WO2018120586A1 - 一种含有苯并噁嗪树脂组合物的制备方法及由其制成的预浸料和层压板 - Google Patents

一种含有苯并噁嗪树脂组合物的制备方法及由其制成的预浸料和层压板 Download PDF

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Publication number
WO2018120586A1
WO2018120586A1 PCT/CN2017/084314 CN2017084314W WO2018120586A1 WO 2018120586 A1 WO2018120586 A1 WO 2018120586A1 CN 2017084314 W CN2017084314 W CN 2017084314W WO 2018120586 A1 WO2018120586 A1 WO 2018120586A1
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Prior art keywords
parts
benzoxazine
weight
resin
resin composition
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PCT/CN2017/084314
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English (en)
French (fr)
Inventor
李江
奚龙
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广东生益科技股份有限公司
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Priority to KR1020177023876A priority Critical patent/KR101963071B1/ko
Priority to US15/737,661 priority patent/US11180617B2/en
Publication of WO2018120586A1 publication Critical patent/WO2018120586A1/zh

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    • H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates

Definitions

  • the invention relates to the technical field of copper clad laminates, in particular to a preparation method comprising a benzoxazine composite material and a prepreg and a laminate prepared therefrom.
  • Benzooxazine is a thermosetting polymer with excellent comprehensive properties, excellent moldability and good overall performance.
  • the resin has a wide range of raw materials, low price and simple synthesis process; the curing reaction is ring-opening polymerization, which is characterized by no small molecule release, low shrinkage, low porosity and high dimensional accuracy; the cured product has a high glass transition temperature and high Elastic modulus, good heat resistance, high carbon ratio, excellent flame retardancy and low water absorption.
  • the benzoxazine resin has self-polymerization ability, but the polymerization temperature is above 200 ° C and the brittleness is large. It is difficult to be applied in the field of composite materials with main bearing structure.
  • components such as epoxy resin and rubber are added to improve benzoxazine.
  • Resilience to improve the brittleness of benzoxazine; adding catalyst or accelerator to reduce curing temperature, shorten curing time, improve product curing degree, achieve energy consumption and cost saving; add filler to reduce cost and improve thermal expansion coefficient, Meet the needs of use.
  • CN102575006A describes curable compositions comprising a benzoxazine compound and a pentafluorodecanoic acid catalyst.
  • the curable composition can be cured to prepare a cured composition for coatings, sealants, adhesives, and many other applications.
  • No. 6,376,080 A1 describes a process for the preparation of polybenzoxazines which comprises heating a molding composition comprising benzoxazine and a heterocyclic dicarboxylic acid to a temperature sufficient to cure the molding composition to form the polybenzoic acid Oxazine.
  • the composition is said to have a volume change close to zero after post-cure.
  • one of the objects of the present invention is to provide a process for producing a benzoxazine-containing resin composition and a prepreg and a laminate thereof.
  • an acidic filler By adding an acidic filler to the resin composition, on the one hand, it can promote the ring-opening crosslinking of the benzoxazine, lower the curing temperature of the benzoxazine resin composition, and act as a catalyst, and on the other hand, the reactive functional group on the surface of the acidic filler participates.
  • the filler and the resin interface can form a strong covalent bond, which increases the bonding force of the filler resin composition without remaining in the system after the reaction is completed, thereby improving the peeling.
  • the strength stability, the bending strength, the coefficient of thermal expansion are lowered, and at the same time, the development of microcracks in the resin composition can be suppressed, and good toughness is exhibited.
  • the inventors conducted intensive studies and found that the above object can be attained by appropriately mixing an acidic filler with a benzoxazine-containing resin composition to prepare a resin composition.
  • One of the objects of the present invention is to provide a process for preparing a resin composition containing benzoxazine, which is:
  • An acidic filler is added to the benzoxazine-containing resin composition, and the pH of the acidic filler is between 2 and 6, to obtain the resin composition.
  • the ring-opening polymerization reaction of benzoxazine and an epoxy resin can be catalyzed, and the thermal expansion coefficient of the benzoxazine resin composition can be lowered.
  • the curing temperature may be 214 ° C or lower, for example, 202 ° C, 203 ° C, 204 ° C, 205 ° C, 206 ° C, 207 ° C, 208 ° C, 209 ° C, 210 ° C, 211 ° C, 212 ° C, 213 ° C or 214 ° C, and the specific values between the above values, limited by the space and for the sake of brevity, the present invention is no longer exhaustive to enumerate the specific points included in the scope value.
  • the pH of the acidic filler is between 2 and 6, for example 2, 2.5, 3, 3.5, 4, 5 or 6, and the specific values between the above values, limited by space and for simplicity It is contemplated that the present invention is no longer exhaustive of the specific point values included in the scope.
  • the acidic filler is characterized in that the filler and the deionized water are formulated into an aqueous solution at a mass ratio of 1:9, and the pH of the filler is obtained between 2 and 6.
  • the acidic filler of the present invention has a pH between 3 and 5.
  • the acidic filler is selected from any one or a mixture of at least two of silicon micropowder, quartz powder, mica powder, clay, calcium oxalate or carbon black, wherein a typical but non-limiting mixture is silicon micropowder and Quartz powder, clay and calcium oxalate, carbon black and mica powder.
  • the acidic filler has a particle diameter of between 50 nm and 50 ⁇ m, such as 50 nm, 60 nm, 70 nm, 80 nm, 90 nm, 100 nm, 300 nm, 500 nm, 800 nm, 5 ⁇ m, 10 ⁇ m, 30 ⁇ m, 40 ⁇ m, 45 ⁇ m or 50 ⁇ m, and
  • the specific point values between the above values are limited to the length and for the sake of brevity, the present invention will not exhaustively enumerate the specific point values included in the range.
  • the physical form of the acidic filler is not particularly limited, and may be, for example, a sheet, a rod, a sphere, a hollow sphere, a granule, a fiber or a plate; or a silane coupling agent.
  • the acidic filler is treated.
  • the acidic filler is added in an amount of 5 to 200 parts by weight, for example, 5 parts by weight, 8 parts by weight, or 10 parts by weight based on 100 parts by weight of the organic solid content of the benzoxazine-containing resin composition.
  • the content of the benzoxazine resin is 10 to 100 parts by weight, for example, 10 parts by weight, 12 parts by weight, based on 100 parts by weight of the organic solid content. 15 parts by weight, 18 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 45 parts by weight, 50 parts by weight, 60 parts by weight, 70 parts by weight, 80 parts by weight, 90 parts by weight or 100 parts by weight, and the above
  • the specific point values between the numerical values are limited to the length and for the sake of brevity, the present invention is no longer exhaustively enumerated.
  • the benzoxazine resin is selected from the group consisting of a diphenol type benzoxazine and/or a diamine type benzoxazine, and may be a diphenol type benzoxazine or a diamine type benzoxazine or mixture.
  • the structure of the diphenol type benzoxazine resin monomer is as shown in the formula (I):
  • R 1 is R 2 is -CH 2 -, -O-, or Any of them.
  • R 2 When R 2 is When the formula (I) is a bisphenol A type benzoxazine resin monomer; when R 2 is -CH 2 -, the formula (I) is a bisphenol F type benzoxazine resin monomer; when R 2 is When the formula (I) is a phenolphthalein type benzoxazine resin monomer; when R 2 is In the formula, the structural formula (I) is a biscyclopentadiene type benzoxazine resin monomer.
  • R 3 is Any of -CH 2 - or -O-.
  • R 3 When R 3 is When the formula (II) is a DDS type benzoxazine resin monomer; when R 3 is -CH 2 -, the structural formula (II) is a MDA type benzoxazine resin monomer; when R 3 is -O- The structural formula (II) is an ODA type benzoxazine resin monomer.
  • the benzoxazine-containing resin composition may further contain an epoxy resin in an amount of from 0 to 75 parts by weight, for example, 1 part by weight, based on 100 parts by weight of the organic solid. 5 parts by weight, 8 parts by weight, 12 parts by weight, 15 parts by weight, 18 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 45 parts by weight, 50 parts by weight, 60 parts by weight, 65 parts by weight, 70 parts by weight Part or 75 parts by weight, and the specific point values between the above values, are limited to the length and for the sake of brevity, the present invention will not exhaustively enumerate the specific point values included in the range.
