CN105504681B - A kind of compositions of thermosetting resin and the prepreg, laminate and printed circuit board containing it - Google Patents
A kind of compositions of thermosetting resin and the prepreg, laminate and printed circuit board containing it Download PDFInfo
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- CN105504681B CN105504681B CN201510953042.1A CN201510953042A CN105504681B CN 105504681 B CN105504681 B CN 105504681B CN 201510953042 A CN201510953042 A CN 201510953042A CN 105504681 B CN105504681 B CN 105504681B
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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
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- 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
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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
- 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
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- 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
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- 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
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- 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
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- 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
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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
- 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
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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
- B32B2250/00—Layers arrangement
- B32B2250/20—All layers being fibrous or filamentary
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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
- 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
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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
- 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
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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
- 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
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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
- 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
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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
- 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 Kinetics & Catalysis (AREA)
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- Reinforced Plastic Materials (AREA)
Abstract
Prepreg, laminate and printed circuit board the present invention provides a kind of compositions of thermosetting resin and containing it.The mass percent that the compositions of thermosetting resin is accounted for compositions of thermosetting resin by each component includes：The low bulk inorganic filler of thermosetting resin, curing agent and 30~70wt%, the low bulk inorganic filler are represented by following chemical formula：xLi2O‑yAl2O3‑zSiO2, wherein, x, y and z independently represent mixing molar ratio, and x and y are independently each that 0.9~1.1, z is 2.5~8.The present invention, can be on the basis of plate insulating properties not be influenced by the low bulk inorganic filler of the certain content that addition is formed with specified chemical in compositions of thermosetting resin, hence it is evident that is reduced plate coefficient of thermal expansion, is applicable to printed circuit board.
Description
Technical field
The invention belongs to copper-clad plate technical fields, and in particular to a kind of compositions of thermosetting resin and the preimpregnation containing it
Material, laminate and printed circuit board.
Background technology
With electronic product to densification, multifunction and it is " light, thin, small " change develop so that circuit is produced with electronics
Fast development of the product to miniaturization, multifunction, high performance and high reliability etc., as electronic product critical piece it
As soon as printed circuit board also begin to towards the directions such as high-precision, high density, high-performance, microporous, slimming grow rapidly, this
Need laminate base material that there is low coefficient of thermal expansion and high dimensional stability.
Under the development trends such as laminate slimming, high density and microporous, in order to ensure high precision, it is necessary to plate
Dimensional stability caused by keeping good stability, especially temperature under electricity, machinery, Warm status.In IC (Integrated
Circuit) encapsulation field, IC are fixed on laminate base material, if plate coefficient of thermal expansion mismatches, by thermally-induced plate
Deformation may cause phenomena such as broken wire, IC damages or short circuit and open circuit, so reducing plate CTE becomes especially to weigh
It will.
In order to reduce the coefficient of thermal expansion of laminate, it will usually select the resin of low thermal coefficient of expansion and improve titanium dioxide
The content of the inorganic fillers such as silicon, aluminium oxide.But low thermal coefficient of expansion resin price is expensive, and silica and aluminium oxide etc. are inorganic
Filler is limited due to itself coefficient of thermal expansion, limited to reducing plate CTE effects.
CN 103881312A disclose one kind for printed circuit board (PCB) resin combination, contain eucryptite ceramic packing
Spherical or oval with section as inorganic filler, particle size is 0.01~1 μm.The eucryptite ceramics are filled out
Material has following chemical composition：xLi2O-yAl2O3-zSiO2, wherein, x, y and z each represent mixing molar ratio, and x and y are each only
It is on the spot that 0.9~1.1, z is 1.2~2.1.
CN 104559055A disclose one kind for printed circuit board (PCB) resin combination, contain eucryptite ceramic packing
As inorganic filler, the eucryptite ceramic packing has following chemical composition：xLi2O-yAl2O3-zSiO2, wherein, x, y
Mixing molar ratio is each represented with z, x and y are each independently 0.9~1.1, z as 1.2~2.1.
