WO2017101539A1 - 一种热固性树脂组合物以及含有它的预浸料、层压板以及印制电路板 - Google Patents

一种热固性树脂组合物以及含有它的预浸料、层压板以及印制电路板 Download PDF

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WO2017101539A1
WO2017101539A1 PCT/CN2016/099129 CN2016099129W WO2017101539A1 WO 2017101539 A1 WO2017101539 A1 WO 2017101539A1 CN 2016099129 W CN2016099129 W CN 2016099129W WO 2017101539 A1 WO2017101539 A1 WO 2017101539A1
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thermosetting resin
resin composition
inorganic filler
weight
low
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PCT/CN2016/099129
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English (en)
French (fr)
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郝良鹏
柴颂刚
杜翠鸣
邢燕侠
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广东生益科技股份有限公司
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Publication of WO2017101539A1 publication Critical patent/WO2017101539A1/zh

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/02—Layered products essentially comprising sheet glass, or glass, slag, or like fibres in the form of fibres or filaments
    • B32B17/04—Layered products essentially comprising sheet glass, or glass, slag, or like fibres in the form of fibres or filaments bonded with or embedded in a plastic substance
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/04—Layered products comprising a layer of synthetic resin as impregnant, bonding, or embedding substance
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02—Organic and inorganic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
    • C08K5/3445—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/20—All layers being fibrous or filamentary
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • 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
    • B32B2260/021—Fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—Synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

Definitions

  • the invention belongs to the technical field of copper clad laminates, and particularly relates to a thermosetting resin composition and a prepreg, a laminate and a printed circuit board containing the same.
  • a resin having a low coefficient of thermal expansion is generally used and the content of an inorganic filler such as silica or alumina is increased.
  • an inorganic filler such as silica or alumina
  • low thermal expansion coefficient resins are expensive, and inorganic fillers such as silica and alumina are limited in their ability to reduce CTE due to their limited thermal expansion coefficient.
  • CN 103881312 A discloses a resin composition for a printed circuit board comprising a eucryptite ceramic filler as an inorganic filler having a spherical or elliptical cross section and a particle size of 0.01 to 1 ⁇ m.
  • the eucryptite ceramic filler has the following chemical composition: xLi 2 O-yAl 2 O 3 -zSiO 2, wherein, x, y and z each represent a molar mixing ratio, x and y are each independently of 0.9 ⁇ 1.1, z is 1.2 to 2.1.
  • CN 104559055A printed circuit board is disclosed a resin composition for a ceramic filler comprising eucryptite as the inorganic filler, the eucryptite ceramic filler having a chemical composition: xLi 2 O-yAl 2 O 3 -zSiO 2 Wherein x, y and z each represent a mixing molar ratio, x and y are each independently from 0.9 to 1.1, and z is from 1.2 to 2.1.
  • the use of the above-mentioned chemical composition of the nepheline ceramic filler can reduce the insulation properties of the sheet.
  • thermosetting resin composition and a prepreg, a laminate and a printed circuit board containing the same.
  • the use of the thermosetting resin composition can significantly reduce the thermal expansion coefficient and thermal deformation of the prepreg, the laminate, and the printed circuit board without affecting the insulating properties.
  • thermosetting resin composition comprising, by weight of each component, of a thermosetting resin composition, a thermosetting resin, a curing agent, and 30 to 70% by weight of a low expansion inorganic filler, the low expansion inorganic filler being represented by the following chemical formula:
  • x, y and z each independently represent a mixing molar ratio
  • x and y are each independently from 0.9 to 1.1
  • z is from 2.5 to 8, preferably from 3 to 5.
  • the mass percentage can be obtained by dividing the mass of each component by the total mass of the thermosetting resin composition.
  • the inventors of the present invention have found in experiments that adding a specific content of a low-expansion inorganic filler having a specific chemical composition to a thermosetting resin composition can significantly reduce the thermal expansion coefficient of the sheet without affecting the insulating properties of the sheet, and thereby The present invention has been completed.
  • the low expansion inorganic filler is prepared by a glass crystallization method, specifically:
  • a certain proportion of Li 2 O, Al 2 O 3 and SiO 2 powders are uniformly mixed, transferred into a high temperature glass melting furnace, melted at 1550 to 1600 ° C, and kept for 3 to 4 hours, and then cast on a stainless steel plate at 500 to 550 ° C. Annealed for 4 h.
  • the ball was prepared by a flame method. The sample after the ball is placed in the furnace, kept in the nucleation holding zone for 2 h, and then heated to 1050 ⁇ 1300 ° C for crystallization, heat preservation for 4 h, and slowly cooled to room temperature.
  • the low expansion inorganic filler obtained by the method has lower thermal expansion coefficient, better sphericity and lower specific surface area, and has better dispersibility and fluidity when used in a thermosetting resin composition. There is not much limit on the amount of filling.
  • the low-expansion inorganic filler content is 30 to 70% by weight, such as 33% by weight, 36% by weight, 39% by weight, 42% by weight, 45% by weight, 48% by weight, 51% by weight, 54% by weight, based on the total mass of the thermosetting resin composition. 57 wt%, 60 wt%, 63 wt%, 66 wt% or 69 wt%, preferably 50 to 70 wt%. If the content of the low-expansion inorganic filler is less than 30% by weight, the CTE of the sheet is not significantly improved. If the content of the low-expansion inorganic filler is more than 70% by weight, the properties of the sheet of the thermosetting resin composition such as fluidity and wettability may be affected.
  • the low-expansion inorganic filler is spherical or elliptical particles having an average particle diameter of 0.1 to 5.0 ⁇ m, preferably 0.3 to 1.0 ⁇ m.
