CN108102125A - prepreg, laminate and printed circuit board - Google Patents
prepreg, laminate and printed circuit board Download PDFInfo
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- CN108102125A CN108102125A CN201711439413.XA CN201711439413A CN108102125A CN 108102125 A CN108102125 A CN 108102125A CN 201711439413 A CN201711439413 A CN 201711439413A CN 108102125 A CN108102125 A CN 108102125A
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- molybdenum
- compound
- tungsten
- prepreg
- group vib
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
-
- 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
- B32B17/067—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 of fibres or filaments
-
- 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
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
-
- 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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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating 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
- 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
- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
The disclosure provides prepreg and laminate and printed circuit board comprising prepreg.Prepreg includes reinforcing material and passes through compositions of thermosetting resin attached thereto after impregnation drying.The reinforcing material is handled by group vib compound cladding.Group vib compound can be selected from molybdenum compound, tungsten compound or its mixture.By the way that group vib compound is coated in reinforcing material, both the scattered and settlement issues of group vib compound can effectively have been solved, it can be evenly distributed in prepreg, while also greatly increase the contact area of drill and group vib compound, effectively reduce the abrasion of drill and be obviously improved drilling quality.
Description
Technical field
This disclosure relates to a kind of prepreg.Specifically, this disclosure relates to a kind of prepreg and include the prepreg
Laminate and printed circuit board.
Background technology
With rapid development of the electronic product in terms of miniaturization, multifunction, high performance and high reliability, printing electricity
Road plate starts to grow rapidly towards high-precision, high density, high-performance, microporous, slimming and multiple stratification direction, application range
It is more and more extensive, it is fast from departments such as industrial giant brain, communication instrument, electric measurement, national defence and Aeronautics and Astronautics
Speed enters civil electric appliance and its Related product.And basis material largely determines the performance of printed circuit board, because
There is an urgent need to develop the basis materials of a new generation for this.Basis material as future new era must possess high heat resistance, low
Coefficient of thermal expansion and excellent chemical stability and mechanical performance.
In order to reduce the coefficient of thermal expansion of laminate, it will usually select the resin of low thermal coefficient of expansion or improve inorganic filler
Content.But low thermal coefficient of expansion resin structure is more special, cost is higher；And by the way of inorganic filler content is improved
The coefficient of thermal expansion of compound can not only be effectively reduced, and cost can also substantially reduce.But high fillingization resin can be apparent
Reduce the drill processability and interlayer adhesion of laminate.Therefore someone uses and talcum is added in compositions of thermosetting resin
Block fillers are waited as lubricant, improvement processability, but effect unobvious, and the addition of these block fillers is further
It is degrading interlayer adhesion.In addition, in order to improve drill processability, metal molybdenum compound is added, such as
The addition metals such as zinc molybdate molybdenum compound in compositions of thermosetting resin is mentioned in CN102656234A improves processability, and should
It is recommended in patent and is carried on the molybdenum compound particle that talcum etc. forms, there are the interlayer adhesions of laminate to be substantially reduced for this
The problem of, and dispersiveness of such molybdenum compound in resin is poor, and density is also larger, easily settles, and can not be expired
The result of meaning.CN103554844A is mentioned can reduce the hot swollen of laminate in compositions of thermosetting resin comprising tungsten compound
Swollen coefficient, and can effectively stop UV light and reduce light transmission.But the tungsten compound in compositions of thermosetting resin
Distributing homogeneity in the presence of scattered and settlement issues and on reinforcing material and obtained reinforcing material thickness evenness are inadequate
Problem, and need further to reduce the drill wear rate of the laminate thus prepared.
The content of the invention
The first purpose of the disclosure is to provide a kind of prepreg and laminate and printing electricity comprising the prepreg
Road plate effectively solves the scattered and settlement issues of group vib compound and the distributing homogeneity on reinforcing material and obtains
The problem of reinforcing material thickness evenness is inadequate, and further reduce the drill wear rate of the laminate thus prepared.
In one aspect, the disclosure provides a kind of prepreg, and the prepreg includes reinforcing material and passes through impregnation drying
Compositions of thermosetting resin attached thereto afterwards, wherein the reinforcing material is handled by group vib compound cladding.
Optionally, the group vib compound is selected from molybdenum compound, tungsten compound or its mixture.
Preferably, the group vib compound is liquid or solid-state.
Optionally, the molybdenum compound is selected from：Molybdenum dialkyl-dithiophosphate, nitrogenous molybdenum dialkyl-dithiophosphate, two
Alkyl molybdenum dithiocarbamate, molybdenum amine complex, molybdenum naphthenate, alkyl salicylate molybdenum, thiophene cyclopentadienyl molybdenum, dimercaptothiazole molybdenum, alkane
Any one in base amine molybdenum, organic molybdates esters or molybdenum caprylate or the arbitrary mixture of two or more.
Optionally, the molybdenum compound is selected from：Molybdic acid, molybdate, molybdenum oxide, the heteropoly acid of molybdenum and its sodium salt, sylvite and
Ammonium salt, the multi-acid salt of molybdenum, molybdenum blue, the sulfide of molybdenum, the selenides of molybdenum, the tellurides of molybdenum, the halide of molybdenum, molybdenum alloy or two silicon
Change any one in molybdenum or the arbitrary mixture of two or more.
