CN105504681A - Thermosetting resin composition and prepreg, laminated board and printed circuit board including thermosetting resin composition - Google Patents

Thermosetting resin composition and prepreg, laminated board and printed circuit board including thermosetting resin composition Download PDF

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Publication number
CN105504681A
CN105504681A CN201510953042.1A CN201510953042A CN105504681A CN 105504681 A CN105504681 A CN 105504681A CN 201510953042 A CN201510953042 A CN 201510953042A CN 105504681 A CN105504681 A CN 105504681A
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thermosetting resin
compositions
prepreg
low bulk
resin composition
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CN105504681B (en
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郝良鹏
柴颂刚
杜翠鸣
邢燕侠
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Shengyi Technology Co Ltd
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Shengyi Technology Co Ltd
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Priority to CN201510953042.1A priority Critical patent/CN105504681B/en
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Priority to PCT/CN2016/099129 priority patent/WO2017101539A1/en
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    • 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
    • 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
    • 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

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Reinforced Plastic Materials (AREA)

Abstract

The invention provides a thermosetting resin composition and prepreg, laminated board and printed circuit board including the thermosetting resin composition. The thermosetting resin composition is prepared from, by mass, thermosetting resin, a curing agent and 30wt% to 70wt% of low expansion inorganic filler. The low expansion inorganic filler is shown as the following chemical formula: xLi2O-yAl2O3-zSiO2, wherein x, y and z all independently express the mixed molar ratio, x and y independently range from 0.9 to 1, and z ranges from 2.5 to 8. The low expansion inorganic filler with the specific chemical composition and specific content is added to the thermosetting resin composition, the thermal expansion coefficient of the board can be obviously reduced on the basis of not influencing the insulation performance of the board, and the thermosetting resin composition can be suitable for the printed circuit board.

Description

A kind of compositions of thermosetting resin and containing its prepreg, veneer sheet and printed circuit board
Technical field
The invention belongs to copper-clad plate technical field, be specifically related to a kind of compositions of thermosetting resin and prepreg, veneer sheet and printed circuit board containing it.
Background technology
Along with electronic product is to densification, multifunction and " light, thin, little " change development, make circuit along with electronic product is to the fast development of the aspects such as miniaturization, multifunction, high performance and high reliability, printed circuit board as one of electronic product major parts also starts towards direction fast developments such as high precision, high-density, high-performance, microporous, slimmings, and this just needs veneer sheet base material to have low thermal expansivity and high dimensional stability.
Under the development trends such as veneer sheet slimming, high-density and microporous, in order to ensure high precision, just needing sheet material at electricity, machinery, keeping satisfactory stability under Warm status, especially the dimensional stability that causes of temperature.In IC (Integratedcircuit) encapsulation field, IC is fixed on veneer sheet base material, if sheet material thermal expansivity does not mate, the sheet deformation then caused by heat may cause broken wire, IC to damage or the phenomenon such as short circuit and open circuit, so reduce sheet material CTE to become especially important.
In order to the thermal expansivity of lower layer pressing plate, usually can select the resin of low thermal coefficient of expansion and improve the content of the mineral filler such as silicon-dioxide, aluminum oxide.But low thermal coefficient of expansion resin price is expensive, and limited due to itself thermal expansivity of the mineral filler such as silicon-dioxide and aluminum oxide, to reduction sheet material CTE limited efficiency.
CN103881312A discloses a kind of for printed circuit board (PCB) resin combination, and it contains eucryptite ceramic packing as inorganic filler, and it is spherical or oval that it has section, and particle size is 0.01 ~ 1 μm.Described eucryptite ceramic packing has following chemical constitution: xLi 2o-yAl 2o 3-zSiO 2, wherein, x, y and z represent mixing mol ratio separately, x and y is 0.9 ~ 1.1, z is independently of one another 1.2 ~ 2.1.
CN104559055A discloses a kind of for printed circuit board (PCB) resin combination, and it contains eucryptite ceramic packing as inorganic filler, and described eucryptite ceramic packing has following chemical constitution: xLi 2o-yAl 2o 3-zSiO 2, wherein, x, y and z represent mixing mol ratio separately, x and y is 0.9 ~ 1.1, z is independently of one another 1.2 ~ 2.1.
