WO2022088239A1 - Maleimide-modified active ester, preparation method therefor and use thereof - Google Patents
Maleimide-modified active ester, preparation method therefor and use thereof Download PDFInfo
- Publication number
- WO2022088239A1 WO2022088239A1 PCT/CN2020/127671 CN2020127671W WO2022088239A1 WO 2022088239 A1 WO2022088239 A1 WO 2022088239A1 CN 2020127671 W CN2020127671 W CN 2020127671W WO 2022088239 A1 WO2022088239 A1 WO 2022088239A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- active ester
- substituted
- maleimide
- branched
- unsubstituted
- Prior art date
Links
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- 238000002360 preparation method Methods 0.000 title claims abstract description 25
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- 229920000647 polyepoxide Polymers 0.000 claims abstract description 51
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 claims abstract description 27
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 23
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- 150000004677 hydrates Chemical class 0.000 description 2
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L45/00—Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such polymers
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C08L61/14—Modified phenol-aldehyde condensates
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/02—Composition of the impregnated, bonded or embedded layer
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
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- 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
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- 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
- C08J2445/00—Characterised by the use of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Derivatives of such polymers
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- 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
- C08J2461/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2461/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2461/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C08J2461/14—Modified phenol-aldehyde condensates
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- C—CHEMISTRY; METALLURGY
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
Definitions
- the invention belongs to the technical field of copper clad laminates, and particularly relates to a maleimide-modified active ester and a preparation method and application thereof.
- Basic electronic materials represented by copper clad laminates and circuit substrates usually include a reinforcing substrate and a resin layer attached to the substrate.
- the performance of electronic materials depends largely on the composition and properties of the resin layer. At present, most of the resin layer materials in electronic materials use epoxy resin systems.
- the epoxy resin composition with epoxy resin and curing agent as essential components shows good heat resistance and insulation after curing, and has excellent processability and cost advantages, so it is widely used in electronic films, semiconductors or In electronic materials such as multilayer printed circuit boards.
- epoxy resin itself has high dielectric constant (D k ) and dielectric loss (D f ), and is cured with traditional curing agents such as amines and phenolic resins, and the cured product will generate a large number of secondary hydroxyl groups, resulting in The water absorption rate increases, and the dielectric properties and damp heat resistance decrease.
- the active ester contains a highly active ester group, which can be used as a curing agent to undergo a transesterification reaction with epoxy resin.
- the network structure formed after the reaction does not contain secondary alcohol hydroxyl groups, so that the cured product has low dielectric loss and low water absorption. rate and lower dielectric constant.
- JP2009235165 discloses an epoxy resin composition and a cured product thereof, wherein an active ester compound having the following structure is used in the epoxy resin composition:
- the resin composition has both high heat resistance and low dielectric tangent, and at the same time, when dissolved in an organic solvent, the viscosity is low enough to facilitate the later processing.
- the crosslinking density of the cured products is not high, which is manifested in the shortcomings of low glass transition temperature (T g ) and high thermal expansion coefficient. To a certain extent, it restricts its application in high-performance printed circuit board substrates.
- Bismaleimide resin is a kind of high-performance matrix resin, and its cured product has high glass transition temperature, high heat resistance and good mechanical and dielectric properties.
- the resin composition disclosed in CN101885900A includes brominated epoxy resin, bismaleimide resin, cyanate ester resin, zinc isooctanoate catalyst and solvent, which has the characteristics of high T g and low thermal expansion coefficient, so that it can be used
- the copper clad laminate produced by it has good heat resistance, peel strength and dielectric properties, and is suitable for the domestic IC packaging industry and HDI multi-layer PCB.
- bismaleimide resin is brittle and cannot react directly with epoxy resin. It is often modified or mixed with amine, diallyl bisphenol A, etc. before it can be used with epoxy resin.
- the structure of maleimide is also easy to absorb water, which greatly reduces the dielectric properties and resistance to humidity and heat of the cured product, and cannot be used in high performance in printed circuit board substrates.
- the purpose of the present invention is to provide a maleimide-modified active ester and its preparation method and application.
- the active ester is prepared from specific raw materials, and its molecular structure contains active esters. Ester group and maleimide group, the two groups cooperate with each other, so that the active ester has the characteristics of high reaction crosslinking site, low water absorption rate, low dielectric loss, low dielectric constant and low thermal expansion coefficient.
- the epoxy resin composition using the active ester as a curing agent exhibits excellent dielectric properties, heat resistance, damp heat resistance and low thermal expansion coefficient after curing, and has good bonding force with metal, which can fully meet the high performance requirements. Application requirements for circuit substrates.
- the present invention provides a maleimide-modified active ester, and the preparation raw materials of the active ester include: a diphenol compound having a structure as shown in formula A1, a diphenolic compound having a structure as shown in formula A2 A diacyl compound and a maleimide group-containing compound having the structure shown in formula A3.
- Ar is a substituted or unsubstituted C6-C150 divalent aromatic group; the substituted substituent in Ar is selected from fluorine, C1-C5 (such as C1, C2, C3, C4 or C5) straight chain Or branched chain alkyl group, C2-C5 (eg C2, C3, C4 or C5) straight chain or branched chain alkene group, group containing aryl phosphorus oxygen structure.
- C1-C5 such as C1, C2, C3, C4 or C5
- C2-C5 eg C2, C3, C4 or C5 straight chain or branched chain alkene group, group containing aryl phosphorus oxygen structure.
- the "divalent aromatic group” refers to a group containing an aryl group with two bonding sites, including an arylene group, and at least two aryl groups are connected through a linking group (for example, -O-, -S-, carbonyl, sulfone, alkylene, cycloalkylene or arylene alkyl, etc.) are linked together to form a substituent.
- a linking group for example, -O-, -S-, carbonyl, sulfone, alkylene, cycloalkylene or arylene alkyl, etc.
- the C1-C5 straight-chain or branched-chain alkyl groups include C1, C2, C3, C4 or C5 straight-chain or branched-chain alkyl groups, exemplarily including but not limited to: methyl, ethyl, n-propyl, isopropyl propyl, n-butyl, isobutyl, tert-butyl, pentyl or isopentyl, etc.
- X is a substituted or unsubstituted C6-C18 (such as C6, C9, C10, C12, C14, C16 or C18, etc.) divalent aromatic group; the substituted substituent in X is selected from fluorine, C1-C5 (eg C1, C2, C3, C4 or C5) straight or branched chain alkyl.
- X 1 is selected from halogen or hydroxyl.
- Ar 1 is a substituted or unsubstituted C6-C12 (such as C6, C9, C10 or C12, etc.) arylene; the substituted substituent in Ar 1 is selected from fluorine, C1-C5 (such as C1, C2, C3, C4 or C5) straight or branched chain alkyl;
- R 1 and R 2 are each independently selected from hydrogen, fluorine, C1-C5 (eg C1, C2, C3, C4 or C5) linear or branched alkyl.
- the active ester provided by the present invention is prepared from three types of raw materials: diphenolic compound, diphenolic compound and maleimide group-containing compound, and the active ester contains two kinds of maleimide group and active ester group functional groups, the two synergize with each other, so that the active ester has the advantages of low dielectric loss, low dielectric constant, low water absorption, high reactive crosslinking sites, high T g , high heat resistance and low thermal expansion coefficient, etc.
- As a curing agent it reacts with epoxy resin, and the obtained cured product has excellent dielectric properties, heat resistance, damp heat resistance, low thermal expansion coefficient and strong metal bonding force.
- the active ester of the present invention can undergo transesterification reaction with epoxy groups to generate alkyl ester structures, that is, as active esters with good reactivity with epoxy groups, in its structure, ester groups are
- the connection mode must be in the form of phenolic oxygen rather than the form of alcohol oxygen, so the part directly connected to the oxygen atom in the Ar and Ar 1 are all aromatic rings, that is, the diphenolic compound with the structure shown in formula A1 and the
- the maleimide group-containing compound of the structure represented by formula A3 is a phenolate rather than an alcoholate.
- the Ar is selected from
- Ar 2 is selected from
- Ar 3 is selected from
- R 3 and R 4 are each independently selected from fluorine, C1-C5 (eg C1, C2, C3, C4 or C5) linear or branched alkyl, C2-C5 (eg C2, C3, C4 or C5) linear chain or branched chain alkene,
- the short straight line on one side or both sides of the group structure represents the access bond of the group, and does not represent the methyl group.
- R 5 is a C1-C5 (eg C1, C2, C3, C4 or C5) linear or branched alkylene group.
- n 1 and n 3 are each independently selected from an integer of 0 to 4, for example, 0, 1, 2, 3 or 4.
- n 2 is selected from an integer from 0 to 6, such as 0, 1, 2, 3, 4, 5 or 6.
- Y 1 and Y 2 are each independently selected from -O-, -S-, carbonyl, sulfone, substituted or unsubstituted C1-C20 (eg C1, C2, C3, C4, C5, C6, C8, C10, C12 , C14, C16, C18 or C20, etc.) straight or branched chain alkylene, substituted or unsubstituted C3 to C30 (such as C3, C4, C5, C6, C8, C10, C12, C15, C18, C20, C22 , C25, C28 or C29, etc.) cycloalkylene, substituted or unsubstituted C6-C30 (such as C6, C7, C8, C9, C10, C12, C15, C18, C20, C22, C25, C28 or C29, etc.) Aralkylene; the substituted substituents are each independently selected from fluorine, C1-C5 (eg C1, C2, C3, C4 or
- m represents the average value of repeating units, selected from 0 to 10, such as 0.2, 0.5, 0.8, 1, 1.2, 1.5, 1.8, 2, 2.2, 2.5, 2.8, 3, 3.3, 3.5, 3.7, 4, 4.2, 4.5 , 4.7, 5, 5.3, 5.5, 5.8, 6, 6.2, 6.5, 6.8, 7, 7.5, 8, 8.5, 9, 9.5 or 10, and specific point values between the above-mentioned point values, are limited by space and for brevity Considering that the present invention does not exhaustively list the specific point values included in the range.
- the Y 1 and Y 2 are each independently selected from -O-, -S-, C1-C5 (eg C1, C2, C3, C4 or C5) straight or branched chain alkylene,
- the X is selected from substituted or unsubstituted phenylene, substituted or unsubstituted biphenylene Substituted or unsubstituted naphthylene, substituted or unsubstituted biphenylene ether
- the substituted substituents are each independently selected from fluorine, C1-C5 (eg, C1, C2, C3, C4, or C5) straight or branched chain alkyl.
- the X 1 is selected from chlorine, bromine, iodine or hydroxyl.
- the Ar 1 is selected from substituted or unsubstituted phenylene, substituted or unsubstituted naphthylene; the substituted substituent is selected from fluorine, C1-C5 (such as C1, C2, C3, C4 or C5) Linear or branched alkyl.
- both R 1 and R 2 are hydrogen.
- the molar ratio of the diacyl compound to the diphenolic compound is 1:(0.5-0.9), for example, 1:0.52, 1:0.55, 1:0.58, 1:0.6, 1:0.62, 1:0.65 , 1:0.68, 1:0.7, 1:0.72, 1:0.75, 1:0.78, 1:0.8, 1:0.82, 1:0.85, 1:0.87 or 1:0.89, etc., preferably 1:(0.5 ⁇ 0.8 ).
- the molar ratio of the diacyl compound to the maleimide group-containing compound is 1:(0.2-1), for example, 1:0.22, 1:0.25, 1:0.28, 1:0.3, 1:0.32 , 1:0.35, 1:0.38, 1:0.4, 1:0.42, 1:0.45, 1:0.48, 1:0.5, 1:0.52, 1:0.55, 1:0.58, 1:0.6, 1:0.62, 1 :0.65, 1:0.68, 1:0.7, 1:0.72, 1:0.75, 1:0.78, 1:0.8, 1:0.82, 1:0.85, 1:0.88, 1:0.9, 1:0.92, 1:0.95 , 1:0.97 or 1:0.99, etc., preferably 1:(0.4 to 1).
- the diacyl compound is in excess relative to the diphenolic compound, the reaction between the diphenolic compound and the diacyl compound plays a role in chain extension, and the maleimide group-containing compound is a capping agent, Played a role in terminating chain growth.
- the diphenolic compound is in excess relative to the diacyl compound, and the maleimide group-containing monoacyl halide or its carboxylic acid compound is used as the end-capping agent for the excess phenolic compound.
- the structural form of "maleimide group-containing monoacyl halide or its carboxylic acid compound as the end-capping agent" is better than the maleimide modification defined in the present invention.
- the performance of the active esters in dielectric constant, dielectric loss and adhesion is comparable, its performance in terms of heat and humidity resistance is not good, which affects its subsequent application. Therefore, the present invention selects specific structures of diphenolic compounds, diacyl compounds and maleimide group-containing compounds as reaction raw materials, so that the maleimide-modified active esters have good dielectric properties, heat resistance The best balance has been achieved in terms of comprehensive properties such as , heat and humidity resistance and adhesion.
- the higher the proportion of the diphenolic compound the higher the proportion of maleimide groups.
- the performance of the cured product tends to be more like the general active ester, that is, the dielectric properties are slightly better, but the T g and thermal expansion coefficient are insufficient, and the molecular weight of the obtained maleimide-modified active ester is higher.
- the molar ratio of the diacyl compound to the diphenolic compound is 1:(0.5-0.8), and the diacyl compound and the maleimide group-containing The molar ratio of the compounds is 1:(0.4-1).
- the present invention provides a preparation method of the above-mentioned active ester, the preparation method comprises: a diphenol compound having a structure as shown in formula A1, a diacyl compound having a structure as shown in formula A2, and The maleimide group-containing compound having the structure shown in formula A3 is reacted to obtain the active ester.
- the temperature of the reaction is -10 to 60°C, such as -10°C, -8°C, -5°C, -2°C, -0°C, 2°C, 5°C, 8°C, 10°C, 12°C , 15°C, 18°C, 20°C, 22°C, 25°C, 28°C, 30°C, 32°C, 35°C, 38°C, 40°C, 42°C, 45°C, 48°C, 50°C, 52°C, 55°C °C or 58 °C, as well as specific point values between the above-mentioned point values, limited by space and for the sake of brevity, the present invention will not exhaustively list the specific point values included in the range.
- the reaction is carried out in the presence of a basic catalyst.
- the basic catalyst includes inorganic basic compounds and/or organic bases;
- the inorganic basic compounds include sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, sodium acetate, potassium acetate, Any one or a combination of at least two of sodium bicarbonate or potassium bicarbonate;
- the organic base includes triethylamine, pyridine, 4-dimethylaminopyridine, tributylamine, N,N-diisopropylethyl Amine, benzyltriethylammonium chloride, tetraethylammonium bromide, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate, trioctylmethylammonium chloride, dodecyl Any one or a combination of at least two of alkyl trimethyl ammonium chloride or tetradecyl trimethyl ammonium
- the reaction is carried out in a protective atmosphere, and the protective atmosphere is preferably nitrogen or argon.
- the reaction is carried out in the presence of a solvent.
- the reaction is carried out in the presence of a solvent, which is not particularly limited as long as it does not hinder the reaction, exemplarily including but not limited to: tetrahydrofuran, dioxane, benzene, toluene, xylene, dichloromethane , dichloroethane, butanone, methyl isobutyl ketone, cyclohexanone, 1,4-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylidene Either one or a combination of at least two of sulfone or N-methylpyrrolidone.