  • the average particle diameter of the low-expansion inorganic filler is less than 0.1 ⁇ m, the specific surface area of the particles increases sharply, the oil absorption value increases, and the maximum filling amount of the low-expansion inorganic filler decreases.
  • the average particle diameter of the low-expansion inorganic filler is larger than 5.0 ⁇ m, it is not suitable for thin type. Plate.
  • the average particle diameter refers to a particle diameter at a point corresponding to a volume of 50% when the cumulative volume distribution curve based on the particle diameter is obtained by taking the total volume of the particles as 100%, and the laser diffraction scattering method can be used. Particle size distribution determination.
  • the thermosetting resin has a mass of 20 to 70% by weight, such as 21% by weight, 24% by weight, 27% by weight, 31% by weight, 35% by weight, 39% by weight, 43% by weight, 47% by weight, 51% by weight, based on the total mass of the thermosetting resin composition. 55 wt%, 59 wt%, 63 wt%, 66 wt% or 69 wt%.
  • the thermosetting resin is any one or a mixture of at least two of an epoxy resin, a phenol resin, a benzoxazine resin, a cyanate ester, a phosphorus-containing active ester compound, or a liquid crystal resin.
  • the epoxy resin is a bisphenol A type epoxy resin.
  • the curing agent has a mass of 1 to 30% by weight, such as 2% by weight, 5% by weight, 8% by weight, 11% by weight, 14% by weight, 17% by weight, 20% by weight, 23% by weight, 26% by weight or less, based on the total mass of the thermosetting resin composition. 29wt%.
  • the curing agent is any one of a phenolic type curing agent, an amine based curing agent, an acid anhydride based curing agent or a dicyandiamide curing agent, or a combination of at least two.
  • the thermosetting resin composition further comprises a curing accelerator having a mass of 0 to 10% by weight based on the total mass of the thermosetting resin composition and excluding 0, for example, 0.5% by weight, 1% by weight, 1.5% by weight, 2% by weight, 2.5 Wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, 5 wt%, 5.5 wt%, 6 wt%, 6.5 wt%, 7 wt%, 7.5 wt%, 8 wt%, 8.5 wt%, 9 wt% or 9.5 wt %.
  • a curing accelerator having a mass of 0 to 10% by weight based on the total mass of the thermosetting resin composition and excluding 0, for example, 0.5% by weight, 1% by weight, 1.5% by weight, 2% by weight, 2.5 Wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, 5 wt%,
  • the curing accelerator is an imidazole-based curing accelerator or/and an amine-based curing accelerator.
  • thermosetting resin composition further includes a dispersing agent.
  • the dispersing agent is any one of a silane coupling agent, a phosphate treating agent or a silicone treating agent or a mixture of at least two.
  • the thermosetting resin composition further includes other inorganic fillers including silica, boehmite, talc, mica, kaolin, aluminum hydroxide, magnesium hydroxide, zinc borate, zinc stannate, zinc oxide, Titanium oxide, aluminum oxide, aluminum nitride, boron nitride, calcium carbonate, barium sulfate, barium titanate, aluminum borate, potassium titanate, E glass powder, S glass powder, D glass powder, NE glass powder or hollow glass fine powder Any one or a mixture of at least two.
  • other inorganic fillers including silica, boehmite, talc, mica, kaolin, aluminum hydroxide, magnesium hydroxide, zinc borate, zinc stannate, zinc oxide, Titanium oxide, aluminum oxide, aluminum nitride, boron nitride, calcium carbonate, barium sulfate, barium titanate, aluminum borate, potassium titanate, E glass powder, S glass powder, D glass powder, NE glass powder or
  • the mixture is, for example, a mixture of silica and alumina, a mixture of mica and kaolin, a mixture of aluminum hydroxide and magnesium hydroxide, a mixture of zinc borate and zinc stannate, a mixture of zinc oxide and titanium oxide, boron nitride and a mixture of calcium carbonate, a mixture of barium sulfate and aluminum borate, a mixture of potassium titanate and E glass powder, S glass powder, D glass powder and hollow glass fine powder mixture.
  • thermosetting resin composition Regardless of the composition of the thermosetting resin composition, the sum of the mass percentages of the components is 100% by weight.
  • thermosetting resin composition further contains a curing agent, an accelerator, and various additives.
  • the additive include a flame retardant, a coupling agent, an antioxidant, a heat stabilizer, an antistatic agent, and an ultraviolet ray. Absorbents, pigments, colorants or lubricants, etc. These various additives may be used singly or in combination of two or more kinds.
  • thermosetting resin compositions of the present invention can be prepared by mixing, stirring, and mixing the above-mentioned thermosetting resin, curing agent, curing accelerator, low expansion inorganic filler, and various additives by a known method.
  • a resin glue obtained by dissolving or dispersing a thermosetting resin composition as described above in a solvent.
  • a prepreg comprising a reinforcing material and a thermosetting resin composition as described above adhered thereto by dipping and drying.
  • a laminate comprising at least one prepreg as described above.
  • the present invention has the following beneficial effects:
  • the present invention can significantly reduce the thermal expansion coefficient of the sheet by adding a specific content of the low expansion inorganic filler having a specific chemical composition to the thermosetting resin composition, and the thermal expansion coefficient of the sheet can reach 92 to 221 (ppm/° C.).
  • the low-expansion inorganic filler has a spherical or elliptical shape and an average particle diameter of 0.1 to 5.0 ⁇ m, which has a small specific surface area and oil absorption value, good dispersibility and fluidity, and is surface-modified ( After treatment with a treating agent such as a dispersing agent or a coupling agent, the dispersibility and compatibility with the resin system can be increased, and a large content of the filling can be ensured in the resin.
