CN107353642A - Resin combination and prepreg, metal foil laminate and the interlayer dielectric using its making - Google Patents

Resin combination and prepreg, metal foil laminate and the interlayer dielectric using its making Download PDF

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Publication number
CN107353642A
CN107353642A CN201710560587.5A CN201710560587A CN107353642A CN 107353642 A CN107353642 A CN 107353642A CN 201710560587 A CN201710560587 A CN 201710560587A CN 107353642 A CN107353642 A CN 107353642A
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resin
epoxy resin
parts
prepreg
diamines
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CN107353642B (en
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戴善凯
崔春梅
肖升高
陈诚
黄荣辉
季立富
谌香秀
任科秘
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Suzhou Shengyi Technology Co Ltd
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Suzhou Shengyi Technology Co Ltd
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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
    • C08L79/085—Unsaturated polyimide precursors
    • 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
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/092—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/12—Unsaturated polyimide precursors
    • C08G73/121—Preparatory processes from unsaturated precursors and polyamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/12—Unsaturated polyimide precursors
    • C08G73/126—Unsaturated polyimide precursors the unsaturated precursors being wholly aromatic
    • 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
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
    • 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
    • B32B2307/54—Yield strength; Tensile strength
    • 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
    • B32B2307/70—Other properties
    • B32B2307/73—Hydrophobic
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • 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
    • 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

Abstract

The invention discloses a kind of resin combination, with solid weight meter, including：(a) the diamines modified bismaleimide resin containing benzoxazine structure：40 ~ 90 parts；(b) epoxy resin：10 ~ 30 parts；(c) cyanate：10 ~ 30 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 defects of base material dried flower or lineae ablicantes occurs because reaction is too fast in bonding processes.