But, adopt the eucryptite ceramic packing of above-mentioned chemical constitution can reduce the insulating property of sheet material.
Summary of the invention
For the problem of prior art, the object of the present invention is to provide a kind of compositions of thermosetting resin and prepreg, veneer sheet and printed circuit board containing it.Adopt this compositions of thermosetting resin significantly can reduce the thermal expansivity of prepreg, veneer sheet and printed circuit board and thermal distortion and not affect insulating property.
To achieve these goals, present invention employs following technical scheme:
A kind of compositions of thermosetting resin, its mass percent accounting for compositions of thermosetting resin by each component comprises: the low bulk mineral filler of thermosetting resin, solidifying agent and 30 ~ 70wt%, and described low bulk mineral filler is by following chemical formulation:
xLi 2O-yAl 2O 3-zSiO 2
Wherein, x, y and z represent mixing mol ratio all independently, x and y is independently 0.9 ~ 1.1, z is separately 2.5 ~ 8, are preferably 3 ~ 5.
In the present invention, described mass percent is by obtaining the total mass of the quality of each component divided by compositions of thermosetting resin.
The present inventor finds in an experiment, the low bulk mineral filler of the certain content with specified chemical composition is added in compositions of thermosetting resin, on the basis not affecting sheet material insulating property, obviously can reduce sheet material thermal expansivity, and this completes the present invention.
In the present invention, when z is less than 2.5, can reduce sheet material insulating property, when z is greater than 8, sheet material CTE reduces DeGrain, and when z is in 3 ~ 5 scopes, sheet material CTE reduces most pronounced effects.
In the present invention, described low bulk mineral filler adopts the preparation of glass crystallization process, is specially:
By a certain proportion of Li 2o, Al 2o 3and SiO 2powder mixes, and proceeds in high-temperature glass melter, melting at 1550 ~ 1600 DEG C, and cast on stainless steel after insulation 3 ~ 4h, anneal 4h at 500 ~ 550 DEG C.Sample, after cutting, being ground to submicron order, adopts flame method to prepare balling-up.Sample after balling-up is put into stove, and at nucleation heat preservation zone insulation 2h, be then warming up to 1050 ~ 1300 DEG C and carry out crystalline substance China, insulation 4h, progressively cools to room temperature.The low bulk mineral filler thermal expansivity adopting the method to obtain is lower, and has good sphericity, lower specific surface area, when using it in compositions of thermosetting resin, has dispersed and mobility preferably, to loading level not too large restriction.
In the present invention, described low bulk inorganic filler content is 30 ~ 70wt% of compositions of thermosetting resin total mass, such as 33wt%, 36wt%, 39wt%, 42wt%, 45wt%, 48wt%, 51wt%, 54wt%, 57wt%, 60wt%, 63wt%, 66wt% or 69wt%, be preferably 50 ~ 70wt%.If low bulk inorganic filler content is lower than 30wt%, then sheet material CTE improves not obvious, if low bulk inorganic filler content is higher than 70wt%, then can impact plate properties such as compositions of thermosetting resin mobility, wetting properties.
Preferably, described low bulk mineral filler is spherical or oval particle, and median size is 0.1 ~ 5.0 μm, is preferably 0.3 ~ 1.0 μm.When low bulk mineral filler median size is less than 0.1 μm, specific grain surface is long-pending sharply to be increased, and oil-absorption(number) increases, and low bulk mineral filler is maximum can be reduced by loading level, when low bulk mineral filler median size is greater than 5.0 μm, is not suitable for slim sheet material.At this, when median size refers to the accumulation number of degrees distribution curve obtained as 100% by the cumulative volume of particle based on particle diameter, be just equivalent to the particle diameter that volume is the point of 50%, can to use the particle size distribution of laser diffraction and scattering method.
Preferably, the quality of described thermosetting resin accounts for 20 ~ 70wt% of compositions of thermosetting resin total mass, such as 21wt%, 24wt%, 27wt%, 31wt%, 35wt%, 39wt%, 43wt%, 47wt%, 51wt%, 55wt%, 59wt%, 63wt%, 66wt% or 69wt%.
