WO2020108310A1 - 阻燃型树脂预聚物及使用其制备的树脂组合物、半固化片和层压板 - Google Patents

阻燃型树脂预聚物及使用其制备的树脂组合物、半固化片和层压板 Download PDF

Info

Publication number
WO2020108310A1
WO2020108310A1 PCT/CN2019/118113 CN2019118113W WO2020108310A1 WO 2020108310 A1 WO2020108310 A1 WO 2020108310A1 CN 2019118113 W CN2019118113 W CN 2019118113W WO 2020108310 A1 WO2020108310 A1 WO 2020108310A1
Authority
WO
WIPO (PCT)
Prior art keywords
flame
retardant resin
resin
bismaleimide
amine compound
Prior art date
Application number
PCT/CN2019/118113
Other languages
English (en)
French (fr)
Inventor
戴善凯
崔春梅
黄荣辉
谌香秀
Original Assignee
苏州生益科技有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 苏州生益科技有限公司 filed Critical 苏州生益科技有限公司
Publication of WO2020108310A1 publication Critical patent/WO2020108310A1/zh

Links

Classifications

    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/12—Unsaturated polyimide precursors
    • C08G73/125—Unsaturated polyimide precursors the unsaturated precursors containing atoms other than carbon, hydrogen, oxygen or nitrogen in the main chain
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • 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
    • B32B27/281—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 polyimides
    • 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
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • 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
    • 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
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/558—Impact strength, toughness
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/22—Halogen free composition

