CN107163576A - Resin combination and the prepreg and metal foil laminate made using it - Google Patents
Resin combination and the prepreg and metal foil laminate made using it Download PDFInfo
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- CN107163576A CN107163576A CN201710561155.6A CN201710561155A CN107163576A CN 107163576 A CN107163576 A CN 107163576A CN 201710561155 A CN201710561155 A CN 201710561155A CN 107163576 A CN107163576 A CN 107163576A
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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
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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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
-
- 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
- B32B17/061—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 metal
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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
- 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
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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
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/02—Composition of the impregnated, bonded or embedded layer
- B32B2260/021—Fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/04—Impregnation, embedding, or binder material
- B32B2260/046—Synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/10—Inorganic fibres
- B32B2262/101—Glass fibres
-
- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
-
- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/546—Flexural strength; Flexion stiffness
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
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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 & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Reinforced Plastic Materials (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Laminated Bodies (AREA)
Abstract
The invention discloses a kind of resin combination, in terms of 100 parts of solid weight, including：(a) the diamines modified bismaleimide resin containing benzoxazine structure：40 ~ 90 parts；(b) epoxy resin：10 ~ 60 parts.The present invention is by BMI and the pre-reaction preferential at low temperature of the diamine resin containing benzoxazine, and open loop does not almost occur for benzoxazine under low temperature；A part of reactive group is consumed by pre-reaction, form the prepolymer with certain molecular weight, increase the steric hindrance of benzoxazine ring-opening reaction, slowed down benzoxazine structure in resin structure reaction rate, the rheology Process window of resin combination is have adjusted well, reduces resin combination and the risk of the defect of base material dried flower or lineae ablicantes occurs because reaction is too fast in bonding processes.
Description
Technical field
The prepreg and metal foil laminate made the present invention relates to a kind of resin combination and using it, belongs to electronics
Field of material technology.
Background technology
The progress of electronic technology is maked rapid progress, portability, it is lightening become the direction that electronic system product is pursued always,
And machine product is lightening, it is thin comprising the component including printed circuit board to need to prepare electronic product, therefore, just needs
Want copper-clad plate base material that there is higher rigidity and resistance to warping, the structural support and procedure for processing of printed circuit board could be met
Demand.
In the prior art, the material prepared using epoxy resin and its curing agent as the compositions of thermosetting resin of necessary component
There is good heat resistance, insulating properties, processability and with low cost, therefore be widely used in semiconductor, printed circuit
In the electronic materials such as plate.The conventional curing agent of epoxy resin has polyamines, acid anhydrides, phenolic resin etc..As amine, phenolic resin are this kind of
There is substantial amounts of hydroxyl in curing agent containing reactive hydrogen in molecular structure, its epoxy resin solidified, this can cause solidfied material
Water absorption rate rise, wet-hot aging performance and dielectric properties decline.
On the other hand, the resin material of printed circuit board is prepared existing, BMI is very outstanding
One of resin, it is a kind of thermosetting resin containing imide structure, and its crosslink density high after solidifying makes it have high glass
Glass transition temperature, excellent heat endurance and higher rigidity, are one of current preferred material for making thin base.So
And, bismaleimide monomer have higher fusing point, dissolubility is poor, curing reaction temperature is high, solidification after resin fragility
It is larger to wait not enough, limit its application.
For above-mentioned technical problem, there are allyl compound or aromatic diamine compound modified bismaleimide tree at present
Fat is two kinds of more ripe technology paths, the Kerimid series plastics that such as Huntsman companies release in last century, northwest industry
The allyl compound of Liang Guo full professors team of university exploitation is modified span series plastics, obtained modified bismaleimide
Resin has high tenacity, excellent dissolubility (dissolving in the organic solvents such as acetone/butanone), high glass transition temperature etc. are excellent
Different in nature energy.
But, although above-mentioned 2 kinds of technical schemes can solve the dissolubility and tough sex chromosome mosaicism of resin, but span well
There is high water absorbing capacity still without being resolved in itself intrinsic imide group of bismaleimide resin, this comes to span
Imide resin brings some problems in the application of electronic circuit field, when the base material for preparing electronic circuit --- copper-clad plate tree
When modified bismaleimide resin (generally first passing through pi-allyl or diamines modification) component in fat formula is higher, its base material
Water absorption rate is often bigger than normal, so as to cause the warpage after base material water suction higher.In addition, water absorption rate not only easily causes greatly metal connection
Corrosion under fitting wet environment, and breathing increase, the warpage increase that it can be caused to be made after slim sheet material, are leveraged
The processing procedure of printed circuit board.Therefore, how while modified bismaleimide, the water absorption rate of its resin is reduced, it is reduced
The warpage after slim sheet material is made, one of difficult point applied into bimaleimide resin in electronic circuit field.
The bismaleimide-triazine resin (BT resins) of Mitsubishi's gas can be described as BMI and cyanate should
Model, though the water absorption rate of bimaleimide resin application is successfully solved the problems, such as, and patented technology is disclosed, it is closed
Key technology main points are still difficult for domestic technique personnel and grasped.