But the insulation performance of plate can be reduced using the eucryptite ceramic packing of above-mentioned chemical composition.
The content of the invention
The problem of for prior art, it is an object of the invention to provide a kind of compositions of thermosetting resin and contains it
Prepreg, laminate and printed circuit board.Using the compositions of thermosetting resin can significantly reduce prepreg, laminate and
The coefficient of thermal expansion of printed circuit board and thermal deformation are without influencing insulation performance.
To achieve these goals, present invention employs following technical solutions：
A kind of compositions of thermosetting resin, the mass percent of compositions of thermosetting resin is accounted for by each component to be included：Heat
The low bulk inorganic filler of thermosetting resin, curing agent and 30~70wt%, the low bulk inorganic filler is by following chemical formula table
Show：
xLi2O-yAl2O3-zSiO2
Wherein, x, y and z independently represent mixing molar ratio, and x and y are independently each that 0.9~1.1, z is 2.5~8,
Preferably 3~5.
In the present invention, the mass percent can be by by the total of the quality of each component divided by compositions of thermosetting resin
Quality obtains.
The present inventor has found in an experiment, is added in compositions of thermosetting resin with specified chemical composition
The low bulk inorganic filler of certain content, can be on the basis of plate insulation performance not be influenced, hence it is evident that reduces plate thermal expansion
Coefficient, and have thus completed the present invention.
In the present invention, when z is less than 2.5, plate insulation performance can be reduced, when z is more than 8, plate CTE reducing effects
Unobvious, when z is in the range of 3~5, plate CTE reducing effects are most notable.
In the present invention, the low bulk inorganic filler is prepared using glass crystallization method, is specially：
By a certain proportion of Li2O、Al2O3And SiO2Powder is uniformly mixed, and is transferred in high-temperature glass melter, 1550~
It melts, casts on stainless steel after keeping the temperature 3~4h, anneal 4h at 500~550 DEG C at 1600 DEG C.Sample is cleaved, grinding
To submicron order, balling-up is prepared using flame method.Sample after balling-up is put into stove, keeps the temperature 2h in nucleation heat preservation zone, so
After be warming up to 1050~1300 DEG C and carry out brilliant China, keep the temperature 4h, be slowly cooled to room temperature.The low bulk obtained using this method is inorganic
Filler coefficient of thermal expansion is lower, and has preferable sphericity, and relatively low specific surface area uses it for compositions of thermosetting resin
When middle, there is preferable dispersiveness and mobility, to loading without too big limitation.
In the present invention, the low bulk inorganic filler content for compositions of thermosetting resin gross mass 30~
70wt%, for example, 33wt%, 36wt%, 39wt%, 42wt%, 45wt%, 48wt%, 51wt%, 54wt%, 57wt%,
60wt%, 63wt%, 66wt% or 69wt% are preferably 50~70wt%.If low bulk inorganic filler content is less than 30wt%,
Then plate CTE improves unobvious, if low bulk inorganic filler content is higher than 70wt%, compositions of thermosetting resin can be flowed
The plate properties such as property, wellability impact.
Preferably, the low bulk inorganic filler is spherical or oval particle, and average grain diameter is 0.1~5.0 μm, preferably
For 0.3~1.0 μm.When low bulk inorganic filler average grain diameter is less than 0.1 μm, specific grain surface product increased dramatically, and oil factor increases
Greatly, low bulk inorganic filler maximum can loading reduce, low bulk inorganic filler average grain diameter be more than 5.0 μm when, be not suitable for
Slim plate.Here, average grain diameter refers to be obtained the accumulation number of degrees distribution based on grain size using the total volume of particle as 100%
During curve, the grain size for the point that volume is 50% is just equivalent to, it can be to use the particle size distribution of laser diffraction scattering method.
Preferably, the quality of the thermosetting resin accounts for 20~70wt% of compositions of thermosetting resin gross mass, such as
21wt%, 24wt%, 27wt%, 31wt%, 35wt%, 39wt%, 43wt%, 47wt%, 51wt%, 55wt%, 59wt%,
63wt%, 66wt% or 69wt%.