  • the epoxy resin is selected from the group consisting of bisphenol A type epoxy resin, bisphenol F type epoxy resin, o-cresol novolac epoxy resin, bisphenol A type novolac epoxy resin, and trisphenol novolac epoxy resin.
  • the limiting mixtures are bisphenol A epoxy resin and bisphenol F epoxy resin, bisphenol A epoxy resin and bisphenol F epoxy resin, trisphenol novolac epoxy resin and dicyclopentadiene phenolic resin.
  • Epoxy resin, biphenyl type novolac epoxy resin and alkyl phenol novolac epoxy resin are examples of epoxy resin, biphenyl type novolac epoxy resin and alkyl phenol novolac epoxy resin.
  • the epoxy resin is selected from the group consisting of epoxy resins having the following structure:
  • X 1 , X 2 and X 3 are each independently selected from R 4 is selected from the group consisting of a substituted or unsubstituted C1-C5 linear alkyl group or a substituted or unsubstituted C1-C5 branched alkyl group, wherein the C1-C5 linear alkyl group may be a methyl group or an ethyl group. , propyl, n-butyl or n-pentyl, C1-C5 branched alkyl group may be isopropyl, isobutyl or isopentyl, etc.;
  • Y 1 and Y 2 are each independently selected from -CH 2 - Any one of R 5 is selected from a hydrogen atom, a substituted or unsubstituted C1-C5 linear alkyl group or a substituted or unsubstituted C1-C5 branched alkyl group, wherein the C1-C5 linear chain
  • the alkyl group may be a methyl group, an ethyl group, a propyl group, a n-butyl group or a n-pentyl group, and the C1-C5 branched alkyl group may be an isopropyl group, an isobutyl group or an isopentyl group;
  • n is an arbitrary integer from 1 to 10, such as 1, 2, 3, 4, 5, 6, 7, 9, or 10.
  • the benzoxazine-containing resin composition may further contain a phenol resin, and the content of the phenol resin is from 0 to 40 parts by weight, for example, 1 part by weight, 2 parts by weight based on 100 parts by weight of the organic solid content. Parts, 5 parts by weight, 8 parts by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 28 parts by weight, 30 parts by weight, 35 parts by weight or 40 parts by weight, and specific points between the above values Values, limited by length and for the sake of brevity, the present invention is no longer exhaustive of the specific point values included in the scope.
  • the phenolic resin is selected from the group consisting of a linear phenolic resin, a bisphenol A phenolic resin, an o-cresol novolac resin, a phosphorus-containing phenolic resin or a trifunctional phenolic resin, or a mixture of at least two thereof, of which typical but Non-limiting mixtures are novolac resins and bisphenol A phenolic resins, bisphenol A phenolic resins and o-cresol novolac resins, phosphorus-containing phenolic resins and trifunctional phenolic resins.
  • the benzoxazine-containing resin composition may further contain a cyanate ester, and the content of the cyanate ester is from 0 to 50 parts by weight, for example, 1 part by weight, based on 100 parts by weight of the organic solid content. 2 parts by weight, 5 parts by weight, 8 parts by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 28 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight or 50 parts by weight.
  • the specific point values between the above and the above values are limited, and for the sake of brevity, the present invention will not exhaustively enumerate the specific point values included in the scope.
  • the cyanate ester is selected from any one or a mixture of at least two of a bisphenol A type cyanate, a novolac type cyanate or a dicyclopentadiene type phenol resin, of which typical but not limited.
  • the mixture is: bisphenol A type cyanate and novolac type cyanate, novolac type cyanate and dicyclopentadiene type phenolic resin.
  • the benzoxazine-containing resin composition may further contain a thermosetting polyphenylene ether in an amount of from 0 to 40 parts by weight, such as 1 weight, based on 100 parts by weight of the organic solids. Parts, 2 parts by weight, 5 parts by weight, 8 parts by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 28 parts by weight, 30 parts by weight, 35 parts by weight or 40 parts by weight, and the above values Between The specific point values, limited by the length and for the sake of brevity, are not exhaustively enumerated.
  • the benzoxazine-containing resin composition may further contain an active ester.
  • the specific active ester species is not particularly limited in the present invention; the active ester content is 100 parts by weight based on the organic solid content. 0 to 40 parts by weight, for example, 1 part by weight, 2 parts by weight, 5 parts by weight, 8 parts by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 28 parts by weight, 30 parts by weight, 35 parts by weight Part or 40 parts by weight, and the specific point values between the above values, are limited to the length and for the sake of brevity, the present invention will not exhaustively enumerate the specific point values included in the range.
  • the benzoxazine-containing resin composition may further contain a styrene maleic anhydride copolymer, and the content of the styrene maleic anhydride copolymer is from 0 to 40 based on 100 parts by weight of the organic solid.
  • Parts by weight for example, 1 part by weight, 2 parts by weight, 5 parts by weight, 8 parts by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 28 parts by weight, 30 parts by weight, 35 parts by weight or 40 parts by weight
  • the specific point values between the above and the above values are limited, and for the sake of brevity, the present invention will not exhaustively enumerate the specific point values included in the scope.
  • the mass ratio of styrene to maleic anhydride in the styrene maleic anhydride copolymer is from 9:1 to 6:4, such as 9:1, 8:2, 7:3 or 6:4, and
  • the specific point values between the above values are limited to the length and for the sake of brevity, the present invention will not exhaustively enumerate the specific point values included in the range.
  • the "organic solid” means a benzoxazine resin and optionally an epoxy resin, a phenol resin, a cyanate ester, a thermosetting polyphenylene ether and a styrene maleic anhydride copolymer, which can participate together Cross-linking polymerization.
  • the benzoxazine-containing resin composition may further contain a flame retardant.
  • the flame retardant of the present invention is not particularly limited as long as it can flame retard the benzoxazine resin composition.
  • the flame retardant is selected from the group consisting of decabromodiphenyl ether, octabromoether, hexabromocyclododecane, tetrabromobisphenol A, decabromodiphenylethane, triphenyl phosphate, tricresyl phosphate, Trioctyl phosphate, diphenyloctyl phosphate, diphenylisodecyl phosphate, tris(xylylene) phosphate, diphenyl tert-butyl phosphate, diphenylphenylphenyl phosphate, resorcinol double [two ( 2,6-Dimethylphenyl)phosphate], diphenylisooctyl phosphate, aluminum methylethylphosphinate, aluminum diethylphosphinate, aluminum hydroxymethylphenylphosphinate, 3- Hydroxyphenylphosphorylpropionic acid, hydroxyphenylphosphoryl
  • the benzoxazine-containing resin composition may further contain a curing accelerator.
  • the curing accelerator is not particularly limited as long as it can catalyze the reaction between the epoxy functional group and the benzo ring and lower the reaction temperature of the curing system, and preferably an imidazole compound, a derivative of an imidazole compound, or a piperidine compound. Any one or a mixture of at least two of Lewis acid or triphenylphosphine, further preferably 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole or triphenylphosphine Any one or a mixture of at least two.
  • the imidazole compound may, for example, be any one of a mixture of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole or 2-undecylimidazole or a mixture of at least two.
  • the piperidine compound may, for example, be 2,3-diaminopiperidine, 2,5-diaminopiperidine, 2,6-diaminopiperidine, 2-amino-3-methylpiperidine or 2-amino Any one or at least -4-methylpiperidine, 2-amino-3-nitropiperidine, 2-amino-5-nitropiperidine or 2-amino-4,4-dimethylpiperidine a mixture of two.
  • the curing accelerator is added in an amount of from 0 to 1 part by weight, such as 0.05 parts by weight, 0.1 part by weight, 0.15 by weight, based on 100 parts by weight of the acidic filler, the benzoxazine, and the epoxy resin.