Chinese invention patent application CN104725781A discloses amine modified bismaleimide resin, benzoxazine resin
And the composition of epoxy resin, although which reducing the water absorption rate of span.Found however, the applicant has carried out experiment：Amine changes
Property bimaleimide resin can effectively improve benzoxazine reactivity (this point Li Ling's et al.《BMI is modified benzene
And oxazines resin and its composite research》Also it is described in one text), this also results in its rheology window in bonding processes
Also therefore narrow, secondary to copper-clad plate base material apparent causes certain dried flower and lineae ablicantes risk.
For above-mentioned phenomenon, inventor has carried out numerous studies, it is believed that its reason is as follows：Due in CN104725781A
Amine modified bismaleimide resin is to carry out pre-polymerization in organic solvent by amine modifiers and BMI to form.Amine
Class material, is epoxy curing agent, after amine reacts with epoxy resin, epoxy resin open loop generation great amount of hydroxy group, and hydroxyl
The Open loop temperature of benzoxazine colophony can be reduced, accelerates the ring-opening reaction of benzoxazine, so as to quickly be produced in system substantial amounts of
Hydroxyl and amino, so as to cause the curing reaction of whole system to accelerate so that rheology windows narrow.
Therefore, a kind of resin combination and the prepreg and laminate that are made using it are developed, make its have concurrently it is excellent
Heat resistance, intensity, hard and soft, dielectric properties and low water absorption, on the basis of high glass-transition temperature, copper will not covered
The secondary apparent phenomenon for forming dried flower and lineae ablicantes of plate base material, it is clear that with positive realistic meaning.
The content of the invention
The goal of the invention of the present invention is to provide a kind of resin combination and the prepreg and laminate that are made using it.
To achieve the above object of the invention, the technical solution adopted by the present invention is：A kind of resin combination, with solid weight
100 parts of meters, including：
(a) the diamines modified bismaleimide resin containing benzoxazine structure：40~90 parts；
(b) epoxy resin：10~60 parts；
The preparation method of said components (a) is as follows：
Bimaleimide resin is dissolved in organic solvent, in temperature 60~89 with the diamines containing benzoxazine structure
1~24hr is reacted at DEG C；
The mass ratio of the bimaleimide resin and the diamines containing benzoxazine structure is 100：30~30：100；
The chemical formula of the diamine compound containing benzoxazine structure is as follows：
Wherein, R is selected from-C (CH3)2-、-SO2- or-CH2-, n=2~4.
The mass ratio of the bimaleimide resin and the diamines containing benzoxazine structure is 100：30~30：100, example
Such as, the mass ratio of bimaleimide resin and the diamines containing benzoxazine structure is 100：30、100：40、100：50、100：
60、100：70、100：80、100：90、100：100、90：30、90：40、90：50、90：60、90：70、90：80、90：90、90：
100、80：30、80：40、80：50、80：60、80：70、80：80、80：90、80：100、70：30、70：40、70：50、70：60、
70：70、70：80、70：90、70：100、60：30、60：40、60：50、60：60、60：70、60：80、60：90、60：100、50：
30、50：40、50：50、50：60、50：70、50：80、50：90、50：100、40：30、40：40、40：50、40：60、40：70、
40：80、40：90、40：100、30：30、30：40、30：50、30：60、30：70、30：80、30：90、30：100 etc..
It is preferred that, the solids content of the diamines modified bismaleimide resin containing benzoxazine structure for 30~
90%.It is preferred that 50~80%.The typical but non-limiting solids content can be 40%, 60%, 70%, 85% etc..
It is preferred that, the mass ratio of the bimaleimide resin and the diamines containing benzoxazine structure is 60：30~30：
60。
It is preferred that, in terms of 100 parts of solid weight, including：
(a) the diamines modified bismaleimide resin containing benzoxazine structure：50~80 parts；
(b) epoxy resin：20~50 parts.
It is furthermore preferred that with solid weight meter, component (a) and component (b) add up to 100 parts, including：
(a) the diamines modified bismaleimide resin containing benzoxazine structure：50~80 parts；
(b) epoxy resin：20~50 parts；
(c) inorganic filler：0~100 part；
(d) fire retardant：5~30 parts；
(e) curing accelerator：0.001~1 part.
Above, the fire retardant can be commonly used for the copper-clad plate such as brominated flame-retardant or phosphonium flame retardant or nitrogenous flame ratardant
One or two or more kinds of mixtures in fire retardant.