Preferably, the thermosetting resin is epoxy resin, phenolic resin, benzoxazine colophony, cyanate, phosphorous activity
In ester compounds or liquid crystalline resin any one or at least two mixture.The epoxy resin such as bisphenol type epoxy
Resin.
Preferably, the quality of the curing agent accounts for 1~30wt% of compositions of thermosetting resin gross mass, such as 2wt%,
5wt%, 8wt%, 11wt%, 14wt%, 17wt%, 20wt%, 23wt%, 26wt% or 29wt%.
Preferably, the curing agent is phenol aldehyde type curing agent, amine based curative, anhydride group curing agent or dicy-curing agent
In any one or at least two combination.
Preferably, the compositions of thermosetting resin further includes curing accelerator, and quality accounts for compositions of thermosetting resin
0~10wt% of gross mass and not include 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, the curing accelerator is imidazole radicals curing accelerator or/and amido curing accelerator.
Preferably, the compositions of thermosetting resin further includes dispersant.
Preferably, the dispersant is arbitrary in silane coupling agent, phosphoric acid ester inorganic agent or organic silicon inorganic agent
It is a kind of or at least two mixture.
Preferably, the compositions of thermosetting resin further includes other inorganic fillers, including silica, boehmite,
Talcum, mica, kaolin, aluminium hydroxide, magnesium hydroxide, zinc borate, zinc stannate, zinc oxide, titanium oxide, aluminium oxide, aluminium nitride,
Boron nitride, calcium carbonate, barium sulfate, barium titanate, aluminium borate, potassium titanate, E glass dust, S glass dust, D glass dust, NE glass dust or
In hollow glass micro mist any one or at least two mixture.The mixture such as silica and aluminium oxide
The mixture of mixture, mica and kaolinic mixture, aluminium hydroxide and magnesium hydroxide, the mixing of zinc borate and zinc stannate
The mixture of the mixture of the mixture of object, zinc oxide and titanium oxide, boron nitride and calcium carbonate, barium sulfate and aluminium borate, metatitanic acid
The mixture of potassium and E glass dust, the mixture of S glass dust, D glass dust and hollow glass micro mist.
" comprising " of the present invention, it is intended that it can also include other components, these other components in addition to the component
Assign the resin combination different characteristics.In addition, " comprising " of the present invention may be replaced by enclosed
" for " or " by ... form ".
No matter it is 100wt% that the compositions of thermosetting resin, which includes the sum of which kind of component, each component mass percent,.
For example, the compositions of thermosetting resin also contains curing agent, accelerating agent and various additives, as additive
Concrete example, fire retardant, coupling agent can be enumerated, antioxidant, heat stabilizer, antistatic agent, ultra-violet absorber, pigment,
Toner or lubricant etc..These various additives can be used alone, and two kinds or two or more can also be used in mixed way.
As the preparation method of one of compositions of thermosetting resin of the present invention, can be coordinated by well known method, stirring,
Mixing thermosetting resin, curing agent, curing accelerator and the low bulk inorganic filler and various additives, to prepare.
A kind of resin adhesive liquid is that compositions of thermosetting resin as described above is dissolved or dispersed in solvent to obtain.
A kind of prepreg including reinforcing material and passes through thermosetting property as described above attached thereto after impregnation drying
Resin combination.
A kind of laminate, the laminate contain an at least prepreg as described above.
A kind of printed circuit board, the printed circuit board contain an at least prepreg as described above.
Compared with the prior art, the present invention has the advantages that：
The low bulk that the present invention passes through the certain content that addition is formed with specified chemical in compositions of thermosetting resin
Inorganic filler, can be substantially reduced plate coefficient of thermal expansion, and plate coefficient of thermal expansion can reach 92~221 (ppm/ DEG C).
In addition, the low bulk inorganic filler has for spherical or elliptical shape, average grain diameter at 0.1~5.0 μm
Smaller specific surface area and oil factor, preferable dispersiveness and mobility, surface treated are modified (such as dispersant, coupling agent
Inorganic agent processing) after, its dispersiveness and the compatibility with resin system can be increased, can ensure that larger content is filled out in resin
It fills.