Definitions

  • the invention relates to the technical field of electronic materials, in particular to a flame-retardant resin prepolymer and a resin composition, a prepreg and a laminate prepared using the same.
  • bismaleimide resin As a high-performance resin material, bismaleimide resin has excellent heat resistance and high high-temperature modulus retention, but bismaleimide resin has poor solubility and can only be dissolved at some high boiling points Solvents such as N,N-dimethylformamide, N-methylpyrrolidone, etc. have harsh process conditions, and at the same time, the cured bismaleimide has high cross-linking density and high brittleness, which seriously affects other performance. Therefore, in the prior art, aromatic diamine or diallyl compounds are generally used for modification.
  • the modified bismaleimide resin has good processability and excellent performance, but regardless of diamine or diene
  • the propyl compound modified maleimide resin can not reach the UL94V-0 level through intrinsic flame retardant, and it needs to add halogen-free flame retardant to meet the halogen-free flame retardant requirements of the EU directive.
  • the method for achieving halogen-free flame retardancy of printed circuit board laminates is generally to add resins containing flame retardant elements such as nitrogen, phosphorus, silicon and inorganic fillers (such as aluminum hydroxide, magnesium hydroxide and other inorganic compounds containing crystalline water to the resin matrix) ).
  • flame retardant elements such as nitrogen, phosphorus, silicon and inorganic fillers (such as aluminum hydroxide, magnesium hydroxide and other inorganic compounds containing crystalline water to the resin matrix)
  • silicon-containing, nitrogen-containing resin or inorganic filler flame retardants have the problem of low flame retardant efficiency, and cannot meet the requirements of UL94V-0. Therefore, phosphorus-containing resin as the main flame retardant occupies a dominant position in the current halogen-free substrate materials.
  • phosphorus-containing flame retardants are mainly reactive resins and additive flame retardants, such as phosphorus-containing epoxy resins, phosphazene compounds, phosphate esters or phosphorus-containing phenolic resins.
  • additive flame retardants such as phosphorus-containing epoxy resins, phosphazene compounds, phosphate esters or phosphorus-containing phenolic resins.
  • the prior art discloses a scheme of adding a phosphorus-containing flame retardant to the bismaleimide resin system.
  • the patent CN102276837A discloses a technical solution of adding a phosphorus-containing compound (phosphazenes) to a bi-horse resin system.
  • a halogen-free cured product with good flame retardant performance can be obtained, these flame retardants do not It forms a better cross-linked network structure with the bismaleimide resin system.
  • the phosphazene compounds that did not participate in the reaction are similar to "sweating"
  • the way of floating on the surface of the substrate not only affects the heat resistance of the board, but also affects the bonding force between the board and the copper foil.
  • the patent JP2012153896 discloses a technical solution of adding a phosphorus-containing epoxy resin to the double-horse resin system, which can also meet the halogen-free flame retardant requirements, but the presence of phosphorus-containing epoxy resin greatly reduces the resin Glass transition temperature, heat resistance and modulus retention at high temperature.
  • the laminate or copper clad laminate prepared using it has excellent halogen-free Flame retardancy, high heat resistance, low thermal expansion coefficient and high modulus retention rate at high temperature.
  • the object of the present invention is to provide a flame-retardant resin prepolymer that solves the above technical problems and a resin composition, a prepreg, and a laminate prepared using the flame-retardant resin prepolymer, in addition to having better solubility
  • the laminates made with it also have excellent halogen-free flame retardancy, high heat resistance, excellent toughness, low coefficient of thermal expansion and high modulus retention at high temperatures.
  • the flame retardant resin prepolymer is pre-polymerized from at least bismaleimide resin and an amine compound, and the amine compound contains an amine compound represented by structural formula (1) and/or structural formula (2) :
  • A1 is R1 is a C1-C10 linear alkylene group or substituted alkylene group or a C6-C20 aromatic group; n is an integer of 1-10.
  • the present invention has the following advantages compared with the prior art:
  • an amine compound containing DOPO or DPPO is used as a bismaleimide resin modifier.
  • the phosphorus-containing groups are well Introduced into the cross-linked network structure of bismaleimide resin, therefore nitrogen and phosphorus elements are synergistically flame-retardant in a cross-linked network structure, which can reduce the phosphorus content of the cured product to achieve the UL94V-0 flame retardancy. It is necessary to add other flame retardants to obtain a cured product with excellent halogen-free flame retardancy, high heat resistance, high glass transition temperature, high modulus retention rate at high temperature, excellent toughness and coefficient of thermal expansion;
  • the crosslinking density of the overall bismaleimide polymer crosslinking network structure can be adjusted to effectively reduce bismaleic
  • the brittleness of the imide resin relieves the stress during the curing reaction and reduces the coefficient of thermal expansion of the board.
  • a flame retardant resin prepolymer specifically a modified bismaleimide prepolymer, which is prepolymerized by at least a bismaleimide resin and an amine compound
  • the amine compound contains the amine compound represented by structural formula (1) and/or structural formula (2):
  • a 1 is
  • R 1 is a C1-C10 linear alkylene group or a substituted alkylene group or a C6-C20 aromatic group;
  • n is an integer of 1-10;
  • the weight ratio of bismaleimide resin and amine compound is 100:15-50, preferably 100:20-40.
  • R1 is a C2-C6 straight-chain alkylene group
  • R1 when R1 is a straight-chain alkylene group, it is placed in the middle position containing DOPO or DPPO on both sides,
  • the crosslinking density of the overall bismaleimide polymer crosslinking network structure can be adjusted to effectively reduce the brittleness of the bismaleimide resin and relieve the stress during the curing reaction.
  • the chain length of the R1 linear alkylene is too long, the linear long chain is soft under high temperature conditions, which affects the rigidity of the cured product.
  • the chain length of the R1 linear alkylene is too short, it is difficult to obtain a toughening effect .
  • the aromatic group is which is preferably
  • Linear alkylene is Or a substituted alkylene group, of which preferred is
  • the bismaleimide resin has the following structural formula:
  • R group is selected from at least one of the following structural formulas:
  • the amine compound also contains a phosphorus-free diamine compound.
  • the phosphorus-free diamine compound is selected from diaminodiphenylmethane, diaminodiphenyl ether, diaminodiphenyl sulfone, diaminobenzophenone, di At least one of aminobiphenyl, the content of the phosphorus-free diamine compound is based on 100 parts by mass of the total amine compound, and contains 10-60 parts, preferably 30-40 parts, more preferably 30 parts, 31 parts, 32 One part, 33 parts, 34 parts, 35 parts, 36 parts, 37 parts, 38 parts, 39 parts, 40 parts.
  • the addition of a phosphorus-free diamine compound can effectively adjust the preparation process of the flame retardant resin prepolymer.
  • the diamine compound is easier to be used with bismaleimide than the phosphorus-containing diamine compound.
  • the addition reaction of the resin is beneficial to improve the solubility of the modified bismaleimide resin.