Description

Resin combination and prepreg, metal foil laminate and the interlayer using its making Dielectric film
Technical field
Prepreg, metal foil laminate and layer insulation the present invention relates to a kind of resin combination and using its making Film, belong to technical field of electronic materials.
Background technology
The progress of electronic technology is maked rapid progress, portability, the lightening direction for becoming electronic system product and pursuing always, And machine product is lightening, it is thin to need to prepare the component that electronic product is included including printed circuit board, 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 that prepared by the compositions of thermosetting resin using epoxy resin and its curing agent as necessary component Have the advantages that good heat resistance, insulating properties, processability and cost are cheap, 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 Curing agent containing reactive hydrogen in molecular structure, its solidify epoxy resin in substantial amounts of hydroxyl be present, this can cause solidfied material Water absorption rate rise, wet-hot aging performance and dielectric properties decline.
Cyanate ester resin has excellent heat resistance and dielectric properties, but cyanate ester resin has the presence of hydroxyl in system Under, the generation of its self-polymeric reaction can be catalyzed, during autohemagglutination, hydroxyl can react with cyano group first produces a kind of imido-carbonic ester Binary intermediate, so as to accelerate the formation of triazine ring.At the same time, presence of the polyhydroxy in resin system is crossed, also results in Asia The excessive residual of the binary intermediate of amine carbonic ester, and imido-carbonic ester is after humid heat treatment, 200 DEG C or so easily occur Decomposition reaction, it is one of the reason for cyanate ester resin humidity resistance is poor.Therefore, the cyanate in high performance resin composition Using certain limitation being present.
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, to make one of preferred material of thin base at present.So And bismaleimide monomer has higher fusing point, dissolubility is poor, curing reaction temperature is high, the resin fragility after solidification The deficiencies of larger, 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, such as the Kerimid series plastics that 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. excellent Different in nature energy.
However, although above-mentioned 2 kinds of technical schemes can solve the dissolubility of resin and tough sex chromosome mosaicism, 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 which the warpage after causing base material to absorb water is higher.In addition, water absorption rate not only easily causes greatly metal connection Corrosion under fitting wet environment, and its breathing increase after slim sheet material is made, warpage increase can be caused, leverage The processing procedure of printed circuit board.Therefore, how while modified bismaleimide, the water absorption rate of its resin is reduced, reduces it 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 successfully solve the problems, such as the water absorption rate of bimaleimide resin application, 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, it 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, is produced largely so as to quick in system Hydroxyl and amino, so as to cause the curing reaction of whole system to accelerate so that rheology windows narrow.
Therefore, develop a kind of resin combination and using its making prepreg and laminate, 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 there is 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, metal foil laminated using its making Plate and interlayer dielectric.
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：40~80 parts；
(b) epoxy resin：10~30 parts；
(c) cyanate：10~30 parts；
The preparation method of said components (a) is as follows：
Bimaleimide resin and the diamines containing benzoxazine structure are dissolved in organic solvent, in temperature 60~89 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..
Preferably, the mass ratio of the bimaleimide resin and the diamines containing benzoxazine structure is 60：30~30： 60。
Preferably, the solids content of the diamines modified bismaleimide resin containing benzoxazine structure be 30~ 90%.The typical but non-limiting solids content can be 40%, 60%, 70%, 85% etc..It is preferred that 50~80%.
Preferably, in terms of 100 parts of solid weight, including：
(a) the diamines modified bismaleimide resin containing benzoxazine structure：40~70 parts；
(b) epoxy resin：15~30 parts；
(c) cyanate：15~30 parts.
It is furthermore preferred that with solid weight meter, component (a), component (b) and component (c) add up to 100 parts, including：
(a) the diamines modified bismaleimide resin containing benzoxazine structure：40~70 parts；
(b) epoxy resin：15~30 parts；
(c) cyanate：15~30 parts；
(d) inorganic filler：0~100 part；
(e) fire retardant：5~30 parts；
(f) curing accelerator：0.001~1 part.
Above, the fire retardant can be that the copper-clad plate such as brominated flame-retardant or phosphonium flame retardant or nitrogenous flame ratardant is commonly used 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 be spherical, tabular, needle-like, horn shape or unformed shape or It mixes shape.Above-mentioned inorganic filler can be surface-treated using silane coupler, be improved 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.
Preferably, the chemical formula of the bimaleimide resin is as follows：
Wherein,
R1 is selected from：R2 is identical with R3 Or it is different, it is respectively selected from H-, H3C- 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.
Preferably, 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.
Preferably, bimaleimide resin and the diamines containing benzoxazine structure are dissolved in organic solvent, 60 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..Preferable reaction temperature is 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..
Preferably, bimaleimide resin and the diamines containing benzoxazine structure are dissolved in organic solvent, 70 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.