- a solvent which is not particularly limited as long as it does not hinder the reaction, exemplarily including but not limited to: tetrahydrofuran, dioxane, benzene, toluene, xylene, dichloromethane , dichloroethane, butanone, methyl isobutyl ket
- the amount of the solvent can be appropriately adjusted according to the different solubility of raw materials and products, so that each raw material and product can be dissolved in the solvent, preferably 3 to 15 times the sum of the mass of each raw material, such as 3.5 times, 4 times, 4.5 times times, 5 times, 5.5 times, 6 times, 6.5 times, 7 times, 7.5 times, 8 times, 8.5 times, 9 times, 10 times, 11 times, 12 times, 13 times, or 14 times, etc.
- the reaction further includes post-treatment of the product after completion.
- the post-processing method includes filtration, water washing, concentration, extraction, recrystallization or column chromatography, etc., to achieve separation and purification of the active ester.
- the present invention provides a thermosetting resin composition comprising an epoxy resin and an active ester as described above.
- thermosetting resin composition provided by the present invention includes epoxy resin and maleimide-modified active ester as described above, and the molecular structure of the active ester contains both active ester group (aryl ester group) and maleic acid ester group.
- the imide group has more reactive sites.
- the aryl ester group reacts with the epoxy resin, it will not produce a strongly polar secondary hydroxyl group, thereby The cured product has low dielectric loss, low water absorption and low dielectric constant; on the other hand, the maleimide group can be cured to form an imide ring structure with high rigidity and high heat resistance, and the reaction process is not Generates polar groups such as hydroxyl and amino groups, so it has excellent heat resistance (high T g ) and mechanical properties, as well as good dielectric properties and processing properties, thus overcoming the general active ester curing epoxy resin in T g and Defects in the coefficient of thermal expansion.
- the epoxy resin refers to an epoxy resin having at least two epoxy groups in one molecule, exemplarily including but not limited to: bifunctional bisphenol A epoxy resin, bifunctional bisphenol F type epoxy resin, bifunctional bisphenol S type epoxy resin, phenol formaldehyde type epoxy resin, cresol novolac type epoxy resin, bisphenol A type novolac epoxy resin, dicyclopentadiene (DCPD) epoxy resin Resin, biphenyl epoxy resin, DCPD epoxy resin, biphenyl novolac epoxy resin, resorcinol epoxy resin, naphthalene epoxy resin, phosphorus-containing epoxy resin, silicon-containing epoxy resin, shrinkage Glycerylamine type epoxy resin, alicyclic epoxy resin, polyethylene glycol type epoxy resin, tetraphenol ethane tetraglycidyl ether, triphenol methane type epoxy resin, bifunctional cyanate ester and epoxy resin Any one or a combination of at least two of a condensate of a resin or a condensate of a
- thermosetting resin composition further includes any one or a combination of at least two of other curing agents, flame retardants, inorganic fillers, organic fillers or curing accelerators.
- the other curing agent is selected from amine curing agent, phenol curing agent, benzoxazine curing agent, cyanate ester curing agent, common active ester curing agent (with maleic acid described in the present invention) Any one or a combination of at least two of imine-modified active ester), acid anhydride curing agent or amine-modified maleimide curing agent.
- the flame retardant is selected from any one or a combination of at least two of halogen-based organic flame retardants, phosphorus-based organic flame retardants, nitrogen-based organic flame retardants or silicon-containing organic flame retardants.
- the inorganic filler includes any one or a combination of at least two of non-metal oxides, metal nitrides, non-metal nitrides, inorganic hydrates, inorganic salts, metal hydrates or inorganic phosphorus; more preferably Fused silica, crystalline silica, spherical silica, hollow silica, aluminum hydroxide, alumina, talc, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, Any one or a combination of at least two of strontium titanate, calcium carbonate, calcium silicate or mica.
- the organic filler includes any one or a combination of at least two of polytetrafluoroethylene powder, polyphenylene sulfide powder or polyethersulfone powder.
- the curing accelerator includes any one or a combination of at least two of imidazoles, derivatives of imidazoles, piperidines, pyridines, organic metal salt Lewis acids or triphenylphosphine .
- “comprising” means that in addition to the above-mentioned components, other components may be included, and these other components impart different properties to the thermosetting resin composition.
- “comprising” can also be replaced with closed “is” or “consisting of”.
- thermosetting resin composition of the present invention can be as follows: first put the solid matter, then add the solvent, stir until the solid matter is completely dissolved, then add the liquid resin and the curing accelerator, and continue to stir evenly.
- the solvent is not particularly limited, including any one or a combination of at least two of alcohol solvents, ether solvents, aromatic hydrocarbon solvents, ester solvents, ketone solvents or nitrogen-containing solvents, preferably ketone solvents .
- the alcohol solvent includes any one or a combination of at least two of methanol, ethanol or butanol
- the ether solvent includes ethyl cellosolve, butyl cellosolve, ethylene glycol methyl ether, carbitol Any one or a combination of at least two of alcohol or butyl carbitol
- the aromatic hydrocarbon solvent includes any one or a combination of at least two of benzene, toluene or xylene
- the ester solvent includes Any one or a combination of at least two of ethyl acetate, butyl acetate or ethoxyethyl acetate
- the ketone solvent includes acetone, methyl ethyl ketone, methyl ethy
- the amount of the solvent can be adjusted according to actual processing and application requirements.
- the present invention also relates to a cured product prepared by curing the aforementioned thermosetting resin composition.
- the present invention provides a semiconductor sealing material whose raw material includes the thermosetting resin composition as described above.
- the present invention provides a prepreg comprising a base material, and the above-mentioned thermosetting resin composition adhered to the base material by impregnation and drying.
- the base material includes any one or a combination of at least two of glass fiber cloth, non-woven fabric or quartz cloth.
- the glass fiber cloth can be E-glass fiber cloth, D-glass fiber cloth, S-glass fiber cloth, T glass fiber cloth, NE-glass fiber cloth, or the like.
- the thickness of the substrate is not particularly limited; for the consideration of good dimensional stability, the thickness of the substrate is preferably 0.01-0.2 mm, such as 0.02 mm, 0.05 mm, 0.08 mm, 0.1 mm, 0.12 mm, 0.15 mm mm, 0.17mm or 0.19mm, etc.
- the substrate is a substrate that has undergone fiber opening treatment and/or surface treatment with a silane coupling agent.
- the silane coupling agent is preferably any one or a combination of at least two of epoxy silane coupling agent, amino silane coupling agent or vinyl silane coupling agent.
- the preparation method of the prepreg is as follows: the base material is dipped in the resin glue solution of the thermosetting resin composition, taken out and then dried to obtain the prepreg.
- the drying temperature is 100-250°C, such as 105°C, 110°C, 115°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, 190°C, 200°C , 210°C, 220°C, 230°C, 240°C or 245°C, etc.
- the drying time is 1 to 15 minutes, such as 2 minutes, 3 minutes, 4 minutes, 5 minutes, 6 minutes, 7 minutes, 8 minutes, 9 minutes, 10 minutes, 11 minutes, 12 minutes, 13 minutes, or 14 minutes.
- the present invention provides a circuit substrate comprising at least one prepreg as described above, and metal foils disposed on one or both sides of the prepreg.
- the material of the metal foil is not particularly limited; preferably, the metal foil includes copper foil, nickel foil, aluminum foil or SUS foil.
- the preparation method of the circuit substrate is as follows: pressing a metal foil on one side or both sides of a prepreg and curing to obtain the circuit substrate; or, adhering at least two prepregs to make the circuit substrate. A laminate is formed, and then metal foil is laminated on one side or both sides of the laminate and cured to obtain the circuit substrate.
- the curing is carried out in a hot press.
- the curing temperature is 150-250°C, such as 150°C, 155°C, 160°C, 165°C, 170°C, 175°C, 180°C, 185°C, 190°C, 195°C, 200°C, 205°C , 210°C, 215°C, 220°C, 225°C, 230°C, 235°C, 240°C or 245°C, etc.
- the curing pressure is 10-60kg/cm 2 , such as 15kg/cm 2 , 20kg/cm 2 , 25kg/cm 2 , 30kg/cm 2 , 35kg/cm 2 , 40kg/cm 2 , 45kg/cm 2 2 , 50kg/cm 2 or 55kg/cm 2 , etc.
- the present invention provides a laminated film comprising a base film or metal foil, and the above-mentioned thermosetting resin coated on at least one surface of the base film or metal foil combination.
- the present invention has the following beneficial effects:
- the maleimide-modified active ester provided by the present invention contains active ester group (aromatic ester group) and maleimide group, and has more reactive cross-linking sites and low dielectric loss , low dielectric constant and low water absorption, can be used as a curing agent for curing reaction with epoxy resin, and the obtained cured product has excellent dielectric properties, heat resistance, moisture and heat resistance, low thermal expansion coefficient and processing performance.
- thermosetting resin composition provided by the present invention is used in combination with a maleimide-modified active ester with a high cross-linking site and an epoxy resin.
- the aryl ester group in the active ester and the ring The oxygen resin does not generate strong polar secondary hydroxyl groups during the reaction, so that the obtained cured product has low dielectric loss, low dielectric constant and low water absorption;
- the maleimide group in the active ester It can be cured to form an imide ring structure with high rigidity and high heat resistance.
- the reaction process does not produce polar groups such as hydroxyl and amino groups, so it has excellent heat resistance, so that the cured product has high T g and excellent resistance. Thermal properties, mechanical properties and bonding properties, as well as good dielectric properties and processing properties.
- thermosetting resin composition comprising the active ester and a circuit substrate thereof, having a low coefficient of thermal expansion, low dielectric constant and dielectric loss, and exhibiting excellent dielectric properties, heat resistance, moist heat resistance and The bonding strength with metal can meet the high performance requirements of circuit substrates.
- Fig. 1 is the infrared spectrogram of the maleimide-modified active ester that embodiment 1 provides;
- Fig. 2 is the ultra-efficient polymer chromatogram of the maleimide-modified active ester provided in Example 1.
- a maleimide-modified active ester K-1 comprising the steps:
- the reaction system was controlled below 60° C., 420 g (2.1 mol) of a 20% aqueous sodium hydroxide solution was added dropwise for 3 h, and the mixture was stirred for 1 h after the dropwise addition. After completion of the reaction, the aqueous layer was removed by standing for liquid separation. Deionized water was added to the obtained toluene layer and stirred for 15 min, the water layer was removed by standing for liquid separation, and the obtained toluene layer was repeatedly washed with water until the pH of the water layer was 7. Finally, the maleimide-modified active ester K-1 is obtained by heating and drying under reduced pressure.
- the ester group equivalent of the maleimide-modified active ester K-1 provided in this example is 237 g/eq.
- a maleimide-modified active ester K-2 comprising the steps:
- the reaction system was controlled below 30°C, 0.5 g of tetrabutylammonium bromide was added, and then 589 g (2.1 mol) of a 20% aqueous potassium hydroxide solution was added dropwise over 3 h, and the mixture was stirred for 1 h after the dropwise addition. After completion of the reaction, the aqueous layer was removed by standing for liquid separation. In the obtained dichloromethane layer, deionized water was added and stirred for 15min, the water layer was removed by standing for liquid separation, and the obtained dichloromethane layer was repeatedly washed with water until the pH of the water layer was 7. Finally, the maleimide-modified active ester K-2 is obtained by heating and drying under reduced pressure.
- the ester group equivalent of the maleimide-modified active ester K-2 provided in this example is 242 g/eq.
- a maleimide-modified active ester K-3 comprising the steps:
- the reaction system was controlled below 30°C, 0.5 g of tetrabutylammonium bromide was added, and then 589 g (2.1 mol) of a 20% aqueous potassium hydroxide solution was added dropwise over 3 h, and the mixture was stirred for 1 h after the dropwise addition. After completion of the reaction, the aqueous layer was removed by standing for liquid separation. Deionized water was added to the obtained dichloromethane layer and stirred for 15 min. The aqueous layer was removed by standing for liquid separation. The obtained dichloromethane layer was repeatedly washed with water until the pH of the water layer was 7. Finally, the maleimide-modified active ester K-3 is obtained by heating and drying under reduced pressure.
- the ester group equivalent of the maleimide-modified active ester K-3 provided in this example is 204 g/eq.
- a maleimide-modified active ester K-4 comprising the steps:
- the aqueous layer was removed by standing for liquid separation.
- Deionized water was added to the obtained dichloromethane layer and stirred for 15 min.
- the aqueous layer was removed by standing for liquid separation.
- the obtained dichloromethane layer was repeatedly washed with water until the pH of the water layer was 7.
- the maleimide-modified active ester K-4 is obtained by heating and drying under reduced pressure.
- the ester group equivalent of the maleimide-modified active ester K-4 provided in this example is 283 g/eq.
- a maleimide-modified active ester K-5 comprising the steps:
- the aqueous layer was removed by standing for liquid separation.
- Deionized water was added to the obtained dichloromethane layer and stirred for 15 min.
- the aqueous layer was removed by standing for liquid separation.
- the obtained dichloromethane layer was repeatedly washed with water until the pH of the water layer was 7.
- the maleimide-modified active ester K-5 is obtained by heating and drying under reduced pressure.
- the ester group equivalent of the maleimide-modified active ester K-5 provided in this example is 253.5 g/eq.
- a modified active ester L-1 the preparation method comprises the steps:
- the reaction system was controlled below 60°C, and 420 g (2.1 mol) of a 20% aqueous sodium hydroxide solution was added dropwise for 3 h, and the mixture was stirred for 1 h after the dropwise addition. After completion of the reaction, the aqueous layer was removed by standing for liquid separation. Deionized water was added to the obtained toluene layer and stirred for 15 min, the water layer was removed by standing for liquid separation, and the obtained toluene layer was repeatedly washed with water until the pH of the water layer was 7. Finally, the modified active ester L-1 is obtained by heating and drying under reduced pressure.
- the ester group equivalent of the modified active ester L-1 provided by this comparative example is 237 g/eq.
- a modified active ester L-2 the preparation method comprises the steps:
- the ester group equivalent of the modified active ester L-2 provided by this comparative example is 183 g/eq.
- the ultra-high-efficiency polymer chromatogram (APC diagram) of the maleimide-modified active ester K-1 provided in Example 1 is shown in Figure 2, and it can be seen from Figure 2 that the maleimide The weight-average molecular weight M w of the imine-modified active ester K-1 was 2745.
- thermosetting resin composition and a prepreg and a circuit substrate comprising the same, the preparation method is as follows:
- thermosetting resin composition and a prepreg and a circuit substrate comprising the same, the preparation method is as follows:
- thermosetting resin composition and a prepreg and a circuit substrate comprising the same, the preparation method is as follows:
- thermosetting resin composition and a prepreg and circuit substrate comprising the same.
- the components and contents of the thermosetting resin composition are shown in Table 2.
- the preparation methods of the prepreg and the circuit substrate are the same as those in Application Example 1.
- thermosetting resin compositions provided in Application Examples 1 to 5 and Comparative Examples 3 to 6 and the circuit substrates comprising the thermosetting resin compositions were tested for performance, and the methods were as follows:
- PCT heat and humidity resistance
- thermosetting resin composition used is modified with the maleimide provided by the present invention.
- Active ester is used as a curing component, so it has a high glass transition temperature (T g ) and a low coefficient of thermal expansion (Z-CTE), as well as a low dielectric constant and low dielectric loss, excellent heat resistance, and moisture and heat resistance and good bonding strength with metal; among them, the glass transition temperature reaches 190 ⁇ 235 °C, the Z-CTE is as low as 2.2 ⁇ 3.1%, the dielectric constant is lower than 4.10 (10GHz), and the dielectric loss is lower than 0.010 (10GHz). ), T300 (with copper)> 60min, peel strength is greater than 1.10N/mm, reaching 1.15 ⁇ 1.25N/mm, and can pass the PCT (3h) heat and humidity test.
- thermosetting resin composition and circuit substrate cured by the maleimide-modified active ester of the present invention are more stable than the ordinary active ester-cured system. It shows more obvious advantages in terms of T g and Z-CTE.