  • the content of the phosphorus-free diamine is high, it will have a strong competition reaction with the phosphorus-containing amine compound. Thus affecting the introduction of phosphorus-containing diamine compounds in the bismaleimide resin.
  • the flame retardant resin prepolymer of the present invention does not contain an epoxy resin.
  • an epoxy resin is added to the flame retardant resin prepolymer, the amino group in the amine compound is more likely to react with the epoxy group , Affect the degree of prepolymerization of bismaleimide resin, thereby reducing the solubility of bismaleimide resin in the solvent, affecting the overall performance of the final cured product, and at the same time due to the presence of a large number of epoxy groups affect the cured product
  • the heat resistance and high temperature modulus retention rate are difficult to meet the requirements of high-performance substrate materials such as carrier boards and similar carrier boards. Therefore, no epoxy resin is added to the flame retardant resin prepolymer of the present invention.
  • the present invention also provides a flame-retardant resin composition, based on solid weight, including:
  • the above flame retardant resin prepolymer that is, modified bismaleimide prepolymer: 100 parts;
  • Curing accelerator 0.005-5 copies
  • Elastomer 0-50 parts.
  • the filler is selected from an organic filler or an inorganic filler, wherein the inorganic filler is selected from one of non-metal oxide, metal nitride, non-metal nitride, inorganic hydrate, inorganic salt, metal hydrate, or inorganic phosphorus or A mixture of at least any two kinds, any one of materials or inorganic phosphorus or a mixture of at least two kinds, preferably fused silica, crystalline silica, spherical silica, hollow silica, aluminum hydroxide, Any one or at least two of alumina, talc, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, calcium carbonate, calcium silicate, mica or glass fiber powder Mixture; the organic filler is selected from any one of polytetrafluoroethylene powder, polyphenylene sulfide or polyethersulfone powder or at least the organic fill
  • the filler is preferably an inorganic filler, and further preferably a surface-treated inorganic filler, the preferred content of which is 40-100 parts.
  • the surface treatment agent for the surface treatment of the inorganic filler is selected from any one or a mixture of at least two of silane coupling agent, silicone oligomer or titanate coupling agent, and the median particle size of the filler is 0.2 -20 ⁇ m, preferably the median value of the filler is 0.5-5 ⁇ m, the filler located in this particle size segment has good dispersibility and good processability.
  • the amount of the surface treatment agent is 0.1-5.0%, preferably 0.5-3.0%, and more preferably 0.75-2.0%, based on the mass of the inorganic filler being 100%.
  • the curing accelerator is selected from dimethylaminopyridine, tertiary amine and its salt, imidazole, organic metal salt, triphenylphosphine and its phosphonium salt and the like.
  • the curing accelerator is added and used according to the actual situation, and can be selected from dimethylaminopyridine, tertiary amine and its salt, imidazole, organic metal salt, triphenylphosphine and its phosphonium salt, etc., the content of which is flame retardant resin prepolymer 100 In terms of parts, the curing accelerator is preferably 0.01 to 2.0% parts.
  • the elastomer is a low modulus component selected from at least one of polybutadienes, styrenes, olefins, polyurethanes, polyesters, polyimines, acrylates or silicones It is preferably a low-modulus component containing a reactive group in the low-modulus component.
  • the reactive group may be an epoxy group, a hydroxyl group, an amino group, an acid anhydride group, a carboxyl group or a vinyl group, and more preferably an epoxy-modified polymer.
  • the elastomer content is preferably 1-20 parts based on 100 parts.
  • the low-modulus elastomer When the low-modulus elastomer is properly added to the flame-retardant resin composition, it can reduce the stress during the curing reaction, effectively improve the thermal expansion coefficient of the sheet, and further improve the brittleness of the bismaleimide resin.
  • antioxidants heat stabilizers, antistatic agents, ultraviolet absorbers, pigments, colorants, lubricants, etc. may be added to the resin composition according to actual conditions. These various additives may be used alone or in combination of two or more.
  • the invention also provides a prepreg prepared by using the above resin composition, the preparation steps are as follows:
  • the prepreg in the present invention can be obtained by immersing the reinforcing material in the glue solution of the above resin composition, and then baking the immersed reinforcing material in an environment of 50-170°C for 1-10 minutes and drying.
  • the reinforcing material is natural fiber, organic synthetic fiber, organic fabric or inorganic fabric.
  • the solvent is selected from acetone, methyl ethyl ketone, toluene, methyl isobutyl ketone, N, N-dimethylformamide, N, N-dimethylacetamide, ethylene glycol methyl ether, propylene glycol methyl ether, benzene, toluene, One or any combination of cyclohexane.
  • the invention also provides a laminate prepared by using the prepreg, and the preparation steps are as follows:
  • At least one of the above prepregs is covered with a release film and hot-pressed to obtain a laminate.
  • the number of prepregs can be determined according to the thickness of the laminate required, and one or more sheets can be used.
  • the release film may be a PET film or a release aluminum foil.
  • the invention also provides another laminate prepared by using the prepreg, and the preparation steps are as follows:
  • One or both sides of one prepreg are covered with metal foil, or at least two of the above prepregs are stacked, and then one or both sides are covered with metal foil, and hot-pressed to obtain a metal foil laminate.
  • the number of prepregs can be determined according to the required thickness of the laminate, and one or more sheets can be used.
  • the metal foil may be copper foil or aluminum foil, and their thickness is not particularly limited.
  • a resin composition is prepared by using the solid components and proportions in Table 1 and Table 2 as follows:
  • Table 1 is a specific embodiment of the present invention
  • the preparation methods of the diamine compounds A-1 to A-4 are as follows:
  • Diamine compound A-1 Structural formula (1), R1 is A1 is
  • Diamine compound A-2 Structural formula (1), R1 is A1 is
  • Diamine compound A-3 Structural formula (2), R1 is A1 is
  • Diamine compound A-4 Structural formula (2), R1 is A1 is
  • Phosphorus-containing phenolic resin LC950, SHIN-A;
  • Phosphorus-containing epoxy KEG-H5138, Kolon;
  • Phosphazene SPB100, Otsuka Chemical
  • silica surface treated with silane coupling agent, average particle size is 1.0 ⁇ m, Jiangsu Lianrui;
  • Curing accelerator 2-methylimidazole, 2-methyl-4-ethylimidazole, Shikoku Chemicals;
  • Elastomer KMP-605, Shin-Etsu Chemical.
  • Modulus measured by DMA, the temperature rise rate is 10°C/min, and the modulus values at 50°C and 260°C are measured at a frequency of 10 Hz, and the unit is GPa.
  • an amine compound containing DOPO or DPPO is used as a bismaleimide resin modifier, and on the basis of not affecting the performance of the bismaleimide resin, the phosphorus-containing group is introduced into the bismalea well
  • nitrogen and phosphorus elements are synergistically flame-retardant in a cross-linked network structure, which can reduce the phosphorus content required for the flame retardancy of the cured product to reach UL94V-0.
  • a flame retardant a cured product having excellent halogen-free flame retardancy, high heat resistance, high glass transition temperature, high modulus retention rate at high temperature, excellent toughness and coefficient of thermal expansion is obtained at the same time.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Reinforced Plastic Materials (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

