0.01.
  • Both the resin composition of Examples 1-4 and the resin composition of Comparative Example 1 have a dielectric loss Df lower than or equal to 0.01, indicating that the resin composition of the present invention has excellent dielectric properties.
  • Glass transition temperature refers to the temperature at which a material changes from a highly elastic state to a glass state or from a glass state to a high elastic state.
  • Tg Glass transition temperature
  • the later preparation and processing of copper clad laminates The better the stability during the process.
  • the resin composition of Examples 1-4 and the resin composition of Comparative Example 1 both use the A component and the D component, so that the higher the Tg of these resin compositions, the better the heat resistance, and the later preparation and processing of copper clad laminates The higher the medium stability, the better the heat resistance of the resin composition of the present invention.
  • the copper peel strength (N/mm) at 180°C characterizes the adhesion between the copper foil and the substrate. The higher the value, the more difficult the separation between the copper foil and the substrate, and the more advantageous the performance of the copper clad laminate.
  • the resin composition of Examples 1-4 has higher copper peel strength than the resin composition of Comparative Example 1, indicating that the polyphenylene ether using the resin composition of the present invention has better adhesion to metal.
  • the resin composition of the present invention improves the adhesion between polyphenylene ether and metal, and has good heat resistance and excellent dielectric properties.
  • the resin composition of the present invention is based on the composition ratio and selection of glycidyl ether compounds having both epoxy groups and unsaturated double bonds as compatibilizers or the second resin component and polyphenylene ether. Blending and copolymerization to prepare a resin composition with good processability, excellent heat resistance and dielectric properties