Optionally, the molybdenum compound is selected from：Ammonium molybdate, sodium molybdate, zinc molybdate, calcium molybdate, magnesium molybdate, molybdenum oxide or sulphur
Change any one in molybdenum or the arbitrary mixture of two or more.
Optionally, the tungsten compound is selected from：Tungsten disulfide, tetrathio wolframic acid amine, tungsten oxybromide, tungsten tetrachloride, four
Tungsten bromide, Zinc Tungstate, artificial schellite, magnesium tungstate, ammonium tungstate, tungsten selenide, tungsten oxide, dioctyl aminodithioformic acid tungsten, two sulphur
Phenol closes tungsten, 3,4- dimercapto toluenes close tungsten, amido diisopropyl disulfide for phosphoric acid tungsten, organic W-Mo complex, dithiocarbamates
In formic acid tungsten compound, aromatic hydrocarbons tungsten compound or alkane (virtue) base amido D2EHDTPA tungsten any one or at least two it is mixed
Close object.
Optionally, the tungsten compound is selected from tungsten disulfide, tetrathio wolframic acid amine, tungsten oxybromide, tungsten tetrachloride, tetrabromo
Change in tungsten or alkane (virtue) base amido D2EHDTPA tungsten any one or at least two mixture.
Optionally, the group vib compound is selected from the mixture of molybdenum compound and tungsten compound, wherein in molybdenum compound and
In the mixture of tungsten compound, the mixing ratio of molybdenum compound and tungsten compound by weight is in the scope of about 1: 100 to about 100: 1
It is interior.
Optionally, the group vib compound is solid-state, and average grain diameter is 0.01 to 1 μm.
Optionally, the group vib compound is in the reinforcing material by group vib compound cladding processing
Content be 0.01 to 5 weight %.
The reinforcing material can be inorganic or organic material.The example of inorganic reinforcement can include glass fibre, carbon
The woven fabric or non-woven fabrics or paper of fiber, boron fibre, metal etc..The example of glass fabric or non-woven fabrics can include E-
Glass, Q type cloth, NE cloth, D types cloth, S types cloth, high silica cloth etc..The example of reinforcing material can include organic fiber such as polyester,
The woven fabric or non-woven fabrics or paper of the manufactures such as polyamine, polyacrylic acid, polyimides, aramid fiber, polytetrafluoroethylene (PTFE), syndiotactic polytyrene.
However reinforcing material is without being limited thereto, others can be used for the reinforcing material of resin tooth that can equally use in the disclosure.It is excellent
Selection of land, reinforcing material are glass-fiber-fabric.
On the other hand, the disclosure provides a kind of laminate, wherein the laminate contains at least one as described above
Prepreg.
In another aspect, the disclosure provides a kind of printed circuit board, wherein the printed circuit board contains at least one such as
The upper prepreg.
According to the disclosure, by the way that group vib compound is coated in reinforcing material, group vib compound both can be effectively solved
Scattered and settlement issues, can be evenly distributed in prepreg, while also greatly increase drill and group vib compound
Contact area effectively reduces the abrasion of drill and is obviously improved drilling quality.
Specific embodiment
Below in conjunction with the specific embodiment of the disclosure, the technical solution in the embodiment of the present disclosure is carried out clear, complete
Site preparation describes, it is clear that described embodiment and/or embodiment are only a part of embodiment of the disclosure and/or implementation
The embodiment and/or embodiment of example rather than whole.Based on the embodiment and/or embodiment in the disclosure, this field is general
The every other embodiment and/or every other implementation that logical technical staff is obtained without making creative work
Example belongs to the scope of disclosure protection.
In the disclosure, all numerical characteristics all refer within the error range of measurement, for example, the numerical value limited ±
Within 10% or within ± 5% or within ± 1%.
"comprising", " comprising " or " containing " described in the disclosure, it is intended that it can also have other groups in addition to the component
Part, these other components assign the prepreg different characteristics.In addition, the "comprising" described in the disclosure, " comprising " or
" containing " can also include " substantially by ... form ", and could alternatively be " for " or " by ... form ".
In the disclosure, if do not particularly pointed out, what amount, ratio etc. were by weight.
As described above, the disclosure can provide a kind of prepreg.The prepreg can include reinforcing material and pass through dipping
Compositions of thermosetting resin attached thereto after drying.Reinforcing material is handled by group vib compound cladding.
The example of reinforcing material can include glass-fiber-fabric.In the following description, glass-fiber-fabric reinforcing material and glass-fiber-fabric can
To be used interchangeably.
According to the disclosure embodiment, the group vib compound is selected from molybdenum compound, tungsten compound or its mixing
Object.According to another embodiment of the disclosure, the molybdenum compound can include inorganic molybdenum compounds and organic molybdenum.
According to another embodiment of the disclosure, the molybdenum compound is selected from：Molybdenum dialkyl-dithiophosphate, nitrogenous two
Alkyl dithiophosphoric acid molybdenum, molybdenum dialkyldithiocarbamacompositions, molybdenum amine complex, molybdenum naphthenate, alkyl salicylate molybdenum, thiophene cyclopentadienyl
Any one in molybdenum, dimercaptothiazole molybdenum, alkylamine molybdenum, molybdates esters, molybdenum caprylate or the arbitrary mixing of two or more
Object.