  • Parts 0.2 parts by weight, 0.25 parts by weight, 0.3 parts by weight, 0.35 parts by weight, 0.4 parts by weight, 0.45 parts by weight Parts, 0.5 parts by weight, 0.55 parts by weight, 0.6 parts by weight, 0.65 parts by weight, 0.7 parts by weight, 0.75 parts by weight, 0.8 parts by weight, 0.85 parts by weight, 0.9 parts by weight, 0.95 parts by weight or 1 part by weight, and the above values
  • the specific point values between the two are limited to the length and for the sake of brevity, the present invention is not limited to the specific point values included in the range, and is preferably 0.05 to 0.8 parts by weight, and more preferably 0.05 to 0.6 parts by weight.
  • the benzoxazine-containing resin composition may further contain a non-acidic filler, for example, any one selected from the group consisting of calcium carbonate, calcium sulfate, aluminum oxide, barium sulfate, ceramic powder, talc or hydrotalcite.
  • a non-acidic filler for example, any one selected from the group consisting of calcium carbonate, calcium sulfate, aluminum oxide, barium sulfate, ceramic powder, talc or hydrotalcite.
  • a typical but non-limiting mixture is: calcium carbonate and calcium sulfate, alumina and barium sulfate, ceramic powder and talc.
  • a second object of the present invention is to provide a benzoxazine-containing resin composition comprising a oxoxazine resin and an acidic filler, wherein the organic solid content of the benzoxazine-containing resin composition is 100% by weight.
  • the acidic filler is added in an amount of 5 to 200 parts by weight, and the acidic filler has a pH of 2 to 6.
  • the benzoxazine-containing resin composition may optionally contain an epoxy resin or a phenolic aldehyde according to one of the objects of the present invention, in addition to the benzoxazine resin and the acidic filler.
  • a component such as a resin, a cyanate ester, a thermosetting polyphenylene ether, an active ester, a styrene maleic anhydride copolymer, a flame retardant, a curing accelerator, and a non-acidic filler, and each component contained in the resin composition and The content can be exemplarily referenced to the scope of one of the objects of the invention.
  • the present invention employs a benzoxazine resin composition containing an acidic filler, wherein the acidic filler not only catalyzes ring-opening polymerization of benzoxazine and epoxy resin, but also reduces the coefficient of thermal expansion of the benzoxazine resin composition.
  • Improve the anti-peeling stability of the copper-clad laminate at the same time, greatly improve the curing efficiency of the benzoxazine resin composition and reduce the use of the catalyst; the laminate prepared by using the resin composition has excellent anti-peeling stability and high vitrification Transition temperature, high heat resistance, high bending strength and good processability, and low coefficient of thermal expansion.
  • the benzoxazine-containing resin composition may further contain various additives, and specific examples thereof include an antioxidant, a heat stabilizer, an antistatic agent, an ultraviolet absorber, a pigment, a colorant, or a lubricant. Wait. These additives may be used singly or in combination of two or more.
  • the present invention also provides a prepreg comprising the resin composition prepared according to the method of one of the objects of the present invention or the resin composition of the second aspect, and the reinforcing material; the reinforcing material used is not particularly
  • the limitation may be organic fiber, inorganic fiber woven cloth or non-woven fabric.
  • the organic fiber may be selected from aramid nonwoven fabric, and the inorganic fiber woven fabric may be E-glass fabric, D-glass fabric, S-glass fabric, T-glass fabric, NE-glass fabric. Or quartz cloth.
  • the thickness of the reinforcing material is not particularly limited, and the thickness of the woven fabric and the nonwoven fabric is preferably 0.01 to 0.2 mm, and preferably the fiber-opening treatment and the silane coupling agent are considered.
  • the silane coupling agent is preferably any one or at least two of an epoxy silane coupling agent, an amino silane coupling agent or a vinyl silane coupling agent.
  • the prepreg is obtained by impregnating the above composite material by impregnation with the above composite material at 100 to 250 ° C for 1 to 15 minutes.
  • the copper-clad laminate for a printed circuit board of the present invention comprises a laminate obtained by bonding two or more prepregs together by heat and pressure, and bonded to one or both sides of the laminate.
  • the above copper foil; the copper-clad laminate lamination needs to meet the following requirements: 1.
  • the heating rate of the lamination is generally controlled at a temperature of 80-160 ° C at a temperature of 1.0 to 3.0 ° C / min; Pressure setting of the pressure, the temperature of the outer layer is 80-100 ° C When full pressure is applied, the full pressure is about 300 psi; 3.
  • the temperature of the control material is 180-210 ° C, and the temperature is kept for 60-180 min;
  • the metal foil covered may be nickel foil, aluminum foil and SUS foil, etc., the material is not limited.
  • the present invention has at least the following beneficial effects:
  • the present invention greatly promotes polymerization of benzoxazine and epoxy resin by adding an acidic filler to a resin composition containing benzoxazine, and reduces the polymerization required for benzoxazine and epoxy polymerization.
  • the curing temperature lowers the curing temperature, makes the reaction of benzoxazine and epoxy more complete, improves the curing efficiency of the benzoxazine resin composition, and reduces the use of the catalyst;
  • the laminate of the present invention produced by using the benzoxazine resin composition to which the acidic filler is added has high peeling stability, high glass transition temperature, high heat resistance, high bending strength, and good process. Processability and low coefficient of thermal expansion.
  • the parts represent parts by weight, and the % represents "% by weight”.
  • A-1 Acidic filler: spherical silicon micropowder, pH: 4, purchased from Jiangsu Lianrui model is DQ1030
  • A-2 Acidic filler: Quartz powder, pH: 3, purchased from Zhangzhou Yingfeng Mining Model 3000 mesh airflow quartz powder
  • A-3 Acidic filler: mica powder, pH: 5, purchased from Anhui Ge Rui model GD-2
  • A-4 Acidic filler: carbon black, pH: 3, purchased from Tianjin Xinglongtai Chemical Products Technology Co., Ltd.
  • B-2 Diamine type benzoxazine: 4,4'-diaminodiphenyl ether type benzoxazine, purchased from Sichuan Dongmu model D125
  • DCPD type epoxy resin purchased from Japan DIC model is HP-7200
  • C-2 Biphenyl type epoxy resin: purchased from Nippon Chemical Co., Ltd. model NC-3000H
  • Linear phenolic purchased from Korea KOLON model is KGH-3300
  • Cyanate ester purchased from Longsha model BA-3000S
  • Thermosetting polyphenylene ether purchased from SABIC model SA-90
  • K-1 non-acidic filler: spherical silicon micropowder, pH: 8, purchased from Japan admatechs model SC2500-SEJ
  • K-2 non-acidic filler: alumina, pH: 9, purchased from Yu Xinyuan model is SJA-0051
  • K-3 non-acidic filler: calcium carbonate, pH: 9, purchased in Guangdong Zhongqi model is 1500 mesh light carbonic acid calcium
  • K-4 non-acidic filler: talc, pH: 8, purchased in the US special mine model is AG-609
  • laminates for printed circuit boards were prepared as follows, and the prepared laminates were subjected to performance tests.
  • the preparation method of the laminate for printed circuit board comprises:
  • step 2 8 pieces of prepreg and 2 pieces of one ounce (35 ⁇ m thick) metal foil are laminated together;
  • the operating conditions of the lamination are: when the temperature is 80-140 ° C, the controlled heating rate is 1.5-2.5 ° C / min; when the outer layer temperature is 80-100 ° C, the full pressure is applied, the full pressure is applied. It is about 350 psi; when curing, the temperature of the material is controlled at 195 ° C and kept for more than 60 minutes.
  • DSC differential scanning calorimetry
  • the measurement was carried out according to the DSC method specified in IPC-TM-6502.4.25 by differential scanning calorimetry (DSC).
  • the bending strength was measured by measuring according to the method of IPC-TM-6502.4.4B.
  • the peel strength of the metal cap layer was tested in accordance with the "after thermal stress" experimental conditions in the IPC-TM-6502.4.8 method.
  • the sheets obtained in Examples 1 to 6 had a high glass transition temperature and a low coefficient of thermal expansion. And high bending strength; in addition, after comparing Example 1 with Example 2, it was found that by adding more acidic filler, the glass transition temperature can be further increased, the curing temperature and the coefficient of thermal expansion of the resin composition can be lowered.