Preferably, described thermosetting resin is the mixture of any one or at least two kinds in epoxy resin, resol, benzoxazine colophony, cyanate, phosphorous active ester compound or liquid crystalline resin.Described epoxy resin is as bisphenol A type epoxy resin.
Preferably, the quality of described solidifying agent accounts for 1 ~ 30wt% of compositions of thermosetting resin total mass, such as 2wt%, 5wt%, 8wt%, 11wt%, 14wt%, 17wt%, 20wt%, 23wt%, 26wt% or 29wt%.
Preferably, described solidifying agent is the combination of any one or at least two kinds in phenol aldehyde type solidifying agent, amine based curative, anhydride group solidifying agent or dicy-curing agent.
Preferably, described compositions of thermosetting resin also comprises curing catalyst, its quality accounts for 0 ~ 10wt% of compositions of thermosetting resin total mass and does not comprise 0, such as 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% or 9.5wt%.
Preferably, described curing catalyst is that imidazolyl curing catalyst is or/and amido curing catalyst.
Preferably, described compositions of thermosetting resin also comprises dispersion agent.
Preferably, described dispersion agent is the mixture of any one or at least two kinds in silane coupling agent, phosphoric acid ester treatment agent or silicone based treatment agent.
Preferably, described compositions of thermosetting resin, also comprise other mineral fillers, it comprises the mixture of any one or at least two kinds in silicon-dioxide, boehmite, talcum, mica, kaolin, aluminium hydroxide, magnesium hydroxide, zinc borate, zinc, zinc oxide, titanium oxide, aluminum oxide, aluminium 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 double glazing micro mist.The mixture of described mixture such as silicon-dioxide and aluminum oxide, mica and kaolinic mixture, the mixture of aluminium hydroxide and magnesium hydroxide, the mixture of zinc borate and zinc, the mixture of zinc oxide and titanium oxide, the mixture of boron nitride and calcium carbonate, the mixture of barium sulfate and aluminum borate, the mixture of potassium titanate and E glass powder, the mixture of S glass powder, D glass powder and double glazing micro mist.
" comprising " of the present invention, mean it except described component, can also comprise other components, these other components give described resin combination different characteristics.In addition, " comprising " of the present invention, can also replace with enclosed " being " or " by ... composition ".
No matter which kind of component described compositions of thermosetting resin comprises, and its each constituent mass per-cent sum is 100wt%.
Such as, described compositions of thermosetting resin is also containing solidifying agent, promotor and various additive, as the concrete example of additive, fire retardant, coupling agent, oxidation inhibitor, thermo-stabilizer, static inhibitor, UV light absorber, pigment, tinting material or lubricant etc. can be enumerated.These various additives can be used alone, also can two kinds or two or more used in combination.
As the preparation method of one of compositions of thermosetting resin of the present invention, can be coordinated by known method, stir, thermosetting resin described in mixing, solidifying agent, curing catalyst and low bulk mineral filler, and various additive, prepare.
A kind of resin adhesive liquid, it is dissolved or dispersed in solvent by compositions of thermosetting resin as above to obtain.
A kind of prepreg, it comprises strongthener and by impregnation drying postadhesion compositions of thermosetting resin as above thereon.
A kind of veneer sheet, described veneer sheet contains at least one prepreg as above.
A kind of printed circuit board, described printed circuit board contains at least one prepreg as above.
Compared with the prior art, the present invention has following beneficial effect:
The present invention by adding the low bulk mineral filler of the certain content with specified chemical composition in compositions of thermosetting resin, and can obviously reduce sheet material thermal expansivity, sheet material thermal expansivity can reach 92 ~ 221 (ppm/ DEG C).
In addition, described low bulk mineral filler is spherical or elliptical shape, median size is at 0.1 ~ 5.0 μm, it has less specific surface area and oil-absorption(number), preferably dispersed and mobility, after surface treatment modification (as the process of the treatment agent such as dispersion agent, coupling agent), its dispersiveness and the consistency with resin system can be increased, can ensure in resin that larger content is filled.
Embodiment
Technical scheme of the present invention is further illustrated below by embodiment.
In order to better the object, technical solutions and advantages of the present invention are described, below in conjunction with specific embodiment, the present invention is described further.