Specific embodiment
The technical solution further illustrated the present invention below by specific embodiment.
In order to better illustrate the object, technical solutions and advantages of the present invention, below in conjunction with specific embodiment to this hair
It is bright to be described further.
In the present invention, the low bulk inorganic filler is prepared using glass crystallization method, is specially：
By a certain proportion of Li2O、Al2O3And SiO2Powder is uniformly mixed, and is transferred in high-temperature glass melter, 1550~
It melts, casts on stainless steel after keeping the temperature 3~4h, anneal 4h at 500~550 DEG C at 1600 DEG C.Sample is cleaved, grinding
To submicron order, balling-up is prepared using flame method.Sample after balling-up is put into stove, keeps the temperature 2h in nucleation heat preservation zone, so
After be warming up to 1050-1300 DEG C and carry out brilliant China, keep the temperature 4h, be slowly cooled to room temperature.Using the low bulk inorganic filler thermal expansion
Coefficient is lower, and has preferable sphericity, and relatively low specific surface area when using it in compositions of thermosetting resin, has
Preferable dispersiveness and mobility, to loading without too big limitation.
Embodiment 1
By brominated epoxy resin (45.69wt%), bromination linear phenolic resin (21.93wt%), epoxy resin
(2.29wt%), imidazoles accelerating agent (0.09wt%, the 2MI of Japanese four countries' chemical conversion production), low bulk inorganic filler
(30wt%) is dissolved in organic solvent, and mechanical agitation, emulsification are configured to the glue of 65wt%, are then impregnated with glass fabric, pass through
Prepreg (prepreg) is formed after crossing heat drying, copper foil is placed on two sides, and copper clad laminate is made in pressurized, heated.In the present embodiment
Low bulk inorganic filler chemical composition used is Li2O-Al2O3-3SiO2, measure, evaluation result is shown in table 1.
Embodiment 2
By brominated epoxy resin (39.16wt%), bromination linear phenolic resin (18.80wt%), epoxy resin
(1.96wt%), imidazoles accelerating agent (0.08wt%, the 2MI of Japanese four countries' chemical conversion production), low bulk inorganic filler
(40wt%) is dissolved in organic solvent, and mechanical agitation, emulsification are configured to the glue of 65wt%, are then impregnated with glass fabric, pass through
Prepreg (prepreg) is formed after crossing heat drying, copper foil is placed on two sides, and copper clad laminate is made in pressurized, heated.In the present embodiment
Low bulk inorganic filler chemical composition used is Li2O-Al2O3-3SiO2.It measures, evaluation result is shown in table 1.
Embodiment 3
By brominated epoxy resin (32.64wt%), bromination linear phenolic resin (15.66wt%), epoxy resin
(1.63wt%), imidazoles accelerating agent (0.07wt%, the 2MI of Japanese four countries' chemical conversion production), low bulk inorganic filler
(50wt%) is dissolved in organic solvent, and mechanical agitation, emulsification are configured to the glue of 65wt%, are then impregnated with glass fabric, pass through
Prepreg (prepreg) is formed after crossing heat drying, copper foil is placed on two sides, and copper clad laminate is made in pressurized, heated.In the present embodiment
Low bulk inorganic filler chemical composition used is Li2O-Al2O3-3SiO2.It measures, evaluation result is shown in table 1.
Embodiment 4
By brominated epoxy resin (26.11wt%), bromination linear phenolic resin (12.53wt%), epoxy resin
(1.31wt%), imidazoles accelerating agent (0.05wt%, the 2MI of Japanese four countries' chemical conversion production), low bulk inorganic filler
(60wt%) is dissolved in organic solvent, and mechanical agitation, emulsification are configured to the glue of 65wt%, are then impregnated with glass fabric, pass through
Prepreg (prepreg) is formed after crossing heat drying, copper foil is placed on two sides, and copper clad laminate is made in pressurized, heated.In the present embodiment
Low bulk inorganic filler chemical composition used is Li2O-Al2O3-3SiO2.It measures, evaluation result is shown in table 1.