- Application Example 1 has a more superior performance in heat and humidity resistance (PCT test), which shows that Using the diphenol compounds, diacyl compounds and maleimide group-containing compounds defined in the present invention as reaction raw materials, the maleimide-modified active esters can be improved in dielectric properties, heat resistance, The best balance has been achieved in terms of comprehensive properties such as moisture and heat resistance and adhesion.
- PCT test heat and humidity resistance
- thermosetting resin composition and circuit substrate have excellent T g and low thermal expansion coefficient; if the maleimide group content in the active ester is too low, it will make the thermosetting resin composition and circuit substrate. T g and Z-CTE performance decreased.
- the present invention illustrates a maleimide-modified active ester of the present invention and its preparation method and application through the above-mentioned examples, but the present invention is not limited to the above-mentioned process steps, that is, it does not mean that the present invention The invention must rely on the above process steps to be implemented.
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Abstract
Provided are a maleimide-modified active ester, a preparation method therefor and the use thereof. Raw materials for preparing the active ester comprise: a diphenol compound having the structure as shown in formula A1, a diacyl compound having the structure as shown in formula A2 and a maleimide group-containing compound having the structure as shown in formula A3. The active ester is prepared from the three specific raw materials. The molecular structure of the active ester contains an active ester group and maleimide group, and the two functional groups cooperate with each other, such that the active ester has the characteristics of a highly reactive crosslinking site, a low water absorption rate, low dielectric loss, a low dielectric constant and a low thermal expansion coefficient, etc. An epoxy resin composition with the active ester serving as a curing agent and a circuit board comprising same exhibit excellent dielectric properties, heat resistance, resistance to heat and humidity and low thermal expansion coefficients after curing, and have good bonding forces with metal, and the application requirements for a high performance circuit board can be fully met.
Description
本发明属于覆铜板技术领域，具体涉及一种马来酰亚胺改性的活性酯及其制备方法和应用。The invention belongs to the technical field of copper clad laminates, and particularly relates to a maleimide-modified active ester and a preparation method and application thereof.
近年来，随着通信网络、大数据、云计算、数据中心等电子信息领域的快速发展，以及应用端手机、基站、物联网、汽车等硬件载体的不断进步，要求电子材料和电子元器件等具有高速、高频和大容量存储及传输信号的功能；同时，电子设备安装的小型化和高密度化的发展趋势，这就要求基板材料不仅具有良好的介电常数和介电损耗因子来满足信号高频传输的需要，而且还要求其具有良好的耐热性、尺寸稳定性、耐湿热性等来满足多层印制电路板或HDI制程工艺的需求。In recent years, with the rapid development of electronic information fields such as communication networks, big data, cloud computing, and data centers, as well as the continuous progress of hardware carriers such as application-side mobile phones, base stations, Internet of Things, and automobiles, electronic materials and electronic components are required. It has the functions of high-speed, high-frequency and large-capacity storage and signal transmission; at the same time, the development trend of miniaturization and high-density installation of electronic equipment requires that the substrate material not only has good dielectric constant and dielectric loss factor to meet the The need for high-frequency signal transmission, and it is also required to have good heat resistance, dimensional stability, moisture and heat resistance, etc. to meet the needs of multi-layer printed circuit boards or HDI process technology.
以覆铜板和电路基板为代表的基础类电子材料通常包括具有增强作用的基材以及与基材贴合的树脂层，电子材料的性能很大程度上依赖于树脂层的组分和性质。目前电子材料中的树脂层材料大都采用环氧树脂体系。Basic electronic materials represented by copper clad laminates and circuit substrates usually include a reinforcing substrate and a resin layer attached to the substrate. The performance of electronic materials depends largely on the composition and properties of the resin layer. At present, most of the resin layer materials in electronic materials use epoxy resin systems.
以环氧树脂和固化剂为必需成分的环氧树脂组合物，在固化后表现出良好的耐热性和绝缘性，且具有优异的加工性与成本优势，因此广泛用于电子薄膜、半导体或多层印刷电路基板等电子材料中。然而，环氧树脂本身具有较高的介电常数(D
k)和介电损耗(D
f)，使用胺类、酚醛树脂等传统固化剂固化，其固化物会产生大量的二次羟基，导致吸水率上升，介电性能和耐湿热性能下降。
The epoxy resin composition with epoxy resin and curing agent as essential components shows good heat resistance and insulation after curing, and has excellent processability and cost advantages, so it is widely used in electronic films, semiconductors or In electronic materials such as multilayer printed circuit boards. However, epoxy resin itself has high dielectric constant (D k ) and dielectric loss (D f ), and is cured with traditional curing agents such as amines and phenolic resins, and the cured product will generate a large number of secondary hydroxyl groups, resulting in The water absorption rate increases, and the dielectric properties and damp heat resistance decrease.
活性酯含有较高活性的酯基，其作为固化剂可与环氧树脂发生酯交换反应， 反应后所形成的网架结构不含仲醇羟基，使其固化产物具有低介电损耗、低吸水率和较低的介电常数。例如JP2009235165公开了一种环氧树脂组合物及其固化产物，所述环氧树脂组合物中使用了具有如下结构的活性酯化合物：The active ester contains a highly active ester group, which can be used as a curing agent to undergo a transesterification reaction with epoxy resin. The network structure formed after the reaction does not contain secondary alcohol hydroxyl groups, so that the cured product has low dielectric loss and low water absorption. rate and lower dielectric constant. For example, JP2009235165 discloses an epoxy resin composition and a cured product thereof, wherein an active ester compound having the following structure is used in the epoxy resin composition:
其中，X是苯环或萘环，k表示0或1，n为0.25至1.5。该树脂组合物在兼备高耐热性和低介电正切的同时，溶解于有机溶剂中时粘度足够低，便于后期的加工过程。但是，以上述树脂组合物为代表的活性酯固化环氧树脂体系中，因活性酯反应基团的分子量较大，且与环氧基团发生的化学反应机理为酯交换反应，故相对于芳香胺、酚醛树脂、氰酸酯树脂、双马来酰亚胺树脂等而言，其固化物后的交联密度不高，表现为玻璃化转变温度(T
g)低、热膨胀系数较高等缺点，一定程度上制约了其在高性能印制线路板基材的应用。
wherein X is a benzene ring or a naphthalene ring, k represents 0 or 1, and n is 0.25 to 1.5. The resin composition has both high heat resistance and low dielectric tangent, and at the same time, when dissolved in an organic solvent, the viscosity is low enough to facilitate the later processing. However, in the active ester curing epoxy resin system represented by the above resin composition, because the molecular weight of the active ester reactive group is relatively large, and the chemical reaction mechanism with the epoxy group is transesterification For amines, phenolic resins, cyanate resins, bismaleimide resins, etc., the crosslinking density of the cured products is not high, which is manifested in the shortcomings of low glass transition temperature (T g ) and high thermal expansion coefficient. To a certain extent, it restricts its application in high-performance printed circuit board substrates.
双马来酰亚胺树脂是一类高性能的基体树脂，其固化物具有高玻璃化转变温度、高耐热性和良好的力学性能和介电性能。例如CN101885900A公开的树脂组合物中，包括溴化环氧树脂、双马来酰亚胺树脂、氰酸酯树脂、异辛酸锌催化剂及溶剂，其具有高T
g、低热膨胀系数的特征，从而使用其制作的覆铜板具有良好的耐热性、剥离强度和介电性能，适用于国内IC封装行业以及HDI多层PCB。然而，双马来酰亚胺树脂性脆且与环氧树脂不能直接反应，常通过胺、二烯丙基双酚A等进行改性或混合后才能与环氧树脂搭配使用，反应后所形成的网架结构中含有极性大且易吸水的仲醇羟基，加之马来酰亚胺结构本身也易吸水，使其固化产物的介电性能和耐湿热性等表现大打折扣，无法应用于高性能的印制线路板基材中。
Bismaleimide resin is a kind of high-performance matrix resin, and its cured product has high glass transition temperature, high heat resistance and good mechanical and dielectric properties. For example, the resin composition disclosed in CN101885900A includes brominated epoxy resin, bismaleimide resin, cyanate ester resin, zinc isooctanoate catalyst and solvent, which has the characteristics of high T g and low thermal expansion coefficient, so that it can be used The copper clad laminate produced by it has good heat resistance, peel strength and dielectric properties, and is suitable for the domestic IC packaging industry and HDI multi-layer PCB. However, bismaleimide resin is brittle and cannot react directly with epoxy resin. It is often modified or mixed with amine, diallyl bisphenol A, etc. before it can be used with epoxy resin. In addition, the structure of maleimide is also easy to absorb water, which greatly reduces the dielectric properties and resistance to humidity and heat of the cured product, and cannot be used in high performance in printed circuit board substrates.
因此，开发一种交联密度高、介电损耗且吸水率低的固化剂以及包含其的 树脂组合物，以满足高性能电路基板的性能及应用需求，是本领域的研究重点。Therefore, developing a curing agent with high crosslinking density, low dielectric loss and low water absorption and a resin composition containing it to meet the performance and application requirements of high-performance circuit substrates is a research focus in this field.
发明内容SUMMARY OF THE INVENTION
针对现有技术的不足，本发明的目的在于提供一种马来酰亚胺改性的活性酯及其制备方法和应用，所述活性酯通过特定的原料制备而成，其分子结构中含有活性酯基和马来酰亚胺基，两种基团相互协同，使所述活性酯高的反应交联位点、低吸水率、低介电损耗、低介电常数和低热膨胀系数等特点。以所述活性酯作为固化剂的环氧树脂组合物在固化后表现出优异的介电性能、耐热性、耐湿热性和低热膨胀系数，并且与金属的结合力良好，能够充分满足高性能电路基板的应用要求。In view of the deficiencies of the prior art, the purpose of the present invention is to provide a maleimide-modified active ester and its preparation method and application. The active ester is prepared from specific raw materials, and its molecular structure contains active esters. Ester group and maleimide group, the two groups cooperate with each other, so that the active ester has the characteristics of high reaction crosslinking site, low water absorption rate, low dielectric loss, low dielectric constant and low thermal expansion coefficient. The epoxy resin composition using the active ester as a curing agent exhibits excellent dielectric properties, heat resistance, damp heat resistance and low thermal expansion coefficient after curing, and has good bonding force with metal, which can fully meet the high performance requirements. Application requirements for circuit substrates.
为达到此发明目的，本发明采用以下技术方案：In order to achieve this object of the invention, the present invention adopts the following technical solutions:
第一方面，本发明提供一种马来酰亚胺改性的活性酯，所述活性酯的制备原料包括：具有如式A1所示结构的二酚类化合物、具有如式A2所示结构的二酰基化合物和具有如式A3所示结构的含马来酰亚胺基化合物。In a first aspect, the present invention provides a maleimide-modified active ester, and the preparation raw materials of the active ester include: a diphenol compound having a structure as shown in formula A1, a diphenolic compound having a structure as shown in formula A2 A diacyl compound and a maleimide group-containing compound having the structure shown in formula A3.
HO-Ar-OHHO-Ar-OH
式A1；formula A1;
式A1中，Ar为取代或未取代的C6～C150二价芳香族基团；Ar中所述取代的取代基选自氟、C1～C5(例如C1、C2、C3、C4或C5)直链或支链烷基、C2～C5(例如C2、C3、C4或C5)直链或支链烯烃基、含有芳基磷氧结构的基团。In formula A1, Ar is a substituted or unsubstituted C6-C150 divalent aromatic group; the substituted substituent in Ar is selected from fluorine, C1-C5 (such as C1, C2, C3, C4 or C5) straight chain Or branched chain alkyl group, C2-C5 (eg C2, C3, C4 or C5) straight chain or branched chain alkene group, group containing aryl phosphorus oxygen structure.
本发明中，所述“二价芳香族基团”意指含有芳基的具有2个键合位点的基团，包括亚芳基，以及至少2个芳基之间通过连接基团(例如-O-、-S-、羰基、砜基、亚烷基、亚环烷基或亚芳基烷基等)相连形成的取代基。下文中涉及相同描述时，均具有相同的含义。In the present invention, the "divalent aromatic group" refers to a group containing an aryl group with two bonding sites, including an arylene group, and at least two aryl groups are connected through a linking group (for example, -O-, -S-, carbonyl, sulfone, alkylene, cycloalkylene or arylene alkyl, etc.) are linked together to form a substituent. When referring to the same description hereinafter, all have the same meaning.
所述C1～C5直链或支链烷基包括C1、C2、C3、C4或C5的直链或支链烷 基，示例性地包括但不限于：甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、戊基或异戊基等。下文中涉及相同描述时，均具有相同的含义。The C1-C5 straight-chain or branched-chain alkyl groups include C1, C2, C3, C4 or C5 straight-chain or branched-chain alkyl groups, exemplarily including but not limited to: methyl, ethyl, n-propyl, isopropyl propyl, n-butyl, isobutyl, tert-butyl, pentyl or isopentyl, etc. When referring to the same description hereinafter, all have the same meaning.
式A2中，X为取代或未取代的C6～C18(例如C6、C9、C10、C12、C14、C16或C18等)二价芳香族基团；X中所述取代的取代基选自氟、C1～C5(例如C1、C2、C3、C4或C5)直链或支链烷基。In formula A2, X is a substituted or unsubstituted C6-C18 (such as C6, C9, C10, C12, C14, C16 or C18, etc.) divalent aromatic group; the substituted substituent in X is selected from fluorine, C1-C5 (eg C1, C2, C3, C4 or C5) straight or branched chain alkyl.
式A2中，X
1选自卤素或羟基。
In formula A2, X 1 is selected from halogen or hydroxyl.
式A3中，Ar
1为取代或未取代的C6～C12(例如C6、C9、C10或C12等)亚芳基；Ar
1中所述取代的取代基选自氟、C1～C5(例如C1、C2、C3、C4或C5)直链或支链烷基；
In formula A3, Ar 1 is a substituted or unsubstituted C6-C12 (such as C6, C9, C10 or C12, etc.) arylene; the substituted substituent in Ar 1 is selected from fluorine, C1-C5 (such as C1, C2, C3, C4 or C5) straight or branched chain alkyl;
式A3中，R
1、R
2各自独立地选自氢、氟、C1～C5(例如C1、C2、C3、C4或C5)直链或支链烷基。
In formula A3, R 1 and R 2 are each independently selected from hydrogen, fluorine, C1-C5 (eg C1, C2, C3, C4 or C5) linear or branched alkyl.
本发明提供的活性酯由二酚类化合物、二酚类化合物和含马来酰亚胺基化合物三类原料制备而成，所述活性酯中含有马来酰亚胺基和活性酯基两种官能团，二者相互协同，使所述活性酯兼具低介电损耗、低介电常数、低吸水率、高反应交联位点、高T
g、高耐热和低热膨胀系数等优点，能够作为固化剂与环氧树脂发生固化反应，得到的固化产物具有优异的介电性能、耐热性、耐湿热性、低热膨胀系数以及较强的金属结合力。
The active ester provided by the present invention is prepared from three types of raw materials: diphenolic compound, diphenolic compound and maleimide group-containing compound, and the active ester contains two kinds of maleimide group and active ester group functional groups, the two synergize with each other, so that the active ester has the advantages of low dielectric loss, low dielectric constant, low water absorption, high reactive crosslinking sites, high T g , high heat resistance and low thermal expansion coefficient, etc. As a curing agent, it reacts with epoxy resin, and the obtained cured product has excellent dielectric properties, heat resistance, damp heat resistance, low thermal expansion coefficient and strong metal bonding force.