  • a treating agent such as a dispersing agent or a coupling agent
  • the low expansion inorganic filler is prepared by a glass crystallization method, specifically:
  • a certain proportion of Li 2 O, Al 2 O 3 and SiO 2 powders are uniformly mixed, transferred into a high temperature glass melting furnace, melted at 1550 to 1600 ° C, and kept for 3 to 4 hours, and then cast on a stainless steel plate at 500 to 550 ° C. Annealed for 4 h.
  • the ball was prepared by a flame method. The sample after the ball is placed in the furnace, kept in the nucleation holding zone for 2 h, and then heated to 1050-1300 ° C for crystallization, heat preservation for 4 h, and slowly cooled to room temperature.
  • the low expansion inorganic filler has a lower thermal expansion coefficient, has better sphericity, lower specific surface area, and has better dispersibility and fluidity when used in a thermosetting resin composition, and has no filling amount. Too big a limit.
  • the expanded inorganic filler (30wt%) is dissolved in an organic solvent, mechanically stirred and emulsified to prepare 65wt% of glue, then impregnated with glass fiber cloth, dried by heating to form a prepreg, copper foil is placed on both sides, and heated under pressure. A copper foil substrate is formed.
  • the chemical composition of the low-expansion inorganic filler used in the present example was Li 2 O-Al 2 O 3 -3SiO 2 , and the results of measurement and evaluation are shown in Table 1.
  • the expanded inorganic filler (40wt%) is dissolved in an organic solvent, mechanically stirred and emulsified to prepare 65wt% of glue, then impregnated with glass fiber cloth, dried by heating to form a prepreg, copper foil is placed on both sides, and heated under pressure. A copper foil substrate is formed.
  • the chemical composition of the low expansion inorganic filler used in this embodiment is Li 2 O-Al 2 O 3 -3SiO 2 . The measurement and evaluation results are shown in Table 1.
  • the expanded inorganic filler (50wt%) is dissolved in an organic solvent, mechanically stirred and emulsified to prepare 65wt% of glue, then impregnated with glass fiber cloth, dried by heating to form a prepreg, copper foil is placed on both sides, and heated under pressure. A copper foil substrate is formed.
  • the chemical composition of the low expansion inorganic filler used in this embodiment is Li 2 O-Al 2 O 3 -3SiO 2 . The measurement and evaluation results are shown in Table 1.
  • the expanded inorganic filler (60wt%) is dissolved in an organic solvent, mechanically stirred and emulsified to prepare 65wt% of glue, then impregnated with glass fiber cloth, heated to dry to form a prepreg, placed on both sides of the copper foil, pressurized heating A copper foil substrate is formed.
  • the chemical composition of the low expansion inorganic filler used in this embodiment is Li 2 O-Al 2 O 3 -3SiO 2 . The measurement and evaluation results are shown in Table 1.
  • the expanded inorganic filler (70wt%) is dissolved in an organic solvent, mechanically stirred and emulsified to prepare 65wt% of glue, then impregnated with glass fiber cloth, dried to form a prepreg after heating, placed on both sides of the copper foil, pressurized heating A copper foil substrate is formed.
  • the chemical composition of the low expansion inorganic filler used in this embodiment is Li 2 O-Al 2 O 3 -3SiO 2 . The measurement and evaluation results are shown in Table 1.
  • the expanded inorganic filler (50wt%) is dissolved in an organic solvent, mechanically stirred and emulsified to prepare 65wt% of glue, then impregnated with glass fiber cloth, dried by heating to form a prepreg, copper foil is placed on both sides, and heated under pressure. A copper foil substrate is formed.
  • the chemical composition of the low expansion inorganic filler used in this embodiment is Li 2 O-Al 2 O 3 -2.5SiO 2 . The measurement and evaluation results are shown in Table 1.
  • the expanded inorganic filler (50wt%) is dissolved in an organic solvent, mechanically stirred and emulsified to prepare 65wt% of glue, then impregnated with glass fiber cloth, dried by heating to form a prepreg, copper foil is placed on both sides, and heated under pressure. A copper foil substrate is formed.
  • the chemical composition of the low expansion inorganic filler used in this embodiment is Li 2 O-Al 2 O 3 -8SiO 2 . The measurement and evaluation results are shown in Table 1.
  • the expanded inorganic filler (50wt%) is dissolved in an organic solvent, mechanically stirred and emulsified to prepare 65wt% of glue, then impregnated with glass fiber cloth, dried by heating to form a prepreg, copper foil is placed on both sides, and heated under pressure. A copper foil substrate is formed.
  • the chemical composition of the low expansion inorganic filler used in this embodiment is Li 2 O-Al 2 O 3 -10SiO 2 . The measurement and evaluation results are shown in Table 1.
  • the expanded inorganic filler (20wt%) is dissolved in an organic solvent, mechanically stirred and emulsified to prepare 65wt% of glue, then impregnated with glass fiber cloth, heated to dry to form a prepreg, copper foil placed on both sides, heated under pressure A copper foil substrate is formed.
  • the chemical composition of the low expansion inorganic filler used in this embodiment is Li 2 O-Al 2 O 3 -3SiO 2 . The measurement and evaluation results are shown in Table 1.
  • the expanded inorganic filler (80% by weight) is dissolved in an organic solvent, mechanically stirred and emulsified to prepare 65 wt% of glue, then impregnated with glass fiber cloth, dried to form a prepreg after heating, and copper foil is placed on both sides, and heated under pressure. A copper foil substrate is formed.