  • the laminate obtained by adding the resin composition of the present invention has a more stable peel strength, a higher glass transition temperature, a high bending strength, a lower coefficient of thermal expansion, and is suitable for a thermosetting resin. Modulus, high strength, low thermal expansion and other fields.

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Abstract

本发明涉及一种含有苯并噁嗪的树脂组合物的制备方法及由其制成的预浸料和层压板，所述含有苯并噁嗪的树脂组合物的制备方法为：向含有苯并噁嗪的树脂组合物中添加酸性填料。本发明通过在树脂组合物中添加酸性填料，极大地促进了苯并噁嗪和环氧树脂的聚合反应，降低了苯并噁嗪和环氧聚合所需的固化温度；使用该添加有酸性填料的组合物制作的层压板具有高的抗剥稳定性、高玻璃化转变温度、低吸水率、高耐热性、高弯曲强度和良好的工艺加工性，并能实现低热膨胀系数。

Description

一种含有苯并噁嗪树脂组合物的制备方法及由其制成的预浸料和层压板 技术领域
本发明涉及覆铜板技术领域，尤其涉及一种含有苯并噁嗪复合材料的制备方法及由其制成的预浸料和层压板。
背景技术
苯并噁嗪是一种综合性能优异的热固性聚合物，具有优良的成型加工性，综合性能好。该树脂原材料来源广泛，价格低廉，合成工艺简单；固化反应为开环聚合，突出特点在于无小分子释放，收缩率小，孔隙率低，尺寸精度高；固化产物具有高玻璃化转变温度，高弹性模量，耐热性好，较高成碳率，优良的阻燃性能和低吸水性。
苯并噁嗪树脂具有自聚合能力，但是聚合温度在200℃以上且脆性大，很难在主承力结构的复合材料领域得到应用，通常加入环氧树脂、橡胶等组份提高苯并噁嗪韧性，达到改善苯并噁嗪脆性的目的；加入催化剂或促进剂降低固化温度，缩短固化时间、提高制品固化程度，达到降低能耗、节约成本的目的；加入填料降低成本并改善热膨胀系数，以满足使用需求。
CN102575006A描述了包含苯并噁嗪化合物和五氟锑酸催化剂的可固化组合物。所述可固化组合物可固化以制备用于涂层、密封剂、粘合剂和许多其他应用的固化组合物。
US6376080A1描述了制备聚苯并噁嗪的方法，该方法包括加热包含苯并噁嗪和杂环二羧酸的模制组合物至足以固化该模制组合物的温度，从而形成所述聚苯并噁嗪。该组合物据称在后固化之后体积变化接近零。
目前经常采用的降低苯并噁嗪固化温度的方法包括添加各种酚类或路易斯 酸等催化剂，在反应结束后仍然以原结构残留在体系中，对体系的耐热性带来一定的负面影响，而高沸点有机酸则会在树脂组合物中残留，在制作过程中增加了PCB板受热分层爆板的风险。因此，对于苯并噁嗪树脂的应用，一直存在难题。
发明内容
基于此，本发明的目的之一在于提供一种含有苯并噁嗪的树脂组合物的制备方法及由其制成的预浸料和层压板。通过在树脂组合物中添加酸性填料，一方面能够促进苯并噁嗪开环交联，降低苯并噁嗪树脂组合物固化温度，起到催化剂的作用，另一方面酸性填料表面的活性官能团参加树脂组合物交联网络结构的形成，填料和树脂界面能够形成强有力地共价键结合，增加了填料树脂组合物的结合力，而不会在反应结束后残留在体系中，因而提高了剥离强度稳定性、弯曲强度，降低热膨胀系数，同时能够遏止树脂组合物微裂纹的发展，表现出良好的韧性。
发明人为实现上述目的，进行了反复深入的研究，结果发现：通过将酸性填料与含有苯并噁嗪的树脂组合物适当混合从而进行树脂组合物的制备，可达到上述目的。
为了实现上述目的，本发明采用了如下技术方案：
本发明的目的之一在于提供了一种含有苯并噁嗪的树脂组合物的制备方法，所述方法为：
向含有苯并噁嗪的树脂组合物中添加酸性填料，所述酸性填料的pH值在2～6之间，得到所述树脂组合物。
本发明中通过向含有苯并噁嗪的树脂组合物中添加酸性填料，可以催化苯并噁嗪和环氧树脂的开环聚合反应，且能够降低苯并噁嗪树脂组合物热膨胀系数， 改善苯并噁嗪树脂组合物覆铜箔层压板抗剥稳定性；酸性填料的加入大大提高苯并噁嗪树脂组合物固化效率，减少催化剂的使用；使用该树脂组合物制作的层压板具有高的抗剥稳定性、高玻璃化转变温度、高耐热性、高弯曲强度和良好的工艺加工性，并能实现低热膨胀系数。
本发明中所述含有苯并噁嗪的树脂材料的制备方法中，固化温度可以达到214℃以下，例如可以是202℃、203℃、204℃、205℃、206℃、207℃、208℃、209℃、210℃、211℃、212℃、213℃或214℃，以及上述数值之间的具体点值，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。
根据本发明，所述酸性填料的pH值在2～6之间，例如2、2.5、3、3.5、4、5或6，以及上述数值之间的具体点值，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。
本发明中，所述酸性填料的特征是：将该填料与去离子水按1∶9的质量比配制成水溶液，对其进行测定从而得到该填料的pH值在2～6之间。
优选地，本发明所述酸性填料的pH值在3～5之间。
根据本发明，所述酸性填料选自硅微粉、石英粉、云母粉、黏土、草酸钙或炭黑中的任意一种或至少两种的混合物，其中典型但非限制性的混合物为硅微粉和石英粉、黏土和草酸钙、炭黑和云母粉。
本发明中，所述酸性填料的粒径在50nm～50μm之间，例如50nm、60nm、70nm、80nm、90nm、100nm、300nm、500nm、800nm、5μm、10μm、30μm、40μm、45μm或50μm，以及上述数值之间的具体点值，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。
对于所述酸性填料的物理形态，本发明不做特殊限定，例如可以是片材、棒状、球形、空心球形、粒状、纤维状或板状等；也可以选择性以硅烷偶联剂 对酸性填料进行处理。
根据本发明，以所述含有苯并噁嗪的树脂组合物中有机固形物为100重量份计，所述酸性填料的添加量为5～200重量份，例如5重量份、8重量份、10重量份、15重量份、20重量份、30重量份、40重量份、55重量份、60重量份、65重量份、70重量份、80重量份、90重量份、100重量份、120重量份、150重量份、180重量份或200重量份，以及上述数值之间的具体点值，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。
根据本发明，所述含有苯并噁嗪的树脂组合物中，以有机固形物为100重量份计，苯并噁嗪树脂的含量为10～100重量份，例如10重量份、12重量份、15重量份、18重量份、20重量份、25重量份、30重量份、45重量份、50重量份、60重量份、70重量份、80重量份、90重量份或100重量份，以及上述数值之间的具体点值，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。
本发明中，所述苯并噁嗪树脂选自二酚型苯并噁嗪和/或二胺型苯并噁嗪，可以是二酚型苯并噁嗪、二胺型苯并噁嗪或其混合物。
所述二酚型苯并噁嗪树脂单体的结构如式(I)所示：
Figure PCTCN2017084314-appb-000001
其中，R1为
Figure PCTCN2017084314-appb-000002
R2为
Figure PCTCN2017084314-appb-000003
-CH2-、-O-、
Figure PCTCN2017084314-appb-000004