本发明所述活性酯可以与环氧基团发生酯交换反应从而生成烷基酯结构，即作为与环氧基团具有良好反应活性的活性酯，其结构中与酯基
的连接方式必须为酚氧形式而非醇氧形式，故所述Ar和Ar
1中直接与氧原子连接的部分均为芳香环，即具有如式A1所示结构的二酚类化合物和具有如式A3所示结构的含马来酰亚胺基化合物为酚化物而非醇化物。
The active ester of the present invention can undergo transesterification reaction with epoxy groups to generate alkyl ester structures, that is, as active esters with good reactivity with epoxy groups, in its structure, ester groups are The connection mode must be in the form of phenolic oxygen rather than the form of alcohol oxygen, so the part directly connected to the oxygen atom in the Ar and Ar 1 are all aromatic rings, that is, the diphenolic compound with the structure shown in formula A1 and the The maleimide group-containing compound of the structure represented by formula A3 is a phenolate rather than an alcoholate.
优选地，所述Ar选自
Preferably, the Ar is selected from
Ar
2选自
Ar 2 is selected from
Ar
3选自
Ar 3 is selected from
R
3、R
4各自独立地选自氟、C1～C5(例如C1、C2、C3、C4或C5)直链或支链烷基、C2～C5(例如C2、C3、C4或C5)直链或支链烯烃基、
R 3 and R 4 are each independently selected from fluorine, C1-C5 (eg C1, C2, C3, C4 or C5) linear or branched alkyl, C2-C5 (eg C2, C3, C4 or C5) linear chain or branched chain alkene,
本发明中，基团结构一侧或两侧的短直线代表基团的接入键，不代表甲基。In the present invention, the short straight line on one side or both sides of the group structure represents the access bond of the group, and does not represent the methyl group.
R
5为C1～C5(例如C1、C2、C3、C4或C5)直链或支链亚烷基。
R 5 is a C1-C5 (eg C1, C2, C3, C4 or C5) linear or branched alkylene group.
n
1、n
3各自独立地选自0～4的整数，例如0、1、2、3或4。
n 1 and n 3 are each independently selected from an integer of 0 to 4, for example, 0, 1, 2, 3 or 4.
n
2选自0～6的整数，例如0、1、2、3、4、5或6。
n 2 is selected from an integer from 0 to 6, such as 0, 1, 2, 3, 4, 5 or 6.
Y
1、Y
2各自独立地选自-O-、-S-、羰基、砜基、取代或未取代的C1～C20(例如C1、C2、C3、C4、C5、C6、C8、C10、C12、C14、C16、C18或C20等)直链或支链亚烷基、取代或未取代的C3～C30(例如C3、C4、C5、C6、C8、C10、C12、C15、C18、C20、C22、C25、C28或C29等)亚环烷基、取代或未取代的C6～C30(例如C6、C7、C8、C9、C10、C12、C15、C18、C20、C22、C25、C28或C29等)亚芳烷基；所述取代的取代基各自独立地选自氟、C1～C5(例如C1、C2、C3、C4或C5)直链或支链烷基、C6～C18(例如C6、C8、C9、C10、C12、C14、C16或C18等)芳基。
Y 1 and Y 2 are each independently selected from -O-, -S-, carbonyl, sulfone, substituted or unsubstituted C1-C20 (eg C1, C2, C3, C4, C5, C6, C8, C10, C12 , C14, C16, C18 or C20, etc.) straight or branched chain alkylene, substituted or unsubstituted C3 to C30 (such as C3, C4, C5, C6, C8, C10, C12, C15, C18, C20, C22 , C25, C28 or C29, etc.) cycloalkylene, substituted or unsubstituted C6-C30 (such as C6, C7, C8, C9, C10, C12, C15, C18, C20, C22, C25, C28 or C29, etc.) Aralkylene; the substituted substituents are each independently selected from fluorine, C1-C5 (eg C1, C2, C3, C4 or C5) straight or branched chain alkyl, C6-C18 (eg C6, C8, C9, C10, C12, C14, C16 or C18 etc.) aryl.
m代表重复单元的平均值，选自0～10，例如0.2、0.5、0.8、1、1.2、1.5、1.8、2、2.2、2.5、2.8、3、3.3、3.5、3.7、4、4.2、4.5、4.7、5、5.3、5.5、5.8、6、6.2、6.5、6.8、7、7.5、8、8.5、9、9.5或10，以及上述点值之间的具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举所述范围包括的具体点值。m represents the average value of repeating units, selected from 0 to 10, such as 0.2, 0.5, 0.8, 1, 1.2, 1.5, 1.8, 2, 2.2, 2.5, 2.8, 3, 3.3, 3.5, 3.7, 4, 4.2, 4.5 , 4.7, 5, 5.3, 5.5, 5.8, 6, 6.2, 6.5, 6.8, 7, 7.5, 8, 8.5, 9, 9.5 or 10, and specific point values between the above-mentioned point values, are limited by space and for brevity Considering that the present invention does not exhaustively list the specific point values included in the range.
优选地，所述Y
1、Y
2各自独立地选自-O-、-S-、C1～C5(例如C1、C2、C3、C4或C5)直链或支链亚烷基、
Preferably, the Y 1 and Y 2 are each independently selected from -O-, -S-, C1-C5 (eg C1, C2, C3, C4 or C5) straight or branched chain alkylene,
优选地，所述X选自取代或未取代的亚苯基、取代或未取代的亚联苯基
取代或未取代的亚萘基、取代或未取代的亚联苯醚基
所述取代的取代基各自独立地选自氟、C1～C5(例如C1、C2、C3、C4或C5)直链或支链烷基。
Preferably, the X is selected from substituted or unsubstituted phenylene, substituted or unsubstituted biphenylene Substituted or unsubstituted naphthylene, substituted or unsubstituted biphenylene ether The substituted substituents are each independently selected from fluorine, C1-C5 (eg, C1, C2, C3, C4, or C5) straight or branched chain alkyl.
优选地，所述X
1选自氯、溴、碘或羟基。
Preferably, the X 1 is selected from chlorine, bromine, iodine or hydroxyl.
优选地，所述Ar
1选自取代或未取代的亚苯基、取代或未取代的亚萘基；所述取代的取代基选自氟、C1～C5(例如C1、C2、C3、C4或C5)直链或支链烷基。
Preferably, the Ar 1 is selected from substituted or unsubstituted phenylene, substituted or unsubstituted naphthylene; the substituted substituent is selected from fluorine, C1-C5 (such as C1, C2, C3, C4 or C5) Linear or branched alkyl.
优选地，所述R
1、R
2均为氢。
Preferably, both R 1 and R 2 are hydrogen.
本发明中，所述二酰基化合物与二酚类化合物的摩尔比为1:(0.5～0.9)，例如1:0.52、1:0.55、1:0.58、1:0.6、1:0.62、1:0.65、1:0.68、1:0.7、1:0.72、1:0.75、1:0.78、1:0.8、1:0.82、1:0.85、1:0.87或1:0.89等，优选为1:(0.5～0.8)。In the present invention, the molar ratio of the diacyl compound to the diphenolic compound is 1:(0.5-0.9), for example, 1:0.52, 1:0.55, 1:0.58, 1:0.6, 1:0.62, 1:0.65 , 1:0.68, 1:0.7, 1:0.72, 1:0.75, 1:0.78, 1:0.8, 1:0.82, 1:0.85, 1:0.87 or 1:0.89, etc., preferably 1:(0.5～0.8 ).
本发明中，所述二酰基化合物与含马来酰亚胺基化合物的摩尔比为1:(0.2～1)，例如1:0.22、1:0.25、1:0.28、1:0.3、1:0.32、1:0.35、1:0.38、1:0.4、1:0.42、1:0.45、1:0.48、1:0.5、1:0.52、1:0.55、1:0.58、1:0.6、1:0.62、1:0.65、1:0.68、1:0.7、1:0.72、1:0.75、1:0.78、1:0.8、1:0.82、1:0.85、1:0.88、1:0.9、1:0.92、1:0.95、1:0.97或1:0.99等，优选为1:(0.4～1)。In the present invention, the molar ratio of the diacyl compound to the maleimide group-containing compound is 1:(0.2-1), for example, 1:0.22, 1:0.25, 1:0.28, 1:0.3, 1:0.32 , 1:0.35, 1:0.38, 1:0.4, 1:0.42, 1:0.45, 1:0.48, 1:0.5, 1:0.52, 1:0.55, 1:0.58, 1:0.6, 1:0.62, 1 :0.65, 1:0.68, 1:0.7, 1:0.72, 1:0.75, 1:0.78, 1:0.8, 1:0.82, 1:0.85, 1:0.88, 1:0.9, 1:0.92, 1:0.95 , 1:0.97 or 1:0.99, etc., preferably 1:(0.4 to 1).
本发明中，以所述二酰基化合物为1mol计，则理论上所述二酚类化合物和所述含马来酰亚胺基化合物中的酚羟基之和为2mol。其中，所述二酰基化合物相对于二酚类化合物是过量的，二酚类化合物和二酰基化合物的反应起到了链增长的作用，而所述含马来酰亚胺基化合物为封端剂，起到了终止链增长的作用。作为活性酯的另一种结构形式，还可以是二酚类化合物相对于二酰基化合物为过量，采用含马来酰亚胺基的单酰卤或其羧酸化合物作为封端剂对过量的酚羟基进行封端。但本发明通过进一步深入研究发现，采用“含马来酰亚胺基的单酰卤或其羧酸化合物作为封端剂”的结构形式，相对于本发明所限定的马来酰亚胺改性的活性酯，虽然在介电常数、介电损耗和粘结性等方面的性能表现相当，但其在耐湿热性方面的表现不佳，影响其后续应用。因此，本发明选 择了特定结构二酚类化合物、二酰基化合物和含马来酰亚胺基化合物作为反应原料，使所述马来酰亚胺改性的活性酯在介电性能、耐热性、耐湿热性和粘结性等综合性能方面取得了最佳的平衡。In the present invention, based on 1 mol of the diacyl compound, the sum of the phenolic hydroxyl groups in the diphenolic compound and the maleimide group-containing compound is theoretically 2 mol. Wherein, the diacyl compound is in excess relative to the diphenolic compound, the reaction between the diphenolic compound and the diacyl compound plays a role in chain extension, and the maleimide group-containing compound is a capping agent, Played a role in terminating chain growth. As another structural form of the active ester, it can also be that the diphenolic compound is in excess relative to the diacyl compound, and the maleimide group-containing monoacyl halide or its carboxylic acid compound is used as the end-capping agent for the excess phenolic compound. hydroxyl end capped. However, in the present invention, it is found through further in-depth research that the structural form of "maleimide group-containing monoacyl halide or its carboxylic acid compound as the end-capping agent" is better than the maleimide modification defined in the present invention. Although the performance of the active esters in dielectric constant, dielectric loss and adhesion is comparable, its performance in terms of heat and humidity resistance is not good, which affects its subsequent application. Therefore, the present invention selects specific structures of diphenolic compounds, diacyl compounds and maleimide group-containing compounds as reaction raw materials, so that the maleimide-modified active esters have good dielectric properties, heat resistance The best balance has been achieved in terms of comprehensive properties such as , heat and humidity resistance and adhesion.
对于本发明提供的马来酰亚胺改性的活性酯，以所述二酰基化合物的用量为1mol计，所述二酚类化合物的比例越高，则马来酰亚胺基的占比越低，固化物的性能表现越趋向于一般的活性酯，即介电性能略优，而在T
g和热膨胀系数方面有所不足，并且所得的马来酰亚胺改性的活性酯的分子量越大，其在有机溶剂中的溶解性越差，可供选择的有机溶剂越来越少，一方面会增加合成过程的工艺难度，甚至会造成局部爆聚而出现凝胶的现象，另一方面也会造成树脂应用时工艺难度的增加；反之，所述二酚类化合物的投入比例越低，而所述含马来酰亚胺基化合物投入比例越高，即反应生成的马来酰亚胺改性的活性酯中马来酰亚胺基团的比例越高，其在有机溶剂中的溶解性也越差。因此，综合上述几个方面的综合考量，进一步优选地，所述二酰基化合物与二酚类化合物的摩尔比为1:(0.5～0.8)，所述二酰基化合物与含马来酰亚胺基化合物的摩尔比为1:(0.4～1)。
For the maleimide-modified active ester provided by the present invention, based on the amount of the diacyl compound being 1 mol, the higher the proportion of the diphenolic compound, the higher the proportion of maleimide groups. Low, the performance of the cured product tends to be more like the general active ester, that is, the dielectric properties are slightly better, but the T g and thermal expansion coefficient are insufficient, and the molecular weight of the obtained maleimide-modified active ester is higher. Large, the worse its solubility in organic solvents, the less and less organic solvents to choose from, on the one hand, it will increase the technological difficulty of the synthesis process, and even cause local explosion and gel phenomenon, on the other hand It will also cause the increase in the difficulty of the process when the resin is applied; on the contrary, the lower the input ratio of the diphenolic compound, and the higher the input ratio of the maleimide group-containing compound, that is, the maleimide generated by the reaction is higher. The higher the proportion of maleimide groups in the modified active ester, the worse its solubility in organic solvents. Therefore, based on the comprehensive consideration of the above aspects, further preferably, the molar ratio of the diacyl compound to the diphenolic compound is 1:(0.5-0.8), and the diacyl compound and the maleimide group-containing The molar ratio of the compounds is 1:(0.4-1).
另一方面，本发明提供一种如上所述的活性酯的制备方法，所述制备方法包括：具有如式A1所示结构的二酚类化合物、具有如式A2所示结构的二酰基化合物和具有如式A3所示结构的含马来酰亚胺基化合物进行反应，得到所述活性酯。On the other hand, the present invention provides a preparation method of the above-mentioned active ester, the preparation method comprises: a diphenol compound having a structure as shown in formula A1, a diacyl compound having a structure as shown in formula A2, and The maleimide group-containing compound having the structure shown in formula A3 is reacted to obtain the active ester.
优选地，所述反应的温度为-10～60℃，例如-10℃、-8℃、-5℃、-2℃、-0℃、2℃、5℃、8℃、10℃、12℃、15℃、18℃、20℃、22℃、25℃、28℃、30℃、32℃、35℃、38℃、40℃、42℃、45℃、48℃、50℃、52℃、55℃或58℃，以及上述点值之间的具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列 举所述范围包括的具体点值。Preferably, the temperature of the reaction is -10 to 60°C, such as -10°C, -8°C, -5°C, -2°C, -0°C, 2°C, 5°C, 8°C, 10°C, 12°C , 15℃, 18℃, 20℃, 22℃, 25℃, 28℃, 30℃, 32℃, 35℃, 38℃, 40℃, 42℃, 45℃, 48℃, 50℃, 52℃, 55℃ °C or 58 °C, as well as specific point values between the above-mentioned point values, limited by space and for the sake of brevity, the present invention will not exhaustively list the specific point values included in the range.
优选地，所述反应在碱性催化剂存在下进行。Preferably, the reaction is carried out in the presence of a basic catalyst.
优选地，所述碱性催化剂包括无机碱性化合物和/或有机碱；所述无机碱性化合物包括氢氧化钠、氢氧化钾、氢氧化钙、碳酸钠、碳酸钾、醋酸钠、醋酸钾、碳酸氢钠或碳酸氢钾中的任意一种或至少两种的组合；所述有机碱包括三乙胺、吡啶、4-二甲氨基吡啶、三丁胺、N,N-二异丙基乙胺、苄基三乙基氯化铵、四乙基溴化铵、四丁基溴化铵、四丁基氯化铵、四丁基硫酸氢铵、三辛基甲基氯化铵、十二烷基三甲基氯化铵或十四烷基三甲基氯化铵中的任意一种或至少两种的组合。Preferably, the basic catalyst includes inorganic basic compounds and/or organic bases; the inorganic basic compounds include sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, sodium acetate, potassium acetate, Any one or a combination of at least two of sodium bicarbonate or potassium bicarbonate; the organic base includes triethylamine, pyridine, 4-dimethylaminopyridine, tributylamine, N,N-diisopropylethyl Amine, benzyltriethylammonium chloride, tetraethylammonium bromide, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate, trioctylmethylammonium chloride, dodecyl Any one or a combination of at least two of alkyl trimethyl ammonium chloride or tetradecyl trimethyl ammonium chloride.