本发明揭示了一种阻燃型树脂预聚物及使用其制备的树脂组合物、半固化片和层压板，所述阻燃型树脂预聚物至少由双马来酰亚胺树脂和胺类化合物预聚而成，在不影响双马来酰亚胺树脂性能的基础上，很好地将含磷基团导入至双马来酰亚胺树脂的交联网络结构中。

Description

阻燃型树脂预聚物及使用其制备的树脂组合物、半固化片和层压板 技术领域
本发明涉及电子材料技术领域，特别涉及一种阻燃型树脂预聚物及使用其制备的树脂组合物、半固化片和层压板。
背景技术
近年来，随着移动互联网技术的不断发展，多功能化、便携性、轻薄化不断成为电子产品的追寻目标，意味着电子产品装载的元器件更多、印制电路更多地采用高密度互联技术(HDI)且印制电路整板厚度更薄，因此，对制作印制电路板的基材——覆铜板提出了更高的要求，要求其具有类似封装基板的性能，即行业内兴起的类封装材料，要求覆铜板具有高的耐热性、高的玻璃化转变温度、优异的粘结力、良好的加工性，更重要的是板材在高温下具有较好的模量保持率。
双马来酰亚胺树脂作为一种高性能的树脂材料，具有优异的耐热性和较高的高温模量保持率，但是双马来酰亚胺树脂溶解性差，只能溶解于一些高沸点溶剂如N，N-二甲基甲酰胺、N-甲基吡咯烷酮等，工艺条件苛刻，同时双马来酰亚胺的固化物交联密度高、脆性大，严重影响其它的使用性能。因此，现有技术中普遍采用芳香族二胺或二烯丙基化合物进行改性，改性后的双马来酰亚胺树脂具有良好的加工性及优异的性能，但是不论二胺或二烯丙基化合物改性马来酰亚胺树脂，均无法通过本征阻燃达到UL94V-0级，需要添加无卤阻燃剂来满足欧盟指令要求的无卤阻燃。
实现印刷电路用层压板无卤阻燃的方法一般是在树脂基体中添加含氮、磷、硅等阻燃性元素树脂及无机填料(如氢氧化铝、氢氧化镁等含结晶水的无机化合物)。而含硅、氮树脂或无机填料阻燃剂相比含磷树脂阻燃剂，存在着阻燃效率低的问题，无法满足UL94V-0的要求。因此，含磷树脂作为主阻燃剂在目前的无卤基板材料中占有主导地位。这些含磷阻燃剂主要为反应型树脂和添加型阻燃剂，如含磷环氧树脂、磷腈化合物、磷酸酯或含磷酚醛树脂等。引入上述组分后，板材的阻燃性能得以改善，但是这些以环氧树脂或酚醛树脂为基体的阻燃树脂，较大地降低了改性双马来酰亚胺树脂体系的耐热性、玻璃化转变温度及高温下模量保持率等，难以满足其在高密度互连或集成电路封装/类封装等高性能领域的应用要求。
因此，为了获得无卤阻燃高性能双马来酰亚胺树脂，现有技术中公开了在双马来酰亚胺树脂体系中添加含磷阻燃剂的方案。
如专利CN102276837A中公开了在双马树脂体系中添加含磷化合物(磷腈类)的技术方案，虽然可以获得不含卤素，并具有较好的阻燃性能的固化物，但是这些阻燃剂没有与双马树脂体系形成较好的交联网络结构，在双马来酰亚胺树脂的高温固化条件(往往高于200℃)下，未参与反应的磷腈类化合物以类似于“出汗”的方式浮出于基材表面，不仅仅影响板材的耐热性，更影响了板材与铜箔之间的结合力。
如专利JP2012153896中公开了在双马树脂体系中添加了含磷环氧树脂的技术方案，该技术方案也可以满足无卤阻燃要求，但因含磷环氧树脂的存在，大大降低了树脂的玻璃化转变温度、耐热性及高温下的模量保持率。
综上所述，有必要开发一种适合用于类载板、封装载板及高密度互联技术领域的高性能印制线路板基板材料，使用其制备的层压板或覆铜板具有优异的无卤阻燃性、高耐热性、低热膨胀系数及高温下高的模量保持率。
发明内容
本发明的目的在于提供一种解决上述技术问题的阻燃型树脂预聚物及使用其制备的树脂组合物、半固化片和层压板，该阻燃型树脂预聚物除了具有较好的溶解性外，使用其制成的层压板还同时具有优异的无卤阻燃性、高耐热性、优异的韧性、低热膨胀系数和高温下高的模量保持率。
其中，阻燃型树脂预聚物至少由双马来酰亚胺树脂和胺类化合物预聚而成，所述胺类化合物中含有结构式(1)和/或结构式(2)所示的胺化合物：
Figure PCTCN2019118113-appb-000001
其中，A1为
Figure PCTCN2019118113-appb-000002
Figure PCTCN2019118113-appb-000003
R1为C1-C10的直链亚烷基或取代亚烷基或C6-C20的芳香族基；n为1-10的整数。
由于上述技术方案运用，本发明与现有技术相比具有下列优点：
(1)本发明中采用含DOPO或DPPO的胺类化合物作为双马来酰亚胺树脂改性剂，在不影响双马来酰亚胺树脂性能的基础上，很好地将含磷基团导入至双马来酰亚胺树脂的交联网络结构中，因此在一个交联网络结构中氮元素和磷元素协同阻燃，能减少固化物阻燃性达到UL94V-0所需磷含量，不需要再增加其他阻燃剂，获得同时具有优异的无卤阻燃性、高耐热性、高玻璃化转变温度、高的高温下模量保持率、优异的韧性和热膨胀系数的固化物；
(2)当胺类化合物结构中，在DOPO或DPPO的中间位置处设置直链烷基时，可以调节整体双马来酰亚胺聚合物交联网络结构的交联密度，有效降低双马来酰亚胺树脂的脆性，缓解固化反应过程中应力的产生,降低板材的热膨胀系数。
(3)当制备预聚物时，适当添加无磷二胺化合物可以有效控制预聚物的制备工艺和改善改性后的双马来酰亚胺树脂的溶解性，但是当含量较高时，影响阻燃效率。
具体实施方式
以下将结合具体实施方式对本发明进行详细描述。但这些实施方式并不限制本发明，本领域的普通技术人员根据这些实施方式所做出的结构、方法、或功能上的变换均包含在本发明的保护范围内。本领域的普通技术人员根据这些实施方式所做的反应条件、反应物或原料用量上的变换均包含在本发明的保护范围内。
在本发明一具体实施方式中，一种阻燃型树脂预聚物，具体为改性双马来酰亚胺预聚物，其至少由双马来酰亚胺树脂和胺类化合物预聚而成，胺类化合物中含有结构式(1)和/或结构式(2)所示的胺化合物：
Figure PCTCN2019118113-appb-000004
Figure PCTCN2019118113-appb-000005
其中，A 1为