或
Figure PCTCN2017084314-appb-000005
中的任意一种。
当R2为
Figure PCTCN2017084314-appb-000006
时，结构式(I)为双酚A型苯并噁嗪树脂单体；当R2为-CH2-时，结构式(I)为双酚F型苯并噁嗪树脂单体；当R2为
Figure PCTCN2017084314-appb-000007
时，结构式(I)为酚酞型苯并噁嗪树脂单体；当R2为
Figure PCTCN2017084314-appb-000008
时，结构式(I)为双环戊二烯型苯并噁嗪树脂单体。
所述二胺型苯并噁嗪树脂单体的结构式如式(II)所示：
Figure PCTCN2017084314-appb-000009
其中，R3为
Figure PCTCN2017084314-appb-000010
-CH2-或-O-中的任意一种。
当R3为
Figure PCTCN2017084314-appb-000011
时，结构式(II)为DDS型苯并噁嗪树脂单体；当R3为-CH2-时，结构式(II)为MDA型苯并噁嗪树脂单体；当R3为-O-时，结构式(II)为ODA型苯并噁嗪树脂单体。
根据本发明，所述含有苯并噁嗪的树脂组合物中还可以含有环氧树脂，以有机固形物为100重量份计，环氧树脂的含量为0～75重量份，例如1重量份、5重量份、8重量份、12重量份、15重量份、18重量份、20重量份、25重量份、30重量份、45重量份、50重量份、60重量份、65重量份、70重量份或75重量份，以及上述数值之间的具体点值，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。
优选地，所述环氧树脂选自双酚A型环氧树脂、双酚F型环氧树脂、邻甲酚酚醛环氧树脂、双酚A型酚醛环氧树脂、三酚型酚醛环氧树脂、双环戊二烯酚醛环氧树脂、联苯型酚醛环氧树脂、烷基苯型酚醛环氧树脂或萘酚型酚醛环氧树脂中的任意一种或至少两种的混合物，其中典型但非限制性的混合物为双酚A型环氧树脂和双酚F型环氧树脂、双酚A型环氧树脂和双酚F型环氧树脂、三酚型酚醛环氧树脂和双环戊二烯酚醛环氧树脂、联苯型酚醛环氧树脂和烷基苯型酚醛环氧树脂。
优选地，所述环氧树脂选自具有如下结构的环氧树脂：
Figure PCTCN2017084314-appb-000012
其中，X1、X2和X3各自独立地选自
Figure PCTCN2017084314-appb-000013
R4选自取代或未取代的C1-C5直链烷基或者取代或未取代的C1-C5支链烷基中的任意一种，其中C1-C5直链烷基可以是甲基、乙基、丙基、正丁基或正戊基，C1-C5支链烷基可以是异丙基、异丁基或异戊基等；
Y1和Y2各自独立地选自-CH2-
Figure PCTCN2017084314-appb-000014
Figure PCTCN2017084314-appb-000015
中的任意一种，R5选自氢原子、取代或未取代的C1-C5直链烷基或者取代或未取代的C1-C5支链烷基中的任意一种，其中C1-C5直链烷基可以是甲基、乙基、丙基、正丁基或正戊基，C1-C5支链烷基可以是异丙基、异丁基或异戊基等；
m为1～10的任意整数，例如1、2、3、4、5、6、7、9或10。
根据本发明，所述含有苯并噁嗪的树脂组合物中还可以含有酚醛树脂，以有机固形物为100重量份计，酚醛树脂的含量为0～40重量份，例如1重量份、2重量份、5重量份、8重量份、10重量份、15重量份、20重量份、25重量份、28重量份、30重量份、35重量份或40重量份，以及上述数值之间的具体点值，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。
本发明中，所述酚醛树脂选自线性酚醛树脂、双酚A酚醛树脂、邻甲酚酚醛树脂、含磷酚醛树脂或三官能酚醛树脂中的任意一种或至少两种的混合物，其中典型但非限制性的混合物为线性酚醛树脂和双酚A酚醛树脂、双酚A酚醛树脂和邻甲酚酚醛树脂、含磷酚醛树脂和三官能酚醛树脂。
根据本发明，所述含有苯并噁嗪的树脂组合物中还可以含有氰酸酯，以有机固形物为100重量份计，氰酸酯的含量为0～50重量份，例如1重量份、2重量份、5重量份、8重量份、10重量份、15重量份、20重量份、25重量份、28重量份、30重量份、35重量份、40重量份、45重量份或50重量份，以及上述数值之间的具体点值，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。
本发明中，所述氰酸酯选自双酚A型氰酸酯、酚醛型氰酸酯或双环戊二烯型酚醛树脂中的任意一种或至少两种的混合物，其中典型但非限制性的混合物为：双酚A型氰酸酯和酚醛型氰酸酯、酚醛型氰酸酯和双环戊二烯型酚醛树脂。
根据本发明，所述含有苯并噁嗪的树脂组合物中还可以含有热固性聚苯醚，以有机固形物为100重量份计，热固性聚苯醚的含量为0～40重量份，例如1重量份、2重量份、5重量份、8重量份、10重量份、15重量份、20重量份、25重量份、28重量份、30重量份、35重量份或40重量份，以及上述数值之间的 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。
根据本发明，所述含有苯并噁嗪的树脂组合物中还可以含有活性酯，对于具体的活性酯种类，本发明不做特殊限定；以有机固形物为100重量份计，活性酯的含量为0～40重量份，例如1重量份、2重量份、5重量份、8重量份、10重量份、15重量份、20重量份、25重量份、28重量份、30重量份、35重量份或40重量份，以及上述数值之间的具体点值，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。
根据本发明，所述含有苯并噁嗪的树脂组合物中还可以含有苯乙烯马来酸酐共聚物，以有机固形物为100重量份计，苯乙烯马来酸酐共聚物的含量为0～40重量份，例如1重量份、2重量份、5重量份、8重量份、10重量份、15重量份、20重量份、25重量份、28重量份、30重量份、35重量份或40重量份，以及上述数值之间的具体点值，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。
优选地，所述苯乙烯马来酸酐共聚物中的苯乙烯与马来酸酐的质量比为9∶1～6∶4，例如9∶1、8∶2、7∶3或6∶4，以及上述数值之间的具体点值，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。
本发明中，所述“有机固形物”是指苯并噁嗪树脂以及可选地环氧树脂、酚醛树脂、氰酸酯、热固性聚苯醚和苯乙烯马来酸酐共聚物，其可共同参与交联聚合反应。
根据本发明，所述含有苯并噁嗪的树脂组合物中还可以含有阻燃剂。
本发明对所述阻燃剂没有特别的限定，只要能够阻燃苯并噁嗪树脂组合物即可。
优选地，所述阻燃剂选自十溴二苯醚、八溴醚、六溴环十二烷、四溴双酚A、十溴二苯乙烷，磷酸三苯酯、磷酸三甲苯酯、磷酸三辛酯、磷酸二苯辛酯、磷酸二苯异癸酯、磷酸三(二甲苯)酯、磷酸二苯叔丁苯酯、磷酸二苯异丙苯酯、间苯二酚双[二(2，6-二甲基苯基)磷酸酯]、磷酸二苯异辛酯、甲基乙基次膦酸铝、二乙基次膦酸铝、羟甲基苯基次膦酸铝、3-羟基苯基磷酰丙酸、羟基苯膦酰丙酸、羟基丙酸基苯膦酰、2-羧基乙基(苯基)次膦酸、9，10-二氢-9-氧杂-10-磷杂菲-10-氧化物或聚(二(苯氧基)偶磷氮烯)中的任意一种或至少两种的混合物，其中典型但非限制性的混合物为：十溴二苯醚和八溴醚、六溴环十二烷和四溴双酚A、磷酸三苯酯和磷酸三甲苯酯、磷酸二苯异辛酯和甲基乙基次膦酸铝。
根据本发明，所述含有苯并噁嗪的树脂组合物中还可以含有固化促进剂。