优选地，所述反应的保护气氛中进行，所述保护气氛优选为氮气或氩气。Preferably, the reaction is carried out in a protective atmosphere, and the protective atmosphere is preferably nitrogen or argon.
优选地，所述反应在溶剂存在下进行。Preferably, the reaction is carried out in the presence of a solvent.
优选地，所述反应在溶剂存在下进行，所述溶剂没有特别限定，只要其不妨碍反应即可，示例性地包括不限于：四氢呋喃、二恶烷、苯、甲苯、二甲苯、二氯甲烷、二氯乙烷、丁酮、甲基异丁酮、环己酮、1,4-丁内酯、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、二甲亚砜或N-甲基吡咯烷酮中的任意一种或至少两种的组合。所述溶剂的用量可根据原料和产物的不同溶解性进行适当调整，使得各原料和产物能够溶解在溶剂中，优选为各原料质量之和的3～15倍，例如3.5倍、4倍、4.5倍、5倍、5.5倍、6倍、6.5倍、7倍、7.5倍、8倍、8.5倍、9倍、10倍、11倍、12倍、13倍或14倍等。Preferably, the reaction is carried out in the presence of a solvent, which is not particularly limited as long as it does not hinder the reaction, exemplarily including but not limited to: tetrahydrofuran, dioxane, benzene, toluene, xylene, dichloromethane , dichloroethane, butanone, methyl isobutyl ketone, cyclohexanone, 1,4-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylidene Either one or a combination of at least two of sulfone or N-methylpyrrolidone. The amount of the solvent can be appropriately adjusted according to the different solubility of raw materials and products, so that each raw material and product can be dissolved in the solvent, preferably 3 to 15 times the sum of the mass of each raw material, such as 3.5 times, 4 times, 4.5 times times, 5 times, 5.5 times, 6 times, 6.5 times, 7 times, 7.5 times, 8 times, 8.5 times, 9 times, 10 times, 11 times, 12 times, 13 times, or 14 times, etc.
优选地，所述反应在完成后还包括对产物进行后处理。Preferably, the reaction further includes post-treatment of the product after completion.
优选地，所述后处理的方法包括过滤、水洗、浓缩、萃取、重结晶或柱色谱法等，以实现所述活性酯的分离和纯化。Preferably, the post-processing method includes filtration, water washing, concentration, extraction, recrystallization or column chromatography, etc., to achieve separation and purification of the active ester.
另一方面，本发明提供一种热固性树脂组合物，所述热固性树脂组合物包 括环氧树脂和如上所述的活性酯。In another aspect, the present invention provides a thermosetting resin composition comprising an epoxy resin and an active ester as described above.
本发明提供的热固性树脂组合物包括环氧树脂和如上所述的马来酰亚胺改性的活性酯，所述活性酯的分子结构中同时含有活性酯基团(芳酯基)和马来酰亚胺基，具有较多的反应活性位点，其作为固化剂与环氧树脂发生反应时，一方面，芳酯基与环氧树脂反应时不会产生强极性的二次羟基，从而使固化产物具有低介电损耗、低吸水率和较低的介电常数；另一方面，马来酰亚胺基既可以固化形成高刚性和高耐热的酰亚胺环结构，反应过程不产生羟基、氨基等极性基团，故具有优异的耐热性能(高T
g)和力学性能，以及良好的介电性能和加工性能，从而克服了一般活性酯固化环氧树脂在T
g和热膨胀系数方面的缺陷。
The thermosetting resin composition provided by the present invention includes epoxy resin and maleimide-modified active ester as described above, and the molecular structure of the active ester contains both active ester group (aryl ester group) and maleic acid ester group. The imide group has more reactive sites. When it reacts with the epoxy resin as a curing agent, on the one hand, when the aryl ester group reacts with the epoxy resin, it will not produce a strongly polar secondary hydroxyl group, thereby The cured product has low dielectric loss, low water absorption and low dielectric constant; on the other hand, the maleimide group can be cured to form an imide ring structure with high rigidity and high heat resistance, and the reaction process is not Generates polar groups such as hydroxyl and amino groups, so it has excellent heat resistance (high T g ) and mechanical properties, as well as good dielectric properties and processing properties, thus overcoming the general active ester curing epoxy resin in T g and Defects in the coefficient of thermal expansion.
优选地，所述环氧树脂是指在1个分子中具有至少两个环氧基团的环氧树脂，示例性地包括但不限于：双官能双酚A型环氧树脂、双官能双酚F型环氧树脂、双官能双酚S型环氧树脂、苯酚甲醛型环氧树脂、甲基苯酚酚醛型环氧树脂、双酚A型酚醛环氧树脂、双环戊二烯(DCPD)环氧树脂、联苯环氧树脂、DCPD型酚醛环氧树脂、联苯酚醛环氧树脂、间苯二酚型环氧树脂、萘系环氧树脂、含磷环氧树脂、含硅环氧树脂、缩水甘油胺型环氧树脂、脂环族类环氧树脂、聚乙二醇型环氧树脂、四苯酚乙烷四缩水甘油醚、三酚基甲烷型环氧树脂、双官能氰酸酯与环氧树脂的缩合物或双官能异氰酸酯与环氧树脂的缩合物中的任意一种或至少两种的组合；示例性的组合包括：双官能双酚A型环氧树脂和双官能双酚F型环氧树脂的组合，双官能双酚S型环氧树脂和苯酚甲醛型环氧树脂的组合，间苯二酚型环氧树脂和萘系环氧树脂的组合，脂环族类环氧树脂和聚乙二醇型环氧树脂的组合。Preferably, the epoxy resin refers to an epoxy resin having at least two epoxy groups in one molecule, exemplarily including but not limited to: bifunctional bisphenol A epoxy resin, bifunctional bisphenol F type epoxy resin, bifunctional bisphenol S type epoxy resin, phenol formaldehyde type epoxy resin, cresol novolac type epoxy resin, bisphenol A type novolac epoxy resin, dicyclopentadiene (DCPD) epoxy resin Resin, biphenyl epoxy resin, DCPD epoxy resin, biphenyl novolac epoxy resin, resorcinol epoxy resin, naphthalene epoxy resin, phosphorus-containing epoxy resin, silicon-containing epoxy resin, shrinkage Glycerylamine type epoxy resin, alicyclic epoxy resin, polyethylene glycol type epoxy resin, tetraphenol ethane tetraglycidyl ether, triphenol methane type epoxy resin, bifunctional cyanate ester and epoxy resin Any one or a combination of at least two of a condensate of a resin or a condensate of a bifunctional isocyanate and an epoxy resin; exemplary combinations include: bifunctional bisphenol A-type epoxy resins and bifunctional bisphenol F-type rings Combination of oxygen resin, combination of bifunctional bisphenol S type epoxy resin and phenol formaldehyde type epoxy resin, combination of resorcinol type epoxy resin and naphthalene type epoxy resin, alicyclic epoxy resin and poly A combination of glycol type epoxy resins.
优选地，所述热固性树脂组合物中还包括其他固化剂、阻燃剂、无机填料、 有机填料或固化促进剂中的任意一种或至少两种的组合。Preferably, the thermosetting resin composition further includes any one or a combination of at least two of other curing agents, flame retardants, inorganic fillers, organic fillers or curing accelerators.
优选地，所述其他固化剂选自胺类固化剂、酚类固化剂、苯并噁嗪类固化剂、氰酸酯类固化剂、普通活性酯固化剂(与本发明所述的马来酰亚胺改性的活性酯不同)、酸酐类固化剂或胺改性的马来酰亚胺固化剂中的任意一种或至少两种的组合。Preferably, the other curing agent is selected from amine curing agent, phenol curing agent, benzoxazine curing agent, cyanate ester curing agent, common active ester curing agent (with maleic acid described in the present invention) Any one or a combination of at least two of imine-modified active ester), acid anhydride curing agent or amine-modified maleimide curing agent.
优选地，所述阻燃剂选自卤系有机阻燃剂、磷系有机阻燃剂、氮系有机阻燃剂或含硅有机阻燃剂中的任意一种或至少两种的组合。Preferably, the flame retardant is selected from any one or a combination of at least two of halogen-based organic flame retardants, phosphorus-based organic flame retardants, nitrogen-based organic flame retardants or silicon-containing organic flame retardants.
优选地，所述无机填料包括非金属氧化物、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任意一种或者至少两种的组合；进一步优选为熔融二氧化硅、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、硅酸钙或云母中的任意一种或至少两种的组合。Preferably, the inorganic filler includes any one or a combination of at least two of non-metal oxides, metal nitrides, non-metal nitrides, inorganic hydrates, inorganic salts, metal hydrates or inorganic phosphorus; more preferably Fused silica, crystalline silica, spherical silica, hollow silica, aluminum hydroxide, alumina, talc, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, Any one or a combination of at least two of strontium titanate, calcium carbonate, calcium silicate or mica.
优选地，所述有机填料包括聚四氟乙烯粉末、聚苯硫醚粉末或聚醚砜粉末中的任意一种或至少两种的组合。Preferably, the organic filler includes any one or a combination of at least two of polytetrafluoroethylene powder, polyphenylene sulfide powder or polyethersulfone powder.
优选地，所述固化促进剂包括咪唑类化合物、咪唑类化合物的衍生物、哌啶类化合物、吡啶类化合物、有机金属盐路易斯酸或三苯基膦中的任意一种或至少两种的组合。Preferably, the curing accelerator includes any one or a combination of at least two of imidazoles, derivatives of imidazoles, piperidines, pyridines, organic metal salt Lewis acids or triphenylphosphine .
本发明中所述“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热固性树脂组合物不同的特性。除此之外，本发明所述“包括”还可以替换为封闭式的“为”或“由……组成”。In the present invention, "comprising" means that in addition to the above-mentioned components, other components may be included, and these other components impart different properties to the thermosetting resin composition. In addition, in the present invention, "comprising" can also be replaced with closed "is" or "consisting of".
本发明所述热固性树脂组合物的制备方法可以为：先将固形物放入，然后加入溶剂，搅拌至固形物完全溶解后，再加入液态树脂和固化促进剂，继续搅拌均匀即可。The preparation method of the thermosetting resin composition of the present invention can be as follows: first put the solid matter, then add the solvent, stir until the solid matter is completely dissolved, then add the liquid resin and the curing accelerator, and continue to stir evenly.
所述溶剂无特别限定，包括醇类溶剂、醚类溶剂、芳香烃类溶剂、酯类溶剂、酮类溶剂或含氮类溶剂中的任意一种或至少两种的组合，优选为酮类溶剂。其中，所述醇类溶剂包括甲醇、乙醇或丁醇中的任意一种或至少两种的组合；所述醚类溶剂包括乙基溶纤剂、丁基溶纤剂、乙二醇甲醚、卡必醇或丁基卡必醇中的任意一种或至少两种的组合；所述芳香烃类溶剂包括苯、甲苯或二甲苯中的任意一种或至少两种的组合；所述酯类溶剂包括乙酸乙酯、乙酸丁酯或乙氧基乙基乙酸酯中的任意一种或至少两种的组合；所述酮类溶剂包括丙酮、丁酮、甲基乙基甲酮或环己酮中的任意一种或至少两种的组合；所述含氮类溶剂包括N,N-二甲基甲酰胺和/或N,N-二甲基乙酰胺。The solvent is not particularly limited, including any one or a combination of at least two of alcohol solvents, ether solvents, aromatic hydrocarbon solvents, ester solvents, ketone solvents or nitrogen-containing solvents, preferably ketone solvents . Wherein, the alcohol solvent includes any one or a combination of at least two of methanol, ethanol or butanol; the ether solvent includes ethyl cellosolve, butyl cellosolve, ethylene glycol methyl ether, carbitol Any one or a combination of at least two of alcohol or butyl carbitol; the aromatic hydrocarbon solvent includes any one or a combination of at least two of benzene, toluene or xylene; the ester solvent includes Any one or a combination of at least two of ethyl acetate, butyl acetate or ethoxyethyl acetate; the ketone solvent includes acetone, methyl ethyl ketone, methyl ethyl ketone or cyclohexanone Any one or a combination of at least two; the nitrogen-containing solvent includes N,N-dimethylformamide and/or N,N-dimethylacetamide.
所述溶剂的用量可以根据实际加工和应用需求进行调节。The amount of the solvent can be adjusted according to actual processing and application requirements.
本发明还涉及固化物，所述固化物为将如前所述的热固性树脂组合物固化而制备得到的。The present invention also relates to a cured product prepared by curing the aforementioned thermosetting resin composition.
另一方面，本发明提供一种半导体密封材料，所述半导体密封材料的原料包括如上所述的热固性树脂组合物。In another aspect, the present invention provides a semiconductor sealing material whose raw material includes the thermosetting resin composition as described above.
另一方面，本发明提供一种预浸料，所述预浸料包括基材，以及通过浸渍干燥附着于所述基材上的如上所述的热固性树脂组合物。In another aspect, the present invention provides a prepreg comprising a base material, and the above-mentioned thermosetting resin composition adhered to the base material by impregnation and drying.
优选地，所述基材包括玻纤布、无纺布或石英布中的任意一种或至少两种的组合。Preferably, the base material includes any one or a combination of at least two of glass fiber cloth, non-woven fabric or quartz cloth.
所述玻纤布可以为E-玻纤布、D-玻纤布、S-玻纤布、T玻纤布或NE-玻纤布等。The glass fiber cloth can be E-glass fiber cloth, D-glass fiber cloth, S-glass fiber cloth, T glass fiber cloth, NE-glass fiber cloth, or the like.
所述基材的厚度无特别限定；出于良好的尺寸稳定性的考虑，所述基材的厚度优选为0.01～0.2mm，例如0.02mm、0.05mm、0.08mm、0.1mm、0.12mm、0.15mm、0.17mm或0.19mm等。The thickness of the substrate is not particularly limited; for the consideration of good dimensional stability, the thickness of the substrate is preferably 0.01-0.2 mm, such as 0.02 mm, 0.05 mm, 0.08 mm, 0.1 mm, 0.12 mm, 0.15 mm mm, 0.17mm or 0.19mm, etc.
优选地，所述基材为经过开纤处理和/或硅烷偶联剂表面处理的基材。为了提供良好的耐水性和耐热性，所述硅烷偶联剂优选为环氧硅烷偶联剂、氨基硅烷偶联剂或乙烯基硅烷偶联剂中的任意一种或至少两种的组合。Preferably, the substrate is a substrate that has undergone fiber opening treatment and/or surface treatment with a silane coupling agent. In order to provide good water resistance and heat resistance, the silane coupling agent is preferably any one or a combination of at least two of epoxy silane coupling agent, amino silane coupling agent or vinyl silane coupling agent.
示例性的，所述预浸料的制备方法为：将基材浸于所述热固性树脂组合物的树脂胶液中，取出后干燥，得到所述预浸料。Exemplarily, the preparation method of the prepreg is as follows: the base material is dipped in the resin glue solution of the thermosetting resin composition, taken out and then dried to obtain the prepreg.