Figure PCTCN2019118113-appb-000006
Figure PCTCN2019118113-appb-000007
R 1为C1-C10的直链亚烷基或取代亚烷基或C6-C20的芳香族基；
n为1-10的整数；
双马来酰亚胺树脂和胺类化合物的重量比例为100:15-50，优选为100:20-40。
进一步地，上述胺类化合物结构式(1)和(2)中，R1为C2-C6的直链亚烷基，当R1为直链亚烷基，设置在两侧含DOPO或DPPO的中间位置，可以调节整体双马来酰亚胺聚合物交联网络结构的交联密度，有效降低双马来酰亚胺树脂的脆性，缓解固化反应过程中应力的产生。但是当R1直链亚烷基的链长过长时，在高温条件下线性长链较柔软，影响固化物的刚性，当R1直链亚烷基的链长过短时，难以获得增韧效果。
芳香族基为
Figure PCTCN2019118113-appb-000008
Figure PCTCN2019118113-appb-000009
其中优选为
Figure PCTCN2019118113-appb-000010
Figure PCTCN2019118113-appb-000011
直链亚烷基为
Figure PCTCN2019118113-appb-000012
Figure PCTCN2019118113-appb-000013
或其取代亚烷基，其中优选为
Figure PCTCN2019118113-appb-000014
进一步地，双马来酰亚胺树脂具有以下结构式：
Figure PCTCN2019118113-appb-000015
其中，R基选自下列结构式中的至少一种：
Figure PCTCN2019118113-appb-000016
进一步地，胺类化合物中还含有无磷二胺化合物，优选地，无磷二胺化合物选自二氨基二苯甲烷，二氨基二苯醚，二氨基二苯砜，二氨基二苯酮，二氨基联苯中的至少一种，无磷二胺化合物的含量为以总胺类化合物100质量分计，含有10-60份，优选为30-40份，更优选为30份，31份，32份，33份，34份，35份，36份，37份，38份，39份，40份。
当制备阻燃型树脂预聚物时，添加无磷二胺化合物，可以有效调节阻燃型树脂预聚物的制备工艺，该二胺化合物较含磷二胺化合物更易与双马来酰亚胺树脂进行加成反应，有利于提高改性的双马酰亚胺树脂的溶解性，但是，当该无磷二胺含量较高时，又会与含磷胺化合物产生较强的竞聚反应，从而影响含磷二胺化合物的在双马来酰亚胺树脂中的引入。
特别地，本发明的阻燃型树脂预聚物中不含有环氧树脂，当在上述阻燃型树脂预聚物中添加环氧树脂时，胺类化合物中的氨基更易与环氧基发生反应，影响双马来酰亚胺树脂的预聚程度，从而降低了双马来酰亚胺树脂在溶剂中的溶解性，影响最终固化物的综合性能，同时因大量环氧基的存在影响固化物的耐热性及高温模量保持率，难以满足载板及类载板等高性能基板材料要求。故，本发明的阻燃型树脂预聚物中不添加环氧树脂。
本发明还提供一种阻燃型树脂组合物，以固体重量计，包括：
上述阻燃型树脂预聚物，即改性双马来酰亚胺预聚物：100份；
填料：0-150份；
固化促进剂：0.005-5份；
弹性体：0-50份。
进一步地，填料选自有机填料或无机填料，其中，无机填料选自非金属氧化物、金属氮化物、非金属氮化物、无机水合物、无机盐、金属水合物或无机磷中的一种或者至少任意两种的混合物，物或无机磷中的任意一种或者至少两种的混合物，优选熔融二氧化硅、结晶型二氧化硅、球型二氧化硅、空心二氧化硅、氢氧化铝、氧化铝、滑石粉、氮化铝、氮化硼、碳化硅、硫酸钡、钛酸钡、钛酸锶、碳酸钙、硅酸钙、云母或玻璃纤维粉中的任意一种或者至少两种的混合物；有机填料选自聚四氟乙烯粉末、聚苯硫醚或聚醚砜粉末中的任意一种或者至少所述有机填料选自聚四氟乙烯粉末、聚苯硫醚或聚醚砜粉末中的一种或者至少任意两种的混合物。
本发明中，填料优选无机填料，进一步优选经过表面处理的无机填料，其优选含量为40-100 份。对无机填料进行表面处理的表面处理剂选自硅烷偶联剂、有机硅低聚物或钛酸酯偶联剂中的任意一种或至少两种的混合物，填料的粒径中度值为0.2-20μm，优选填料的中度值为0.5-5μm，位于此粒径段的填料具有良好的分散性与较好的加工性。
更优选地，以无机填料质量为100％计，表面处理剂的用量为0.1-5.0％，优选0.5-3.0％，进一步优选0.75-2.0％。
进一步地，固化促进剂选自二甲基氨基吡啶、叔胺及其盐、咪唑、有机金属盐、三苯基膦及其鏻盐等。固化促进剂根据实际情况添加使用，可以选自二甲基氨基吡啶、叔胺及其盐、咪唑、有机金属盐、三苯基膦及其鏻盐等，含量以阻燃型树脂预聚物100份计，固化促进剂优选为0.01-2.0％份。
进一步地，弹性体为低模量组分，选自聚丁二烯类、苯乙烯类、烯烃类、聚氨酯类、聚酯类、聚亚胺类、丙烯酸酯类或硅酮类中的至少一种，优选为在低模量组分中含反应基的低模量组分，反应基可以为环氧基、羟基、氨基、酸酐基、羧基或乙烯基等，更优选为环氧改性聚丁二烯、酸酐改性聚丁二烯、苯乙烯丁二烯共聚物、聚乙烯、聚丙烯、聚酯、聚亚胺、丙烯酸酯、聚氨酯或硅酮，含量以阻燃型树脂预聚物100份计，弹性体含量优选为1-20份。
当阻燃型树脂组合物中适当添加低模量弹性体时，可在固化反应过程中减少应力的产生，有效改善板材的热膨胀系数，同时进一步改善双马来酰亚胺树脂脆性。
进一步地，树脂组合物中还可以根据实际情添加使用抗氧剂、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。
本发明还提供一种采用上述树脂组合物制备的半固化片，其制备步骤如下：
将上述阻燃型树脂组合物用溶剂溶解，固体含量为50％-80％，搅拌均匀，并熟化，制成树脂组合物胶液；
将增强材料浸渍在上述树脂组合物胶液中，然后将浸渍后的增强材料在50-170℃环境下烘烤1-10min干燥后即可得本发明中的半固化片。