  • the chemical composition of the low expansion inorganic filler used in this embodiment is Li 2 O-Al 2 O 3 -3SiO 2 . The measurement and evaluation results are shown in Table 1.
  • the copper foil of the copper clad laminate was removed by an etching solution, and then cut into a size of 5 mm ⁇ 5 mm square to prepare a test piece.
  • the average linear thermal expansion coefficient of the test piece in the Z-axis direction (the vertical direction of the glass cloth) at 30 ° C to 260 ° C was measured using a TMA test apparatus at a temperature increase rate of 10 ° C / min. The smaller the coefficient of thermal expansion, the better the effect.
  • the sample was cut into a size of 76 mm ⁇ 50 mm, and two circular holes having a diameter of 4.8 mm were drilled along the center line of the long side and the center point of the short side, and the pitch of the two holes was 25 ⁇ 0.25mm.
  • the sample was treated in distilled water at 50 ⁇ 2 ° C for 48 + 2 / -0 h, and then the sample was immersed in room temperature distilled water for 0.5-4 h, and the sample was brought to temperature equilibrium under the condition that the water content was substantially unchanged.
  • the test was boosted at a rate of 500 v/s using a high pressure tester, and the sample was observed until breakdown, and the voltage at the time of breakdown was recorded.
  • the plate was cut into test pieces of 10 mm ⁇ 100 mm, and the copper foil on both sides of the test piece was removed, except that the copper foil of 3 mm ⁇ 100 mm was retained in the middle, and the remaining copper foil was removed with an etching solution.
  • Example 6-7 and Comparative Example 3-4 As can be seen, when the chemical composition of the inorganic filler is low-expansion xLi 2 O-yAl 2 O 3 -zSiO 2 , Z is less than 2.5, the insulating sheet decreased, Z is greater than At 8 o'clock, the CTE reduction effect of the sheet was not obvious. As can be seen from Example 3 and Examples 6-7, when z is in the range of 3 to 5, the CTE reduction effect of the sheet material is most remarkable.

Abstract

本发明提供了一种热固性树脂组合物以及含有它的预浸料、层压板和印制电路板。所述热固性树脂组合物按各组分占热固性树脂组合物的质量百分比包括：热固性树脂、固化剂和30～70wt％的低膨胀无机填料，所述低膨胀无机填料由如下化学式表示：xLi2O-yAl2O3-zSiO2，其中，x、y和z均独立地表示混合摩尔比，x和y各自独立的为0.9～1.1，z为2.5～8。本发明通过在热固性树脂组合物中加入具有特定化学组成的特定含量的低膨胀无机填料，可以在不影响板材绝缘性的基础上，明显降低板材热膨胀系数，可适用于印制电路板。

Description