of the cured product, and relatively low cost, so that the resin composition of the present invention and the prepreg using the resin composition Materials, laminates, copper-clad laminates and printed circuit boards can improve the viscosity of polyphenylene ether and have good manufacturability, make the compatibility of polyphenylene ether and glycidyl ether good, and improve the adhesion between polyphenylene ether and metal. Relay, good heat resistance, excellent dielectric properties and low cost.

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  • Materials Engineering (AREA)
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  • Polymers & Plastics (AREA)
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Abstract

本发明提供了一种树脂组合物，所述树脂组合物按质量份包括如下组分：反应性官能团封端的改性聚苯醚共聚物，65～80质量份；具有能够与所述反应性官能团封端的改性聚苯醚共聚物反应的反应性基团的缩水甘油醚，20～35质量份；具有两个及以上环氧基团的交联剂，5-25质量份；自由基引发剂，0-3质量份；以及环氧基团的催化或固化剂，0-1.5质量份。本发明还提供了一种预浸料和层压板、覆铜箔层压板以及印制电路板。与相关技术相比，本发明的所述树脂组合物、预浸料、层压板、覆铜箔层压板以及印制电路板具有改善聚苯醚粘度大且工艺性良好，使聚苯醚和缩水甘油醚的相容性好，提高了聚苯醚与金属的粘接力，并耐热性好、介电性能优且成本低。

Description

树脂组合物、预浸料及相关基板 【技术领域】
本发明涉及覆铜板技术领域，尤其涉及一种树脂组合物和使用该树脂组合物的预浸料、层压板、覆铜箔层压板以及印制电路板。
【背景技术】
随着5G技术的来临，电子元器件的小型化、高密度化对电路基板材料的介电性能，耐热性等要求越来越高，因此开发新一代的高频用低介电材料得到了大家的广泛关注。
聚苯醚具有诸多优异的性能，如耐高温，耐水耐湿，优异的电气性能以及良好的尺寸稳定性等。其中，聚苯醚具有低的绝缘材料介质常数Dk和低的介质损耗因子Df。就介电性能而言，在高速电路中，信号的传输速率与绝缘材料介质常数Dk的关系为绝缘材料介质常数Dk越低，信号传输速率越快。因此要实现信号传输速率的高速化，必须开发低介电常数的基板。随着信号速率的高速化，基板中信号的损耗不能再忽略不计。信号损耗与速率、介电常数Dk、介质损耗因子Df的关系为基板介电常数Dk越小、介质损耗因子Df越小，信号损失就越小。综合上述，聚苯醚是制备高频覆铜板基材的一种理想树脂。
环氧树脂种类繁多，价格低廉，具有优异的工艺性，力学性能，尺寸稳定性和金属粘接性能，且其结构中的环氧基能够在特定条件下发生开环聚合反应，形成耐热性较好的固化物。将环氧树脂与聚苯醚共混，不仅能够降低树脂的成型工艺性，提高基板与铜箔之间的粘接力(环氧基提高粘接性)，还能够有效降低原料的成本。
然而，单一的聚苯醚的树脂熔点高，熔融粘度大，难以同时满足覆铜板材料工艺性和使用性能的要求。另外，由于环氧树脂和聚苯醚树脂化学结构的差异性较大，单独的将两者共混难以制备出均相的树脂及固化物，从而无法满足基板稳定性的基本要求。
因此，实有必要提供一种新的树脂组合物及相关基板解决上述技术问题。
【发明内容】
本发明的目的在于提供一种具有改善聚苯醚粘度大且工艺性良好，使聚苯醚和缩水甘油醚的相容性好，提高了聚苯醚与金属的粘接力，并耐热性好、介电性能优且成本低的树脂组合物和使用该树脂组合物的预浸料、层压板、覆铜箔层压板以及印制电路板。
为达到上述目的，本发明提供了一种树脂组合物，所述树脂组合物按质量份包括如下组分：
反应性官能团封端的改性聚苯醚共聚物，65～80质量份；具有能够与所述反应性官能团封端的改性聚苯醚共聚物反应的反应性基团的缩水甘油醚，20～35质量份；
具有两个及以上环氧基团的交联剂，5-25质量份；
自由基引发剂，0-3质量份；以及
环氧基团的催化或固化剂，0-1.5质量份。