其中，增强材料为天然纤维、有机合成纤维、有机织物或者无机织物。溶剂选自丙酮、丁酮、甲苯、甲基异丁酮、N、N-二甲基甲酰胺、N、N-二甲基乙酰胺、乙二醇甲醚、丙二醇甲醚、苯、甲苯、环己烷中的一种或任意几种的组合。
本发明还提供一种采用上述半固化片制备的层压板，其制备步骤如下：
在至少一张上述的半固化片的双面覆上离型膜，热压成形，即可得到层压板，半固化片的数量可根据需要的层压板的厚度来确定，可用一张或多张。离型膜可以是PET膜或离型铝箔。
本发明还提供另一种采用上述半固化片制备的层压板，其制备步骤如下：
在一张上述半固化片的单面或双面覆上金属箔，或者将至少2张上述半固化片叠加 后，在其单面或双面覆上金属箔，热压成形，即可得到金属箔层压板。
半固化片的数量可根据需要的层压板的厚度来确定，可用一张或多张。所述金属箔，可以是铜箔，也可以是铝箔，它们的厚度没有特别限制。
上述半固化片、层压板和金属箔层压板均用于制备线路板。
为了更好的阐述本发明，以下提供一些具体实施例，对本发明做进一步描述，以下为阻燃型双马来酰亚胺树脂预聚物的制备具体合成例：
合成例一
在500mL三口烧瓶中加入100g溶剂N,N-二甲基甲酰胺，将4,4’-二苯甲烷双马来酰亚胺、含DOPO基的二胺化合物A-1(直链基型)与二氨基二苯甲烷，按照质量份100g:20g:20g依次于投入三口烧瓶中，在90℃的油浴条件下持续搅拌，待烧瓶中固体完全溶解后开始计时，持续搅拌2.5hr后，将所得产物进行蒸馏，得到固含量为75％的改性双马来酰亚胺预聚物1。
合成例二
在500mL三口烧瓶中加入100g溶剂N,N-二甲基甲酰胺，将4,4’-二苯甲烷双马来酰亚胺、含DOPO基的二胺化合物A-2(芳香族基型)与二氨基二苯甲烷，按照质量份100g:20g:15g依次于投入三口烧瓶中，在90℃的油浴条件下持续搅拌，待烧瓶中固体完全溶解后开始计时，持续搅拌2.5hr后，将所得产物进行蒸馏，得到固含量为75％的改性双马来酰亚胺预聚物2。
合成例三
在500mL三口烧瓶中加入100g溶剂N,N-二甲基甲酰胺，将4,4’-二苯甲烷双马来酰亚胺、含DPPO基的二胺化合物A-3(直链基型)与二氨基二苯砜，按照质量份100g:30g:20g依次于投入三口烧瓶中，在90℃的油浴条件下持续搅拌，待烧瓶中固体完全溶解后开始计时，持续搅拌2.5hr后，将所得产物进行蒸馏，得到固含量为75％的改性双马来酰亚胺预聚物3。
合成例四
在500mL三口烧瓶中加入100g溶剂N,N-二甲基甲酰胺，将4,4’-二苯甲烷双马来酰亚胺、含DPPO基的二胺化合物A-4(芳香族基型)与二氨基二苯甲烷，按照质量份100g:20g:30g依次于投入三口烧瓶中，在90℃的油浴条件下持续搅拌，待烧瓶中固体完全溶解后开始计时，持续搅拌2.5hr后，将所得产物进行蒸馏，得到固含量为75％的改性双马来酰亚胺预聚物4。
合成例五(相比合成例一，不同含量比)
在500mL三口烧瓶中加入100g溶剂N,N-二甲基甲酰胺，将4,4’-二苯甲烷双马来酰亚胺、含DOPO基的二胺化合物A-1(直链基型)与二氨基二苯醚，按照质量份100g:40g:15g依次于投入三口烧瓶中，在90℃的油浴条件下持续搅拌，待烧瓶中固体完全溶解后开始计 时，持续搅拌2.5hr后，将所得产物进行蒸馏，得到固含量为75％的改性双马来酰亚胺预聚物5。
合成例六
在500mL三口烧瓶中加入100g溶剂N,N-二甲基甲酰胺，将4,4’-二苯甲烷双马来酰亚胺与含DOPO基的二胺化合物A-1(直链基型)，按照质量份100g:20g依次于投入三口烧瓶中，在90℃的油浴条件下持续搅拌，待烧瓶中固体完全溶解后开始计时，持续搅拌2.5hr后，将所得产物进行蒸馏，得到固含量为75％的改性双马来酰亚胺预聚物6。
对比合成例1
在500mL三口烧瓶中加入100g溶剂N,N-二甲基甲酰胺，将4,4’-二苯甲烷双马来酰亚胺与4，4’-二氨基二苯基甲烷，按照质量份100g:30g依次于投入三口烧瓶中，在90℃的油浴条件下持续搅拌，待烧瓶中固体完全溶解后开始计时，持续搅拌2.5hr后，将所得产物进行蒸馏，得到固含量为75％的改性双马来酰亚胺预聚物7。
对比合成例2
在500mL三口烧瓶中加入100g溶剂N,N-二甲基甲酰胺，将4,4’-二苯甲烷双马来酰亚胺与二氨基二苯砜，按照质量份100g:40g依次于投入三口烧瓶中，在90℃的油浴条件下持续搅拌，待烧瓶中固体完全溶解后开始计时，持续搅拌2.5hr后，将所得产物进行蒸馏，得到固含量为75％的改性双马来酰亚胺预聚物8。
对比合成例3
在500mL三口烧瓶中加入100g溶剂N,N-二甲基甲酰胺，将4,4’-二苯甲烷双马来酰亚胺、4，4’-二氨基二苯基甲烷和环氧树脂，按照质量份100g:30g:20g依次于投入三口烧瓶中，在90℃的油浴条件下持续搅拌，待烧瓶中固体完全溶解后开始计时，持续搅拌2.5hr后，将所得产物进行蒸馏，得到固含量为75％的改性双马来酰亚胺预聚物9。
该预聚物9中发现较多的未完全溶解或析出的双马来酰亚胺树脂颗粒，因此未评估进一步固化物的性能。
一种树脂组合物，采用如下表1和表2中的固体组分和配比制得：
表1为本发明的具体实施例
Figure PCTCN2019118113-appb-000017
Figure PCTCN2019118113-appb-000018
表2本发明的对比例
Figure PCTCN2019118113-appb-000019
Figure PCTCN2019118113-appb-000020
*板材去铜后表面有析出物
其中，二胺化合物A-1至A-4的制备方法为以下：
Figure PCTCN2019118113-appb-000021
在烧瓶中加入去离子水、取1mol二氨基二苯甲烷，搅拌并加热至90℃并使其完全溶解，然后向烧瓶中滴加0.5mol对苯二甲醛，在氮气保护下反应2h；待反应结束后，经多次回流洗涤抽滤过程，获得中间产物；然后再加入适量的DOPO化合物继续反应4小时，获得所述的含DOPO的胺类化合物.