一种热固性树脂组合物以及含有它的预浸料、层压板以及印制电路板 技术领域
本发明属于覆铜板技术领域，具体涉及一种热固性树脂组合物以及含有它的预浸料、层压板和印制电路板。
背景技术
随着电子产品向高密度化、多功能化和“轻、薄、小”化发展，使得电路随着电子产品向小型化、多功能化、高性能化及高可靠性等方面的快速发展，作为电子产品主要部件之一的印制电路板也开始朝着高精度、高密度、高性能、微孔化、薄型化等方向迅猛发展，这就需要层压板基材具有低的热膨胀系数和高的尺寸稳定性。
在层压板薄型化、高密度和微孔化等发展趋势下，为了保证高的精度，就需要板材在电、机械、热状态下保持良好的稳定性，尤其是温度引起的尺寸稳定性。在IC(Integrated circuit)封装领域，IC固定在层压板基材上，若板材热膨胀系数不匹配，则由热引起的板材变形可能导致线路破坏、IC损坏或电路短路和断路等现象，所以降低板材CTE变得格外重要。
为了降低层压板的热膨胀系数，通常会选用低热膨胀系数的树脂和提高二氧化硅、氧化铝等无机填料的含量。但低热膨胀系数树脂价格昂贵，而二氧化硅和氧化铝等无机填料由于其本身热膨胀系数的受限，对降低板材CTE效果有限。
CN 103881312A公开了一种用于印刷电路板树脂组合物，其含有锂霞石陶瓷填料作为无机填充剂，其具有剖面球形或者椭圆形，颗粒尺寸为0.01～1μm。所述锂霞石陶瓷填料具有如下化学组成：xLi2O-yAl2O3-zSiO2，其中，x、y和z 各自表示混合摩尔比，x和y各自独立地为0.9～1.1，z为1.2～2.1。
CN 104559055A公开了一种用于印刷电路板树脂组合物，其含有锂霞石陶瓷填料作为无机填充剂，所述锂霞石陶瓷填料具有如下化学组成：xLi2O-yAl2O3-zSiO2，其中，x、y和z各自表示混合摩尔比，x和y各自独立地为0.9～1.1，z为1.2～2.1。
但是，采用上述化学组成的锂霞石陶瓷填料会降低板材的绝缘性能。
发明内容
针对已有技术的问题，本发明的目的在于提供一种热固性树脂组合物以及含有它的预浸料、层压板和印制电路板。采用该热固性树脂组合物可以显著降低预浸料、层压板和印制电路板的热膨胀系数和热变形而不影响绝缘性能。
为了实现上述目的，本发明采用了如下技术方案：
一种热固性树脂组合物，其按各组分占热固性树脂组合物的质量百分比包括：热固性树脂、固化剂和30～70wt％的低膨胀无机填料，所述低膨胀无机填料由如下化学式表示：
xLi2O-yAl2O3-zSiO2
其中，x、y和z均独立地表示混合摩尔比，x和y各自独立的为0.9～1.1，z为2.5～8，优选为3～5。
在本发明中，所述质量百分比可通过将各组分的质量除以热固性树脂组合物的总质量得到。
本发明的发明人在实验中发现，在热固性树脂组合物中加入具有特定化学组成的特定含量的低膨胀无机填料，可以在不影响板材绝缘性能的基础上，明显降低板材热膨胀系数，并由此完成了本发明。
在本发明中，当z小于2.5时，会降低板材绝缘性能，当z大于8时，板材 CTE降低效果不明显，当z在3～5范围内时，板材CTE降低效果最显著。
在本发明中，所述低膨胀无机填料采用玻璃结晶法制备，具体为：
将一定比例的Li2O、Al2O3和SiO2粉末混合均匀，转入高温玻璃熔炉中，在1550～1600℃下熔融，保温3～4h后浇铸在不锈钢板上，在500～550℃下退火4h。样品经切割、研磨至亚微米级后，采用火焰法制备成球。将成球后的样品放入炉中，在成核保温区保温2h，然后升温至1050～1300℃进行晶华，保温4h，缓慢冷却到室温。采用该方法得到的低膨胀无机填料热膨胀系数更低，且具有较好的球形度，较低的比表面积，将其用于热固性树脂组合物中时，具有较好的分散性和流动性，对填充量没有太大限制。
在本发明中，所述低膨胀无机填料含量为热固性树脂组合物总质量的30～70wt％，例如33wt％、36wt％、39wt％、42wt％、45wt％、48wt％、51wt％、54wt％、57wt％、60wt％、63wt％、66wt％或69wt％，优选为50～70wt％。若低膨胀无机填料含量低于30wt％，则板材CTE改善不明显，若低膨胀无机填料含量高于70wt％，则会对热固性树脂组合物流动性、浸润性等板材性能造成影响。
优选地，所述低膨胀无机填料为球形或椭圆形颗粒，平均粒径为0.1～5.0μm，优选为0.3～1.0μm。低膨胀无机填料平均粒径小于0.1μm时，颗粒比表面积急剧增大，吸油值增大，低膨胀无机填料最大可填充量降低，低膨胀无机填料平均粒径大于5.0μm时，不适用于薄型板材。在此，平均粒径是指将粒子的总体积作为100％而求出基于粒径的累积度数分布曲线时，刚好相当于体积为50％的点的粒径，可以以使用激光衍射散射法的粒度分布测定。
优选地，所述热固性树脂的质量占热固性树脂组合物总质量的20～70wt％，例如21wt％、24wt％、27wt％、31wt％、35wt％、39wt％、43wt％、47wt％、51wt％、55wt％、59wt％、63wt％、66wt％或69wt％。
优选地，所述热固性树脂为环氧树脂、酚醛树脂、苯并噁嗪树脂、氰酸酯、含磷活性酯化合物或液晶树脂中的任意一种或者至少两种的混合物。所述环氧树脂如双酚A型环氧树脂。
优选地，所述固化剂的质量占热固性树脂组合物总质量的1～30wt％，例如2wt％、5wt％、8wt％、11wt％、14wt％、17wt％、20wt％、23wt％、26wt％或29wt％。
优选地，所述固化剂为酚醛型固化剂、胺基固化剂、酸酐基固化剂或双氰胺固化剂中的任意一种或者至少两种的组合。