本发明对所述固化促进剂没有特别的限定，只要能催化环氧官能团和苯并环反应并降低固化体系的反应温度即可，优选咪唑类化合物、咪唑类化合物的衍生物、哌啶类化合物、路易斯酸或三苯基膦中的任意一种或至少两种的混合物，进一步优选2-甲基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑或三苯基膦中的任意一种或至少两种的混合物。
所述咪唑类化合物可以列举有2-甲基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑或2-十一烷基咪唑中的任意一种或至少两种的混合物。
所述哌啶类化合物可以列举有2，3-二氨基哌啶、2，5-二氨基哌啶、2，6-二氨基哌啶、2-氨基-3-甲基哌啶、2-氨基-4-甲基哌啶、2-氨基-3-硝基哌啶、2-氨基-5-硝基哌啶或2-氨基-4，4-二甲基哌啶中的任意一种或至少两种的混合物。
优选地，以酸性填料、苯并噁嗪和环氧树脂的添加量为100重量份计，所述固化促进剂的添加量为0～1重量份，例如0.05重量份、0.1重量份、0.15重量份、0.2重量份、0.25重量份、0.3重量份、0.35重量份、0.4重量份、0.45重量 份、0.5重量份、0.55重量份、0.6重量份、0.65重量份、0.7重量份、0.75重量份、0.8重量份、0.85重量份、0.9重量份、0.95重量份或1重量份，以及上述数值之间的具体点值，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，优选0.05～0.8重量份，进一步优选0.05～0.6重量份。
根据本发明，所述含有苯并噁嗪的树脂组合物中还可以含有非酸性填料，例如可以选自碳酸钙、硫酸钙、氧化铝，硫酸钡，陶瓷粉、滑石粉或水滑石中的任意一种或至少两种的混合物，其中典型但非限制性的混合物为：碳酸钙和硫酸钙、氧化铝和硫酸钡、陶瓷粉和滑石粉。
本发明的目的之二在于提供了一种含有苯并噁嗪的树脂组合物，其包含并噁嗪树脂和酸性填料，以所述含有苯并噁嗪的树脂组合物中有机固形物为100重量份计，所述酸性填料的添加量为5～200重量份，所述酸性填料的pH值在2～6之间。
本领域技术人员可以明了，所述含有苯并噁嗪的树脂组合物中除了包含苯并噁嗪树脂和酸性填料外，还可以任选地含有本发明目的之一所述的环氧树脂、酚醛树脂、氰酸酯、热固性聚苯醚、活性酯、苯乙烯马来酸酐共聚物、阻燃剂、固化促进剂以及非酸性填料等组分，且所述树脂组合物中含有的各个组分和含量均可示例性地参考本发明目的之一所述的范围。
本发明通过采用含有酸性填料的苯并噁嗪树脂组合物，其中酸性填料不仅可以催化苯并噁嗪和环氧树脂的开环聚合反应，还能降低苯并噁嗪树脂组合物的热膨胀系数，改善覆铜箔层压板抗剥稳定性；同时可大大提高苯并噁嗪树脂组合物固化效率，减少催化剂的使用；使用该树脂组合物制作的层压板具有优异的抗剥稳定性、高玻璃化转变温度、高耐热性、高弯曲强度和良好的工艺加工性，并能实现低热膨胀系数。
本发明所述的“含有”，意指其除所述组份外，还可以包括其他组份，这些其他组份赋予所述树脂组合物不同的特性。除此之外，本发明所述的“含有”，还可以替换为封闭式的“为”或“由......组成”。
例如，所述含有苯并噁嗪的树脂组合物还可以含有各种添加剂，作为具体例，可以举出抗氧剂、热稳定剂、抗静电剂、紫外线吸收剂、颜料、着色剂或润滑剂等。这些添加剂可以单独使用，也可以两种或者两种以上混合使用。
对于本发明中未进一步限定的含有苯并噁嗪的树脂组合物的制备步骤，本领域技术人员可以参考现有的树脂组合物及复合材料的制备方法，结合实际情况进行选择，本发明不做特殊限定。
本发明还提供了一种预浸料，其含有根据本发明的目的之一所述方法制备得到的树脂组合物或目的之二所述树脂组合物，以及增强材料；所使用的增强材料无特别的限定，可以为有机纤维、无机纤维编织布或无纺布。所述的有机纤维可以选择芳纶无纺布，所述的无机纤维编织布可以为E-玻纤布、D-玻纤布、S-玻纤布、T玻纤布、NE-玻纤布或石英布。所述增强材料的厚度无特别限定，处于层压板有良好的尺寸稳定性的考虑，所述编织布及无纺布厚度优选0.01～0.2mm，且最好是经过开纤处理及硅烷偶联剂表面处理的，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混合物。将增强材料通过含浸上述的复合材料，在100～250℃条件下，烘烤1～15分钟得到所述预浸料。
本发明的印刷电路板用覆铜箔层压板包括通过加热和加压，使两片或两片以上的预浸料粘合在一起而制成的层压板、粘合在层压板的一面或两面以上的铜箔；所述的覆铜箔层压需满足以下要求：1、层压的升温速率通常在料温80～160℃时的升温速度应控制在1.0～3.0℃/min；2、层压的压力设置，外层料温在80～100℃ 时施加满压，满压压力为300psi左右；3、固化时，控制料温在180～210℃，并保温60～180min；所覆盖的金属箔除铜箔外，还可以是镍箔、铝箔及SUS箔等，其材质不限。
与现有技术相比，本发明至少具有以下有益效果：
(1)本发明通过在含有苯并噁嗪的树脂组合物中添加酸性填料，极大地促进了苯并噁嗪和环氧树脂的聚合反应，降低了苯并噁嗪和环氧聚合所需的固化温度，使固化温度降低，使苯并噁嗪和环氧的反应更完全，提高了苯并噁嗪树脂组合物的固化效率，减少了催化剂的使用；
(2)本发明通过使用该添加有酸性填料的苯并噁嗪树脂组合物制作的层压板具有高的抗剥稳定性、高玻璃化转变温度、高耐热性、高弯曲强度和良好的工艺加工性，并能实现低热膨胀系数。
具体实施方式
下面通过具体实施方式来进一步说明本发明的技术方案。
以下所述是本发明实施例的具体实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明实施例原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也视为本发明实施例的保护范围。
下面分多个实施例对本发明实施例进行进一步的说明。本发明实施例不限定于以下的具体实施例。在不改变权利要求的范围内，可以适当的进行变更实施。
下文中如无特别说明，其份代表重量份，其％代表“重量％”。
实施例和对比例涉及的材料及牌号信息如下：
(A)酸性填料
A-1：酸性填料：球形硅微粉，pH：4，购于江苏联瑞型号为DQ1030
A-2：酸性填料：石英粉，pH：3，购于梧州颖丰矿业型号为3000目气流石英粉
A-3：酸性填料：云母粉，pH：5，购于安徽格锐型号为GD-2
A-4：酸性填料：炭黑，pH：3，购于天津星龙泰化工产品科技有限公司
(B)苯并噁嗪
B-1：二酚型苯并噁嗪：双酚A型苯并噁嗪，购于HUNSTMAN型号为LZ8290
B-2：二胺型苯并噁嗪：4，4’-二氨基二苯醚型苯并恶嗪，购于四川东材型号为D125
(C)环氧树脂
C-1：DCPD型环氧树脂：购于日本DIC型号为HP-7200
C-2：联苯型环氧树脂：购于日本化药型号为NC-3000H
D：线性酚醛：购于韩国KOLON型号为KGH-3300
E：氰酸酯：购于龙沙型号为BA-3000S
F：热固性聚苯醚：购于沙伯基型号为SA-90
G：活性酯：购于韩国SHINA型号为SHC-4314
H：苯乙烯马来酸酐共聚物，购于沙多玛型号为EF-40
I：阻燃剂，购于大塚化学型号为SPB-100
J：促进剂，购于四国化成型号为2-MI
(K)非酸性填料
K-1：非酸性填料：球形硅微粉，pH：8，购于日本admatechs型号为SC2500-SEJ
K-2：非酸性填料：氧化铝，pH：9，购于蚌埠鑫源型号为SJA-0051
K-3：非酸性填料：碳酸钙，pH：9，购于广东中棋型号为1500目轻质碳酸 钙
K-4：非酸性填料：滑石粉，pH：8，购于美国特矿型号为AG-609
将实施例和比较例提供的树脂组合物，按照如下方法制备印制电路用层压板，并对制备得到的层压板进行性能测试。
所述印制电路用层压板的制备方法包括：
①通过加热和加压作用使一张或一张以上的预浸料粘合在一起，制成的层压板；