In above-mentioned technical proposal, the cyanate is selected from bisphenol A cyanate ester, bisphenol-f type cyanate, bis-phenol M type cyanic acid Ester, bisphenol S type cyanate, bisphenol E-type cyanate, Novolac Cyanate Eater Resin, tetramethyl bisphenol-f type cyanate, dicyclopentadiene type One or more in cyanate, biphenyl type cyanate, naphthalene type cyanate, phosphorous cyanate, cyanurotriamide modified cyanate；Its Cyanate can be monomer, performed polymer, resin or its mixture.
The present invention principle be：By the diamines containing benzoxazine structure and bimaleimide resin in solvent 90 Preferentially reacted under temperature conditionss below DEG C (not including 90 DEG C), formed prepolymer, when reaction temperature below 90 DEG C (no Including 90 DEG C) when, the reaction in resin mainly between Amino End Group and BMI, benzoxazine is not almost opened Ring；In addition, consuming a part of reactive group by pre-reaction in the present invention, 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 in the present invention simultaneously, 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 produce 0.01~0.02mm of thickness laminate, one As using fibrillation cloth, flat fabric.In addition, in order to improve the interface cohesion of 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 an at least 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 Be covered with metal foil, or by least 2 by above-mentioned prepreg superposition after, be covered with metal foil, hot pressing in its single or double Shaping, you can obtain the metal foil laminate.
The quantity of the prepreg is determined according to the metal foil laminated plate thickness of customer requirement, can use one or more .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 an at least prepreg described above；
Or contain an at least laminate described above；
Or contain an at least 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 that 1-10 minutes are toasted 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 Fat (less than 90 degree, not including 90 DEG C) preferential pre-reaction at low temperature, (less than 90 degree, not including 90 DEG C) benzoxazine under 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, the steric hindrance of benzoxazine ring-opening reaction is increased, slowed down the benzoxazine structure in resin structure in system Reaction rate, the rheology Process window (rheology window broadens in rheological curve figure) of resin combination is have adjusted well, reduce Resin combination in bonding processes because react it is too fast there is the risk of the defects of base material dried flower or lineae ablicantes；Experiment shows, With conventional diamines modified bismaleimide resin and benzoxazine resin, the composition phase of epoxy resin and cyanate ester resin Than the present invention has broader rheology window, the technology controlling and process being more beneficial in laminate lamination process, reduces base material time table The risk for dried flower and lineae ablicantes occur is seen, is more beneficial for the manufacture of copper-clad plate；
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 reduce the breathing ratio after base material water suction, more Inhibit the generation of bow warping；
3. with using allyl compound or common diamines modified bismaleimide resin, epoxy resin and cyanate resin The composition of fat is compared, and the present invention is using the modification with high glass transition temperature, good heat resistance, low water absorption rate Bimaleimide resin, the resin are modified with the diamine resin modified bismaleimide resin containing benzoxazine structure Resin afterwards, with high glass transition temperature and low water absorption rate, solves with the product after good dissolubility, solidification The problem of bimaleimide resin water absorption rate is high in the prior art, has been greatly reduced the warpage of sheet material, and maintain High glass transition temperature and excellent dielectric property, be bimaleimide resin in Aero-Space and electronic applications should With solving a great problem.
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, stand 24hr 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, stand 24hr 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 100g:30g is successively in input three-necked flask In, persistently stirred under the conditions of 75 DEG C of oil bath, start timing after solid in flask is completely dissolved, after persistently stirring 2.5hr, Products therefrom is distilled, 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) -2 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, start timing after solid in flask is completely dissolved, will after persistently stirring 1hr 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, start timing after solid in flask is completely dissolved, after persistently stirring 8hr, Products therefrom is distilled, obtains the modified bismaleimide resin solution 3 that solid content is 60%.
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) -1 of the structure containing benzoxazine, according to mass parts 30g:100g successively in putting into three-necked flask, Persistently stirred under the conditions of 80 DEG C of oil bath, start timing after solid in flask is completely dissolved, after persistently stirring 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, start timing after solid in flask is completely dissolved, after persistently stirring 2.5hr, Products therefrom is distilled, obtains the modified bismaleimide resin solution 5 that solid content is 75%.
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 1.
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) -1 of the structure containing benzoxazine, according to mass parts 30g:100g successively in putting into three-necked flask, Persistently stirred under the conditions of 50 DEG C of oil bath, start timing after solid in flask is completely dissolved, after persistently stirring 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 according to the data in table 1 and disliked prepared in above-mentioned resin modified example containing benzo 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%, by glue coated on glass fabric, in infiltration a moment, into 160 DEG C of air dry ovens, toast 3~6min, prepreg is made, prepreg is cut to certain size, respectively placing an electrolytic copper foil up and down, it is folded to be made into Necessarily folded structure, is sent 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