优选地，所述干燥的温度为100～250℃，例如105℃、110℃、115℃、120℃、130℃、140℃、150℃、160℃、170℃、180℃、190℃、200℃、210℃、220℃、230℃、240℃或245℃等。Preferably, the drying temperature is 100-250°C, such as 105°C, 110°C, 115°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, 190°C, 200°C , 210°C, 220°C, 230°C, 240°C or 245°C, etc.
优选地，所述干燥的时间为1～15min，例如2min、3min、4min、5min、6min、7min、8min、9min、10min、11min、12min、13min或14min等。Preferably, the drying time is 1 to 15 minutes, such as 2 minutes, 3 minutes, 4 minutes, 5 minutes, 6 minutes, 7 minutes, 8 minutes, 9 minutes, 10 minutes, 11 minutes, 12 minutes, 13 minutes, or 14 minutes.
另一方面，本发明提供一种电路基板，所述电路基板包括至少一张如上所述的预浸料，以及设置于所述预浸料的一侧或两侧的金属箔。In another aspect, the present invention provides a circuit substrate comprising at least one prepreg as described above, and metal foils disposed on one or both sides of the prepreg.
所述金属箔的材质无特殊限定；优选地，所述金属箔包括铜箔、镍箔、铝箔或SUS箔。The material of the metal foil is not particularly limited; preferably, the metal foil includes copper foil, nickel foil, aluminum foil or SUS foil.
示例性的，所述电路基板的制备方法为：在一张预浸料的一侧或两侧压合金属箔，固化，得到所述电路基板；或，将至少两张预浸料粘合制成层压板，然后在所述层压板的一侧或两侧压合金属箔，固化，得到所述电路基板。Exemplarily, the preparation method of the circuit substrate is as follows: pressing a metal foil on one side or both sides of a prepreg and curing to obtain the circuit substrate; or, adhering at least two prepregs to make the circuit substrate. A laminate is formed, and then metal foil is laminated on one side or both sides of the laminate and cured to obtain the circuit substrate.
优选地，所述固化在热压机中进行。Preferably, the curing is carried out in a hot press.
优选地，所述固化的温度为150～250℃，例如150℃、155℃、160℃、165℃、170℃、175℃、180℃、185℃、190℃、195℃、200℃、205℃、210℃、215℃、220℃、225℃、230℃、235℃、240℃或245℃等。Preferably, the curing temperature is 150-250°C, such as 150°C, 155°C, 160°C, 165°C, 170°C, 175°C, 180°C, 185°C, 190°C, 195°C, 200°C, 205°C , 210°C, 215°C, 220°C, 225°C, 230°C, 235°C, 240°C or 245°C, etc.
优选地，所述固化的压力为10～60kg/cm
2，例如15kg/cm
2、20kg/cm
2、25kg/cm
2、30kg/cm
2、35kg/cm
2、40kg/cm
2、45kg/cm
2、50kg/cm
2或55kg/cm
2 等。
Preferably, the curing pressure is 10-60kg/cm 2 , such as 15kg/cm 2 , 20kg/cm 2 , 25kg/cm 2 , 30kg/cm 2 , 35kg/cm 2 , 40kg/cm 2 , 45kg/cm 2 2 , 50kg/cm 2 or 55kg/cm 2 , etc.
另一方面，本发明提供一种积层薄膜，所述积层薄膜包括基材薄膜或金属箔，以及涂布于所述基材薄膜或金属箔的至少一个表面上的如上所述的热固性树脂组合物。In another aspect, the present invention provides a laminated film comprising a base film or metal foil, and the above-mentioned thermosetting resin coated on at least one surface of the base film or metal foil combination.
相对于现有技术，本发明具有以下有益效果：Compared with the prior art, the present invention has the following beneficial effects:
(1)本发明提供的马来酰亚胺改性的活性酯中含有活性酯基团(芳香酯基)和马来酰亚胺基，具有较多的反应交联位点、低介电损耗、低介电常数和低吸水率，能够作为固化剂与环氧树脂发生固化反应，得到的固化产物具有优异的介电性能、耐热性、耐湿热性、低热膨胀系数和加工性能。(1) The maleimide-modified active ester provided by the present invention contains active ester group (aromatic ester group) and maleimide group, and has more reactive cross-linking sites and low dielectric loss , low dielectric constant and low water absorption, can be used as a curing agent for curing reaction with epoxy resin, and the obtained cured product has excellent dielectric properties, heat resistance, moisture and heat resistance, low thermal expansion coefficient and processing performance.
(2)本发明提供的热固性树脂组合物通过高交联位点的马来酰亚胺改性的活性酯与环氧树脂的搭配使用，一方面，所述活性酯中的芳酯基与环氧树脂反应时不产生强极性的二次羟基，使得到的固化物具有低介电损耗、低介电常数和低吸水率；另一方面，所述活性酯中的马来酰亚胺基可以固化形成高刚性和高耐热的酰亚胺环结构，反应过程不产生羟基、氨基等极性基团，故具有优异的耐热性能，使得到的固化物具有高T
g、优异的耐热性能、力学性能和粘结性能，及良好的介电性能和加工性能。
(2) The thermosetting resin composition provided by the present invention is used in combination with a maleimide-modified active ester with a high cross-linking site and an epoxy resin. On the one hand, the aryl ester group in the active ester and the ring The oxygen resin does not generate strong polar secondary hydroxyl groups during the reaction, so that the obtained cured product has low dielectric loss, low dielectric constant and low water absorption; on the other hand, the maleimide group in the active ester It can be cured to form an imide ring structure with high rigidity and high heat resistance. The reaction process does not produce polar groups such as hydroxyl and amino groups, so it has excellent heat resistance, so that the cured product has high T g and excellent resistance. Thermal properties, mechanical properties and bonding properties, as well as good dielectric properties and processing properties.
(3)包含所述活性酯的热固性树脂组合物及其电路基板，具有低的热膨胀系数、低的介电常数和介电损耗，表现出优异的介电性能、耐热性、耐湿热性和与金属的粘结强度，可以满足电路基板的高性能需求。(3) A thermosetting resin composition comprising the active ester and a circuit substrate thereof, having a low coefficient of thermal expansion, low dielectric constant and dielectric loss, and exhibiting excellent dielectric properties, heat resistance, moist heat resistance and The bonding strength with metal can meet the high performance requirements of circuit substrates.
图1为实施例1提供的马来酰亚胺改性的活性酯的红外光谱图；Fig. 1 is the infrared spectrogram of the maleimide-modified active ester that embodiment 1 provides;
图2为实施例1提供的马来酰亚胺改性的活性酯的超高效聚合物色谱图。Fig. 2 is the ultra-efficient polymer chromatogram of the maleimide-modified active ester provided in Example 1.
下面通过具体实施方式来进一步说明本发明的技术方案。本领域技术人员应该明了，所述实施例仅仅是帮助理解本发明，不应视为对本发明的具体限制。The technical solutions of the present invention are further described below through specific embodiments. It should be understood by those skilled in the art that the embodiments are only for helping the understanding of the present invention, and should not be regarded as a specific limitation of the present invention.
实施例1Example 1
一种马来酰亚胺改性的活性酯K-1，制备方法包括如下步骤：A maleimide-modified active ester K-1, the preparation method comprising the steps:
在安装有温度计、滴液漏斗、冷凝管、分馏管和搅拌器的烧瓶中投入双环戊二烯和苯酚的加聚反应树脂231g(羟基当量：165g/eq.)、间苯二甲酰氯203g(1mol)、4-马来酰亚胺基苯酚113.5g(0.6mol)和甲苯4350g，对体系内进行减压氮气置换，边搅拌溶解。将反应体系控制在60℃以下，用3h滴加20％的氢氧化钠水溶液420g(2.1mol)，滴加结束后搅拌1h。反应结束后，通过静置分液而去除水层。在得到的甲苯层中加入去离子水并搅拌15min，通过静置分液去除水层，得到的甲苯层重复水洗操作直至水层的pH为7。最后，通过加热减压干燥而得到马来酰亚胺改性的活性酯K-1。Into a flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating tube, and a stirrer, 231 g of an addition polymerization reaction resin of dicyclopentadiene and phenol (hydroxyl equivalent: 165 g/eq.), 203 g of isophthaloyl chloride ( 1 mol), 113.5 g (0.6 mol) of 4-maleimidophenol, and 4350 g of toluene, and the inside of the system was replaced with nitrogen under reduced pressure, and dissolved while stirring. The reaction system was controlled below 60° C., 420 g (2.1 mol) of a 20% aqueous sodium hydroxide solution was added dropwise for 3 h, and the mixture was stirred for 1 h after the dropwise addition. After completion of the reaction, the aqueous layer was removed by standing for liquid separation. Deionized water was added to the obtained toluene layer and stirred for 15 min, the water layer was removed by standing for liquid separation, and the obtained toluene layer was repeatedly washed with water until the pH of the water layer was 7. Finally, the maleimide-modified active ester K-1 is obtained by heating and drying under reduced pressure.
根据投料比进行计算并测定，本实施例提供的马来酰亚胺改性的活性酯K-1的酯基当量为237g/eq.。According to the calculation and determination of the feed ratio, the ester group equivalent of the maleimide-modified active ester K-1 provided in this example is 237 g/eq.
实施例2Example 2
一种马来酰亚胺改性的活性酯K-2，制备方法包括如下步骤：A maleimide-modified active ester K-2, the preparation method comprising the steps:
在安装有温度计、滴液漏斗、冷凝管、分馏管和搅拌器的烧瓶中投入114.2g双酚A(0.5mol)、间苯二甲酰氯203g(1.0mol)、1-马来酰亚胺基-7-萘酚239.2g(1.0mol)和二氯甲烷3600g，对体系内进行减压氮气置换，边搅拌溶解。将反应体系控制在30℃以下，加入四丁基溴化铵0.5g，然后用3h滴加20％的氢氧化钾水溶液589g(2.1mol)，滴加结束后搅拌1h。反应结束后，通过静置分液而去除水层。在得到的二氯甲烷层中加入去离子水并搅拌15min，通过静置 分液去除水层，得到的二氯甲烷层重复水洗操作直至水层的pH为7。最后，通过加热减压干燥而得到马来酰亚胺改性的活性酯K-2。Put 114.2 g of bisphenol A (0.5 mol), 203 g (1.0 mol) of isophthaloyl chloride, 1-maleimide group into a flask equipped with a thermometer, dropping funnel, condenser, fractionation tube and agitator -239.2 g (1.0 mol) of 7-naphthol and 3,600 g of methylene chloride were replaced with nitrogen under reduced pressure in the system, and were dissolved while stirring. The reaction system was controlled below 30°C, 0.5 g of tetrabutylammonium bromide was added, and then 589 g (2.1 mol) of a 20% aqueous potassium hydroxide solution was added dropwise over 3 h, and the mixture was stirred for 1 h after the dropwise addition. After completion of the reaction, the aqueous layer was removed by standing for liquid separation. In the obtained dichloromethane layer, deionized water was added and stirred for 15min, the water layer was removed by standing for liquid separation, and the obtained dichloromethane layer was repeatedly washed with water until the pH of the water layer was 7. Finally, the maleimide-modified active ester K-2 is obtained by heating and drying under reduced pressure.
根据投料比进行计算并测定，本实施例提供的马来酰亚胺改性的活性酯K-2的酯基当量为242g/eq.。According to the calculation and determination of the feed ratio, the ester group equivalent of the maleimide-modified active ester K-2 provided in this example is 242 g/eq.
实施例3Example 3
一种马来酰亚胺改性的活性酯K-3，制备方法包括如下步骤：A maleimide-modified active ester K-3, the preparation method comprising the steps:
在安装有温度计、滴液漏斗、冷凝管、分馏管和搅拌器的烧瓶中投入182.7g双酚A(0.8mol)、间苯二甲酰氯203g(1.0mol)、1-马来酰亚胺基-7-萘酚95.7g(0.4mol)和二氯甲烷4815g，对体系内进行减压氮气置换，边搅拌溶解。将反应体系控制在30℃以下，加入四丁基溴化铵0.5g，然后用3h滴加20％的氢氧化钾水溶液589g(2.1mol)，滴加结束后搅拌1h。反应结束后，通过静置分液而去除水层。在得到的二氯甲烷层中加入去离子水并搅拌15min，通过静置分液去除水层，得到的二氯甲烷层重复水洗操作直至水层的pH为7。最后，通过加热减压干燥而得到马来酰亚胺改性的活性酯K-3。Put 182.7 g of bisphenol A (0.8 mol), 203 g (1.0 mol) of isophthaloyl chloride, 1-maleimide group into a flask equipped with a thermometer, dropping funnel, condenser tube, fractionation tube and stirrer -95.7 g (0.4 mol) of 7-naphthol and 4815 g of methylene chloride were substituted with nitrogen under reduced pressure in the system, and were dissolved while stirring. The reaction system was controlled below 30°C, 0.5 g of tetrabutylammonium bromide was added, and then 589 g (2.1 mol) of a 20% aqueous potassium hydroxide solution was added dropwise over 3 h, and the mixture was stirred for 1 h after the dropwise addition. After completion of the reaction, the aqueous layer was removed by standing for liquid separation. Deionized water was added to the obtained dichloromethane layer and stirred for 15 min. The aqueous layer was removed by standing for liquid separation. The obtained dichloromethane layer was repeatedly washed with water until the pH of the water layer was 7. Finally, the maleimide-modified active ester K-3 is obtained by heating and drying under reduced pressure.
根据投料比进行计算并测定，本实施例提供的马来酰亚胺改性的活性酯K-3的酯基当量为204g/eq.。According to the calculation and determination according to the feeding ratio, the ester group equivalent of the maleimide-modified active ester K-3 provided in this example is 204 g/eq.
实施例4Example 4
一种马来酰亚胺改性的活性酯K-4，制备方法包括如下步骤：A maleimide-modified active ester K-4, the preparation method comprising the steps:
在安装有温度计、滴液漏斗、冷凝管、分馏管和搅拌器的烧瓶中投入10-(2,5-二羟基苯基)-10-氢-9-氧杂-10-磷杂菲-10-氧化物210.8g(0.65mol)、4,4'-二酰氯二苯醚295.1g(1.0mol)、4-马来酰亚胺基苯酚132.4g(0.7mol)和二氯甲烷5750g，对体系内进行减压氮气置换，边搅拌溶解。将反应体系控制在30℃以下，用3h滴加三乙胺222.2g(2.2mol)，滴加结束后搅拌1h。反应结束后， 通过静置分液而去除水层。在得到的二氯甲烷层中加入去离子水并搅拌15min，通过静置分液去除水层，得到的二氯甲烷层重复水洗操作直至水层的pH为7。最后，通过加热减压干燥而得到马来酰亚胺改性的活性酯K-4。Put 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10 into a flask equipped with a thermometer, dropping funnel, condenser, fractionation tube and stirrer - oxide 210.8g (0.65mol), 4,4'-diacyl chloride diphenyl ether 295.1g (1.0mol), 4-maleimidophenol 132.4g (0.7mol) and dichloromethane 5750g, for the system The inside was replaced with nitrogen under reduced pressure, and the mixture was dissolved while stirring. The reaction system was controlled below 30° C., 222.2 g (2.2 mol) of triethylamine was added dropwise over 3 h, and the mixture was stirred for 1 h after the dropwise addition. After the completion of the reaction, the aqueous layer was removed by standing for liquid separation. Deionized water was added to the obtained dichloromethane layer and stirred for 15 min. The aqueous layer was removed by standing for liquid separation. The obtained dichloromethane layer was repeatedly washed with water until the pH of the water layer was 7. Finally, the maleimide-modified active ester K-4 is obtained by heating and drying under reduced pressure.
根据投料比进行计算并测定，本实施例提供的马来酰亚胺改性的活性酯K-4的酯基当量为283g/eq.。According to the calculation and determination of the feed ratio, the ester group equivalent of the maleimide-modified active ester K-4 provided in this example is 283 g/eq.