②在步骤①制得的层压板的一面或两面上粘合金属箔；
③在层压机中进行层压；
在步骤②的过程中，使用8片预浸料和2片一盎司(35μm厚)的金属箔叠合在一起；
在步骤③的过程中，层压的操作条件为：料温80～140℃时，控制升温速率为1.5～2.5℃/min；外层料温80-100℃时，施加满压，满压压力为350psi左右；固化时，控制料温在195℃，并保温60min以上。
实施例和比较例提供的树脂组合物的配方及性能测试结果见下表。
表1
Figure PCTCN2017084314-appb-000016
Figure PCTCN2017084314-appb-000017
表2
Figure PCTCN2017084314-appb-000018
Figure PCTCN2017084314-appb-000019
性能测试的项目及具体方法为：
(a)起始反应温度
根据差示扫描量热法(DSC)，氮气氛围，升温速率为10℃/min。
(b)玻璃化转变温度(Tg)
根据差示扫描量热法(DSC)，按照IPC-TM-6502.4.25所规定的DSC方法进行测定。
(c)弯曲强度
按照IPC-TM-6502.4.4B方法进行测定，测试弯曲强度。
(d)CTE
按照IPC-TM-6502.4.41方法进行测定，测试热膨胀系数。
(e)剥离强度(PS)
按照IPC-TM-6502.4.8方法中的“热应力后”实验条件，测试金属盖层的剥离强度。
从表1各实施例以及比较例的性能数据可以看出：对比实施例1～6和比较例1～4的测试结果，添加酸性填料的实施例1～6相比普通非酸性填料的比较例1～4能够明显降低树脂组合物反应温度，其起始反应温度仅为194～201℃，而比 较例1～4得到的起始温度最低也要达到213℃；另外，实施例1～6得到的板材具有更高的剥离强度稳定性，其剥离强度的差值仅在0.06～0.08，而比较例1～4得到的板材的剥离强度的差值可达到0.11以上，剥离强度稳定性变差；再有，实施例1～6得到的板材具有较高玻璃化转变温度，同时还具有低热膨胀系数和高弯曲强度；此外，实施例1与实施例2进行比较后可以发现，添加更多的酸性填料，可进一步提高玻璃化转变温度，降低固化温度以及树脂组合物的热膨胀系数。
从表2各个实施例以及比较例的性能数据可以看出：对比实施例7～14和比较例5～8，在含酸性填料苯并噁嗪体系中添加酚醛树脂、氰酸酯、热固性聚苯醚、活性酯以及苯乙烯马来酸酐共聚物，也能够降低固化反应温度，提高剥离强度稳定性，提高树脂组合物玻璃化转变温度，同时还能降低树脂组合物热膨胀系数。
如上所述，本发明添加酸性填料后的树脂组合物所制得的层压板具有更稳定的剥离强度、更高的玻璃化转变温度、高弯曲强度、更低的热膨胀系数，适用于热固性树脂高模量、高强度、低热膨胀等领域。
申请人声明，本发明通过上述实施例来说明本发明的详细方法，但本发明并不局限于上述详细方法，即不意味着本发明必须依赖上述详细方法才能实施。所属技术领域的技术人员应该明了，对本发明的任何改进，对本发明产品各原料的等效替换及辅助成分的添加、具体方式的选择等，均落在本发明的保护范围和公开范围之内。

Claims (12)

  1. 一种含有苯并噁嗪的树脂组合物的制备方法，其特征在于，所述方法为：
    向含有苯并噁嗪的树脂组合物中添加酸性填料，所述酸性填料的pH值在2～6之间。
  2. 如权利要求1所述的方法，其特征在于，所述酸性填料的pH值在3～5之间；
    优选地，以所述含有苯并噁嗪的树脂组合物中有机固形物为100重量份计，所述酸性填料的添加量为5～200重量份；
    优选地，所述酸性填料选自硅微粉、石英粉、云母粉、黏土、草酸钙或炭黑中的任意一种或至少两种的混合物；
    优选地，所述酸性填料的粒径为50nm～50μm。
  3. 如权利要求1或2所述的方法，其特征在于，所述含有苯并噁嗪的树脂组合物中，以有机固形物为100重量份计，苯并噁嗪树脂的含量为10～100重量份；
    优选地，所述苯并噁嗪树脂选自二酚型苯并噁嗪和/或二胺型苯并噁嗪；
    优选地，所述二酚型苯并噁嗪树脂单体的结构式如式(I)所示：
    Figure PCTCN2017084314-appb-100001
    其中，R1为
    Figure PCTCN2017084314-appb-100002
    R2为
    Figure PCTCN2017084314-appb-100003
    -CH2-、-O-、
    Figure PCTCN2017084314-appb-100004
    Figure PCTCN2017084314-appb-100005
    中的任意一种；
    优选地，所述二胺型苯并噁嗪树脂单体的结构式如式(II)所示：
    Figure PCTCN2017084314-appb-100006
    其中，R3为
    Figure PCTCN2017084314-appb-100007
    -CH2-或-O-中的任意一种。
  4. 如权利要求1-3之一所述的方法，其特征在于，所述含有苯并噁嗪的树脂组合物中含有环氧树脂；
    优选地，以有机固形物为100重量份计，环氧树脂的含量为0～75重量份；
    优选地，所述环氧树脂选自双酚A型环氧树脂、双酚F型环氧树脂、邻甲酚酚醛环氧树脂、双酚A型酚醛环氧树脂、三酚型酚醛环氧树脂、双环戊二烯酚醛环氧树脂、联苯型酚醛环氧树脂、烷基苯型酚醛环氧树脂或萘酚型酚醛环氧树脂中的任意一种或至少两种的混合物；
    优选地，所述环氧树脂选自具有如下结构的环氧树脂：
    Figure PCTCN2017084314-appb-100008
    其中，X1、X2和X3各自独立地选自
    Figure PCTCN2017084314-appb-100009
    R4选自取代或未取代的C1-C5直链烷基或者取代或未取代的C1-C5支链烷基中的任意一种；
    Y1和Y2各自独立地选自-CH2-、
    Figure PCTCN2017084314-appb-100010
    Figure PCTCN2017084314-appb-100011
    中的任意一种， R5选自氢原子、取代或未取代的C1-C5直链烷基或者取代或未取代的C1-C5支链烷基中的任意一种；
    m为1～10的任意整数。
  5. 如权利要求1-4之一所述的方法，其特征在于，所述含有苯并噁嗪的树脂组合物中含有酚醛树脂；
    优选地，以有机固形物为100重量份计，酚醛树脂的含量为0～40重量份；
    优选地，所述酚醛树脂选自线性酚醛树脂、双酚A酚醛树脂、邻甲酚酚醛树脂、含磷酚醛树脂或三官能酚醛树脂中的任意一种或至少两种的混合物；
    优选地，所述含有苯并噁嗪的树脂组合物中含有氰酸酯；
    优选地，以有机固形物为100重量份计，氰酸酯的含量为0～50重量份；
    优选地，所述氰酸酯选自双酚A型氰酸酯、酚醛型氰酸酯或双环戊二烯型酚醛树脂中的任意一种或至少两种的混合物；
    优选地，所述含有苯并噁嗪的树脂组合物中含有热固性聚苯醚；
    优选地，以有机固形物为100重量份计，热固性聚苯醚的含量为0～40重量份；
    优选地，所述含有苯并噁嗪的树脂组合物中含有活性酯；
    优选地，以有机固形物为100重量份计，活性酯的含量为0～40重量份；
    优选地，所述含有苯并噁嗪的树脂组合物中含有苯乙烯马来酸酐共聚物；
    优选地，以有机固形物为100重量份计，苯乙烯马来酸酐共聚物的含量为0～40重量份；
    优选地，所述苯乙烯马来酸酐共聚物中的苯乙烯与马来酸酐的质量比为9∶1～6∶4。
  6. 如权利要求1-5之一所述的方法，其特征在于，所述含有苯并噁嗪的树 脂组合物中含有阻燃剂；