在上述方法中选择不同的醛类化合物、胺类化合物和磷化合物，获得以下结构二胺化合物，其结构为以下所示：
二胺化合物A-1：结构式(1)，R1为
Figure PCTCN2019118113-appb-000022
A1为
Figure PCTCN2019118113-appb-000023
二胺化合物A-2：结构式(1)，R1为
Figure PCTCN2019118113-appb-000024
A1为
Figure PCTCN2019118113-appb-000025
二胺化合物A-3：结构式(2)，R1为
Figure PCTCN2019118113-appb-000026
A1为
Figure PCTCN2019118113-appb-000027
二胺化合物A-4：结构式(2)，R1为
Figure PCTCN2019118113-appb-000028
A1为
Figure PCTCN2019118113-appb-000029
4,4’-二苯甲烷双马来酰亚胺：西安双马新材料有限公司；
含磷酚醛树脂：LC950，SHIN-A；
含磷环氧：KEG-H5138，Kolon；
磷腈：SPB100，大冢化学；
填料：二氧化硅，用硅烷偶联剂表面处理，平均粒径为1.0μm，江苏联瑞；
固化促进剂：2-甲基咪唑，2-甲基-4-乙基咪唑，四国化成；
弹性体：KMP-605，信越化学。
性能评价方法：
(1)玻璃化转变温度(DMA)：用DMA测定，升温速率为10℃/min，频率为10Hz下测定Tg，
温度范围：30-320℃。
(2)模量：用DMA测定，升温速率为10℃/min，频率为10Hz下测定50℃和260℃的模量值，单位为GPa。
(3)阻燃性：UL94垂直燃烧(UL94V0)，根据ASTM(D63-77)方法测试。
本发明采用含DOPO或DPPO的胺类化合物作为双马来酰亚胺树脂改性剂，在不影响双马来酰亚胺树脂性能的基础上，很好地将含磷基团导入至双马来酰亚胺树脂的交联网络结构中，因此在一个交联网络结构中氮元素和磷元素协同阻燃，能减少固化物阻燃性达到UL94V-0所需磷含量，不需要再增加其他阻燃剂，获得同时具有优异的无卤阻燃性、高耐热性、高玻璃化转变温度、高的高温下模量保持率、优异的韧性和热膨胀系数的固化物。
应当理解，虽然本说明书按照实施方式加以描述，但并非每个实施方式仅包含一个独立的技术方案，说明书的这种叙述方式仅仅是为清楚起见，本领域技术人员应当将说明书作为一个整体，各实施方式中的技术方案也可以经适当组合，形成本领域技术人员可以理解的其他实施方式。
上文所列出的一系列的详细说明仅仅是针对本发明的可行性实施方式的具体说明，它们并非用以限制本发明的保护范围，凡未脱离本发明技艺精神所作的等效实施方式或变更均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种阻燃型树脂预聚物，其特征在于，所述阻燃型树脂预聚物至少由双马来酰亚胺树脂和胺类化合物预聚而成，所述胺类化合物中含有结构式(1)和/或结构式(2)所示的胺化合物：
    Figure PCTCN2019118113-appb-100001
    其中，A 1为
    Figure PCTCN2019118113-appb-100002
    Figure PCTCN2019118113-appb-100003
    R 1为C1-C10的直链亚烷基或取代亚烷基或C6-C20的芳香族基；n为1-10的整数。
  2. 根据权利要求1所述的阻燃型树脂预聚物，其特征在于，所述双马来酰亚胺树脂和胺类化合物的重量比例为100:15-50。
  3. 根据权利要求1所述的阻燃型树脂预聚物，其特征在于，所述阻燃型树脂预聚物中不含有环氧树脂。
  4. 根据权利要求1所述的阻燃型树脂预聚物，其特征在于，所述双马来酰亚胺树脂具有以下结构式：
    Figure PCTCN2019118113-appb-100004
    其中，R基选自下列结构式中的至少一种：
    Figure PCTCN2019118113-appb-100005
  5. 根据权利要求1所述的阻燃型树脂预聚物，其特征在于，所述胺类化合物中还含有无磷二胺化合物，其含量为以总胺类化合物100质量分计，含有10-60份。
  6. 一种阻燃型树脂组合物，其特征在于，以固体重量计，包括：
    权利要求1所述的阻燃型树脂预聚物：100份；
    填料：0-150份；
    固化促进剂：0.005-5份；
    弹性体：0-50份。
  7. 根据权利要求6所述的阻燃型树脂组合物，其特征在于，所述填料为无机填料或有机填料，所述无机填料选自非金属氧化物、金属氮化物、非金属氮化物、无机水合物、无机盐、金属水合物或无机磷中的一种或者至少任意两种的混合物；所述有机填料选自聚四氟乙烯粉末、聚苯硫醚或聚醚砜粉末中的一种或者至少任意两种的混合物。
  8. 一种半固化片，其特征在于，在采用如上权利要求6或7所述的阻燃型树脂组合物中加入溶剂溶解制成胶液，将增强材料浸渍在所述胶液中，将浸渍后的所述增强材料加热干燥后，即可得到所述半固化片。
  9. 一种层压板，其特征在于，在至少一张权利要求8所述的半固化片的双面覆上离型膜，热压成形，即可得到所述层压板。
  10. 一种层压板，其特征在于，在至少一张权利要求8所述的半固化片的单面或双面覆上金属箔，热压成形，即可得到所述层压板。
PCT/CN2019/118113 2018-11-28 2019-11-13 阻燃型树脂预聚物及使用其制备的树脂组合物、半固化片和层压板 WO2020108310A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201811436719.4 2018-11-28
CN201811436719.4A CN109593200B (zh) 2018-11-28 2018-11-28 一种阻燃型树脂预聚物及使用其制备的树脂组合物、半固化片和层压板