Embodiment 5
By brominated epoxy resin (19.58wt%), bromination linear phenolic resin (9.40wt%), epoxy resin
(0.98wt%), imidazoles accelerating agent (0.04wt%, the 2MI of Japanese four countries' chemical conversion production), low bulk inorganic filler
(70wt%) is dissolved in organic solvent, and mechanical agitation, emulsification are configured to the glue of 65wt%, are then impregnated with glass fabric, pass through
Prepreg (prepreg) is formed after crossing heat drying, copper foil is placed on two sides, and copper clad laminate is made in pressurized, heated.In the present embodiment
Low bulk inorganic filler chemical composition used is Li2O-Al2O3-3SiO2.It measures, evaluation result is shown in table 1.
Embodiment 6
By brominated epoxy resin (32.64wt%), bromination linear phenolic resin (15.66wt%), epoxy resin
(1.63wt%), imidazoles accelerating agent (0.07wt%, the 2MI of Japanese four countries' chemical conversion production), low bulk inorganic filler
(50wt%) is dissolved in organic solvent, and mechanical agitation, emulsification are configured to the glue of 65wt%, are then impregnated with glass fabric, pass through
Prepreg (prepreg) is formed after crossing heat drying, copper foil is placed on two sides, and copper clad laminate is made in pressurized, heated.In the present embodiment
Low bulk inorganic filler chemical composition used is Li2O-Al2O3-2.5SiO2.It measures, evaluation result is shown in table 1.
Embodiment 7
By brominated epoxy resin (32.64wt%), bromination linear phenolic resin (15.66wt%), epoxy resin
(1.63wt%), imidazoles accelerating agent (0.07wt%, the 2MI of Japanese four countries' chemical conversion production), low bulk inorganic filler
(50wt%) is dissolved in organic solvent, and mechanical agitation, emulsification are configured to the glue of 65wt%, are then impregnated with glass fabric, pass through
Prepreg (prepreg) is formed after crossing heat drying, copper foil is placed on two sides, and copper clad laminate is made in pressurized, heated.In the present embodiment
Low bulk inorganic filler chemical composition used is Li2O-Al2O3-8SiO2.It measures, evaluation result is shown in table 1.
Embodiment 8
Brominated epoxy resin (26.45wt%), cyanate (22wt%), epoxy resin (1.50wt%), imidazoles are promoted
It is dissolved in into agent (0.05wt%, the 2MI of Japanese four countries' chemical conversion production), low bulk inorganic filler (50wt%) in organic solvent, machine
Tool stirring, emulsification are configured to the glue of 65wt%, are then impregnated with glass fabric, prepreg is formed after heat drying
(prepreg), copper foil is placed on two sides, and copper clad laminate is made in pressurized, heated.Low bulk inorganic filler chemistry used in the present embodiment
It forms as Li2O-Al2O3-3SiO2.It measures, evaluation result is shown in table 1.
Comparative example 1
By brominated epoxy resin (45.69wt%), bromination linear phenolic resin (21.93wt%), epoxy resin
(2.29wt%), imidazoles accelerating agent (0.09wt%, the 2MI of Japanese four countries chemical conversion production), silicon powder (30wt%) dissolves in has
In solvent, mechanical agitation, emulsification are configured to the glue of 65wt%, are then impregnated with glass fabric, the shape after heat drying
Into prepreg (prepreg), copper foil is placed on two sides, and copper clad laminate is made in pressurized, heated.It measures, evaluation result is shown in table 1.
Comparative example 2
By brominated epoxy resin (32.64wt%), bromination linear phenolic resin (15.66wt%), epoxy resin
(1.63wt%), imidazoles accelerating agent (0.07wt%, the 2MI of Japanese four countries chemical conversion production), silicon powder (50wt%) dissolves in has
In solvent, mechanical agitation, emulsification are configured to the glue of 65wt%, are then impregnated with glass fabric, the shape after heat drying
Into prepreg (prepreg), copper foil is placed on two sides, and copper clad laminate is made in pressurized, heated.It measures, evaluation result is shown in table 1.