The brominated flame-retardant is selected from deca-BDE, TDE, octa-BDE, pentabromotoluene, hexabromo ring
Dodecane, ethylene double tetrabromo phthalimide, brominated polycarbonate, brominated Polystyrene, bromination triazine, the pentabromo-s of ethylene two
The double tetrabromo acid imides of benzene, ethylene, the phenoxy group benzene of ten tetrabromo two, double (tribromophenoxy) ethane, tetrabromobisphenol A, brominated asphalt mixtures modified by epoxy resin
At least one of fat；The phosphonium flame retardant is selected from three (2,6- 3,5-dimethylphenyl) phosphines, 10- (2,5- dihydroxy phenyl) -9,10-
Miscellaneous -10- phosphines phenanthrene -10- the oxides of dihydro-9-oxy, (2,6- 3,5-dimethylphenyl) the phosphino- benzene of 2,6- bis- or 10- phenyl -910- dihydros -
9- oxa- -10- phosphine phenanthrene -10- oxides, phosphonitrile, phosphorus containing phenolic resin, phosphorous epoxy resin, phenoxy group phosphine cyanogen compound, phosphoric acid
Ester, polyphosphoric acid melamine, aluminium metaphosphate, triphenyl phosphate, bis-phenol biphenyl phosphate, APP, phosphonitrile compound, idol
Phosphorus-nitrogen compound, bisphenol-A double (diphenyl phosphoesters), three (2,6- 3,5-dimethylphenyl) phosphines, double [two (2, the 6- diformazans of resorcinol
At least one of base phenyl) phosphate]；The nitrogenous flame ratardant is selected from triaizine compounds, cyanuric acid compound, isocyanic acid chemical combination
A kind of in thing, phenthazine, its content is preferably 10-20 parts.
In above-mentioned technical proposal, the inorganic filler be selected from containing silica (molten state or non-melt state and Porous),
Aluminum oxide, magnesia, magnesium hydroxide, calcium carbonate, aluminium nitride, boron nitride, aluminium hydroxide, aluminum silicon carbide, carborundum, sodium carbonate,
Titanium dioxide, zinc oxide, zirconium oxide, quartz, diamond dust, class diamond dust, glass dust, graphite, magnesium carbonate, potassium titanate, ceramics are fine
Dimension, mica, boehmite, zinc molybdate, ammonium molybdate, Firebrake ZB, calcium phosphate, calcium silicates, calcium carbonate, calcination of talc, talcum, nitridation
Silicon, section burn at least one of kaolin, clay, magnesium sulfate, barium sulfate, strontium titanates, barium titanate, and its content is preferably 10~80
Part.
The shape of above-mentioned inorganic filler is not particularly limited, can for spherical, tabular, needle-like, horn shape or unformed shape or
It mixes shape.Above-mentioned inorganic filler can use silane coupler to be surface-treated, and improve scattered in resin combination
Property.When in use above-mentioned inorganic filler can direct plunge into previously prepared filler dispersion liquid or be made lotion input resin combination
In thing.
In above-mentioned technical proposal, the curing accelerator is selected from imidazoles, pyridines, triphenylphosphine, boron trifluoride list second
Amine, carboxylic acid metal's salt.The imidazoles are selected from 2-methylimidazole, 2-ethyl-4-methylimidazole, 2- phenylimidazoles, 2- 11
Alkyl imidazole, 1- cyanoethyl substituted imidazoles；The pyridines are selected from triethylamine, benzyl dimethylamine or dimethylamino naphthyridine；It is described
Carboxylic acid metal's salt is acetylacetone,2,4-pentanedione acid metal salt, sad metal salt, isooctyl acid or metal naphthenate, and the metal is selected from such as
Zinc, cobalt, copper, manganese, iron, nickel, aluminium and its mixture.
Epoxy curing agent can also be contained in above-mentioned technical proposal, can be acid amides based compound, acid anhydrides system chemical combination
The epoxy curing agents such as thing, phenol system compound, but do not contain amine curing agent.The acid amides based compound can be double cyanogen
Amine, Versamid etc.；The acid anhydrides based compound can be phthalic anhydride, trimellitic anhydride, Pyromellitic Acid
Dianhydride, maleic anhydride, hydrogenated phthalic anhydride, carbic anhydride etc.；The phenol system compound can be phosphorus containing phenolic resin,
Nitrogen-containing Phenolic Resins, bisphenol A phenolic resin, phenol novolacs, naphthol novolac resin, biphenyl phenol-formaldehyde resin modified, biphenyl change
Property naphthol resin, dicyclopentadiene phenol add-on type resin, phenol aralkyl resin, naphthols aralkyl resin, trihydroxy methyl first
Alkane resin, benzoxazine colophony etc., its content are 100 parts of meters of epoxy resin, contain 1-80 parts.
It is preferred that, the chemical formula of the bimaleimide resin is as follows：
Wherein,
R1 is selected from：- O-,R2 is identical with R3 or not
Together, H-, H are respectively selected from3C- or C2H5-。
In above-mentioned technical proposal, preferably bimaleimide resin is 4,4 '-diphenyl methane dimaleimide, 4,4 '-
Diphenyl Ether Bismaleimide, 4,4 '-diphenyl sulphone (DPS) BMI and double (3- ethyl -5- methyl -4- dimaleoyl iminos
Benzene) one or more kinds of mixtures in methane.