优选地，所述热固性树脂组合物还包括固化促进剂，其质量占热固性树脂组合物总质量的0～10wt％且不包括0，例如0.5wt％、1wt％、1.5wt％、2wt％、2.5wt％、3wt％、3.5wt％、4wt％、4.5wt％、5wt％、5.5wt％、6wt％、6.5wt％、7wt％、7.5wt％、8wt％、8.5wt％、9wt％或9.5wt％。
优选地，所述固化促进剂为咪唑基固化促进剂或/和胺基固化促进剂。
优选地，所述热固性树脂组合物还包括分散剂。
优选地，所述分散剂为硅烷偶联剂、磷酸酯类处理剂或有机硅类处理剂中的任意一种或者至少两种的混合物。
优选地，所述热固性树脂组合物，还包括其他无机填料，其包括二氧化硅、勃姆石、滑石、云母、高岭土、氢氧化铝、氢氧化镁、硼酸锌、锡酸锌、氧化锌、氧化钛、氧化铝、氮化铝、氮化硼、碳酸钙、硫酸钡、钛酸钡、硼酸铝、钛酸钾、E玻璃粉、S玻璃粉、D玻璃粉、NE玻璃粉或中空玻璃微粉中的任意一种或者至少两种的混合物。所述混合物例如二氧化硅和氧化铝的混合物，云母和高岭土的混合物，氢氧化铝和氢氧化镁的混合物，硼酸锌和锡酸锌的混合物，氧化锌和氧化钛的混合物，氮化硼和碳酸钙的混合物，硫酸钡和硼酸铝的混合物，钛酸钾和E玻璃粉的混合物，S玻璃粉、D玻璃粉和中空玻璃微粉的 混合物。
本发明所述的“包括”，意指其除所述组份外，还可以包括其他组份，这些其他组份赋予所述树脂组合物不同的特性。除此之外，本发明所述的“包括”，还可以替换为封闭式的“为”或“由……组成”。
不管所述热固性树脂组合物包括何种组分，其各组分质量百分比之和为100wt％。
例如，所述热固性树脂组合物还含有固化剂、促进剂以及各种添加剂，作为添加剂的具体例，可以举出阻燃剂、偶联剂、抗氧剂、热稳定剂、抗静电剂、紫外线吸收剂、颜料、着色剂或润滑剂等。这些各种添加剂可以单独使用，也可以两种或者两种以上混合使用。
作为本发明热固性树脂组合物之一的制备方法，可以通过公知的方法配合、搅拌、混合所述的热固性树脂、固化剂、固化促进剂和低膨胀无机填料，以及各种添加剂，来制备。
一种树脂胶液，其是将如上所述的热固性树脂组合物溶解或分散在溶剂中得到。
一种预浸料，其包括增强材料及通过浸渍干燥后附着在其上的如上所述的热固性树脂组合物。
一种层压板，所述层压板含有至少一张如上所述的预浸料。
一种印制电路板，所述印制电路板含有至少一张如上所述的预浸料。
与已有技术相比，本发明具有如下有益效果：
本发明通过在热固性树脂组合物中加入具有特定化学组成的特定含量的低膨胀无机填料，可以明显降低板材热膨胀系数，板材热膨胀系数可达到92～221(ppm/℃)。
此外，所述低膨胀无机填料为球形或椭圆形形状，平均粒径在0.1～5.0μm，其具有较小的比表面积和吸油值、较好的分散性和流动性，经表面处理改性(如分散剂、偶联剂等处理剂处理)后，可增加其分散性及与树脂体系的相容性，可以在树脂中保证较大含量填充。
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。
为了更好的说明本发明的目的、技术方案和优点，下面将结合具体实施例对本发明做进一步描述。
在本发明中，所述低膨胀无机填料采用玻璃结晶法制备，具体为：
将一定比例的Li2O、Al2O3和SiO2粉末混合均匀，转入高温玻璃熔炉中，在1550～1600℃下熔融，保温3～4h后浇铸在不锈钢板上，在500～550℃下退火4h。样品经切割、研磨至亚微米级后，采用火焰法制备成球。将成球后的样品放入炉中，在成核保温区保温2h，然后升温至1050-1300℃进行晶华，保温4h，缓慢冷却到室温。采用该低膨胀无机填料热膨胀系数更低，且具有较好的球形度，较低的比表面积，将其用于热固性树脂组合物中时，具有较好的分散性和流动性，对填充量没有太大限制。
实施例1
将溴化环氧树脂(45.69wt％)、溴化线性酚醛树脂(21.93wt％)、环氧树脂(2.29wt％)、咪唑类促进剂(0.09wt％，日本四国化成生产的2MI)、低膨胀无机填料(30wt％)溶入有机溶剂中，机械搅拌、乳化配制成65wt％的胶水，然后含浸玻璃纤维布，经过加热干燥后形成预浸料(prepreg)，两面放置铜箔，加压加热制成铜箔基板。本实施例中所用低膨胀无机填料化学组成为Li2O-Al2O3-3SiO2，测定、评价结果示于表1。
实施例2
将溴化环氧树脂(39.16wt％)、溴化线性酚醛树脂(18.80wt％)、环氧树脂(1.96wt％)、咪唑类促进剂(0.08wt％，日本四国化成生产的2MI)、低膨胀无机填料(40wt％)溶入有机溶剂中，机械搅拌、乳化配制成65wt％的胶水，然后含浸玻璃纤维布，经过加热干燥后形成预浸料(prepreg)，两面放置铜箔，加压加热制成铜箔基板。本实施例中所用低膨胀无机填料化学组成为Li2O-Al2O3-3SiO2。测定、评价结果示于表1。
实施例3
将溴化环氧树脂(32.64wt％)、溴化线性酚醛树脂(15.66wt％)、环氧树脂(1.63wt％)、咪唑类促进剂(0.07wt％，日本四国化成生产的2MI)、低膨胀无机填料(50wt％)溶入有机溶剂中，机械搅拌、乳化配制成65wt％的胶水，然后含浸玻璃纤维布，经过加热干燥后形成预浸料(prepreg)，两面放置铜箔，加压加热制成铜箔基板。本实施例中所用低膨胀无机填料化学组成为Li2O-Al2O3-3SiO2。测定、评价结果示于表1。
实施例4