Comparative example 3
By brominated epoxy resin (32.64wt%), bromination linear phenolic resin (15.66wt%), epoxy resin
(1.63wt%), imidazoles accelerating agent (0.07wt%, the 2MI of Japanese four countries' chemical conversion production), low bulk inorganic filler
(50wt%) is dissolved in organic solvent, and mechanical agitation, emulsification are configured to the glue of 65wt%, are then impregnated with glass fabric, pass through
Prepreg (prepreg) is formed after crossing heat drying, copper foil is placed on two sides, and copper clad laminate is made in pressurized, heated.In the present embodiment
Low bulk inorganic filler chemical composition used is Li2O-Al2O3-2.1SiO2.It measures, evaluation result is shown in table 1.
Comparative example 4
By brominated epoxy resin (32.64wt%), bromination linear phenolic resin (15.66wt%), epoxy resin
(1.63wt%), imidazoles accelerating agent (0.07wt%, the 2MI of Japanese four countries' chemical conversion production), low bulk inorganic filler
(50wt%) is dissolved in organic solvent, and mechanical agitation, emulsification are configured to the glue of 65wt%, are then impregnated with glass fabric, pass through
Prepreg (prepreg) is formed after crossing heat drying, copper foil is placed on two sides, and copper clad laminate is made in pressurized, heated.In the present embodiment
Low bulk inorganic filler chemical composition used is Li2O-Al2O3-10SiO2.It measures, evaluation result is shown in table 1.
Comparative example 5
By brominated epoxy resin (52.22wt%), bromination linear phenolic resin (25.07wt%), epoxy resin
(2.61wt%), imidazoles accelerating agent (0.10wt%, the 2MI of Japanese four countries' chemical conversion production), low bulk inorganic filler
(20wt%) is dissolved in organic solvent, and mechanical agitation, emulsification are configured to the glue of 65wt%, are then impregnated with glass fabric, pass through
Prepreg (prepreg) is formed after crossing heat drying, copper foil is placed on two sides, and copper clad laminate is made in pressurized, heated.In the present embodiment
Low bulk inorganic filler chemical composition used is Li2O-Al2O3-3SiO2.It measures, evaluation result is shown in table 1.
Comparative example 6
By brominated epoxy resin (13.05wt%), bromination linear phenolic resin (6.27wt%), epoxy resin
(0.65wt%), imidazoles accelerating agent (0.03wt%, the 2MI of Japanese four countries' chemical conversion production), low bulk inorganic filler
(80wt%) is dissolved in organic solvent, and mechanical agitation, emulsification are configured to the glue of 65wt%, are then impregnated with glass fabric, pass through
Prepreg (prepreg) is formed after crossing heat drying, copper foil is placed on two sides, and copper clad laminate is made in pressurized, heated.In the present embodiment
Low bulk inorganic filler chemical composition used is Li2O-Al2O3-3SiO2.It measures, evaluation result is shown in table 1.
Comparative example 7
Brominated epoxy resin (26.45wt%), cyanate (22wt%), epoxy resin (1.50wt%), imidazoles are promoted
It is dissolved in into agent (0.05wt%, the 2MI of Japanese four countries' chemical conversion production), low bulk inorganic filler (50wt%) in organic solvent, machine
Tool stirring, emulsification are configured to the glue of 65wt%, are then impregnated with glass fabric, prepreg is formed after heat drying
(prepreg), copper foil is placed on two sides, and copper clad laminate is made in pressurized, heated.Low bulk inorganic filler chemistry used in the present embodiment
It forms as Li2O-Al2O3-10SiO2.It measures, evaluation result is shown in table 1.
Using obtained copper clad laminate, with method described below, to coefficient of thermal expansion, breakdown voltage, peel strength
Evaluation, the results are shown in Table 1.