It is preferred that, the epoxy resin is selected from isocyanate-modified bisphenol A epoxide resin, isocyanate-modified Bisphenol F ring
Oxygen tree fat, isocyanate-modified bisphenol-s epoxy resin, phenol novolac epoxy resins, bisphenol A type epoxy resin, bisphenol F type epoxy
Resin, bisphenol-s epoxy resin, Study On O-cresol Epoxy Resin, trifunctional base epoxy, tetrafunctional base epoxy, two
Cyclopentadiene epoxy resin, para-aminophenol epoxy resin, tricyanic epoxy resin, phosphorous epoxy resin, nitrogenous asphalt mixtures modified by epoxy resin
Fat, brominated epoxy resin, paraxylene epoxy resin, naphthalene type epoxy resin, benzo croak are muttered type epoxy resin, biphenyl epoxy novolac
One or more in resin, phenolic group benzene alkyl novolac epoxy resin.
It is preferred that, bimaleimide resin is dissolved in organic solvent, 60 with the diamines containing benzoxazine structure
1~24hr is reacted at a temperature of~89 DEG C.Wherein, it can be 61 DEG C that reaction temperature is typical but non-limiting, 62 DEG C, 63 DEG C,
64℃、65℃、66℃、67℃、68℃、69℃、70℃、71℃、72℃、73℃、74℃、75℃、76℃、77℃、78℃、79
DEG C, 80 DEG C, 81 DEG C, 82 DEG C, 83 DEG C, 84 DEG C, 85 DEG C, 86 DEG C, 87 DEG C, 89 DEG C etc..It is preferred that reaction temperature be 70~80 DEG C.
Wherein, the reaction time it is typical but non-limiting can be 2hr, 3hr, 4hr, 5hr, 6hr, 7hr, 8hr, 9hr,
10hr, 12hr, 14hr, 16hr, 18hr, 20hr, 21hr, 22hr, 23hr etc..
It is preferred that, bimaleimide resin is dissolved in organic solvent, 70 with the diamines containing benzoxazine structure
2~10hr is reacted at a temperature of~80 DEG C.
The organic solvent is selected from acetone, butanone, toluene, dimethylbenzene, methanol, ethanol, methylisobutylketone, cyclohexanone, first
Base ethyl ketone, N, dinethylformamide, N, N- dimethyl acetamide, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, methoxy ethyl second
One or more in acid esters, ethoxyethyl acetate, Among acetic acid esters, ethyl acetate.
The present invention principle be：By the diamines containing benzoxazine structure and bimaleimide resin in solvent 90
Preferentially reacted under the conditions of temperature (not including 90 DEG C) below DEG C, prepolymer is formed, when reaction temperature is below 90 DEG C
Reaction in (not including 90 DEG C), resin mainly between Amino End Group and BMI, benzoxazine is not almost opened
Ring；In addition, by pre-reaction in the present invention, consuming a part of reactive group, the prepolymer with certain molecular weight, increase are formed
The steric hindrance of benzoxazine ring-opening reaction, slowed down benzoxazine structure in resin structure reaction rate so that pressing
During rheology window broaden, so as to greatly reduce the risk of copper-clad plate base material dried flower or lineae ablicantes.
A kind of prepreg made by resin combination is claimed simultaneously in the present invention, by above-mentioned resin combination with molten
Glue is made in agent dissolving, and then reinforcing material is immersed in above-mentioned glue；After impregnating after reinforcing material heat drying, you can
Obtain the prepreg.
Described solvent is selected from acetone, butanone, toluene, dimethylbenzene, methanol, ethanol, methylisobutylketone, cyclohexanone, methyl
Ethyl ketone, N, dinethylformamide, N, N- dimethyl acetamide, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, methoxy ethyl acetic acid
At least one of ester, ethoxyethyl acetate, Among acetic acid esters, ethyl acetate.
In above-mentioned technical proposal, the reinforcing material is glass fabric, such as D glass, E glass, NE glass, S glass and T
Glass.Here the thickness of glass fabric is not particularly limited, but for producing 0.01~0.02mm of thickness laminate, one
As use fibrillation cloth, flat fabric.In addition, the interface cohesion in order to improve resin and glass fabric, glass fabric is typically all
Need to be chemically treated, main method is coupling agent treatment, coupling agent used such as epoxy silane, amino silane.
A kind of laminate is claimed simultaneously in the present invention, and it includes at least one prepreg described above.
A kind of metal foil laminate is claimed simultaneously in the present invention, in a single or double by above-mentioned prepreg
Metal foil is covered with, or metal foil, hot pressing are covered with its single or double after above-mentioned prepreg superposition by least 2
Shaping, you can obtain the metal foil laminate.
The quantity of the prepreg is the metal foil laminated plate thickness according to customer requirement to determine, can use one or many
.The metal foil, can be copper foil or aluminium foil, and their thickness is not particularly limited.