Cyanate 1 (bisphenol A cyanate ester) Lonza
Cyanate 2 (Novolac Cyanate Eater Resin) Lonza
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, metallic cover layer is tested Peel strength.
Wicking heat resistance：Using 50 × 50mm two sides band copper sample, immerse in 288 DEG C of scolding tin, record sample layering The time of foaming.
Wicking heat resistance after humidity processing：Pressurization of the 3 pieces of 100 × 100mm substrate coupons in 121 DEG C, 105Kpa is steamed Boil after keeping 3hr in processing unit, immerse 2min in 288 DEG C of solder bath, phenomena such as whether sample occurs to be layered bubbling observed, 3 pieces do not occur be layered bubbling be designated as 3/3,2 pieces do not occur be layered bubbling be designated as 2/3,1 piece do not occur be layered 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：It is swollen using the harmomegathus situation after the test substrate water suction of triaxial coordinate method, base material Swollen to be represented using "+numerical value ", base material shrinks to be represented using "-numerical value ", unit ppm, i.e. hundred a ten thousandths.
Dielectric properties：Flat band method is used according to IPC-TM-650 2.5.5.9, determines dielectric constant and dielectric under 1GHz Loss tangent value.
Bending strength：Standard method specified in IPC-TM-650 is tested.
Bow warping degree：Tested using standard method specified in IPC-TM-650, obtain bow maximum percentage and torsion Bent maximum percentage, the angularity of copper-clad plate base material is judged with this.
Base material time is apparent：Tested using standard method specified in IPC-TM-650, by visual observation or section method sentence Whether there is in disconnected base material and the defects of 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, Epoxy resin and cyanate compositions have relatively low dielectric constant, high glass transition temperature and low warpage, make it more Meet the impedance design and rigid requirements of thin base well；Change compared with using allyl compound (comparative example 1) or common diamines Property bimaleimide resin (comparative example 2), the composition of epoxy resin and cyanate ester resin has lower water absorption rate and sticks up Curvature, and maintain high glass transition temperature and excellent dielectric property.
Further, the diamines containing benzoxazine and bimaleimide resin (embodiment 3) are subjected to pre-polymerization, it is normal with inciting somebody to action Advise the composition (comparative example of diamines modified bismaleimide resin and benzoxazine resin, epoxy resin and cyanate ester resin 4) compare, there is broader rheology window, the technology controlling and process being more beneficial in laminate lamination process, it is apparent to reduce base material time There is the risk of dried flower and lineae ablicantes, be more beneficial for the manufacture of copper-clad plate.
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 6) is carried out at a temperature of 90 DEG C, have broader rheology window (referring to Rheology window broadens in Fig. 1 rheological curve figure), while significantly improve 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 5) is compared, obvious 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, professional and technical personnel in the field are enable 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 1. 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 ~ 80 parts；
    (b) epoxy resin：10 ~ 30 parts；
    (c) cyanate：10 ~ 30 parts；
    The preparation method of said components (a) is as follows：
    Bimaleimide resin and the diamines containing benzoxazine structure are dissolved in organic solvent, at 60 ~ 89 DEG C of temperature 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. 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：40 ~ 70 parts；
    (b) epoxy resin：15 ~ 30 parts；
    (c) cyanate：15 ~ 30 parts.
  3. 3. resin combination according to claim 1, it is characterised in that：With solid weight meter, component（a）, component（b）With Component（c）Add up to 100 parts, including：
    (a) the diamines modified bismaleimide resin containing benzoxazine structure：40 ~ 70 parts；
    (b) epoxy resin：15 ~ 30 parts；
    (c) cyanate：15 ~ 30 parts；
    (d) inorganic filler：0 ~ 100 part；
    (e) fire retardant：5 ~ 30 parts；
    (f) curing accelerator：0.001 ~ 1.0 part.
  4. 4. according to the resin combination described in 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 and R3 is identical or not Together, be respectively selected from H-,。
  5. 5. according to the resin combination described in 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. 6. according to the resin combination described in claim 1 or 2 or 3, it is characterised in that：By bimaleimide resin and contain 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. A kind of 7. prepreg that 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 8. laminate, it is characterised in that：It includes an at least prepreg as claimed in claim 7.
  9. A kind of 9. 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 10. 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, after being coated with the carrier film heat drying of resin combination, you can obtain the interlayer dielectric.
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US11274218B2 (en) 2017-12-11 2022-03-15 Lg Chem, Ltd. Thermosetting resin composition for coating metal thin film and metal laminate using the same
CN114367761A (en) * 2022-02-21 2022-04-19 中山翰华锡业有限公司 Halogen-free lead-free soldering paste with low residues after soldering and preparation method thereof
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CN111825875A (en) * 2020-07-25 2020-10-27 周有松 Toughened benzoxazine foamed board and preparation method thereof
CN111825875B (en) * 2020-07-25 2023-01-20 周有松 Toughened benzoxazine foamed plate and preparation method thereof
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CN114836147A (en) * 2022-04-21 2022-08-02 深圳市纽菲斯新材料科技有限公司 Novel FC-BGA packaging substrate is with increasing layer glued membrane and use rubber coating copper foil of its preparation
CN114836147B (en) * 2022-04-21 2023-08-22 深圳市纽菲斯新材料科技有限公司 Layer-increased adhesive film for FC-BGA packaging loading plate and adhesive-coated copper foil manufactured by using same

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