In the present invention, described low bulk mineral filler adopts the preparation of glass crystallization process, is specially:
By a certain proportion of Li 2o, Al 2o 3and SiO 2powder mixes, and proceeds in high-temperature glass melter, melting at 1550 ~ 1600 DEG C, and cast on stainless steel after insulation 3 ~ 4h, anneal 4h at 500 ~ 550 DEG C.Sample, after cutting, being ground to submicron order, adopts flame method to prepare balling-up.Sample after balling-up is put into stove, and at nucleation heat preservation zone insulation 2h, be then warming up to 1050-1300 DEG C and carry out crystalline substance China, insulation 4h, progressively cools to room temperature.Adopt this low bulk mineral filler thermal expansivity lower, and there is good sphericity, lower specific surface area, when using it in compositions of thermosetting resin, there is dispersed and mobility preferably, to loading level not too large restriction.
Embodiment 1
By brominated epoxy resin (45.69wt%), bromination linear phenolic resin (21.93wt%), epoxy resin (2.29wt%), imidazoles promotor (0.09wt%, four countries of Japan change into the 2MI of production), low bulk mineral filler (30wt%) dissolves in organic solvent, mechanical stirring, emulsification are mixed with the glue of 65wt%, then impregnation glasscloth, prepreg (prepreg) is formed after heat drying, Copper Foil is placed on two sides, and pressurized, heated makes copper clad laminate.In the present embodiment, low bulk mineral filler chemical constitution used is Li 2o-Al 2o 3-3SiO 2, mensuration, evaluation result are shown in table 1.
Embodiment 2
By brominated epoxy resin (39.16wt%), bromination linear phenolic resin (18.80wt%), epoxy resin (1.96wt%), imidazoles promotor (0.08wt%, four countries of Japan change into the 2MI of production), low bulk mineral filler (40wt%) dissolves in organic solvent, mechanical stirring, emulsification are mixed with the glue of 65wt%, then impregnation glasscloth, prepreg (prepreg) is formed after heat drying, Copper Foil is placed on two sides, and pressurized, heated makes copper clad laminate.In the present embodiment, low bulk mineral filler chemical constitution used is Li 2o-Al 2o 3-3SiO 2.Mensuration, evaluation result are shown in table 1.
Embodiment 3
By brominated epoxy resin (32.64wt%), bromination linear phenolic resin (15.66wt%), epoxy resin (1.63wt%), imidazoles promotor (0.07wt%, four countries of Japan change into the 2MI of production), low bulk mineral filler (50wt%) dissolves in organic solvent, mechanical stirring, emulsification are mixed with the glue of 65wt%, then impregnation glasscloth, prepreg (prepreg) is formed after heat drying, Copper Foil is placed on two sides, and pressurized, heated makes copper clad laminate.In the present embodiment, low bulk mineral filler chemical constitution used is Li 2o-Al 2o 3-3SiO 2.Mensuration, evaluation result are shown in table 1.
Embodiment 4
By brominated epoxy resin (26.11wt%), bromination linear phenolic resin (12.53wt%), epoxy resin (1.31wt%), imidazoles promotor (0.05wt%, four countries of Japan change into the 2MI of production), low bulk mineral filler (60wt%) dissolves in organic solvent, mechanical stirring, emulsification are mixed with the glue of 65wt%, then impregnation glasscloth, prepreg (prepreg) is formed after heat drying, Copper Foil is placed on two sides, and pressurized, heated makes copper clad laminate.In the present embodiment, low bulk mineral filler chemical constitution used is Li 2o-Al 2o 3-3SiO 2.Mensuration, evaluation result are shown in table 1.
Embodiment 5
By brominated epoxy resin (19.58wt%), bromination linear phenolic resin (9.40wt%), epoxy resin (0.98wt%), imidazoles promotor (0.04wt%, four countries of Japan change into the 2MI of production), low bulk mineral filler (70wt%) dissolves in organic solvent, mechanical stirring, emulsification are mixed with the glue of 65wt%, then impregnation glasscloth, prepreg (prepreg) is formed after heat drying, Copper Foil is placed on two sides, and pressurized, heated makes copper clad laminate.In the present embodiment, low bulk mineral filler chemical constitution used is Li 2o-Al 2o 3-3SiO 2.Mensuration, evaluation result are shown in table 1.