实施例5Example 5
一种马来酰亚胺改性的活性酯K-5，制备方法包括如下步骤：A maleimide-modified active ester K-5, the preparation method comprising the steps:
在安装有温度计、滴液漏斗、冷凝管、分馏管和搅拌器的烧瓶中投入4,4'-联苯二甲醛和苯酚的缩聚反应树脂263.2g(羟基当量：188g/eq.)、间苯二甲酸166.2g(1.0mol)、4-马来酰亚胺基苯酚113.5g(0.6mol)和甲苯6000g，对体系内进行减压氮气置换，边搅拌溶解。将反应体系控制在60℃以下，用3h滴加20％的氢氧化钠水溶液460g(2.3mol)，滴加结束后搅拌1h。反应结束后，通过静置分液而去除水层。在得到的二氯甲烷层中加入去离子水并搅拌15min，通过静置分液去除水层，得到的二氯甲烷层重复水洗操作直至水层的pH为7。最后，通过加热减压干燥而得到马来酰亚胺改性的活性酯K-5。263.2 g (hydroxyl equivalent: 188 g/eq.) of a polycondensation reaction resin of 4,4'-biphenyldicarbaldehyde and phenol (hydroxyl equivalent: 188 g/eq.), m-benzene 166.2 g (1.0 mol) of dicarboxylic acid, 113.5 g (0.6 mol) of 4-maleimidophenol, and 6000 g of toluene were substituted with nitrogen under reduced pressure in the system, and dissolved while stirring. The reaction system was controlled below 60° C., 460 g (2.3 mol) of a 20% aqueous sodium hydroxide solution was added dropwise for 3 h, and the mixture was stirred for 1 h after the dropwise addition. After completion of the reaction, the aqueous layer was removed by standing for liquid separation. Deionized water was added to the obtained dichloromethane layer and stirred for 15 min. The aqueous layer was removed by standing for liquid separation. The obtained dichloromethane layer was repeatedly washed with water until the pH of the water layer was 7. Finally, the maleimide-modified active ester K-5 is obtained by heating and drying under reduced pressure.
根据投料比进行计算并测定，本实施例提供的马来酰亚胺改性的活性酯K-5的酯基当量为253.5g/eq.。According to the calculation and determination of the feeding ratio, the ester group equivalent of the maleimide-modified active ester K-5 provided in this example is 253.5 g/eq.
对比例1Comparative Example 1
一种改性活性酯L-1，制备方法包括如下步骤：A modified active ester L-1, the preparation method comprises the steps:
在安装有温度计、滴液漏斗、冷凝管、分馏管和搅拌器的烧瓶中投入双环戊二烯和苯酚的加聚反应树脂330g(羟基当量：165g/eq.)、间苯二甲酰氯142.1g(0.7mol)、4-马来酰亚胺基苯甲酰氯141.4g(0.6mol)和甲苯4350g，对体系内进行减压氮气置换，边搅拌溶解。将反应体系控制在60℃以下，用3h滴 加20％的氢氧化钠水溶液420g(2.1mol)，滴加结束后搅拌1h。反应结束后，通过静置分液而去除水层。在得到的甲苯层中加入去离子水并搅拌15min，通过静置分液去除水层，得到的甲苯层重复水洗操作直至水层的pH为7。最后，通过加热减压干燥而得到改性活性酯L-1。330 g (hydroxyl equivalent: 165 g/eq.) of an addition polymerization reaction resin of dicyclopentadiene and phenol and 142.1 g of isophthaloyl chloride were put into a flask equipped with a thermometer, dropping funnel, condenser, fractionation tube and agitator. (0.7 mol), 141.4 g (0.6 mol) of 4-maleimidobenzoyl chloride, and 4350 g of toluene, the inside of the system was replaced with nitrogen under reduced pressure, and dissolved while stirring. The reaction system was controlled below 60°C, and 420 g (2.1 mol) of a 20% aqueous sodium hydroxide solution was added dropwise for 3 h, and the mixture was stirred for 1 h after the dropwise addition. After completion of the reaction, the aqueous layer was removed by standing for liquid separation. Deionized water was added to the obtained toluene layer and stirred for 15 min, the water layer was removed by standing for liquid separation, and the obtained toluene layer was repeatedly washed with water until the pH of the water layer was 7. Finally, the modified active ester L-1 is obtained by heating and drying under reduced pressure.
根据投料比进行计算并测定，本对比例提供的改性活性酯L-1的酯基当量为237g/eq.。According to the calculation and determination of the feed ratio, the ester group equivalent of the modified active ester L-1 provided by this comparative example is 237 g/eq.
对比例2Comparative Example 2
一种改性活性酯L-2，制备方法包括如下步骤：A modified active ester L-2, the preparation method comprises the steps:
在安装有温度计、滴液漏斗、冷凝管、分馏管和搅拌器的烧瓶中投入217g双酚A(0.95mol)、间苯二甲酰氯203g(1.0mol)、1-马来酰亚胺基-7-萘酚18.9g(0.1mol)和二氯甲烷10000g，对体系内进行减压氮气置换，边搅拌溶解。将反应体系控制在30℃以下，加入四丁基溴化铵0.5g，然后用3h滴加20％的氢氧化钾水溶液589g(2.1mol)，滴加结束后搅拌1h。反应结束后，通过静置分液而去除水层。在得到的二氯甲烷层中加入去离子水并搅拌15min，通过静置分液去除水层，得到的二氯甲烷层重复水洗操作直至水层的pH为7。最后，通过加热减压干燥而得到改性活性酯L-2。Put 217 g of bisphenol A (0.95 mol), 203 g (1.0 mol) of isophthaloyl chloride, 1-maleimido- 18.9 g (0.1 mol) of 7-naphthol and 10,000 g of dichloromethane were substituted with nitrogen under reduced pressure in the system, and were dissolved while stirring. The reaction system was controlled below 30°C, 0.5 g of tetrabutylammonium bromide was added, and then 589 g (2.1 mol) of a 20% aqueous potassium hydroxide solution was added dropwise over 3 h, and the mixture was stirred for 1 h after the dropwise addition. After completion of the reaction, the aqueous layer was removed by standing for liquid separation. Deionized water was added to the obtained dichloromethane layer and stirred for 15 min. The aqueous layer was removed by standing for liquid separation. The obtained dichloromethane layer was repeatedly washed with water until the pH of the water layer was 7. Finally, the modified active ester L-2 is obtained by heating and drying under reduced pressure.
根据投料比进行计算并测定，本对比例提供的改性活性酯L-2的酯基当量为183g/eq.。According to the calculation and determination of the feeding ratio, the ester group equivalent of the modified active ester L-2 provided by this comparative example is 183 g/eq.
活性酯的性能测试Performance testing of active esters
(1)结构表征：利用傅里叶红外光谱仪(FT-IR)对实施例1～5提供的马来酰亚胺改性的活性酯进行红外测试表征。(1) Structural characterization: Fourier transform infrared spectroscopy (FT-IR) was used to characterize the maleimide-modified active esters provided in Examples 1-5 by infrared testing.
示例性的，实施例1提供的马来酰亚胺改性的活性酯K-1的红外光谱图如图1所示，从图1中可知，所述马来酰亚胺改性的活性酯K-1在波数为1740cm
-1 处出现活性酯的酯基特征吸收峰，在波数为1717.2cm
-1、722.2cm
-1为酰亚胺环特征峰，1606.8cm
-1处为C＝C伸缩振动吸收峰，而在3400cm
-1附近未出现酚羟基的强吸收峰，说明酚羟基已经发生酯基化。
Exemplarily, the infrared spectrum of the maleimide-modified active ester K-1 provided in Example 1 is shown in FIG. 1 , and it can be seen from FIG. 1 that the maleimide-modified active ester K-1 K-1 appears at the wavenumber of 1740cm -1 , the ester group characteristic absorption peak of the active ester, the characteristic peak of the imide ring at the wavenumber of 1717.2cm -1 and 722.2cm -1 , and the C=C stretching at 1606.8cm -1 There is no strong absorption peak of phenolic hydroxyl group near 3400cm -1 , indicating that the phenolic hydroxyl group has undergone esterification.
(2)分子量测试：利用Waters公司的超高效聚合物色谱系统(APC)测定实施例1～5提供的马来酰亚胺改性的活性酯的重均分子量M
w。
(2) Molecular weight test: The weight-average molecular weight Mw of the maleimide-modified active esters provided in Examples 1-5 was determined by using the ultra-high-efficiency polymer chromatography system (APC) of Waters Corporation.
示例性的，实施例1提供的马来酰亚胺改性的活性酯K-1的超高效聚合物色谱图(APC图)如图2所示，从图2中可知，所述马来酰亚胺改性的活性酯K-1的重均分子量M
w为2745。
Exemplarily, the ultra-high-efficiency polymer chromatogram (APC diagram) of the maleimide-modified active ester K-1 provided in Example 1 is shown in Figure 2, and it can be seen from Figure 2 that the maleimide The weight-average molecular weight M w of the imine-modified active ester K-1 was 2745.
本发明以下应用例及对比例所用到的实验材料如表1所示。The experimental materials used in the following application examples and comparative examples of the present invention are shown in Table 1.
表1Table 1
应用例1Application example 1
一种热固性树脂组合物及包含其的预浸料和电路基板，制备方法如下：A thermosetting resin composition and a prepreg and a circuit substrate comprising the same, the preparation method is as follows:
(1)将54.5重量份环氧树脂A-1、45.5重量份马来酰亚胺改性的活性酯K-1、0.7重量份4-二甲氨基吡啶(固化促进剂D-1)和0.4重量份2-乙基-4-甲基咪唑(固化促进剂D-2)于溶剂中混合均匀，得到热固性树脂组合物的树脂胶液，树脂胶液的固含量为65％；用2116玻纤布浸渍上述胶液，控制合适厚度，然后在160℃的烘箱中烘烤10min制成预浸料；(1) 54.5 parts by weight of epoxy resin A-1, 45.5 parts by weight of maleimide-modified active ester K-1, 0.7 parts by weight of 4-dimethylaminopyridine (curing accelerator D-1) and 0.4 2-ethyl-4-methylimidazole (curing accelerator D-2) in parts by weight is mixed evenly in a solvent to obtain a resin glue of the thermosetting resin composition, and the solid content of the resin glue is 65%; use 2116 glass fiber The cloth is impregnated with the above glue, and the thickness is controlled appropriately, and then baked in an oven at 160 ° C for 10 minutes to make a prepreg;
(2)将6张预浸料叠在一起，在其上下两面叠上1Oz的RTF铜箔，在固化温度为200℃、固化压力为45Kg/cm
2、固化时间为120min条件下制成电路基板。
(2) Stack 6 sheets of prepreg together, and stack 1Oz RTF copper foil on the upper and lower sides of the prepreg, and make a circuit substrate under the conditions of a curing temperature of 200° C., a curing pressure of 45Kg/cm 2 and a curing time of 120 minutes. .
应用例2Application example 2
一种热固性树脂组合物及包含其的预浸料和电路基板，制备方法如下：A thermosetting resin composition and a prepreg and a circuit substrate comprising the same, the preparation method is as follows:
(1)将54.0重量份环氧树脂A-1、46重量份马来酰亚胺改性的活性酯K-2、0.6重量份4-二甲氨基吡啶(固化促进剂D-1)和0.5重量份2-乙基-4-甲基咪唑(固化促进剂D-2)于溶剂中混合均匀，得到热固性树脂组合物的树脂胶液，树脂胶液的固含量为65％；用2116玻纤布浸渍上述胶液，控制合适厚度，然后在 145℃的烘箱中烘烤15min制成预浸料；(1) 54.0 parts by weight of epoxy resin A-1, 46 parts by weight of maleimide-modified active ester K-2, 0.6 parts by weight of 4-dimethylaminopyridine (curing accelerator D-1) and 0.5 parts by weight of 2-ethyl-4-methylimidazole (curing accelerator D-2) in parts by weight is mixed evenly in a solvent to obtain a resin glue of the thermosetting resin composition, and the solid content of the resin glue is 65%; use 2116 glass fiber The cloth is impregnated with the above glue, and the thickness is controlled appropriately, and then baked in an oven at 145 ° C for 15 minutes to make a prepreg;
(2)将6张预浸料叠在一起，在其上下两面叠上1Oz的RTF铜箔，在固化温度为190℃、固化压力为60Kg/cm
2、固化时间为150min条件下制成电路基板。
(2) Stack 6 prepregs together, stack 1Oz RTF copper foils on the upper and lower sides of the prepregs, and make circuit substrates under the conditions of a curing temperature of 190°C, a curing pressure of 60Kg/cm 2 and a curing time of 150min. .
应用例3Application example 3
一种热固性树脂组合物及包含其的预浸料和电路基板，制备方法如下：A thermosetting resin composition and a prepreg and a circuit substrate comprising the same, the preparation method is as follows:
(1)将58.5重量份环氧树脂A-1、41.5重量份马来酰亚胺改性的活性酯K-3、0.8重量份4-二甲氨基吡啶(固化促进剂D-1)和0.2重量份2-乙基-4-甲基咪唑(固化促进剂D-2)于溶剂中混合均匀，得到热固性树脂组合物的树脂胶液，树脂胶液的固含量为65％；用2116玻纤布浸渍上述胶液，控制合适厚度，然后在175℃的烘箱中烘烤5min制成预浸料；(1) 58.5 parts by weight of epoxy resin A-1, 41.5 parts by weight of maleimide-modified active ester K-3, 0.8 parts by weight of 4-dimethylaminopyridine (curing accelerator D-1) and 0.2 2-ethyl-4-methylimidazole (curing accelerator D-2) in parts by weight is mixed evenly in a solvent to obtain a resin glue of the thermosetting resin composition, and the solid content of the resin glue is 65%; use 2116 glass fiber The cloth is impregnated with the above glue, and the thickness is controlled appropriately, and then baked in an oven at 175 ° C for 5 minutes to make a prepreg;
(2)将6张预浸料叠在一起，在其上下两面叠上1Oz的RTF铜箔，在固化温度为220℃、固化压力为30Kg/cm
2、固化时间为90min条件下制成电路基板。
(2) Stack 6 pieces of prepreg together, stack 1Oz RTF copper foil on the upper and lower sides of the prepreg, and make a circuit substrate under the conditions of a curing temperature of 220°C, a curing pressure of 30Kg/cm 2 and a curing time of 90 minutes. .
应用例4～5、对比例3～6Application examples 4 to 5, comparative examples 3 to 6
一种热固性树脂组合物及包含其的预浸料和电路基板，热固性树脂组合物的组分及含量如表2所示，预浸料和电路基板的制备方法与应用例1中相同。A thermosetting resin composition and a prepreg and circuit substrate comprising the same. The components and contents of the thermosetting resin composition are shown in Table 2. The preparation methods of the prepreg and the circuit substrate are the same as those in Application Example 1.