A kind of printed circuit board is claimed simultaneously in the present invention, contains at least one prepreg described above；
Or contain at least one laminate described above；
Or contain at least one metal foil laminate described above.
The interlayer dielectric made using above-mentioned resin combination is claimed in the present invention simultaneously, using above-mentioned resin combination
Thing adds solvent dissolving and glue is made, and the glue will be coated in carrier film, after the carrier film heat drying of coating glue, i.e.,
The interlayer dielectric is can obtain, the heat drying condition is to be toasted 1~10 minute at 50~170 DEG C.
In above-mentioned technical proposal, described solvent is selected from acetone, butanone, toluene, dimethylbenzene, methanol, ethanol, methyl tert-butyl
Ketone, cyclohexanone, methyl ethyl ketone, N, dinethylformamide, N, N- dimethyl acetamide, ethylene glycol monomethyl ether, propylene glycol monomethyl ether,
At least one of methoxyethyl acetate, ethoxyethyl acetate, Among acetic acid esters, ethyl acetate.
In above-mentioned technical proposal, carrier film can be polyethylene terephthalate (PET) film, mould release membrance, copper foil, aluminium foil
Deng carrier film is preferably PET film.
In above-mentioned technical proposal, in order to protect insulating resin layer, in resin bed another side covering protection film, the diaphragm
Can material identical with carrier film.
Because above-mentioned technical proposal is used, the present invention has following advantages compared with prior art：
1. the modified bismaleimide resin of the present invention passes through BMI and the diamines tree containing benzoxazine
(less than 90 degree, not including 90 DEG C) benzoxazine under fat (less than 90 degree, not including 90 DEG C) preferential pre-reaction at low temperature, low temperature
Open loop does not almost occur；In addition, the application consumes a part of reactive group by pre-reaction, form with certain molecular weight
Prepolymer, increases the steric hindrance of benzoxazine ring-opening reaction, has slowed down the benzoxazine structure in resin structure in system
Reaction rate, have adjusted the rheology Process window (rheology window broadens in rheological curve figure) of resin combination well, reduction
Resin combination in bonding processes because react it is too fast there is the risk of the defect of base material dried flower or lineae ablicantes；Experiment shows,
The present invention will not copper-clad plate base material the secondary apparent phenomenon for forming dried flower and lineae ablicantes, achieve significant effect；
2. experiment shows that modification span of the invention carrys out amide resin and not only maintains preferable heat resistance and rigidity, drop
Low curing reaction temperature and water absorption rate, are more beneficial for the application in copper-clad plate field, and high heat resistance and rigidity ensure that it
Application in Aero-Space and thin copper clad laminate field, low water absorption rate reduces the breathing ratio after base material water suction, more
Inhibit the generation of bow warping；
3. the present invention is using with high glass transition temperature, good heat resistance, the modification span of low water absorption rate
Bismaleimide resin, the resin is modified with the diamine resin modified bismaleimide resin containing benzoxazine structure
There is resin the product after good dissolubility, solidification to have high glass transition temperature and low water absorption rate, solve existing
There is the problem of bimaleimide resin water absorption rate is high in technology, be greatly reduced the warpage of sheet material, be bismaleimide
Polyimide resin solves a great problem in the application of Aero-Space and electronic applications.
Brief description of the drawings
Fig. 1 is the embodiment of the present invention and the rheological curve figure of the prepreg in comparative example.
Embodiment
With reference to embodiment, the invention will be further described：
It is the preparation of the diamines modified bismaleimide resin containing benzoxazine below, obtains modified resin, it is specific real
Apply mode：
Synthesis example one
In the 500ml three-necked flasks equipped with agitator, reflux condensing tube and thermometer, it is positioned in oil bath pan, adds successively
Enter bisphenol-A：91.2g, p-phenylenediamine：94.4g, formaldehyde：48.0g；80ml ethanol and 20ml toluene are added as solvent, slowly
Be warming up to 75 DEG C and keep 3hr, during be persistently kept stirring for state, and be passed through in three-necked flask nitrogen bubble protection.On
State reaction to terminate, after product is cooled to room temperature, maintain stirring and toward methanol solution is added dropwise in flask, extremely there is no sediment analysis
Go out, stop stirring, 24hr is stood at room temperature, filter off supernatant liquor, collect sediment, sediment is placed into 50 DEG C of vacuum drying and dried
In case, 5hr is dried, the diamines containing benzoxazine structure is obtained, is designated as N (BOZ) -1.