优选的，所述反应性官能团封端的改性聚苯醚共聚物包括聚苯醚，所述聚苯醚的分子量为1000～3000。
优选的，所述聚苯醚的主体结构如式(1)：
Figure PCTCN2019104828-appb-000001
式(1)中，R1、R2、R3以及R4相互独立；R1、R2、R3以及R4为H、烷基及酯基中的任意一种；
所述聚苯醚的端基结构如(2)：
Figure PCTCN2019104828-appb-000002
式(2)中，X和R自由组合；X为-C6H4-、-CH2-、-O-以及-COO-中的任意一种；R为-CH3、-C6H5以及H中的任意一种。
优选的，所述聚苯醚包括丙烯酸酯封端聚苯醚和乙烯基封端聚苯醚中的至少一种。
优选的，所述缩水甘油醚的结构如式(3)：
Figure PCTCN2019104828-appb-000003
式(3)中，Y为-O-、-C6H4-以及-COO-中的任意一种；Z为(-CH2-) n,n为正整数。
优选的，1≤n≤3。
优选的，所述交联剂包括三缩水甘油异氰尿酸酯、1，4-环己烷四缩水甘油醚以及季戊四醇缩水甘油醚中的任意一种。
优选的，所述自由基引发剂包括过氧化物类引发剂、偶氮类引发剂以及联枯。
优选的，所述环氧基团的催化或固化剂结构中不含有活泼氢结构。
优选的，所述环氧基团的催化或固化剂为1取代咪唑、酯类以及叔胺类中任意一种。
本发明还提供一种预浸料，所述预浸料包括基材及通过含浸干燥后附着于基材上的如上中任意一项所述的树脂组合物。
本发明还提供一种层压板，所述层压板包括至少一张叠合的如上所述的预浸料。
本发明还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于叠合后预浸料的一侧或两侧的铜箔。
本发明还提供一种印制电路板，所述印制电路板包括至少一张叠合的如上所述的预浸料。
与相关技术相比，本发明的树脂组合物通过组分配比和选用同时具有环氧基团和不饱和双键的缩水甘油醚类化合物为相容剂或第二树脂组分与聚苯醚进行共混共聚，制备出工艺性良好，固化物耐热性和介电性能优异，且成本相对较低的树脂组合物，从而使本发明的所述树脂组合物和使用该树脂组合物的预浸料、层压板、覆铜箔层压板以及印制电路板具有改善聚苯醚粘度大且工艺性良好，使聚苯醚和缩水甘油醚的相容性好，提高了聚苯醚与金属的粘接力，并耐热性好、介电性能优且成本低。
【具体实施方式】
下面将对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅是本发明的一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其它实施例，都属于本发明保护的范围。
本发明提供了一种树脂组合物，所述树脂组合物按质量份包括如下组分：
组分(A)反应性官能团封端的改性聚苯醚共聚物，65～80质量份；
组分(B)具有能够与所述反应性官能团封端的改性聚苯醚共聚物反应的反应性基团的缩水甘油醚，20～35质量份；
组分(C)具有两个及以上环氧基团的交联剂，5-25质量份；
组分(D)引发烯烃聚合的催化剂，0-3质量份，所述催化剂由至少一种自由基引发剂组成；
组分(E)环氧基团的催化或固化剂，0-1.5质量份。
其中，各组分按照实际需要选用，比如根据所述树脂组合物的性能需求添加。
若组分(A)质量份小于65，树脂的耐热性变差，介电损耗增加；而组分(A)质量份大于80，则树脂体系的粘度增加，工艺性变差，加工困难。
组分(B)主要用于调控树脂的粘度组分(B)含量增加，树脂工艺性 变好但介电损耗增加，组分(B)含量低于20份，树脂体系粘度增加，工艺性变差；
组分(C)含量较少，树脂固化物的耐热性降低，含量过多树脂挥发份增加，成型工艺变差，树脂固化物易产生缺陷；
组分(D)和组分(E)是引发剂或催化剂，含量高加工窗口变窄，含量低导致材料成型周期长。
组分(A)提供高耐热，低介电性能的主体树脂。所述反应性官能团封端的改性聚苯醚共聚物包括聚苯醚，所述聚苯醚的分子量为1000～3000。
在本实施方式中，所述聚苯醚包括丙烯酸酯封端聚苯醚和乙烯基封端聚苯醚中的至少一种。
所述聚苯醚的主体结构如式(1)：
Figure PCTCN2019104828-appb-000004
式(1)中，R1、R2、R3以及R4相互独立。
式(1)中，R1、R2、R3以及R4为H、烷基及酯基中的任意一种。
所述聚苯醚的端基结构如(2)：
Figure PCTCN2019104828-appb-000005
式(2)中，X和R自由组合。
式(2)中，X为-C6H4-、-CH2-、-O-以及-COO-中的任意一种；R为-CH3、-C6H5以及H中的任意一种。
组分(B)降低共混体系粘度，增加聚苯醚与环氧树脂之间的相容性，提高金属与基板材料之间的粘接力。
所述缩水甘油醚的结构如式(3)：
Figure PCTCN2019104828-appb-000006
式(3)中，Y为-O-、-C6H4-以及-COO-中的任意一种。