In the disclosure, alkyl can represent the alkyl with 1 to 12 carbon atom, for example, methyl, ethyl, n-propyl,
Isopropyl, normal-butyl, isobutyl group, tertiary butyl etc..Alkyl can also include cycloalkyl, such as cycloalkanes containing 3 to 8 carbon atoms
Base, such as cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, suberyl and cyclooctyl.Aromatic hydrocarbons can represent benzene,toluene,xylene and
Naphthalene.
The example of molybdenum dialkyl-dithiophosphate can include：Dimethyl disulfide is for molybdenum phosphate, diethyldithioposphoric acid
Molybdenum, dipropyl disulfide is for molybdenum phosphate, and dibutyl dithio molybdenum phosphate, diamyl disulfide is for molybdenum phosphate, dihexyl phosphordithiic acid
Molybdenum, diheptyl molybdenum dithiophosphate etc..
The example of nitrogenous molybdenum dialkyl-dithiophosphate can include：Nitrogenous dimethyl disulfide is for molybdenum phosphate, nitrogenous diethyl
Base molybdenum dithiophosphate, nitrogenous dipropyl disulfide is for molybdenum phosphate, nitrogenous dibutyl dithio molybdenum phosphate, nitrogenous diamyl disulfide generation
Molybdenum phosphate, nitrogenous dihexyl molybdenum dithiophosphate, nitrogenous diheptyl molybdenum dithiophosphate etc..
The example of molybdenum dialkyldithiocarbamacompositions can include：Dimethyl dithiocarbamic acid molybdenum, diethyl two
Thiocarbamic acid molybdenum, dipropyl disulfide is for carbamic acid molybdenum, and dibutyl dithiocaarbamate molybdenum, diamyl disulfide is for amino
Formic acid molybdenum, dihexyl molybdenum dithiocarbamate, diheptyl molybdenum dithiocarbamate etc..
The example of alkyl salicylate molybdenum can include：Cresotinic acid molybdenum, acetyl salicylic acid molybdenum, propyl salicylic acid molybdenum, fourth
Base salicylic acid molybdenum, amyl salicylic acid molybdenum, hexyl salicylic acid molybdenum, heptyl salicylic acid molybdenum etc..
The example of alkylamine molybdenum can include：Methyl amine molybdenum, ethylamine molybdenum, propyl amine molybdenum, butylamine molybdenum, amylamine molybdenum,
Hexyl amine molybdenum, heptyl amine molybdenum etc..
The example of organic molybdates esters can include：Organic molybdic acid methyl esters, organic-molybdenum acetoacetic ester, organic-molybdenum propyl propionate etc..
According to another embodiment of the disclosure, the molybdenum compound can be selected from：Molybdic acid, molybdate, molybdenum oxide, molybdenum
Heteropoly acid and multi-acid salt, molybdenum blue, the sulfide of molybdenum, the selenides of molybdenum, the tellurides of molybdenum, the halide of molybdenum, molybdenum alloy or two
Any one in molybdenum silicide or the arbitrary mixture of two or more.
The example of molybdate can include：Ammonium molybdate, sodium molybdate, zinc molybdate, calcium molybdate, magnesium molybdate etc..
The example of the heteropoly acid of molybdenum can include：H3[P(Mo3O10)4)]·nH2O、H45Si(Mo3O10)4.nH2O and its sodium
Salt, sylvite or ammonium salt etc..
The example of the multi-acid salt of molybdenum can include：Two molybdate (M2O.2MoO3), paramolybdate (3M2O.7MoO), five molybdenum
Hydrochlorate (M2O.5MoO3), octamolybdate (3M2O.8MoO3·3H2) and four molybdate (M O2O.4MoO) etc..
The example of molybdenum alloy can include：Mo-Au alloys, Mo-Ag alloys, Mo-Cu alloys, Mo-Al alloys, Mo-Ti are closed
Gold etc..
According to another embodiment of the disclosure, the molybdenum compound can be selected from：Ammonium molybdate, sodium molybdate, zinc molybdate,
Any one in calcium molybdate, magnesium molybdate, molybdenum oxide or molybdenum sulfide or the arbitrary mixture of two or more.
According to another embodiment of the disclosure, the tungsten compound is selected from：Tungsten disulfide, tetrathio wolframic acid amine, four
Bromine tungsten oxide, tungsten tetrachloride, tetrabormated tungsten, Zinc Tungstate, artificial schellite, magnesium tungstate, ammonium tungstate, tungsten selenide, tungsten oxide, dioctyl two
Thiocarbamic acid tungsten, dithiol close tungsten, 3,4- dimercapto toluenes close tungsten, amido diisopropyl disulfide is for phosphoric acid tungsten, two thio
In carbamic acid tungsten, alkane (virtue) base amido D2EHDTPA tungsten any one or at least two mixture.
The example of alkane (virtue) base amido D2EHDTPA tungsten can include：Methylamino D2EHDTPA tungsten, tolyl amido sulphur
For phosphoric acid tungsten etc..