表2Table 2
性能测试Performance Testing
对应用例1～5、对比例3～6提供的热固性树脂组合物及包含其的电路基板进行性能测试，方法如下：The thermosetting resin compositions provided in Application Examples 1 to 5 and Comparative Examples 3 to 6 and the circuit substrates comprising the thermosetting resin compositions were tested for performance, and the methods were as follows:
(1)玻璃化转变温度(T
g)：使用DSC测试，按照标准IPC-TM-650 2.4.24中规定的DSC测试方法进行测定；
(1) Glass transition temperature (T g ): use DSC test to measure according to the DSC test method specified in the standard IPC-TM-650 2.4.24;
(2)热膨胀系数CTE(Z-axis)：用TMA仪，按照标准IPC-TM-650 2.4.24中规定的CTE(Z-axis)测试方法测定50～260℃之间的热膨胀系数；(2) Coefficient of thermal expansion CTE (Z-axis): use a TMA instrument to measure the coefficient of thermal expansion between 50 and 260°C according to the CTE (Z-axis) test method specified in the standard IPC-TM-650 2.4.24;
(3)介电常数D
k和介电损耗因子D
f：按照标准IEC61189-2-721中规定的SPDR法测定10GHz下的D
k和D
f；
(3) Dielectric constant D k and dielectric loss factor D f : measure D k and D f at 10 GHz according to the SPDR method specified in the standard IEC61189-2-721;
(4)热分层时间T300(带铜)：用TMA仪，按照标准IPC-TM-650 2.4.24.1中规定的T300(带铜)测试方法进行测定；(4) Thermal delamination time T300 (with copper): use a TMA instrument to measure it according to the T300 (with copper) test method specified in the standard IPC-TM-650 2.4.24.1;
(5)耐湿热性(PCT)评价：将3块100×100mm的样品在180℃、105KPa的加压蒸煮处理装置内保持2h或3h后，浸入288℃的焊锡槽中5min，观察样品是否发生分层鼓泡等现象，3块均未发生分层鼓泡记为3/3，2块未发生分层鼓泡记为2/3，1块未发生分层鼓泡记为1/3，0块未发生分层鼓泡记为0/3；(5) Evaluation of heat and humidity resistance (PCT): After keeping three samples of 100 × 100 mm in a pressure cooking treatment device of 180 ° C and 105KPa for 2 h or 3 h, immerse them in a solder bath at 288 ° C for 5 minutes, and observe whether the samples occur. For phenomena such as stratified bubbling, 3 blocks without stratified bubbling were recorded as 3/3, 2 blocks without stratified bubbling were recorded as 2/3, and 1 block without stratified bubbling was recorded as 1/3, 0 block without stratified bubbling is recorded as 0/3;
(6)剥离强度(PS)：按照标准IPC-TM-650 2.4.8中规定的“接收态”实验条件，测试金属盖层的剥离强度；(6) Peel strength (PS): Test the peel strength of the metal cap layer according to the "accepted state" experimental conditions specified in the standard IPC-TM-650 2.4.8;
具体测试结果如表3所示：The specific test results are shown in Table 3:
表3table 3
根据表3的性能测试数据可知，相对于对比例3～6，本发明应用例1～5提供的电路基板中，所使用的热固性树脂组合物以本发明提供的马来酰亚胺改性的活性酯作为固化成分，因此具有高的玻璃化转变温度(T
g)和低的热膨胀系数(Z-CTE)，同时兼具低介电常数和低介电损耗、优异的耐热性、耐湿热性以及与金属的良好粘结强度；其中，玻璃化转变温度达到190～235℃，Z-CTE低至2.2～3.1％，介电常数低于4.10(10GHz)，介电损耗低于0.010(10GHz)，T300 (带铜)>60min，剥离强度大于1.10N/mm，达到1.15～1.25N/mm，并可通过PCT(3h)的耐湿热性测试。
According to the performance test data in Table 3, compared with Comparative Examples 3 to 6, in the circuit substrates provided in Application Examples 1 to 5 of the present invention, the thermosetting resin composition used is modified with the maleimide provided by the present invention. Active ester is used as a curing component, so it has a high glass transition temperature (T g ) and a low coefficient of thermal expansion (Z-CTE), as well as a low dielectric constant and low dielectric loss, excellent heat resistance, and moisture and heat resistance and good bonding strength with metal; among them, the glass transition temperature reaches 190 ~ 235 ℃, the Z-CTE is as low as 2.2 ~ 3.1%, the dielectric constant is lower than 4.10 (10GHz), and the dielectric loss is lower than 0.010 (10GHz). ), T300 (with copper)> 60min, peel strength is greater than 1.10N/mm, reaching 1.15~1.25N/mm, and can pass the PCT (3h) heat and humidity test.
比较应用例1、5与对比例3、6可知，使用本发明所述马来酰亚胺改性的活性酯固化的热固性树脂组合物以及电路基板，相比于普通活性酯固化的体系，在T
g和Z-CTE方面表现出更加明显的优势。
Comparing Application Examples 1, 5 and Comparative Examples 3 and 6, it can be seen that the thermosetting resin composition and circuit substrate cured by the maleimide-modified active ester of the present invention are more stable than the ordinary active ester-cured system. It shows more obvious advantages in terms of T g and Z-CTE.
比较应用例1与对比例4可知，虽然二者在T
g、Z-CTE和介电性能方面的水平接近，但应用例1在耐湿热性能(PCT测试)中具有更加优越的表现，这表明以本发明所限定的二酚类化合物、二酰基化合物和含马来酰亚胺基化合物作为反应原料，才能使所述马来酰亚胺改性的活性酯在介电性能、耐热性、耐湿热性和粘结性等综合性能方面取得了最佳的平衡。
Comparing Application Example 1 and Comparative Example 4, it can be seen that although the two are similar in terms of T g , Z-CTE and dielectric properties, Application Example 1 has a more superior performance in heat and humidity resistance (PCT test), which shows that Using the diphenol compounds, diacyl compounds and maleimide group-containing compounds defined in the present invention as reaction raw materials, the maleimide-modified active esters can be improved in dielectric properties, heat resistance, The best balance has been achieved in terms of comprehensive properties such as moisture and heat resistance and adhesion.
比较应用例2、3和对比例5可知，以本发明限定摩尔比的二酚类化合物、二酰基化合物和含马来酰亚胺基化合物进行反应，得到的所述马来酰亚胺改性的活性酯作为固化剂能够使热固性树脂组合物以及电路基板具有优异的T
g和低热膨胀系数；如果活性酯中马来酰亚胺基含量过低，则会使热固性树脂组合物以及电路基板的T
g和Z-CTE表现有所下降。
Comparing Application Examples 2, 3 and Comparative Example 5, it can be seen that the maleimide modified compound obtained by reacting the diphenolic compound, the diacyl compound and the maleimide group-containing compound with the molar ratio defined in the present invention The active ester as a curing agent can make the thermosetting resin composition and circuit substrate have excellent T g and low thermal expansion coefficient; if the maleimide group content in the active ester is too low, it will make the thermosetting resin composition and circuit substrate. T g and Z-CTE performance decreased.
申请人声明，本发明通过上述实施例来说明本发明的一种马来酰亚胺改性的活性酯及其制备方法和应用，但本发明并不局限于上述工艺步骤，即不意味着本发明必须依赖上述工艺步骤才能实施。所属技术领域的技术人员应该明了，对本发明的任何改进，对本发明所选用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。The applicant declares that the present invention illustrates a maleimide-modified active ester of the present invention and its preparation method and application through the above-mentioned examples, but the present invention is not limited to the above-mentioned process steps, that is, it does not mean that the present invention The invention must rely on the above process steps to be implemented. Those skilled in the art should understand that any improvement to the present invention, the equivalent replacement of the selected raw materials of the present invention, the addition of auxiliary components, the selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.
Claims (10)
- 一种马来酰亚胺改性的活性酯，其特征在于，所述活性酯的制备原料包括：具有如式A1所示结构的二酚类化合物、具有如式A2所示结构的二酰基化合物和具有如式A3所示结构的含马来酰亚胺基化合物；A maleimide-modified active ester, characterized in that the raw materials for the preparation of the active ester include: a diphenolic compound having a structure as shown in formula A1, a diacyl compound having a structure as shown in formula A2 and a maleimide group-containing compound having a structure as shown in formula A3;HO-Ar-OHHO-Ar-OH式A1；formula A1;其中，Ar为取代或未取代的C6～C150二价芳香族基团；Ar中所述取代的取代基选自氟、C1～C5直链或支链烷基、C2～C5直链或支链烯烃基、含有芳基磷氧结构的基团；Wherein, Ar is a substituted or unsubstituted C6-C150 divalent aromatic group; the substituted substituent in Ar is selected from fluorine, C1-C5 linear or branched alkyl, C2-C5 linear or branched chain Alkenyl group, group containing aryl phosphorus oxygen structure;
其中，X为取代或未取代的C6～C18二价芳香族基团；X中所述取代的取代基选自氟、C1～C5直链或支链烷基；Wherein, X is a substituted or unsubstituted C6-C18 divalent aromatic group; the substituted substituent in X is selected from fluorine, C1-C5 straight-chain or branched-chain alkyl;X 1选自卤素或羟基； X 1 is selected from halogen or hydroxyl;
其中，Ar 1为取代或未取代的C6～C12亚芳基；Ar 1中所述取代的取代基选自氟、C1～C5直链或支链烷基； Wherein, Ar 1 is a substituted or unsubstituted C6-C12 arylene group; the substituted substituent in Ar 1 is selected from fluorine, C1-C5 straight-chain or branched-chain alkyl;R 1、R 2各自独立地选自氢、氟、C1～C5直链或支链烷基。 R 1 and R 2 are each independently selected from hydrogen, fluorine, C1-C5 straight-chain or branched-chain alkyl. - 根据权利要求1所述的活性酯，其特征在于，所述Ar选自
Active ester according to claim 1, is characterized in that, described Ar is selected from
Ar 2选自Ar 2 is selected from
Ar 3选自Ar 3 is selected from
R 3、R 4各自独立地选自氟、C1～C5直链或支链烷基、C2～C5直链或支链烯烃基、R 3 and R 4 are each independently selected from fluorine, C1-C5 straight-chain or branched-chain alkyl, C2-C5 straight-chain or branched alkene,
R 5为C1～C5直链或支链亚烷基； R 5 is C1-C5 straight-chain or branched alkylene;n 1、n 3各自独立地选自0～4的整数； n 1 and n 3 are each independently selected from the integers from 0 to 4;n 2选自0～6的整数； n 2 is selected from an integer from 0 to 6;Y 1、Y 2各自独立地选自-O-、-S-、羰基、砜基、取代或未取代的C1～C20直链或支链亚烷基、取代或未取代的C3～C30亚环烷基、取代或未取代的C6～C30亚芳烷基；所述取代的取代基各自独立地选自氟、C1～C5直链或支链烷基、C6～C18芳基； Y 1 and Y 2 are each independently selected from -O-, -S-, carbonyl, sulfone, substituted or unsubstituted C1-C20 linear or branched alkylene, substituted or unsubstituted C3-C30 cycloalkylene Alkyl, substituted or unsubstituted C6-C30 aralkylene; the substituted substituents are each independently selected from fluorine, C1-C5 straight or branched chain alkyl, and C6-C18 aryl;m选自0～10；m is selected from 0 to 10;优选地，所述Y 1、Y 2各自独立地选自-O-、-S-、C1～C5直链或支链亚烷基、Preferably, said Y 1 and Y 2 are each independently selected from -O-, -S-, C1-C5 straight or branched chain alkylene,
优选地，所述X选自取代或未取代的亚苯基、取代或未取代的亚联苯基、 取代或未取代的亚萘基、取代或未取代的亚联苯醚基；所述取代的取代基各自独立地选自氟、C1～C5直链或支链烷基；Preferably, the X is selected from substituted or unsubstituted phenylene, substituted or unsubstituted biphenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted biphenylene; The substituents of each are independently selected from fluorine, C1-C5 straight-chain or branched-chain alkyl;优选地，所述X 1选自氯、溴、碘或羟基； Preferably, the X 1 is selected from chlorine, bromine, iodine or hydroxyl;优选地，所述Ar 1选自取代或未取代的亚苯基、取代或未取代的亚萘基；所述取代的取代基选自氟、C1～C5直链或支链烷基； Preferably, the Ar 1 is selected from substituted or unsubstituted phenylene, substituted or unsubstituted naphthylene; the substituted substituent is selected from fluorine, C1-C5 linear or branched alkyl;优选地，所述R 1、R 2均为氢。 Preferably, both R 1 and R 2 are hydrogen. - 根据权利要求1或2所述的活性酯，其特征在于，所述二酰基化合物与二酚类化合物的摩尔比为1:(0.5～0.9)，优选为1:(0.5～0.8)；The active ester according to claim 1 or 2, wherein the molar ratio of the diacyl compound to the diphenolic compound is 1:(0.5-0.9), preferably 1:(0.5-0.8);优选地，所述二酰基化合物与含马来酰亚胺基化合物的摩尔比为1:(0.2～1)，进一步优选为1:(0.4～1)。Preferably, the molar ratio of the diacyl compound to the maleimide group-containing compound is 1:(0.2-1), more preferably 1:(0.4-1).
- 一种如权利要求1～3任一项所述的活性酯的制备方法，其特征在于，所述制备方法包括：具有如式A1所示结构的二酚类化合物、具有如式A2所示结构的二酰基化合物和具有如式A3所示结构的含马来酰亚胺基化合物进行反应，得到所述活性酯。A method for preparing an active ester according to any one of claims 1 to 3, wherein the preparation method comprises: a diphenolic compound having a structure as shown in formula A1, a diphenolic compound having a structure as shown in formula A2 The diacyl compound is reacted with a maleimide group-containing compound having the structure shown in formula A3 to obtain the active ester.
- 根据权利要求4所述的制备方法，其特征在于，所述反应的温度为-10～60℃；The preparation method according to claim 4, wherein the temperature of the reaction is -10 to 60 °C;优选地，所述反应在碱性催化剂存在下进行；Preferably, the reaction is carried out in the presence of a basic catalyst;优选地，所述反应的保护气氛中进行；Preferably, the reaction is carried out in a protective atmosphere;优选地，所述反应在溶剂存在下进行；Preferably, the reaction is carried out in the presence of a solvent;优选地，所述反应在完成后还包括对产物进行后处理。Preferably, the reaction further includes post-treatment of the product after completion.
- 一种热固性树脂组合物，其特征在于，所述热固性树脂组合物包括环氧树脂和如权利要求1～3任一项所述的活性酯；A thermosetting resin composition, characterized in that the thermosetting resin composition comprises an epoxy resin and the active ester according to any one of claims 1 to 3;优选地，所述热固性树脂组合物中还包括其他固化剂、阻燃剂、无机填料、 有机填料或固化促进剂中的任意一种或至少两种的组合。Preferably, the thermosetting resin composition further includes any one or a combination of at least two of other curing agents, flame retardants, inorganic fillers, organic fillers or curing accelerators.
- 一种半导体密封材料，其特征在于，所述半导体密封材料的原料包括如权利要求6所述的热固性树脂组合物。A semiconductor sealing material, characterized in that the raw material of the semiconductor sealing material comprises the thermosetting resin composition according to claim 6 .
- 一种预浸料，其特征在于，所述预浸料包括基材，以及通过浸渍干燥附着于所述基材上的如权利要求6所述的热固性树脂组合物；A prepreg, characterized in that the prepreg comprises a base material, and the thermosetting resin composition according to claim 6 adhered to the base material by impregnation and drying;优选地，所述基材包括玻纤布、无纺布或石英布中的任意一种或至少两种的组合。Preferably, the base material includes any one or a combination of at least two of glass fiber cloth, non-woven fabric or quartz cloth.
- 一种电路基板，其特征在于，所述电路基板包括至少一张如权利要求8所述的预浸料，以及设置于所述预浸料的一侧或两侧的金属箔。A circuit substrate, characterized in that, the circuit substrate comprises at least one prepreg according to claim 8, and metal foils disposed on one side or both sides of the prepreg.
- 一种积层薄膜，其特征在于，所述积层薄膜包括基材薄膜或金属箔，以及涂布于所述基材薄膜或金属箔的至少一个表面上的如权利要求6所述的热固性树脂组合物。A laminated film, characterized in that the laminated film comprises a base film or metal foil, and the thermosetting resin according to claim 6 coated on at least one surface of the base film or metal foil combination.
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