Z为(-CH2-) n,n为整数。其中，Z中CH2数目少，固化物脆性大，数目高则反应活性低。优选的，1≤n≤3，即n为1～3的整数。
所述交联剂包括三缩水甘油异氰尿酸酯、1，4-环己烷四缩水甘油醚以及季戊四醇缩水甘油醚中的任意一种。
所述自由基引发剂包括过氧化物类引发剂、偶氮类引发剂以及联枯，
所述环氧基团的催化或固化剂结构中不含有活泼氢结构。所述环氧基团的催化或固化剂为1取代咪唑、酯类以及叔胺类中任意一种。
需要说明的是，所述树脂组合物的组分中，所述组分(A)、所述组分(B)、所述组分(C)、所述组分(D)以及所述组分(E)的上述举例仅为一部分，包括但不限于此。
本发明还提供一种预浸料，所述预浸料包括基材及通过含浸干燥后附着于基材上的如上中任意一项所述的树脂组合物。
本发明还提供一种层压板，所述层压板包括至少一张叠合的如上所述的预浸料。
本发明还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于叠合后预浸料的一侧或两侧的铜箔。
本发明还提供一种印制电路板，所述印制电路板包括至少一张叠合的如上所述的预浸料。
为了验证本发明所述树脂组合物的实施效果进行以三组实施例和一组对照例来验证，其中实验用的材料的产权简称，详见如下描述，其他没有具体说明的简称均为本领域内技术人员熟知的产品简称。
组分(A)：
聚苯醚为丙烯酸甲酯或乙烯基封端聚苯醚，
所述聚苯醚的结构如式(4)：
Figure PCTCN2019104828-appb-000007
该聚苯醚的端基结构如式(5)：
Figure PCTCN2019104828-appb-000008
其中，所述丙烯酸酯封端聚苯醚选用Sabic产品SA9000，乙烯基封端聚苯醚选用三菱产品OPE-1st。
组分(B)：
缩水甘油醚为1-烯丙氧基-2,3-环氧丙烷。
该缩水甘油醚的结构如式(6)：
Figure PCTCN2019104828-appb-000009
组分(C)：
交联剂为三缩水甘油异氰尿酸酯。
该交联剂的结构如式(7)：
Figure PCTCN2019104828-appb-000010
组分(D)：
催化剂为过氧化苯甲酸叔丁酯。
该催化剂的结构如式(8)：
Figure PCTCN2019104828-appb-000011
组分(E)：
固化剂为N,N-二甲基苄胺。
该固化剂的结构如式(9)：
Figure PCTCN2019104828-appb-000012
本发明提供以下4组具体实施例和1组具体对照例进行说明，详见表1：
表1实施例和对照例的组分数据
Figure PCTCN2019104828-appb-000013
组分(E)为环氧树脂化合物的催化剂，其作用与组分(D)类似，用来催化环氧树脂发生聚合物反应，组分(D)用来催化聚苯醚发生聚合反应。
其中，具体为：
实施例一
所述树脂组合物包括：70质量份的丙烯酸酯封端聚苯醚、30质量份的1-烯丙氧基-2,3-环氧丙烷、1质量份的过氧化苯甲酸叔丁酯以及0.3质量份 的N,N-二甲基苄胺。
实施例二
所述树脂组合物包括：70质量份的丙烯酸酯封端聚苯醚、30质量份的1-烯丙氧基-2,3-环氧丙烷、20质量份的三缩水甘油异氰尿酸酯、1质量份的过氧化苯甲酸叔丁酯以及0.3质量份的N,N-二甲基苄胺。
实施例三
所述树脂组合物包括：80质量份的丙烯酸酯封端聚苯醚、30质量份的1-烯丙氧基-2,3-环氧丙烷、20质量份的三缩水甘油异氰尿酸酯、1质量份的过氧化苯甲酸叔丁酯以及0.3质量份的N,N-二甲基苄胺。
实施例四
所述树脂组合物包括：70质量份的乙烯基封端聚苯醚、30质量份的1-烯丙氧基-2,3-环氧丙烷、20质量份的三缩水甘油异氰尿酸酯、1质量份的过氧化苯甲酸叔丁酯以及0.3质量份的N,N-二甲基苄胺。
对照例一
所述树脂组合物包括：70质量份的丙烯酸酯封端聚苯醚、1质量份的过氧化苯甲酸叔丁酯以及30质量份的丁苯树脂。
以上仅为几种实施例，其组合并不限于上述举例。
上述树脂组合物的配制后，并按照IPC标准进行测试，并获得以下实验结果，详见表2：
表2实施例和对照例的所述树脂组合物的测试数据
Figure PCTCN2019104828-appb-000014
介电常数DK是材料在电场中储存静电能(电荷)的能力，越低表明其储存电荷的能力越小，信号的传输速度就越快。实施例2-4的介电常数 Dk接近实施例1或对照例1，耐热性Tg明显高于实施例1，剥离强度明显优于对照例1，且成本大幅度低于对照例1，从而说明本发明的树脂组合物介电性能优。如将其用作制备覆铜板，能够展现出良好的信号传输性能。介电损耗Df是指材料在交变电场中，由于消耗部分电能而使材料本身发热的现象，显然，介电损耗因子越低，材料消耗的电能就越少，产生的热量就越小，对信号的损失也越小。通常高频覆铜板领域要求基体树脂的介电损耗Df低于0.01。实施例1-4的树脂组合物与对照例1的树脂组合物均介电损耗Df低于或者等于0.01，说明本发明的树脂组合物介电性能优。