According to another embodiment of the disclosure, the tungsten compound can be selected from tungsten disulfide, tetrathio wolframic acid amine,
In tungsten oxybromide, tungsten tetrachloride, tetrabormated tungsten or methylamino D2EHDTPA tungsten any one or at least two it is mixed
Close object.
According to another embodiment of the disclosure, molybdenum compound and the mixture of tungsten compound can be used.In molybdenum
In the mixture for closing object and tungsten compound, mixing ratio by weight can be excellent in the range of about 1: 100 to about 100: 1
Be selected in the range of about 1: 50 to about 50: 1, more preferably in the range of about 1: 20 to about 20: 1, even more preferably from about 1: 10 to
In the range of about 10: 1, even more preferably in the range of about 1: 5 to about 5: 1, and most preferably in the model in about 1: 2 to about 2: 1
In enclosing.
According to another embodiment of the disclosure, the average grain diameter of the inorganic VIB compounds is 0.01 to 1 μm, excellent
Elect 0.01 to 0.5 μm as.The quality of the inorganic VIB compounds is the increasing by group vib compound cladding processing
0.01 to 5%, preferably the 0.05 to 2% of the quality of strong material.If the dosage, which is greater than or equal to, passes through the group vib compound bag
The 0.01% of the reinforcing material Gu amount of processing is covered, effect becomes apparent.If less than or equal to by the group vib compound
The 5% of the reinforcing material of processing is coated, then can further improve the original overall performance of glass-fiber-fabric.The inorganic VIB
When the usage amount of compound is the 0.05 to 2% of the quality of the reinforcing material by group vib compound cladding processing,
The performance of group vib compound plays best, and the dispersing uniformity of inorganic VIB compounds is also optimal.
According to another embodiment of the disclosure, the average grain diameter of the group vib compound is about 0.01 μm to about 1 μ
M is preferably from about 0.01 μm to about 0.5 μm.By the way that inorganic VIB compounds average grain diameter is arranged in the scope, Ke Yijin
One step keeps the mobility and dispersing uniformity of inorganic VIB compounds well, and can be further reduced oversize grain
It is mixed into probability and inhibits to cause the undesirable generation of oversize grain.Here, average grain diameter refers to the total volume using particle as 100%
And when the accumulation number of degrees distribution curve based on grain size is obtained, 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.
According to another embodiment of the disclosure, the content of the group vib compound is to pass through the group vib chemical combination
About the 0.01% to about 5% of the gross mass of the reinforcing material of object cladding processing, preferably from about 0.05% to about 2%.Passing through will
The content of group vib compound is arranged in the scope, can further be embodied the effect of the disclosure, be further improved glass-fiber-fabric
Original overall performance so that group vib compound dispersing uniformity is more preferably.
Compositions of thermosetting resin can include thermosetting resin, curing agent, accelerating agent and solvent.
Thermosetting resin described in the disclosure is arbitrary a kind or at least 2 in the polymer of cross-linking formation net structure
Kind combination, it is preferred epoxy, phenolic resin, cyanate ester resin, polyamide, polyimide resin, polyether resin, poly-
Arbitrary a kind or at least two kinds of of combination in ester resin, hydrocarbon resin or organic siliconresin；And further preferred epoxy resin or
Phenolic resin.
The concrete example of the combination of the thermosetting resin can be the combination of epoxy resin and polyamide, polyimides
The combination of resin and hydrocarbon resin, the combination of cyanate ester resin, polyamide and polyether resin, cyanate ester resin, polyamide resin
Combination of fat, polyimide resin and epoxy resin etc..
Combination for epoxy resin and its with other resins, the curing agent can be phenolic resin, anhydride compound, work
In property ester type compound, dicyandiamide, diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiphenyl ether and maleimide
One or more kinds of mixtures；The curing accelerator is 2-methylimidazole, 2-ethyl-4-methylimidazole and 2-
Mixture more than one or both of methyl 4-phenyl imidazoles.
Combination for phenolic resin and its with other resins, the curing agent can be organic acid anhydride, organic amine, Louis
This acid, organic amide, glyoxaline compound, organic phosphine compound and its mixture mixed in any proportion.
Reactable polyphenylene oxide resin, polyamide for olefin resin, containing two or more unsaturated double-bonds
Resin and its with other resin combinations, the curing agent be selected from organic peroxide crosslinking agent, be preferably peroxidating diisopropyl
Benzene, benzoyl peroxide, di-tert-butyl peroxide, two carbon of diacetyl peroxide, peroxide tert pivalate ester and peroxidating
One or more in sour hexichol oxide ester.The accelerating agent is allylic organic compound, is preferably triallyl cyanogen urea
In acid esters, Triallyl isocyanurate, trimethylol-propane trimethacrylate and trimethylolpropane trimethacrylate
One or more.
For organic siliconresin, the accelerating agent is selected from organic platinum-like compounds.
The compositions of thermosetting resin can further include silane coupling agent or/and wetting dispersing agent.As these silane
Coupling agent, if be that typically in inorganic orderliness I be surface-treated used in silane coupling agent, there is no special
It limits.It as concrete example, can include, gamma-aminopropyl-triethoxy-silane, N- β-(aminoethyl)-γ-aminopropyl trimethoxy
The epoxy silanes systems such as the aminopropyl silanes such as silane system, γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-methacryloxypropyl third
The vinyl silanes such as base trimethoxy silane system, N- β-(N- vinyl benzene idols sulfonylaminoethyl)-γ-aminopropyl trimethoxy silicon
The anion silicons such as heptane hydrochloride salt methane series, phenyl silane system etc. can select a kind therein or at least two kinds of appropriately combined uses.