    优选地，所述阻燃剂选自十溴二苯醚、八溴醚、六溴环十二烷、四溴双酚A、十溴二苯乙烷，磷酸三苯酯、磷酸三甲苯酯、磷酸三辛酯、磷酸二苯辛酯、磷酸二苯异癸酯、磷酸三(二甲苯)酯、磷酸二苯叔丁苯酯、磷酸二苯异丙苯酯、间苯二酚双[二(2，6-二甲基苯基)磷酸酯]、磷酸二苯异辛酯、甲基乙基次膦酸铝、二乙基次膦酸铝、羟甲基苯基次膦酸铝、3-羟基苯基磷酰丙酸、羟基苯膦酰丙酸、羟基丙酸基苯膦酰、2-羧基乙基(苯基)次膦酸、9，10-二氢-9-氧杂-10-磷杂菲-10-氧化物或聚(二(苯氧基)偶磷氮烯)中的任意一种或至少两种的混合物；
    优选地，所述含有苯并噁嗪的树脂组合物中含有固化促进剂；
    优选地，以酸性填料、苯并噁嗪和环氧树脂的添加量为100重量份计，所述固化促进剂的添加量为0～1重量份，优选0.05～0.8重量份，进一步优选0.05～0.6重量份；
    优选地，所述固化促进剂选自咪唑类化合物、咪唑类化合物的衍生物、哌啶类化合物、路易斯酸或三苯基膦中的任意一种或至少两种的混合物，进一步优选2-甲基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑或三苯基膦中的任意一种或至少两种的混合物。
  7. 如权利要求1-6之一所述的方法，其特征在于，所述含有苯并噁嗪的树脂组合物中含有非酸性填料；
    优选地，所述非酸性填料选自碳酸钙、硫酸钙、氧化铝、硫酸钡、陶瓷粉、滑石粉或水滑石中的任意一种或至少两种的混合物；
    优选地，以酸性填料、苯并噁嗪和环氧树脂的添加量为100重量份计，非酸性填料的添加量为0-100重量份。
  8. 一种含有苯并噁嗪的树脂组合物，其特征在于，包含苯并噁嗪树脂和酸 性填料，以所述含有苯并噁嗪的树脂组合物中有机固形物为100重量份计，所述酸性填料的添加量为5～200重量份；
    优选地，所述酸性填料的pH值在2～6之间，优选pH值在3～5之间；
    优选地，所述酸性填料选自硅微粉、石英粉、云母粉、黏土、草酸钙或炭黑中的任意一种或至少两种的混合物；
    优选地，所述酸性填料的粒径为50nm～50μm；
    优选地，以有机固形物为100重量份计，苯并噁嗪树脂的含量为10～100重量份；
    优选地，所述苯并噁嗪树脂选自二酚型苯并噁嗪和/或二胺型苯并噁嗪；
    优选地，所述二酚型苯并噁嗪树脂单体的结构式如式(I)所示：
    Figure PCTCN2017084314-appb-100012
    其中，R1为
    Figure PCTCN2017084314-appb-100013
    R2为
    Figure PCTCN2017084314-appb-100014
    -CH2-、-O-、
    Figure PCTCN2017084314-appb-100015
    Figure PCTCN2017084314-appb-100016
    中的任意一种；
    优选地，所述二胺型苯并噁嗪树脂单体的结构式如式(II)所示：
    Figure PCTCN2017084314-appb-100017
    其中，R3为
    Figure PCTCN2017084314-appb-100018
    -CH2-或-O-中的任意一种；
    优选地，所述含有苯并噁嗪的树脂组合物还包含环氧树脂；
    优选地，以有机固形物为100重量份计，环氧树脂的含量为0～75重量份；
    优选地，所述环氧树脂选自双酚A型环氧树脂、双酚F型环氧树脂、邻甲酚酚醛环氧树脂、双酚A型酚醛环氧树脂、三酚型酚醛环氧树脂、双环戊二烯酚醛环氧树脂、联苯型酚醛环氧树脂、烷基苯型酚醛环氧树脂或萘酚型酚醛环氧树脂中的任意一种或至少两种的混合物；
    优选地，所述环氧树脂选自具有如下结构的环氧树脂：
    Figure PCTCN2017084314-appb-100019
    其中，X1、X2和X3各自独立地选自
    Figure PCTCN2017084314-appb-100020
    R4选自取代或未取代的C1-C5直链烷基或者取代或未取代的C1-C5支链烷基中的任意一种；
    Y1和Y2各自独立地选自-CH2-、
    Figure PCTCN2017084314-appb-100021
    Figure PCTCN2017084314-appb-100022
    中的任意一种，R5选自氢原子、取代或未取代的C1-C5直链烷基或者取代或未取代的C1-C5支链烷基中的任意一种；
    m为1～10的任意整数；
    优选地，所述含有苯并噁嗪的树脂组合物还包含酚醛树脂；
    优选地，以有机固形物为100重量份计，酚醛树脂的含量为0～40重量份；
    优选地，所述酚醛树脂选自线性酚醛树脂、双酚A酚醛树脂、邻甲酚酚醛 树脂、含磷酚醛树脂或三官能酚醛树脂中的任意一种或至少两种的混合物；
    优选地，所述含有苯并噁嗪的树脂组合物还包含氰酸酯；
    优选地，以有机固形物为100重量份计，氰酸酯的含量为0～50重量份；
    优选地，所述氰酸酯选自双酚A型氰酸酯、酚醛型氰酸酯或双环戊二烯型酚醛树脂中的任意一种或至少两种的混合物；
    优选地，所述含有苯并噁嗪的树脂组合物还包含热固性聚苯醚；
    优选地，以有机固形物为100重量份计，热固性聚苯醚的含量为0～40重量份；
    优选地，所述含有苯并噁嗪的树脂组合物中含有活性酯；
    优选地，以有机固形物为100重量份计，活性酯的含量为0～40重量份；
    优选地，所述含有苯并噁嗪的树脂组合物还包含苯乙烯马来酸酐共聚物；
    优选地，以有机固形物为100重量份计，苯乙烯马来酸酐共聚物的含量为0～40重量份；
    优选地，所述苯乙烯马来酸酐共聚物中的苯乙烯与马来酸酐的质量比为9∶1～6∶4；
    优选地，所述含有苯并噁嗪的树脂组合物还包含阻燃剂；
    优选地，所述阻燃剂选自十溴二苯醚、八溴醚、六溴环十二烷、四溴双酚A、十溴二苯乙烷，磷酸三苯酯、磷酸三甲苯酯、磷酸三辛酯、磷酸二苯辛酯、磷酸二苯异癸酯、磷酸三(二甲苯)酯、磷酸二苯叔丁苯酯、磷酸二苯异丙苯酯、间苯二酚双[二(2，6-二甲基苯基)磷酸酯]、磷酸二苯异辛酯、甲基乙基次膦酸铝、二乙基次膦酸铝、羟甲基苯基次膦酸铝、3-羟基苯基磷酰丙酸、羟基苯膦酰丙酸、羟基丙酸基苯膦酰、2-羧基乙基(苯基)次膦酸、9，10-二氢-9-氧杂-10-磷杂菲-10-氧化物或聚(二(苯氧基)偶磷氮烯)中的任意一种或至少两种的混合物；
    优选地，所述含有苯并噁嗪的树脂组合物还包含固化促进剂；
    优选地，以酸性填料、苯并噁嗪树脂和环氧树脂的添加量为100重量份计，所述固化促进剂的添加量为0～1重量份，优选0.05～0.8重量份，进一步优选0.05～0.6重量份；
    优选地，所述固化促进剂选自咪唑类化合物、咪唑类化合物的衍生物、哌啶类化合物、路易斯酸或三苯基膦中的任意一种或至少两种的混合物，进一步优选2-甲基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑或三苯基膦中的任意一种或至少两种的混合物；
    优选地，所述含有苯并噁嗪的树脂组合物还包含非酸性填料；
    优选地，所述非酸性填料选自碳酸钙、硫酸钙、氧化铝，硫酸钡，陶瓷粉、滑石粉或水滑石中的任意一种或至少两种的混合物；
    优选地，以酸性填料、苯并噁嗪和环氧树脂的添加量为100重量份计，非酸性填料的添加量为0-100重量份。
  9. 一种预浸料，其含有根据权利要求1-7之一所述的方法制得的树脂组合物。
  10. 一种预浸料，其含有根据权利要求8所述的树脂组合物。
  11. 一种层压板，其含有至少1张如权利要求9或10所述的预浸料。
  12. 一种印制电路板，其含有至少1张如权利要求9或10所述的预浸料。
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