Embodiment 6
By brominated epoxy resin (32.64wt%), bromination linear phenolic resin (15.66wt%), epoxy resin (1.63wt%), imidazoles promotor (0.07wt%, four countries of Japan change into the 2MI of production), low bulk mineral filler (50wt%) dissolves in organic solvent, mechanical stirring, emulsification are mixed with the glue of 65wt%, then impregnation glasscloth, prepreg (prepreg) is formed after heat drying, Copper Foil is placed on two sides, and pressurized, heated makes copper clad laminate.In the present embodiment, low bulk mineral filler chemical constitution used is Li 2o-Al 2o 3-2.5SiO 2.Mensuration, evaluation result are shown in table 1.
Embodiment 7
By brominated epoxy resin (32.64wt%), bromination linear phenolic resin (15.66wt%), epoxy resin (1.63wt%), imidazoles promotor (0.07wt%, four countries of Japan change into the 2MI of production), low bulk mineral filler (50wt%) dissolves in organic solvent, mechanical stirring, emulsification are mixed with the glue of 65wt%, then impregnation glasscloth, prepreg (prepreg) is formed after heat drying, Copper Foil is placed on two sides, and pressurized, heated makes copper clad laminate.In the present embodiment, low bulk mineral filler chemical constitution used is Li 2o-Al 2o 3-8SiO 2.Mensuration, evaluation result are shown in table 1.
Embodiment 8
By brominated epoxy resin (26.45wt%), cyanate (22wt%), epoxy resin (1.50wt%), imidazoles promotor (0.05wt%, four countries of Japan change into the 2MI of production), low bulk mineral filler (50wt%) dissolves in organic solvent, mechanical stirring, emulsification are mixed with the glue of 65wt%, then impregnation glasscloth, prepreg (prepreg) is formed after heat drying, Copper Foil is placed on two sides, and pressurized, heated makes copper clad laminate.In the present embodiment, low bulk mineral filler chemical constitution used is Li 2o-Al 2o 3-3SiO 2.Mensuration, evaluation result are shown in table 1.
Comparative example 1
By brominated epoxy resin (45.69wt%), bromination linear phenolic resin (21.93wt%), epoxy resin (2.29wt%), imidazoles promotor (0.09wt%, four countries of Japan change into the 2MI of production), silicon powder (30wt%) dissolves in organic solvent, mechanical stirring, emulsification are mixed with the glue of 65wt%, then impregnation glasscloth, prepreg (prepreg) is formed after heat drying, Copper Foil is placed on two sides, and pressurized, heated makes copper clad laminate.Mensuration, evaluation result are shown in table 1.
Comparative example 2
By brominated epoxy resin (32.64wt%), bromination linear phenolic resin (15.66wt%), epoxy resin (1.63wt%), imidazoles promotor (0.07wt%, four countries of Japan change into the 2MI of production), silicon powder (50wt%) dissolves in organic solvent, mechanical stirring, emulsification are mixed with the glue of 65wt%, then impregnation glasscloth, prepreg (prepreg) is formed after heat drying, Copper Foil is placed on two sides, and pressurized, heated makes copper clad laminate.Mensuration, evaluation result are shown in table 1.
Comparative example 3
By brominated epoxy resin (32.64wt%), bromination linear phenolic resin (15.66wt%), epoxy resin (1.63wt%), imidazoles promotor (0.07wt%, four countries of Japan change into the 2MI of production), low bulk mineral filler (50wt%) dissolves in organic solvent, mechanical stirring, emulsification are mixed with the glue of 65wt%, then impregnation glasscloth, prepreg (prepreg) is formed after heat drying, Copper Foil is placed on two sides, and pressurized, heated makes copper clad laminate.In the present embodiment, low bulk mineral filler chemical constitution used is Li 2o-Al 2o 3-2.1SiO 2.Mensuration, evaluation result are shown in table 1.
Comparative example 4
By brominated epoxy resin (32.64wt%), bromination linear phenolic resin (15.66wt%), epoxy resin (1.63wt%), imidazoles promotor (0.07wt%, four countries of Japan change into the 2MI of production), low bulk mineral filler (50wt%) dissolves in organic solvent, mechanical stirring, emulsification are mixed with the glue of 65wt%, then impregnation glasscloth, prepreg (prepreg) is formed after heat drying, Copper Foil is placed on two sides, and pressurized, heated makes copper clad laminate.In the present embodiment, low bulk mineral filler chemical constitution used is Li 2o-Al 2o 3-10SiO 2.Mensuration, evaluation result are shown in table 1.