As long as in addition, the Ricinate that Ricinate uses in thermosetting resin composition, just there is no particular limitation.It can arrange
It is wet enumerating the Disperbyk-110 such as BYKChemie Japan, 111,180,161, BYK-W996, W9010, W903
Moisten dispersant.
The compositions of thermosetting resin can also contain various additives, as concrete example, can enumerate fire retardant, resist
Oxygen agent, heat stabilizer, antistatic agent, ultra-violet absorber, pigment, colorant or lubricant etc..These various additives can be with
It is used alone, two kinds or two or more can also be used in mixed way.
It, can be by well known method as described in cooperation, stirring, mixing as the preparation method of disclosure resin combination
Thermosetting resin, inorganic filler, porous molybdenum compound, curing agent and accelerating agent and various additives, to prepare.
It as the solvent in the disclosure, is not particularly limited, as concrete example, the alcohol such as methanol, ethyl alcohol, butanol can be enumerated
Class, the ethers such as ethyl cellosolve, butyl cellosolve, ethylene glycol-methyl ether, carbitol, butyl carbitol, acetone, butanone, methyl second
The ketones such as base ketone, hexone, cyclohexanone, toluene, dimethylbenzene, mesitylene etc. are aromatic hydrocarbon, ethyoxyl second
The esters such as yl acetate, ethyl acetate, n,N-Dimethylformamide, n,N-dimethylacetamide, n-methyl-2-pyrrolidone etc.
Nitrogen-containing solvent.Above-mentioned solvent can be used alone, can also two kinds or it is two or more be used in mixed way, preferably toluene,
The aromatic hydrocarbon solvents such as dimethylbenzene, mesitylene and acetone, butanone, methyl ethyl ketone, hexone, cyclohexanone
Ketones flux is waited to be used in mixed way.Usage amount those skilled in the art of the solvent can select according to the experience of oneself, make
Obtained resin adhesive liquid reaches the viscosity being adapted in use to.
According to the disclosure, reinforcing material is handled by group vib compound cladding.Coating the example of the method for processing can wrap
Include spray method and dipping method.When using solid group VIB compound, spray method may be employed.Using liquid group vib
During compound, dipping method may be employed.
Spray method can include：First, appropriate group vib compound is dispersed in solvent；Then in room temperature with
Spray pattern even application is in reinforcing material surface；And after group vib compound solution sprays, it is warming up to 120-160
To get to the reinforcing material by group vib compound cladding when DEG C dry 4-6 is small.It can be disperseed using sand mill.It is preferred that
It is sprayed using nozzle on ground so that the drop of sprinkling is less than 0.2 μm.
Dipping method can include：First, group vib compound is diluted using solvent, then by reinforcing material in 60-
100 DEG C of homogeneous impregnations, be warming up to 120-160 DEG C of dry 2-4 it is small when to get to the reinforcing material by group vib compound cladding.
Disperseed by mechanical agitation, emulsification or ball milling, compositions of thermosetting resin is configured to glue, then using the glue
Glass-fiber-fabric of the liquid infiltration through inorganic filler cladding processing, through dry prepreg.By the prepreg and metal foil such as copper foil true
Hot pressing can prepare laminate in air compressor machine.
Specifically, by by group vib compound cladding processing reinforcing material prepare laminate method can include with
Lower step：
(1) glue：Solvent is added in proportion container, epoxy resin, curing agent solution and rush are separately added under stirring
Into the solution of agent；After stirring, inorganic filler is added in, continues to stir, obtains glue,
(2) impregnate：The reinforcing material of group vib compound cladding processing is immersed in glue.
(3) it is impregnated with：By the reinforcing material of dipped glue by vertical or horizontal type containing dipping machine, by control squeeze wheel speed,
Prepreg is made in the conditions such as linear speed, wind-warm syndrome and furnace temperature.
Specifically using vertical demonstration example containing dipping machine as：Squeeze wheel speed：- 1.3 to -2.5 ± 0.1M/min；Main line speed：4 to 18m/
min；Wind-warm syndrome：120 to 170 DEG C；Furnace temperature：130 to 220 DEG C.
(4) suppress：After the prepreg reduced and metal foil such as copper foil are combined, it is put into vacuum hotpressing machine, by one
Simultaneously metal-coated laminated board such as copper clad laminate is finally made in fixed temperature, time and pressure, and specific demonstration example is：
Temperature formula：
130℃/30min+155℃/30min+190℃/90min+220℃/60min：
Pressure formula：
25kgf·cm-2/30min+50kgf·cm-2/30min+90kgf·cm-2/120min+30kgf·cm-2/
90min；
Vacuum formula：
30mmHg/130min+800mmHg/130min。
By above procedure, prepreg is laminated between metal foil such as copper foil, laminate is can be prepared by after hot pressing
(that is, copper clad laminate).
The disclosure can also provide a kind of laminate and a kind of printed circuit board.
Laminate can contain at least one glass fiber fabric base prepreg as described in any one above.