玻璃化转变温度(Tg)是指材料由高弹态转变为玻璃态或由玻璃态转变为高弹态的温度，Tg越高，材料的耐热性就越好，在后期覆铜板制备及加工过程中稳定性越好。实施例1-4的树脂组合物与对照例1的树脂组合物均用到A组分和D组分，从而这些树脂组合物Tg越高，耐热性好，在后期覆铜板制备及加工过程中稳定性越好，从而说明本发明的树脂组合物耐热性好。
180℃条件下的铜剥离强度(N/mm)表征铜箔与基板之间的粘接性，数值越高，铜箔和基板之间的分离难度越大，覆铜板的性能越有优势。实施例1-4的树脂组合物比对照例1的树脂组合物的铜剥离强度要高，说明采用本发明的树脂组合物的聚苯醚与金属的粘接力好。
通过比较表2中的4组具体实施例和1组具体对照例可以说明本发明的树脂组合物提高了聚苯醚与金属的粘接力，并耐热性好、介电性能优。
与相关技术相比，本发明的树脂组合物通过组分配比和选用同时具有环氧基团和不饱和双键的缩水甘油醚类化合物为相容剂或第二树脂组分与聚苯醚进行共混共聚，制备出工艺性良好，固化物耐热性和介电性能优异，且成本相对较低的树脂组合物，从而使本发明的所述树脂组合物和使用该树脂组合物的预浸料、层压板、覆铜箔层压板以及印制电路板具有改善聚苯醚粘度大且工艺性良好，使聚苯醚和缩水甘油醚的相容性好，提高了聚苯醚与金属的粘接力，并耐热性好、介电性能优且成本低。
以上所述的仅是本发明的实施方式，在此应当指出，对于本领域的普 通技术人员来说，在不脱离本发明创造构思的前提下，还可以做出改进，但这些均属于本发明的保护范围。

Claims (14)

  1. 一种树脂组合物，其特征在于，所述树脂组合物按质量份包括如下组分：
    反应性官能团封端的改性聚苯醚共聚物，65～80质量份；具有能够与所述反应性官能团封端的改性聚苯醚共聚物反应的反应性基团的缩水甘油醚，20～35质量份；
    具有两个及以上环氧基团的交联剂，5-25质量份；
    自由基引发剂，0-3质量份；以及
    环氧基团的催化或固化剂，0-1.5质量份。
  2. 根据权利要求1所述的树脂组合物，其特征在于，所述反应性官能团封端的改性聚苯醚共聚物包括聚苯醚，所述聚苯醚的分子量为1000～3000。
  3. 根据权利要求2所述的树脂组合物，其特征在于，所述聚苯醚的主体结构如式(1)：
    Figure PCTCN2019104828-appb-100001
    式(1)中，R1、R2、R3以及R4相互独立；R1、R2、R3以及R4为H、烷基及酯基中的任意一种；
    所述聚苯醚的端基结构如(2)：
    Figure PCTCN2019104828-appb-100002
    式(2)中，X和R自由组合；X为-C6H4-、-CH2-、-O-以及-COO-中的任意一种；R为-CH3、-C6H5以及H中的任意一种。
  4. 根据权利要求3所述的树脂组合物，其特征在于，所述聚苯醚包括丙烯酸酯封端聚苯醚和乙烯基封端聚苯醚中的至少一种。
  5. 根据权利要求1所述的树脂组合物，其特征在于，所述缩水甘油醚的结构如式(3)：
    Figure PCTCN2019104828-appb-100003
    式(3)中，Y为-O-、-C6H4-以及-COO-中的任意一种；Z为(-CH2-) n,n为正整数。
  6. 根据权利要求5所述的树脂组合物，其特征在于，1≤n≤3。
  7. 根据权利要求1所述的树脂组合物，其特征在于，所述交联剂包括三缩水甘油异氰尿酸酯、1，4-环己烷四缩水甘油醚以及季戊四醇缩水甘油醚中的任意一种。
  8. 根据权利要求1所述的树脂组合物，其特征在于，所述自由基引发剂包括过氧化物类引发剂、偶氮类引发剂以及联枯。
  9. 根据权利要求1所述的树脂组合物，其特征在于，所述环氧基团的催化或固化剂结构中不含有活泼氢结构。
  10. 根据权利要求9所述的树脂组合物，其特征在于，所述环氧基团的催化或固化剂为1取代咪唑、酯类以及叔胺类中任意一种。
  11. 一种预浸料，其特征在于，所述预浸料包括基材及通过含浸干燥后附着于基材上的如权利要求1～10中任意一项所述的树脂组合物。
  12. 一种层压板，其特征在于，所述层压板包括至少一张叠合的如权利要求11所述的预浸料。
  13. 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11所述的预浸料及压覆于叠合后预浸料的一侧或两侧的铜箔。
  14. 一种印制电路板，其特征在于，所述印制电路板包括至少一张叠合的如权利要求11所述的预浸料。
PCT/CN2019/104828 2019-08-13 2019-09-09 树脂组合物、预浸料及相关基板 WO2021026987A1 (zh)

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