Comparative example 5
By brominated epoxy resin (52.22wt%), bromination linear phenolic resin (25.07wt%), epoxy resin (2.61wt%), imidazoles promotor (0.10wt%, four countries of Japan change into the 2MI of production), low bulk mineral filler (20wt%) dissolves in organic solvent, mechanical stirring, emulsification are mixed with the glue of 65wt%, then impregnation glasscloth, prepreg (prepreg) is formed after heat drying, Copper Foil is placed on two sides, and pressurized, heated makes copper clad laminate.In the present embodiment, low bulk mineral filler chemical constitution used is Li 2o-Al 2o 3-3SiO 2.Mensuration, evaluation result are shown in table 1.
Comparative example 6
By brominated epoxy resin (13.05wt%), bromination linear phenolic resin (6.27wt%), epoxy resin (0.65wt%), imidazoles promotor (0.03wt%, four countries of Japan change into the 2MI of production), low bulk mineral filler (80wt%) dissolves in organic solvent, mechanical stirring, emulsification are mixed with the glue of 65wt%, then impregnation glasscloth, prepreg (prepreg) is formed after heat drying, Copper Foil is placed on two sides, and pressurized, heated makes copper clad laminate.In the present embodiment, low bulk mineral filler chemical constitution used is Li 2o-Al 2o 3-3SiO 2.Mensuration, evaluation result are shown in table 1.
Comparative example 7
By brominated epoxy resin (26.45wt%), cyanate (22wt%), epoxy resin (1.50wt%), imidazoles promotor (0.05wt%, four countries of Japan change into the 2MI of production), low bulk mineral filler (50wt%) dissolves in organic solvent, mechanical stirring, emulsification are mixed with the glue of 65wt%, then impregnation glasscloth, prepreg (prepreg) is formed after heat drying, Copper Foil is placed on two sides, and pressurized, heated makes copper clad laminate.In the present embodiment, low bulk mineral filler chemical constitution used is Li 2o-Al 2o 3-10SiO 2.Mensuration, evaluation result are shown in table 1.
Use the copper clad laminate obtained, by the following method illustrated, to thermal expansivity, voltage breakdown, stripping strength evaluation, the results are shown in Table 1.
The mensuration of coefficient of thermal expansion
After utilizing etching solution to remove the Copper Foil of copper-clad laminated board, be cut into the large little makings test film that 5mm × 5mm is square.Use TMA testing apparatus with heat-up rate 10 DEG C/min, measure the average line coefficient of thermal expansion of the Z-direction of this test film at 30 DEG C ~ 260 DEG C (woven fiber glass vertical direction).Coefficient of thermal expansion is less, and effect is better.
The mensuration of voltage breakdown
After utilizing etching solution to remove the Copper Foil of copper-clad laminated board, be cut into the sample of 76mm × 50mm size, boring two diameters along long limit medullary ray and minor face central spot is the circular hole of 4.8mm, and two pitchs of holes are 25 ± 0.25mm.Sample processes 48+2/-0h in the distilled water of 50 ± 2 DEG C, then sample is immersed 0.5-4h in room temperature distilled water, makes sample reach temperature equilibrium when water content is substantially constant.Use high voltage testing device with the speed of 500v/s boosting test, observe sample, until puncture, voltage when record punctures.
The mensuration of stripping strength
Sheet material is cut into the test film of 10mm × 100mm, the Copper Foil on test film two sides, retain except 3mm × 100mm Copper Foil except middle, all the other Copper Foil etching solutions remove.From one end of sample suitable length Copper Foil stripping, clamped by copper chaff fixture shell, use tension testing machine, makes pulling force vertical with copper-clad surface, draws continuously and shells 50mm, draw lowest pull value in stripping process to be stripping strength with the speed of 50mm/min.