The measure of coefficient of thermal expansion
After copper foil using etching solution removal copper-clad laminated board, the big little makings test film of 5mm × 5mm square is cut into.Make
With TMA experimental rigs with 10 DEG C/min of heating rate, measuring Z-direction of the test film at 30 DEG C~260 DEG C, (glass cloth hangs down
Nogata to) average linear thermal expansion ratio.Coefficient of thermal expansion is smaller, and effect is better.
The measure of breakdown voltage
After copper foil using etching solution removal copper-clad laminated board, the sample of 76mm × 50mm sizes is cut into, along long side center
Line and short side central spot bore the circular hole of two a diameter of 4.8mm, and two pitchs of holes are 25 ± 0.25mm.Sample is at 50 ± 2 DEG C
48+2/-0h is handled in distilled water, sample is then immersed into 0.5-4h in room temperature distilled water, in the situation that water content is basically unchanged
Under sample is made to reach equalized temperature.It is boosted and tested with the rate of 500v/s using high voltage testing device, observe sample, until breakdown,
Voltage during record breakdown.
The measure of peel strength
Plate is cut into the test film of 10mm × 100mm, the copper foil on test film two sides, except centre retains 3mm × 100mm copper
Outside paper tinsel, remaining copper foil is removed with etching solution.The suitable length from copper foil is shelled in one end of sample, the copper chaff fixture that will have been shelled
It clamps, using tensile testing machine, makes pulling force vertical with copper-clad surface, stripping 50mm is continuously drawn with the speed of 50mm/min, draws stripping process
Middle lowest pull value is peel strength.
Table 1
Embodiment 1-5 can be seen that plate CTE and raise and reduce with low bulk inorganic filler content from table 1, low at this
When intumescent inorganic filer content is 50~70%, it is maximum to reduce amplitude.When the low bulk is inorganic it can be seen from comparative example 5-6
When filer content is less than 30%, plate CTE reductions are not notable, and when content is higher than 70%, the addition of filler is substantially reduced plate
Peel strength.As the chemical composition xLi of low bulk inorganic filler it can be seen from embodiment 6-7 and comparative example 3-42O-
yAl2O3-zSiO2In, when Z is less than 2.5, plate insulating properties is substantially reduced, when Z is more than 8, plate CTE reducing effect unobvious.By
Embodiment 3 and embodiment 6-7 can be seen that when z is in the range of 3~5, and plate CTE reducing effects are most notable.
The above is only presently preferred embodiments of the present invention, not the content of the composition of the present invention is imposed any restrictions,
For those of ordinary skill in the art, other various phases can be made with technique according to the invention scheme and technical concept
The change and deformation answered, every technical spirit according to the invention or composition composition or content are appointed to what above example was made
What subtle modifications, equivalent variations and modifications, belongs in the range of technical solution of the present invention.
Applicant states that the present invention illustrates the method detailed of the present invention, but not office of the invention by above-described embodiment
It is limited to above-mentioned method detailed, that is, does not mean that the present invention has to rely on above-mentioned method detailed and could implement.Technical field
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention
Addition, selection of concrete mode etc., all fall within protection scope of the present invention and the open scope.
Claims (16)
1. a kind of compositions of thermosetting resin accounts for the mass percent of compositions of thermosetting resin by thermosetting property tree by each component
Fat, curing agent, 0~10wt% and the low bulk inorganic filler composition not including 0 curing accelerator and 30~70wt%, it is described
Low bulk inorganic filler is represented by following chemical formula：
xLi2O-yAl2O3-zSiO2
Wherein, x, y and z independently represent mixing molar ratio, and x and y are independently each that 0.9~1.1, z is 2.5~8；
The low bulk inorganic filler is spherical or oval particle, and average grain diameter is 0.1~5.0 μm.
2. compositions of thermosetting resin as described in claim 1, which is characterized in that z is 3~5.
3. compositions of thermosetting resin as described in claim 1, which is characterized in that the low bulk inorganic filler content is heat
50~70wt% of thermosetting resin composition gross mass.