将溴化环氧树脂(26.11wt％)、溴化线性酚醛树脂(12.53wt％)、环氧树脂(1.31wt％)、咪唑类促进剂(0.05wt％，日本四国化成生产的2MI)、低膨胀无机填料(60wt％)溶入有机溶剂中，机械搅拌、乳化配制成65wt％的胶水，然后含浸玻璃纤维布，经过加热干燥后形成预浸料(prepreg)，两面放置铜箔，加压加热制成铜箔基板。本实施例中所用低膨胀无机填料化学组成为Li2O-Al2O3-3SiO2。测定、评价结果示于表1。
实施例5
将溴化环氧树脂(19.58wt％)、溴化线性酚醛树脂(9.40wt％)、环氧树脂 (0.98wt％)、咪唑类促进剂(0.04wt％，日本四国化成生产的2MI)、低膨胀无机填料(70wt％)溶入有机溶剂中，机械搅拌、乳化配制成65wt％的胶水，然后含浸玻璃纤维布，经过加热干燥后形成预浸料(prepreg)，两面放置铜箔，加压加热制成铜箔基板。本实施例中所用低膨胀无机填料化学组成为Li2O-Al2O3-3SiO2。测定、评价结果示于表1。
实施例6
将溴化环氧树脂(32.64wt％)、溴化线性酚醛树脂(15.66wt％)、环氧树脂(1.63wt％)、咪唑类促进剂(0.07wt％，日本四国化成生产的2MI)、低膨胀无机填料(50wt％)溶入有机溶剂中，机械搅拌、乳化配制成65wt％的胶水，然后含浸玻璃纤维布，经过加热干燥后形成预浸料(prepreg)，两面放置铜箔，加压加热制成铜箔基板。本实施例中所用低膨胀无机填料化学组成为Li2O-Al2O3-2.5SiO2。测定、评价结果示于表1。
实施例7
将溴化环氧树脂(32.64wt％)、溴化线性酚醛树脂(15.66wt％)、环氧树脂(1.63wt％)、咪唑类促进剂(0.07wt％，日本四国化成生产的2MI)、低膨胀无机填料(50wt％)溶入有机溶剂中，机械搅拌、乳化配制成65wt％的胶水，然后含浸玻璃纤维布，经过加热干燥后形成预浸料(prepreg)，两面放置铜箔，加压加热制成铜箔基板。本实施例中所用低膨胀无机填料化学组成为Li2O-Al2O3-8SiO2。测定、评价结果示于表1。
实施例8
将溴化环氧树脂(26.45wt％)、氰酸酯(22wt％)、环氧树脂(1.50wt％)、咪唑类促进剂(0.05wt％，日本四国化成生产的2MI)、低膨胀无机填料(50wt％)溶入有机溶剂中，机械搅拌、乳化配制成65wt％的胶水，然后含浸玻璃纤维布， 经过加热干燥后形成预浸料(prepreg)，两面放置铜箔，加压加热制成铜箔基板。本实施例中所用低膨胀无机填料化学组成为Li2O-Al2O3-3SiO2。测定、评价结果示于表1。
对比例1
将溴化环氧树脂(45.69wt％)、溴化线性酚醛树脂(21.93wt％)、环氧树脂(2.29wt％)、咪唑类促进剂(0.09wt％，日本四国化成生产的2MI)、硅微粉(30wt％)溶入有机溶剂中，机械搅拌、乳化配制成65wt％的胶水，然后含浸玻璃纤维布，经过加热干燥后形成预浸料(prepreg)，两面放置铜箔，加压加热制成铜箔基板。测定、评价结果示于表1。
对比例2
将溴化环氧树脂(32.64wt％)、溴化线性酚醛树脂(15.66wt％)、环氧树脂(1.63wt％)、咪唑类促进剂(0.07wt％，日本四国化成生产的2MI)、硅微粉(50wt％)溶入有机溶剂中，机械搅拌、乳化配制成65wt％的胶水，然后含浸玻璃纤维布，经过加热干燥后形成预浸料(prepreg)，两面放置铜箔，加压加热制成铜箔基板。测定、评价结果示于表1。
对比例3
将溴化环氧树脂(32.64wt％)、溴化线性酚醛树脂(15.66wt％)、环氧树脂(1.63wt％)、咪唑类促进剂(0.07wt％，日本四国化成生产的2MI)、低膨胀无机填料(50wt％)溶入有机溶剂中，机械搅拌、乳化配制成65wt％的胶水，然后含浸玻璃纤维布，经过加热干燥后形成预浸料(prepreg)，两面放置铜箔，加压加热制成铜箔基板。本实施例中所用低膨胀无机填料化学组成为Li2O-Al2O3-2.1SiO2。测定、评价结果示于表1。
对比例4
将溴化环氧树脂(32.64wt％)、溴化线性酚醛树脂(15.66wt％)、环氧树脂(1.63wt％)、咪唑类促进剂(0.07wt％，日本四国化成生产的2MI)、低膨胀无机填料(50wt％)溶入有机溶剂中，机械搅拌、乳化配制成65wt％的胶水，然后含浸玻璃纤维布，经过加热干燥后形成预浸料(prepreg)，两面放置铜箔，加压加热制成铜箔基板。本实施例中所用低膨胀无机填料化学组成为Li2O-Al2O3-10SiO2。测定、评价结果示于表1。
对比例5
将溴化环氧树脂(52.22wt％)、溴化线性酚醛树脂(25.07wt％)、环氧树脂(2.61wt％)、咪唑类促进剂(0.10wt％，日本四国化成生产的2MI)、低膨胀无机填料(20wt％)溶入有机溶剂中，机械搅拌、乳化配制成65wt％的胶水，然后含浸玻璃纤维布，经过加热干燥后形成预浸料(prepreg)，两面放置铜箔，加压加热制成铜箔基板。本实施例中所用低膨胀无机填料化学组成为Li2O-Al2O3-3SiO2。测定、评价结果示于表1。
对比例6
将溴化环氧树脂(13.05wt％)、溴化线性酚醛树脂(6.27wt％)、环氧树脂(0.65wt％)、咪唑类促进剂(0.03wt％，日本四国化成生产的2MI)、低膨胀无机填料(80wt％)溶入有机溶剂中，机械搅拌、乳化配制成65wt％的胶水，然后含浸玻璃纤维布，经过加热干燥后形成预浸料(prepreg)，两面放置铜箔，加压加热制成铜箔基板。本实施例中所用低膨胀无机填料化学组成为Li2O-Al2O3-3SiO2。测定、评价结果示于表1。
对比例7