Printed circuit board can contain at least one glass fiber fabric base prepreg as described in any one above.
According to the disclosure, by the way that group vib compound is coated in reinforcing material, group vib compound both can be effectively solved
Scattered and settlement issues, can be evenly distributed in prepreg, while also greatly increase drill and group vib compound
Contact area effectively reduces the abrasion of drill and is obviously improved drilling quality.
Embodiment
The technical solution of the disclosure is further illustrated below by specific embodiment.
Each code name and its composition used are as follows in embodiment and comparative example：
Epoxy resin A：Hexion Specialty Chemicals company (former U.S.'s Bowden chemical company and German Berlet company) production
Novolac epoxy resin, trade name EPR627-MEK80, epoxide equivalent is between 160 to 250g/eq.
Epoxy resin B：The epoxy resin of Dow Chemical company production, trade name DER-592A80, epoxy are worked as
Amount is between 300 to 460g/eq.
Epoxy resin C：The High Bromine epoxy Resin of Japanese ink chemical company production, trade name EPICLON153, ring
Oxygen equivalent is between 350 to 450g/eq.
Curing agent：The phenolic resin curing agent of Hexion Specialty Chemicals company production, trade name PHL6635M65.
Accelerating agent：The 2MI (methylimidazole) of Japanese four countries' chemical conversion company production.
Inorganic filler E：Fused silica, 0.5 micron of average grain diameter.
Auxiliary agent：W903, Bi Ke chemistry.
Molybdenum dialkyl-dithiophosphate, Pacific Ocean joint (Beijing) petrochemical industry, trade name POUPC1001B.
Zinc molybdate, Kemgard.
Molybdenum disulfide, Changsha Hua Jing powder body materials Science and Technology Ltd..
Tungsten disulfide, Changsha Hua Jing powder body materials Science and Technology Ltd..
Dioctyl aminodithioformic acid tungsten, Shengyi Science and Technology Co., Ltd, Guangdong.
Ammonium octamolybdate, Guangzhou Xi Jia Chemical Co., Ltd.s.
Embodiment 1-17
The reinforcing material of embodiment 1 and 12 is coated using dipping method group vib compound；And embodiment 2-11 and 13-
17 reinforcing material is coated using spray method group vib compound.Used by embodiment 1-17 group vib compound and its
The grain size for the group vib compound that content and embodiment 2-11 and 13-17 in the glass-fiber-fabric of cladding use is listed in Table 1 below.
Spray method：First, group vib compound is dispersed in water to obtain dispersion liquid using sand mill so that group vib
It closes object and accounts for the 20% of dispersion liquid weight；Then using nozzle in room temperature with spray pattern even application in reinforcing material surface, spray
The drop spilt is less than 0.2 μm；And group vib compound solution spray after, be warming up to 140 DEG C of dryings 5 it is small when to get to
The reinforcing material coated by group vib compound.
Dipping method：First, group vib compound is diluted using acetone so that group vib compound and the weight ratio of acetone
For 25%；Then by reinforcing material in 80 DEG C of homogeneous impregnations, be warming up to 140 DEG C of dryings 3 it is small when to get to passing through group vib chemical combination
The reinforcing material of object cladding.
As the compositions of thermosetting resin used in the reinforcing material by the cladding processing of group vib compound prepares laminate
Solid constituent formula composition refers to Tables 1 and 2.It is clear that the thermosetting epoxy resin that uses of manufacture laminate is modulated into using butanone
Paint, wherein solid constituent accounts for 67%.
The copper clad laminate of embodiment 1-17 is prepared according to following preparation process：
(1) glue：Solvent is added in proportion container, epoxy resin, curing agent solution and rush are separately added under stirring
Into the solution of agent；Stir 2 it is small when after, add in inorganic filler, continue stirring 6 it is small when after, obtain glue.
(2) impregnate：The reinforcing material of group vib compound cladding processing is immersed in glue.
(3) it is impregnated with：The reinforcing material of dipped glue is squeezed into wheel speed, linear speed, wind-warm syndrome containing dipping machine by vertical by controlling
And the conditions such as furnace temperature, prepreg is made.The vertical condition containing dipping machine is：Squeeze wheel speed：-1.8±0.1M/min；Main line speed：
10m/min；Wind-warm syndrome：150℃；Furnace temperature：180℃.
(3) suppress：After the prepreg reduced and copper foil are combined, it is put into vacuum hotpressing machine, by certain temperature,
Simultaneously copper clad laminate is finally made in time and pressure, and actual conditions is：
Temperature formula：
130℃/30min+155℃/30min+190℃/90min+220℃/60min；
Pressure formula：
25kgf·cm-2/30min+50kgf·cm-2/30min+90kgf·cm-2/120min+30kgf·cm-2/
90min；
Vacuum formula：
30mmHg/130min+800mmHg/130min。
By above procedure, 8 thickness is used to be laminated on for the prepreg of 0.2mm between the copper foil of 35 μ m-thicks, after hot pressing
It can be prepared by the laminate of 1.6mm thickness.After obtaining copper clad laminate, plate property is tested, table 2 show plate property
Comparison.