Synthesis example two
In the 500ml three-necked flasks equipped with agitator, reflux condensing tube and thermometer, it is positioned in oil bath pan, adds successively
Enter Bisphenol F：79.2g, p-phenylenediamine：94.4g, formaldehyde：48.0g；80ml ethanol and 20ml toluene are added as solvent, slowly
Be warming up to 60 DEG C and keep 5hr, during be persistently kept stirring for state, and be passed through in three-necked flask nitrogen bubble protection.On
State reaction to terminate, after product is cooled to room temperature, maintain stirring and toward methanol solution is added dropwise in flask, extremely there is no sediment analysis
Go out, stop stirring, 24hr is stood at room temperature, filter off supernatant liquor, collect sediment, sediment is placed into 50 DEG C of vacuum drying and dried
In case, 5hr is dried, the diamines containing benzoxazine structure is obtained, is designated as N (BOZ) -2.
Modified resin example one
100g solvent DMFs are added in 500mL three-necked flasks, 4,4 '-diphenyl-methane span is carried out into acyl
Imines and the diamine resin N (BOZ) -1 of the structure containing benzoxazine, according to mass parts 100:30 successively in input three-necked flask in,
Persistently stirred under the conditions of 75 DEG C of oil bath, timing is started after solid in flask is completely dissolved, persistently stirred after 2.5hr, will
Products therefrom is distilled, and obtains the modified bismaleimide resin solution 1 that solid content is 75%.
Modified resin example two
120g solvent DMAs are added in 500mL three-necked flasks, 4,4 '-diphenyl-methane span is carried out into acyl
Imines and the diamine resin N (BOZ) -1 of the structure containing benzoxazine, according to mass parts 100g:50g is successively in input three-necked flask
In, persistently stirred under the conditions of 85 DEG C of oil bath, timing is started after solid in flask is completely dissolved, persistently stirred after 1hr, will
Products therefrom is distilled, and obtains the modified bismaleimide resin solution 2 that solid content is 60%.
Modified resin example three
150g solvent acetones are added in 500mL three-necked flasks, will double (3- ethyl -5- methyl -4- dimaleoyl iminos
Benzene) methane and the structure containing benzoxazine diamine resin N (BOZ) -2, according to mass parts 100g:100g is successively in three mouthfuls of burnings of input
In bottle, persistently stirred under the conditions of 70 DEG C of oil bath, timing started after solid in flask is completely dissolved, persistently stirred after 8hr,
Products therefrom is distilled, the modified bismaleimide resin solution 3 that solid content is 60% is obtained.
Modified resin example four
100g solvent DMAs are added in 500mL three-necked flasks, by 4,4 '-diphenyl ether bismaleimide
Amine and the diamine resin N (BOZ) -2 of the structure containing benzoxazine, according to mass parts 30g:100g successively in input three-necked flask in,
Persistently stirred under the conditions of 80 DEG C of oil bath, timing is started after solid in flask is completely dissolved, persistently stirred after 4hr, by institute
Obtain product to be distilled, obtain the modified bismaleimide resin solution 4 that solid content is 65%.
Modified resin example five
100g solvent DMFs are added in 500mL three-necked flasks, 4,4 '-diphenyl-methane span is carried out into acyl
Imines and the diamine resin N (BOZ) -1 of the structure containing benzoxazine, according to mass parts 100g:30g is successively in input three-necked flask
In, persistently stirred under the conditions of 60 DEG C of oil bath, timing started after solid in flask is completely dissolved, persistently stirred after 2.5hr,
Products therefrom is distilled, the modified bismaleimide resin solution 5 that solid content is 75% is obtained.
Modified resin comparative example one
By 4,4 '-diphenyl methane dimaleimide and diallyl bisphenol resin according to mass ratio 100:60 are placed in burning
In bottle, 100min is reacted under the conditions of 130 DEG C of oil bath, pi-allyl is obtained and is modified span 1.
Modified resin comparative example two
4 are weighed, 4 '-diphenyl methane dimaleimide 100g, MDA 40g is dissolved in DMF solution,
5hr is reacted under the conditions of 100 DEG C, amine is obtained and is modified span 2.
Modified resin comparative example three
100g solvent DMAs are added in 500mL three-necked flasks, by 4,4 '-diphenyl ether bismaleimide
Amine and the diamine resin N (BOZ) -2 of the structure containing benzoxazine, according to mass parts 30g:100g successively in input three-necked flask in,
Persistently stirred under the conditions of 50 DEG C of oil bath, timing is started after solid in flask is completely dissolved, persistently stirred after 4hr, by institute
Obtain product to be distilled, obtain the modified bismaleimide resin solution 6 that solid content is 65%.
Modified resin comparative example four
100g solvent DMFs are added in 500mL three-necked flasks, 4,4 '-diphenyl-methane span is carried out into acyl
Imines and the diamine resin N (BOZ) -1 of the structure containing benzoxazine, according to mass parts 100g:30g is successively in input three-necked flask
In, persistently stirred under the conditions of 100 DEG C of oil bath, start timing after solid in flask is completely dissolved, persistently stir 2.5hr
Afterwards, products therefrom is distilled, obtains the modified bismaleimide resin solution 7 that solid content is 75%.