Publications (1)

Publication Number Publication Date
WO2020108310A1 true WO2020108310A1 (zh) 2020-06-04

Family

ID=65959855

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2019/118113 WO2020108310A1 (zh) 2018-11-28 2019-11-13 阻燃型树脂预聚物及使用其制备的树脂组合物、半固化片和层压板

Country Status (2)

Country Link
CN (1) CN109593200B (zh)
WO (1) WO2020108310A1 (zh)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109593200B (zh) * 2018-11-28 2020-05-26 苏州生益科技有限公司 一种阻燃型树脂预聚物及使用其制备的树脂组合物、半固化片和层压板
CN117325527B (zh) * 2023-10-24 2024-04-19 安能电子有限公司 一种无卤素阻燃层压板

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1887892A (zh) * 2006-07-28 2007-01-03 四川东材企业集团有限公司 一种高热稳定性无卤阻燃含磷化合物及其制备方法
US20090182116A1 (en) * 2008-01-15 2009-07-16 National Chung Hsing University Manufacture of phosphorus-containing diamines and their derivatives
CN104447869A (zh) * 2014-10-27 2015-03-25 复旦大学 一种含dopo且分子结构不对称的双马来酰亚胺、其制备方法及在制备复合树脂中的应用
CN106854222A (zh) * 2016-12-06 2017-06-16 沈阳化工大学 一种磷、氮型阻燃剂及其制备方法
CN107400197A (zh) * 2017-08-04 2017-11-28 武汉工程大学 一种反应型阻燃环氧树脂固化剂及其制备方法
CN107501493A (zh) * 2017-08-10 2017-12-22 长春工业大学 磷氮膨胀型阻燃剂及其制备方法和用途
CN109593200A (zh) * 2018-11-28 2019-04-09 苏州生益科技有限公司 一种阻燃型树脂预聚物及使用其制备的树脂组合物、半固化片和层压板

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013019085A2 (ko) * 2011-08-04 2013-02-07 삼성정밀화학(주) 열경화성 수지 제조용 조성물 및 그의 경화물, 상기 경화물을 포함하는 프리프레그, 및 상기 프리프레그를 채용한 금속박 적층판과 프린트 배선판
CN104961895A (zh) * 2014-11-24 2015-10-07 西安元创化工科技股份有限公司 一种阻燃双马来酰亚胺树脂
CN108129659B (zh) * 2017-12-25 2020-11-10 山东圣泉新材料股份有限公司 一种双马来酰亚胺组合物及其制备方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1887892A (zh) * 2006-07-28 2007-01-03 四川东材企业集团有限公司 一种高热稳定性无卤阻燃含磷化合物及其制备方法
US20090182116A1 (en) * 2008-01-15 2009-07-16 National Chung Hsing University Manufacture of phosphorus-containing diamines and their derivatives
CN104447869A (zh) * 2014-10-27 2015-03-25 复旦大学 一种含dopo且分子结构不对称的双马来酰亚胺、其制备方法及在制备复合树脂中的应用
CN106854222A (zh) * 2016-12-06 2017-06-16 沈阳化工大学 一种磷、氮型阻燃剂及其制备方法
CN107400197A (zh) * 2017-08-04 2017-11-28 武汉工程大学 一种反应型阻燃环氧树脂固化剂及其制备方法
CN107501493A (zh) * 2017-08-10 2017-12-22 长春工业大学 磷氮膨胀型阻燃剂及其制备方法和用途
CN109593200A (zh) * 2018-11-28 2019-04-09 苏州生益科技有限公司 一种阻燃型树脂预聚物及使用其制备的树脂组合物、半固化片和层压板

Also Published As

Publication number Publication date
CN109593200B (zh) 2020-05-26
CN109593200A (zh) 2019-04-09

Similar Documents

Publication Publication Date Title
WO2020108351A1 (zh) 阻燃型树脂组合物及使用其制备的半固化片和层压板
US9629239B2 (en) Resin composition, and prepreg as well as laminate using the same
KR102466877B1 (ko) 열경화성 수지 조성물, 프리프레그, 적층판 및 다층 프린트 배선판
WO2015024256A1 (zh) 树脂组成物及其铜箔基板和印刷电路板
JP2013001807A (ja) 電子回路基板材料用樹脂組成物、プリプレグ及び積層板
CN112250865B (zh) 改性马来酰亚胺树脂预聚物及其制备方法、树脂组合物、半固化片、层压板和印刷电路板
WO2016011705A1 (zh) 一种无卤树脂组合物以及使用它的预浸料和印制电路用层压板
WO2020108334A1 (zh) 阻燃型树脂预聚物及使用其制备的热固性树脂组合物、半固化片和层压板
CN105348742B (zh) 含三聚氰胺型苯并噁嗪树脂的热固性树脂组合物、半固化片及层压板
TW201823335A (zh) 環氧樹脂組合物、預浸料、層壓板和印刷電路板
TW202045622A (zh) 樹脂組合物、預浸料、層壓板、覆金屬箔層壓板以及印刷電路板
TW202106798A (zh) 硬化性樹脂組成物
EP3412722B1 (en) Halogen-free thermosetting resin composition, prepreg containing same, laminate, and printed circuit board
WO2020108310A1 (zh) 阻燃型树脂预聚物及使用其制备的树脂组合物、半固化片和层压板
TW202030255A (zh) 樹脂組成物及其製造方法、清漆、積層板、印刷配線基板以及成形品
CN109504087B (zh) 一种树脂组合物及使用其制备的半固化片和层压板
TWI669340B (zh) 無鹵熱固性樹脂組合物及使用它的預浸料、層壓板、覆金屬箔層壓板和印刷電路板
TW202031783A (zh) 樹脂組成物、預浸體、附樹脂之薄膜、附樹脂之金屬箔、覆金屬積層板及印刷配線板
TW201829578A (zh) 無鹵熱固性樹脂組合物及使用它的預浸料、層壓板、覆金屬箔層壓板和印刷電路板
JP2016065250A (ja) プリプレグ、積層板及び金属張積層板
TW202106796A (zh) 硬化性樹脂組成物
WO2020143336A1 (zh) 高频树脂预聚物及使用其制备的高频树脂组合物、半固化片、层压板和层间绝缘膜
TW202006044A (zh) 滲出抑制劑、樹脂用阻燃劑、樹脂組成物、及其成形體
TWI763282B (zh) 一種無鹵阻燃型樹脂組成物及其應用
KR20220010518A (ko) 수지 조성물, 프리프레그, 적층판, 금속박 적층판 및 인쇄회로기판

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19888771

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19888771

Country of ref document: EP

Kind code of ref document: A1