Comparative example 1
The reinforcing material of comparative example 1 is handled without group vib compound cladding.1 solid constituent formula composition of comparative example is detailed
1 is shown in Table, and the thermosetting epoxy resin glue for manufacturing laminate and using is modulated into using butanone, wherein solid constituent accounts for
67%.In addition to above-mentioned difference, the preparation method of comparative example 1 is such as
Embodiment 1-17.
Comparative example 2
The reinforcing material of comparative example 2 is handled without group vib compound cladding.It is combined to the thermosetting resin of comparative example 2
Zinc molybdate is directly added in object, solid constituent formula composition refers to table 2, and is modulated into manufacture laminate using butanone and uses
Thermosetting epoxy resin glue, wherein solid constituent accounts for 67%.In addition to above-mentioned difference, the preparation method of comparative example 2 is such as
Embodiment 1-17.
Comparative example 3
The reinforcing material of comparative example 3 is handled without group vib compound cladding.It is combined to the thermosetting resin of comparative example 3
Object directly adds tungsten disulfide, and solid constituent formula composition refers to table 2, and is modulated into manufacture laminate using butanone and uses
Thermosetting epoxy resin glue, wherein solid constituent accounts for 67%.In addition to above-mentioned difference, the preparation method of comparative example 3 is such as
Embodiment 1-17.
Performance test：
1st, the evaluation of drill processability：
By the copper-clad plate of making, two piece one is folded, use the new knives of 0.3mm drilling machine (HITACHINDR-1V 212E) with
The rotating speed of 155krmp carries out Drilling operation, and every piece of twist drill 6 is every that knife is bored 6000 holes new knife.By the drill of different hole numbers
Drill bit knife edge part is observed using microscope verifier (herding moral PM-2824 in Taiwan), measures cutting edge tip abrasion back amount to survey
The distance for measuring vertical line and central axes intersection point and abrasion top edge is drill size, and the wear rate of drill is calculated by the following formula
To evaluate drilling effect.
Wear rate %=drilling back edges and central axes distance/drilling leading edge and central axes distance × 100%
2nd, the evaluation of group vib uniformity of distribution：
Reinforcing material after processing is cut into the size of 5mm square, note type is carried out with note type resin, is placed in conducting resinl
Upper, metal spraying, is made observation test film.It is observed with scanning electron microscope, deployment conditions of the observation compound in glass-fiber-fabric,
And it is evaluated.
Table 2
From table 1 to table 2 as can be seen that using the glass-fiber-fabric through the cladding processing of group vib compound can be bright as reinforcing material
The aobvious drill processability for improving laminate uses a small amount of group vib compound cladding processing glass-fiber-fabric, you can by laminate to boring
The wear rate of knife is reduced to 40-82% from 95%, and effect is quite apparent, and its excellent combination property.In addition, from table 1 to table 2
As can be seen that can be seen that from embodiment 8-9 and embodiment 14-15, the grain size of group vib compound is 0.01 μm to 1 μm model
The interior distributing homogeneity that can further improve group vib compound is enclosed, can also further improve the drill processability of laminate.From
Embodiment 2-6 and embodiment 16-17 can be seen that content of the group vib compound in the glass-fiber-fabric of cladding is in 0.01 to 5 weight
The uniformity of glass-fiber-fabric and the drill processability of laminate can be further improved in the range of amount %.In addition, from embodiment
4th, 5,9 and 13 it can be seen that both molybdenum compound and tungsten compound are similarly used with the use of better, same grain size
Amount, the drilling effect that the two compounding use reaches are equivalent to 2 times of dosages of the compound that one of which same particle size is used alone
Quite (i.e. 1: 1 mixture, the 1 weight deal of molybdenum compound and tungsten compound is equivalent to the molybdenum compound of 2 parts by weight or tungsten is closed
Object), significant effect.From embodiment 2-6 and embodiment 11 compared with comparative example 2-3, it can be seen that by by group vib
Compound processing is coated on glass-fiber-fabric, and drill processability is obviously improved, and using same compound, direct additive amount is bag
Cover 5 times for the treatment of capacity, but the drilling effect that coats that treated instead than directly add also than get well, illustrate to pass through disclosure energy
The dosage of enough significant reduction group vib compounds, and can effectively improve the Drilling operation performance of plate.
Obviously, those skilled in the art can carry out the embodiment of the present disclosure various modification and variations without departing from this public affairs
The spirit and scope opened.In this way, if these modifications and variations of the disclosure belong to disclosure claim and its equivalent technologies
Within the scope of, then the disclosure is also intended to comprising including these modification and variations.
Claims (14)
1. a kind of prepreg, the prepreg includes reinforcing material and passes through thermosetting resin attached thereto after impregnation drying
Composition, wherein the reinforcing material is handled by group vib compound cladding.
2. prepreg as described in claim 1, wherein the group vib compound is selected from molybdenum compound, tungsten compound or it is mixed
Close object.
3. prepreg as claimed in claim 2, wherein the molybdenum compound is selected from：Molybdenum dialkyl-dithiophosphate, nitrogenous two
Alkyl dithiophosphoric acid molybdenum, molybdenum dialkyldithiocarbamacompositions, molybdenum amine complex, molybdenum naphthenate, alkyl salicylate molybdenum, thiophene cyclopentadienyl
In molybdenum, dimercaptothiazole molybdenum, alkylamine molybdenum, organic molybdates esters or molybdenum caprylate any one or it is arbitrary two or more
Mixture.