Prepreg and the preparation of copper-clad plate
According to solid masses meter, weigh and disliked prepared in above-mentioned resin modified example containing benzo according to the data in table 1
The diamines modified bismaleimide resin of piperazine, addition epoxy resin, inorganic filler, curing accelerator, and pass through solvent adjustment
When glue solid content is to 60%, glue is coated on glass fabric, infiltration a moment, into 160 DEG C of air dry ovens, baking
3~6min, is made prepreg, and prepreg is cut into certain size, and an electrolytic copper foil is respectively being placed up and down, folded to be made into
Necessarily folded structure, sends into vacuum press and presses, and program is 150 DEG C/60min+200 DEG C/120min, and metal foil laminate is made,
Specific performance detection is as shown in table 3.
The resin composition content data of table 1
The material trademark of table 2 and producer
| Title | Producer |
| Double (3- ethyl -5- methyl -4- Mailed-phenyls) methane | Xi'an span new material |
| 4,4 '-diphenyl methane dimaleimide | Xi'an span new material |
| 4,4 '-hexichol isopropyl BMI | Xi'an span new material |
| Epoxy resin 1 (bisphenol A type epoxy resin) | Dow |
| Epoxy resin 2 (naphthalene nucleus type epoxy resin) | Dic |
| Bisphenol A-type benzoxazine resin | Huntsman |
| Fire retardant 1 (phosphorus containing phenolic resin) | Dow |
| Fire retardant 2 (deca-BDE) | Refined treasured |
| Filler (silica) | Jiangsu connection is auspicious |
| Curing accelerator (2-methylimidazole) | Four countries are melted into |
Performance test is carried out to the prepreg prepared in above-mentioned all embodiments and comparative example and copper-clad plate.Method of testing
For：
Glass transition temperature (TMA)：Using the Tg of the resistance to TMA instrument test sheet materials speeded, heating rate：10 DEG C/min,
Temperature range：30-320℃.
Glass transition temperature (DMA)：Using the Tg of TA DMA Q800 instrument test sheet materials, heating rate：3℃/
Min, temperature range：30-320℃.
Peel strength (PS)：According to " after thermal stress " experiment condition in IPC-TM-650 methods, test metallic cover layer
Peel strength.
Wicking heat resistance：Using 50 × 50mm two sides band copper sample, in the scolding tin for immersing 288 DEG C, record sample layering
The time of foaming.
Wicking heat resistance after humidity processing：Pressurization by 3 pieces of 100 × 100mm substrate coupons in 121 DEG C, 105Kpa is steamed
Boil in processing unit and keep after 3hr, whether 2min in the solder bath of 288 DEG C of immersion, observation sample occurs the phenomenons such as layering bubbling,
3 pieces do not occur layering bubbling be designated as 3/3,2 pieces do not occur layering bubbling be designated as 2/3,1 piece do not occur layering bubbling be designated as 1/3,
0 piece layering bubbling does not occur and is designated as 0/3.
D23 DEG C/24hr water absorption rates：It is measured according to standard method specified in IPC-TM-650
Harmomegathus after D23 DEG C/24hr water suctions：The harmomegathus situation tested using triaxial coordinate method after substrate water suction, base material is swollen
Swollen to be represented using "+numerical value ", base material shrinks represents that unit is ppm, i.e. hundred a ten thousandths using "-numerical value ".
Bow warping degree：Tested using standard method specified in IPC-TM-650, obtain the maximum percentage of bow and torsion
Bent maximum percentage, the angularity of copper-clad plate base material is judged with this.
Bending strength：Standard method specified in IPC-TM-650 is tested.
Base material time is apparent：Tested using standard method specified in IPC-TM-650, by visual observation or dicing method judge
Whether there is in base material and the defects such as dried flower, lineae ablicantes occur.
Prepreg powder rheometer test：Using Anton Paar MCR302 rheometers, the rheological curve of test sample, temperature model
Enclose：80~160 DEG C, heating rate：3℃/min.
The copper-clad plate basic performance data of the embodiment of table 3 and comparative example
From above-described embodiment and comparative example, using the diamines modified bismaleimide resin containing benzoxazine with
The composition (embodiment 1) of epoxy resin, relatively using allyl compound (comparative example 1) or common diamines modified bismaleimide
Polyimide resin (comparative example 2) with lower water absorption rate and angularity, and maintains high glass compared with the composition of epoxy resin
Glass transition temperature and excellent humidity resistance.
Further, the diamines containing benzoxazine and bimaleimide resin are subjected to pre-polymerization and epoxy resin is formed
Composition (embodiment 2), with conventional diamines modified bismaleimide resin, benzoxazine resin and epoxy resin are formed
Composition (comparative example 5) compare, with broader rheology window, be more beneficial for the technology controlling and process in laminate lamination process,
The apparent risk for dried flower and lineae ablicantes occur of base material time is reduced, the manufacture of copper-clad plate is more beneficial for.