Table 1
Embodiment 1-5 as can be seen from table 1, sheet material CTE raise with low bulk inorganic filler content and reduce, and when this low bulk inorganic filler content is 50 ~ 70%, reduce amplitude maximum.As can be seen from comparative example 5-6, when this low bulk inorganic filler content lower than 30% time, sheet material CTE reduces remarkable, when content higher than 70% time, adding of filler obviously reduces sheet material stripping strength.As can be seen from embodiment 6-7 and comparative example 3-4, as the chemical constitution xLi of low bulk mineral filler 2o-yAl 2o 3-zSiO 2in, when Z is less than 2.5, sheet material insulativity obviously reduces, and when Z is greater than 8, sheet material CTE reduces DeGrain.As can be seen from embodiment 3 and embodiment 6-7, when z is in 3 ~ 5 scopes, sheet material CTE reduces most pronounced effects.
The above, be only preferred embodiment of the present invention, not the content of composition of the present invention is imposed any restrictions, for the person of ordinary skill of the art, other various corresponding change and distortion can be made according to technical scheme of the present invention and technical conceive, every above embodiment is done according to technical spirit of the present invention or composition composition or content any trickle amendment, equivalent variations and modification, all belong in the scope of technical solution of the present invention.
Applicant states, the present invention illustrates method detailed of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned method detailed, does not namely mean that the present invention must rely on above-mentioned method detailed and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of ancillary component, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.

Claims (10)

1. a compositions of thermosetting resin, its mass percent accounting for compositions of thermosetting resin by each component comprises: the low bulk mineral filler of thermosetting resin, solidifying agent and 30 ~ 70wt%, and described low bulk mineral filler is by following chemical formulation:
xLi 2O-yAl 2O 3-zSiO 2
Wherein, x, y and z represent mixing mol ratio all independently, x and y is independently 0.9 ~ 1.1, z is separately 2.5 ~ 8.
2. compositions of thermosetting resin as claimed in claim 1, it is characterized in that, z is 3 ~ 5.
3. compositions of thermosetting resin as claimed in claim 1 or 2, it is characterized in that, described low bulk inorganic filler content is 50 ~ 70wt% of compositions of thermosetting resin total mass;
Preferably, described low bulk mineral filler is spherical or oval particle, and median size is 0.1 ~ 5.0 μm, is preferably 0.3 ~ 1.0 μm.
4. the compositions of thermosetting resin as described in one of claim 1-3, is characterized in that, the quality of described thermosetting resin accounts for 20 ~ 70wt% of compositions of thermosetting resin total mass;
Preferably, described thermosetting resin is the mixture of any one or at least two kinds in epoxy resin, resol, benzoxazine colophony, cyanate, phosphorous active ester compound or liquid crystalline resin.
5. the compositions of thermosetting resin as described in one of claim 1-4, is characterized in that, the quality of described solidifying agent accounts for 1 ~ 30wt% of compositions of thermosetting resin total mass;
Preferably, described solidifying agent is the combination of any one or at least two kinds in phenol aldehyde type solidifying agent, amine based curative, anhydride group solidifying agent or dicy-curing agent.
6. the compositions of thermosetting resin as described in one of claim 1-5, is characterized in that, described compositions of thermosetting resin also comprises curing catalyst, and its quality accounts for 0 ~ 10wt% of compositions of thermosetting resin total mass and do not comprise 0;
Preferably, described curing catalyst is that imidazolyl curing catalyst is or/and amido curing catalyst;
Preferably, described compositions of thermosetting resin also comprises dispersion agent;
Preferably, described dispersion agent is the mixture of any one or at least two kinds in silane coupling agent, phosphoric acid ester treatment agent or silicone based treatment agent.
7. the compositions of thermosetting resin as described in one of claim 1-6, it is characterized in that, described compositions of thermosetting resin, also comprise other mineral fillers, it comprises the mixture of any one or at least two kinds in silicon-dioxide, boehmite, talcum, mica, kaolin, aluminium hydroxide, magnesium hydroxide, zinc borate, zinc, zinc oxide, titanium oxide, aluminum oxide, aluminium 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 double glazing micro mist.
8. a prepreg, it comprises strongthener and by the impregnation drying postadhesion compositions of thermosetting resin as described in one of claim 1-7 thereon.
9. a veneer sheet, described veneer sheet contains at least one prepreg as claimed in claim 8.
10. a printed circuit board, described printed circuit board contains at least one prepreg as claimed in claim 8.
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