4. prepreg as described in claim 1, wherein the group vib compound is liquid or solid-state.
5. prepreg as claimed in claim 2, wherein the molybdenum compound is selected from：Molybdic acid, molybdate, molybdenum oxide, molybdenum it is miscellaneous
Polyacid and its sodium salt, sylvite and ammonium salt, the multi-acid salt of molybdenum, molybdenum blue, the sulfide of molybdenum, the selenides of molybdenum, the tellurides of molybdenum, molybdenum
Any one in halide, molybdenum alloy or molybdenum disilicide or the arbitrary mixture of two or more.
6. prepreg as claimed in claim 2, wherein molybdenum compound choosing is white：Ammonium molybdate, sodium molybdate, zinc molybdate, molybdic acid
Any one in calcium, magnesium molybdate, molybdenum oxide or molybdenum sulfide or the arbitrary mixture of two or more.
7. compositions of thermosetting resin as claimed in claim 2, wherein the tungsten compound is selected from：Tungsten disulfide, tetrathio
Wolframic acid amine, tungsten oxybromide, tungsten tetrachloride, tetrabormated tungsten, Zinc Tungstate, artificial schellite, magnesium tungstate, ammonium tungstate, tungsten selenide, oxidation
Tungsten, dioctyl aminodithioformic acid tungsten, dithiol close tungsten, 3,4- dimercapto toluenes close tungsten, amido diisopropyl disulfide for phosphorus
Sour tungsten, organic W-Mo complex, aminodithioformic acid tungsten compound, aromatic hydrocarbons tungsten compound or alkane (virtue) base amido D2EHDTPA
In tungsten any one or at least two mixture.
8. compositions of thermosetting resin as claimed in claim 2, wherein the tungsten compound is selected from tungsten disulfide, tetrathio tungsten
In acid amide, tungsten oxybromide, tungsten tetrachloride, tetrabormated tungsten or alkane (virtue) base amido D2EHDTPA tungsten any one or at least
Two kinds of mixture.
9. prepreg as described in claim 1, wherein the group vib compound is selected from the mixing of molybdenum compound and tungsten compound
Object, wherein in the mixture of molybdenum compound and tungsten compound, the mixing ratio of molybdenum compound and tungsten compound by weight is about 1
: in the range of 100 to about 100: 1.
10. prepreg as claimed in claim 1 or 2, wherein the group vib compound is solid-state, average grain diameter 0.01
To 1 μm.
11. prepreg as described in claim 1, wherein the group vib compound is coated by the group vib compound
Content in the reinforcing material of processing is 0.01 to 5 weight %.
12. prepreg as described in claim 1, wherein the reinforcing material includes glass-fiber-fabric.
13. a kind of laminate, the laminate contains an at least prepreg as described in claim 1.
14. a kind of printed circuit board, the printed circuit board contains an at least prepreg as described in claim 1.
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| CN201711439413.XA CN108102125A (en) | 2017-12-25 | 2017-12-25 | prepreg, laminate and printed circuit board |
| TW107109690A TWI658929B (en) | 2017-12-25 | 2018-03-21 | Prepregs, laminates and printed circuit boards |
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| CN201711439413.XA CN108102125A (en) | 2017-12-25 | 2017-12-25 | prepreg, laminate and printed circuit board |
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| CN109438923A (en) * | 2018-11-07 | 2019-03-08 | 胡石开 | A kind of prepreg and application thereof |
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|---|---|---|---|---|
| CN1332704A (en) * | 1998-10-13 | 2002-01-23 | Ppg工业俄亥俄公司 | Glass fiber-reinforced prepegs, laminates, electronic circuit boards and methods for assembling fabric |
| CN103497488A (en) * | 2013-10-11 | 2014-01-08 | 广东生益科技股份有限公司 | Thermosetting resin composition and use thereof |
| CN103694642A (en) * | 2013-12-27 | 2014-04-02 | 广东生益科技股份有限公司 | Thermosetting resin composition and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102822228B (en) * | 2010-03-26 | 2015-03-25 | 松下电器产业株式会社 | Epoxy resin composition for prepreg, prepreg, and multilayer printed circuit board |
-
2017
- 2017-12-25 CN CN201711439413.XA patent/CN108102125A/en active Pending
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- 2018-03-21 TW TW107109690A patent/TWI658929B/en active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1332704A (en) * | 1998-10-13 | 2002-01-23 | Ppg工业俄亥俄公司 | Glass fiber-reinforced prepegs, laminates, electronic circuit boards and methods for assembling fabric |
| CN103497488A (en) * | 2013-10-11 | 2014-01-08 | 广东生益科技股份有限公司 | Thermosetting resin composition and use thereof |
| CN103694642A (en) * | 2013-12-27 | 2014-04-02 | 广东生益科技股份有限公司 | Thermosetting resin composition and application thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109438923A (en) * | 2018-11-07 | 2019-03-08 | 胡石开 | A kind of prepreg and application thereof |
| CN109438923B (en) * | 2018-11-07 | 2021-06-18 | 威海蓝科复合材料科技有限公司 | Prepreg and application thereof |
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| TWI658929B (en) | 2019-05-11 |
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