Further, the diamines containing benzoxazine is carried out at a temperature of less than 90 DEG C with bimaleimide resin
Pre-polymerization (embodiment 1) compared with more than pre-polymerization (comparative example 7) is carried out at a temperature of 90 DEG C, with broader rheology window (referring to
Rheology window broadens in Fig. 1 rheological curve figure), while significantly improving base material time apparent mass.Benzoxazine will be contained
Diamines and bimaleimide resin enter at a temperature of carrying out pre-polymerization (embodiment 4) and be less than 60 DEG C at a temperature of more than 60 DEG C
Row pre-polymerization (comparative example 6) is compared, substantially excellent in terms of water absorption rate and size harmomegathus.
In addition, compared with embodiment 5 (carrying out pre-polymerization at a temperature of at 60 DEG C), embodiment 1 (is carried out at a temperature of 75 DEG C
Pre-polymerization) combination property it is more preferable.
The foregoing description of the disclosed embodiments, enables professional and technical personnel in the field to realize or using the present invention.
A variety of modifications to these embodiments will be apparent for those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, it is of the invention
The embodiments shown herein is not intended to be limited to, and is to fit to and principles disclosed herein and features of novelty phase one
The most wide scope caused.
Claims (10)
1. a kind of resin combination, it is characterised in that in terms of 100 parts of solid weight, including：
(a) the diamines modified bismaleimide resin containing benzoxazine structure：40 ~ 90 parts；
(b) epoxy resin：10 ~ 60 parts；
The preparation method of said components (a) is as follows：
Bimaleimide resin is dissolved in organic solvent, at 60 ~ 89 DEG C of temperature with the diamines containing benzoxazine structure
React 1 ~ 24hr；
The mass ratio of the bimaleimide resin and the diamines containing benzoxazine structure is 100：30~30：100；
The chemical formula of the diamine compound containing benzoxazine structure is as follows：
,
Wherein, R is selected from-C (CH3)2-、-SO2- or-CH2-, n=2 ~ 4.
2. resin combination according to claim 1, it is characterised in that：In terms of 100 parts of solid weight, including：
(a) the diamines modified bismaleimide resin containing benzoxazine structure：50 ~ 80 parts；
(b) epoxy resin：20 ~ 50 parts.
3. resin combination according to claim 1, it is characterised in that：With solid weight meter, component（a）And component（b）
Add up to 100 parts, including：
(a) the diamines modified bismaleimide resin containing benzoxazine structure：50 ~ 80 parts；
(b) epoxy resin：20 ~ 50 parts；
(c) inorganic filler：0 ~ 100 part；
(d) fire retardant：5 ~ 30 parts；
(e) curing accelerator：0.001 ~ 1 part.
4. the resin combination according to claim 1 or 2 or 3, it is characterised in that：The change of the bimaleimide resin
Formula is as follows：
, wherein,
R1 is selected from：；R2 is identical with R3 or not
Together, be respectively selected from H-,。
5. the resin combination according to claim 1 or 2 or 3, it is characterised in that：The epoxy resin is selected from isocyanates
Modified bisphenol A epoxy resin, isocyanate-modified bisphenol F epoxy resin, isocyanate-modified bisphenol-s epoxy resin, phenol phenol
Formaldehyde epoxy resin, bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, orthoresol phenolic aldehyde asphalt mixtures modified by epoxy resin
Fat, trifunctional base epoxy, tetrafunctional base epoxy, bicyclopentadiene epoxy resin, para-aminophenol epoxy resin, three
Paracyanogen acid epoxy resin, phosphorous epoxy resin, nitrogen-containing epoxy thermoset, brominated epoxy resin, paraxylene epoxy resin, naphthalene type ring
Oxygen tree fat, benzo croak are muttered one kind or several in type epoxy resin, biphenyl novolac epoxy resin, phenolic group benzene alkyl novolac epoxy resin
Kind.
6. the resin combination according to claim 1 or 2 or 3, it is characterised in that：By bimaleimide resin with containing benzene
And the diamines dissolving of oxazine structure is in organic solvent, and 2 ~ 10hr is reacted at a temperature of 70 ~ 80 DEG C.
7. the prepreg that a kind of resin combination using as described in claim 1 or 2 or 3 makes, it is characterised in that：Will power
Profit requires that glue is made in the resin combination solvent dissolving described in 1 or 2 or 3, and reinforcing material then is immersed in into above-mentioned glue
In；After impregnating after reinforcing material heat drying, you can obtain the prepreg.
8. a kind of laminate, it is characterised in that：It includes at least one prepreg as claimed in claim 7.
9. a kind of metal foil laminate, it is characterised in that：In a single or double as the prepreg described in claim 7
Be covered with metal foil, or by least 2 as the prepreg superposition described in claim 7 after, be covered with gold in its single or double
Belong to paper tinsel, hot forming, you can obtain the metal foil laminate.
10. a kind of interlayer dielectric, it is characterised in that：The resin described in the claim 1 or 2 or 3 is coated on a carrier film
Composition, is coated with after the carrier film heat drying of resin combination, you can obtain the interlayer dielectric.
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