将溴化环氧树脂(26.45wt％)、氰酸酯(22wt％)、环氧树脂(1.50wt％)、咪唑类促进剂(0.05wt％，日本四国化成生产的2MI)、低膨胀无机填料(50wt％) 溶入有机溶剂中，机械搅拌、乳化配制成65wt％的胶水，然后含浸玻璃纤维布，经过加热干燥后形成预浸料(prepreg)，两面放置铜箔，加压加热制成铜箔基板。本实施例中所用低膨胀无机填料化学组成为Li2O-Al2O3-10SiO2。测定、评价结果示于表1。
使用得到的覆铜层压板，用以下示出的方法，对热膨胀系数、击穿电压、剥离强度评价，结果见表1。
热膨胀率的测定
利用蚀刻液去除覆铜层叠板的铜箔后，切成5mm×5mm见方的大小制作试验片。使用TMA试验装置以升温速度10℃/min，测定该试验片在30℃～260℃下的Z轴方向(玻璃布垂直方向)的平均线热膨胀率。热膨胀率越小，效果越好。
击穿电压的测定
利用蚀刻液去除覆铜层叠板的铜箔后，切成76mm×50mm大小的试样，沿长边中心线和短边中心点处钻两个直径为4.8mm的圆孔，两孔间距为25±0.25mm。试样在50±2℃的蒸馏水中处理48+2/-0h，然后将试样浸入室温蒸馏水中0.5-4h，在含水量基本不变的情况下使试样达到温度平衡。使用高压测试仪以500v/s的速率升压测试，观察试样，直至击穿，记录击穿时的电压。
剥离强度的测定
将板材切成10mm×100mm的试验片，试验片两面的铜箔，除中间保留3mm×100mm铜箔外，其余铜箔用蚀刻液除去。从试样的一端把铜箔剥起适当长度，将剥起的铜箔条用夹具夹住，使用拉力试验机，使拉力与铜箔面垂直，以50mm/min的速度连续拉剥50mm，拉剥过程中最小拉力值即为剥离强度。
表1
Figure PCTCN2016099129-appb-000001
Figure PCTCN2016099129-appb-000002
从表1中实施例1-5可以看出，板材CTE随低膨胀无机填料含量升高而降低，在该低膨胀无机填料含量为50～70％时，降低幅度最大。由对比例5-6可以看出，当该低膨胀无机填料含量低于30％时，板材CTE降低不显著，当含量高于70％时，填料的加入明显降低板材剥离强度。由实施例6-7和对比例3-4可以看出，当低膨胀无机填料的化学组成xLi2O-yAl2O3-zSiO2中，Z小于2.5时，板材绝缘性明显降低，Z大于8时，板材CTE降低效果不明显。由实施例3和实施例6-7可以看出，当z在3～5范围内时，板材CTE降低效果最显著。
以上所述，仅为本发明的较佳实施例，并非对本发明的组合物的含量作任何限制，对于本领域的普通技术人员来说，可以根据本发明的技术方案和技术构思作出其他各种相应的改变和变形，凡是依据本发明的技术实质或组合物成份或含量对以上实施例所作的任何细微修改、等同变化与修饰，均属于本发明技术方案的范围内。
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 (11)

  1. 一种热固性树脂组合物，其按各组分占热固性树脂组合物的质量百分比包括：热固性树脂、固化剂和30～70wt％的低膨胀无机填料，所述低膨胀无机填料由如下化学式表示：
    xLi2O-yAl2O3-zSiO2
    其中，x、y和z均独立地表示混合摩尔比，x和y各自独立的为0.9～1.1，z为2.5～8。
  2. 如权利要求1所述的热固性树脂组合物，其特征在于，z为3～5。
  3. 如权利要求1或2所述的热固性树脂组合物，其特征在于，所述低膨胀无机填料含量为热固性树脂组合物总质量的50～70wt％。
  4. 如权利要求1-3之一所述的热固性树脂组合物，其特征在于，所述低膨胀无机填料为球形或椭圆形颗粒，平均粒径为0.1～5.0μm，优选为0.3～1.0μm。
  5. 如权利要求1-4之一所述的热固性树脂组合物，其特征在于，所述热固性树脂的质量占热固性树脂组合物总质量的20～70wt％；
    优选地，所述热固性树脂为环氧树脂、酚醛树脂、苯并噁嗪树脂、氰酸酯、含磷活性酯化合物或液晶树脂中的任意一种或者至少两种的混合物。
  6. 如权利要求1-5之一所述的热固性树脂组合物，其特征在于，所述固化剂的质量占热固性树脂组合物总质量的1～30wt％；
    优选地，所述固化剂为酚醛型固化剂、胺基固化剂、酸酐基固化剂或双氰胺固化剂中的任意一种或者至少两种的组合。
  7. 如权利要求1-6之一所述的热固性树脂组合物，其特征在于，所述热固性树脂组合物还包括固化促进剂，其质量占热固性树脂组合物总质量的0～10wt％且不包括0；
    优选地，所述固化促进剂为咪唑基固化促进剂或/和胺基固化促进剂；
    优选地，所述热固性树脂组合物还包括分散剂；
    优选地，所述分散剂为硅烷偶联剂、磷酸酯类处理剂或有机硅类处理剂中的任意一种或者至少两种的混合物。
  8. 如权利要求1-7之一所述的热固性树脂组合物，其特征在于，所述热固性树脂组合物，还包括其他无机填料，其包括二氧化硅、勃姆石、滑石、云母、高岭土、氢氧化铝、氢氧化镁、硼酸锌、锡酸锌、氧化锌、氧化钛、氧化铝、氮化铝、氮化硼、碳酸钙、硫酸钡、钛酸钡、硼酸铝、钛酸钾、E玻璃粉、S玻璃粉、D玻璃粉、NE玻璃粉或中空玻璃微粉中的任意一种或者至少两种的混合物。
  9. 一种预浸料，其包括增强材料及通过浸渍干燥后附着在其上的如权利要求1-8之一所述的热固性树脂组合物。
  10. 一种层压板，所述层压板含有至少一张如权利要求9所述的预浸料。
  11. 一种印制电路板，所述印制电路板含有至少一张如权利要求9所述的预浸料。
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