4. compositions of thermosetting resin as described in claim 1, which is characterized in that the average grain diameter is 0.3~1.0 μm.
5. compositions of thermosetting resin as described in claim 1, which is characterized in that the quality of the thermosetting resin accounts for thermosetting
20~70wt% of property resin combination gross mass.
6. compositions of thermosetting resin as described in claim 1, which is characterized in that the thermosetting resin for epoxy resin,
In phenolic resin, benzoxazine colophony or liquid crystalline resin any one or at least two mixture.
7. compositions of thermosetting resin as described in claim 1, which is characterized in that the quality of the curing agent accounts for thermosetting property tree
1~30wt% of oil/fat composition gross mass.
8. compositions of thermosetting resin as described in claim 1, which is characterized in that the curing agent for phenol aldehyde type curing agent,
In amine based curative or anhydride group curing agent any one or at least two combination.
9. compositions of thermosetting resin as described in claim 1, which is characterized in that the curing agent is dicy-curing agent.
10. compositions of thermosetting resin as described in claim 1, which is characterized in that the curing accelerator is consolidated for imidazole radicals
Change accelerating agent or/and amido curing accelerator.
11. compositions of thermosetting resin as described in claim 1, which is characterized in that the compositions of thermosetting resin also wraps
Include dispersant.
12. compositions of thermosetting resin as claimed in claim 11, which is characterized in that the dispersant for silane coupling agent,
In phosphoric acid ester inorganic agent or organic silicon inorganic agent any one or at least two mixture.
13. the compositions of thermosetting resin as described in one of claim 1-12, which is characterized in that the thermosetting resin combination
Object further includes other inorganic fillers, including silica, boehmite, talcum, mica, kaolin, aluminium hydroxide, hydroxide
Magnesium, zinc borate, zinc stannate, zinc oxide, titanium oxide, aluminium oxide, aluminium nitride, boron nitride, calcium carbonate, barium sulfate, barium titanate, boric acid
In aluminium, potassium titanate, E glass dust, S glass dust, D glass dust, NE glass dust or hollow glass micro mist any one or at least
Two kinds of mixture.
14. a kind of prepreg, including reinforcing material and by after impregnation drying it is attached thereto as claim 1-13 it
Compositions of thermosetting resin described in one.
15. a kind of laminate, the laminate contains an at least prepreg as claimed in claim 14.
16. a kind of printed circuit board, the printed circuit board contains an at least prepreg as claimed in claim 14.
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| CN201510953042.1A CN105504681B (en) | 2015-12-17 | 2015-12-17 | A kind of compositions of thermosetting resin and the prepreg, laminate and printed circuit board containing it |
| PCT/CN2016/099129 WO2017101539A1 (en) | 2015-12-17 | 2016-09-14 | Thermosetting resin composition and prepreg containing same, and laminated plate and printed circuit board |
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| CN201510953042.1A CN105504681B (en) | 2015-12-17 | 2015-12-17 | A kind of compositions of thermosetting resin and the prepreg, laminate and printed circuit board containing it |
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| CN106867251B (en) * | 2017-01-24 | 2019-03-12 | 杭州铠恒新材料有限公司 | A kind of prepreg and the method that honeycomb core is prepared by it |
| JP7279319B2 (en) * | 2017-09-04 | 2023-05-23 | 味の素株式会社 | resin composition |
| CN111826574B (en) * | 2020-07-21 | 2021-10-29 | 黑龙江省科学院石油化学研究院 | Low-expansion phosphate powder for ultra-stable metal matrix composite and preparation method thereof |
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| JPH0641347A (en) * | 1992-01-30 | 1994-02-15 | Kyocera Corp | Filler for electronic part sealer |
| KR101987280B1 (en) * | 2012-12-20 | 2019-06-10 | 삼성전기주식회사 | Resin composition for printed circuit board, insulating film, prepreg and printed circuit board |
| CN105504681B (en) * | 2015-12-17 | 2018-05-29 | 广东生益科技股份有限公司 | A kind of compositions of thermosetting resin and the prepreg, laminate and printed circuit board containing it |
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