CN107245239B - Resin combination and prepreg, metal foil laminate and the interlayer dielectric made using it - Google Patents
Resin combination and prepreg, metal foil laminate and the interlayer dielectric made using it Download PDFInfo
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- CN107245239B CN107245239B CN201710560611.5A CN201710560611A CN107245239B CN 107245239 B CN107245239 B CN 107245239B CN 201710560611 A CN201710560611 A CN 201710560611A CN 107245239 B CN107245239 B CN 107245239B
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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
- C08G73/128—Unsaturated polyimide precursors the unsaturated precursors containing heterocyclic moieties in the main chain
-
- 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
Abstract
The invention discloses a kind of resin combinations, with solid weight meter, comprising: the diamines modified bismaleimide resin of (a) structure containing benzoxazine: 40 ~ 80 parts；(b) epoxy resin: 10 ~ 50 parts；(c) active ester: 10 ~ 40 parts.The present invention passes through bismaleimide 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 for having adjusted resin combination well reduces resin combination and the risk of the defect of substrate dried flower or lineae ablicantes occurs because reacting too fast during the pressing process.
Description
Technical field
The present invention relates to a kind of resin combination and use prepreg, metal foil laminate and the layer insulation of its production
Film belongs to technical field of electronic materials.
Background technique
The progress of electronic technology is maked rapid progress, portability, the lightening direction for becoming electronic system product and pursuing always,
And complete product is lightening, needing to prepare electronic product comprising the component including printed circuit board wants thin, therefore, just needs
Copper-clad plate substrate rigidity with higher and resistance to warping are wanted, the structural support and procedure for processing of printed circuit board are just able to satisfy
Demand.
In the prior art, with the material for the compositions of thermosetting resin preparation that epoxy resin and its curing agent are necessary component
Have many advantages, such as good heat resistance, insulating properties, processability and low in cost, therefore is widely used in semiconductor, printed circuit
In the electronic materials such as plate.The common curing agent of epoxy resin has polyamines, acid anhydrides, phenolic resin, active ester etc..Wherein, active ester
It can react with epoxy resin under the conditions of relatively mild；Meanwhile the cured epoxy resin of active ester does not contain hydroxyl,
Instead ester group, the excellent epoxy resin-cured product of available dielectric properties.Japanese Patent Laid-Open
It is disclosed in JP2002012650A, JP2003082063A, JP2004155990A, JP2009235165A and JP2012246367A
A series of active ester resins, are used as epoxy curing agent, the dielectric that can be substantially reduced epoxy resin cured product is normal
Several and dielectric loss.But there is heat resistance deficiency in the epoxy resin of these active ester resin solidifications, it is difficult to simultaneous
Care for heat resistance and low-k, low-dielectric loss tangent, thus the requirement not being able to satisfy in material practical application.
On the other hand, in the existing resin material for preparing printed circuit board, bismaleimide is very outstanding
One of resin, it is a kind of thermosetting resin containing imide structure, and high crosslink density makes it have high glass after solidifying
Glass transition temperature, excellent thermal stability and higher rigidity, for one of the preferred material of production thin base at present.So
And bismaleimide monomer fusing point with higher, dissolubility is poor, curing reaction temperature is high, solidify after resin brittleness
The deficiencies of larger, limits its application.
In view of the above technical problems, there are allyl compound or aromatic diamine compound modified bismaleimide tree at present
Rouge is two kinds of more mature technology paths, such as the Kerimid series plastics that Huntsman company releases in last century, northwest industry
The modified span series plastics of the allyl compound of Liang Guo full professor team, university exploitation, obtained modified bismaleimide
Resin has high tenacity, excellent dissolubility (dissolving in the organic solvents such as acetone/butanone), high glass transition temperature etc. excellent
Anisotropic energy.
However, although above-mentioned 2 kinds of technical solutions can well solve the dissolubility and toughness problem of resin, span
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 substrate for preparing electronic circuit --- copper-clad plate tree
When modified bismaleimide resin (usually first passing through allyl or diamines modification) component in rouge formula is higher, substrate
Water absorption rate is often bigger than normal, higher so as to cause the warpage after substrate water suction.In addition, water absorption rate not only easily causes metal to join greatly
Corrosion under fitting wet environment, and will lead to its breathing increase after slim plate is made, warpage increase, it leverages
The processing procedure of printed circuit board.Therefore, how while modified bismaleimide, the water absorption rate of its resin is reduced, it is reduced
Warpage after slim plate is made, one of the difficult point applied at bimaleimide resin in electronic circuit field.
The bismaleimide-triazine resin (BT resin) of Mitsubishi's gas can be described as bismaleimide and cyanate is answered
Model, though successfully solving the problems, such as the water absorption rate of bimaleimide resin application, and patented technology discloses, it is closed
Key technology main points are still difficult for domestic technique personnel and are grasped.
Chinese invention patent application CN104725781A discloses amine modified bismaleimide resin, benzoxazine resin
And the composition of epoxy resin, although which reduce the water absorption rates of span.However, the applicant has carried out experiment discovery: amine changes
Property bimaleimide resin can effectively improve reactivity (" the modified benzene of BMI of this point Li Ling et al. of benzoxazine
And oxazines resin and its composite material research " be also described in a text), this also results in its rheology window during the pressing process
Also therefore narrow, secondary to copper-clad plate substrate apparently causes certain dried flower and lineae ablicantes risk.
For above-mentioned phenomenon, inventor is had conducted extensive research, it is believed that itself the reason is as follows that: due in CN104725781A
Amine modified bismaleimide resin is to carry out pre-polymerization in organic solvent by amine modifiers and bismaleimide to form.Amine
Substance is epoxy curing agent, after amine is reacted with epoxy resin, epoxy resin open loop generation great amount of hydroxy group, and hydroxyl
The Open loop temperature that benzoxazine resin can be reduced accelerates the ring-opening reaction of benzoxazine, to quickly generate in system a large amount of
Hydroxyl and amino accelerate so as to cause the curing reaction of whole system, so that rheology windows narrow.
Therefore, a kind of resin combination and prepreg and laminate using its production are developed, make its have both 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
Time apparent the phenomenon that forming dried flower and lineae ablicantes of plate substrate, it is clear that there is positive realistic meaning.
Summary of the invention
Goal of the invention of the invention is to provide a kind of resin combination and the prepreg, metal foil laminated using its production
Plate and interlayer dielectric.
To achieve the above object of the invention, the technical solution adopted by the present invention is that: a kind of resin combination, with solid weight
100 parts of meters, comprising:
(a) the diamines modified bismaleimide resin of the structure containing benzoxazine: 40~80 parts；
(b) epoxy resin: 10~50 parts；
(c) active ester: 10~40 parts；
Said components (a) the preparation method is as follows:
In organic solvent by bimaleimide resin and the dissolution of the diamines of the structure containing benzoxazine, in temperature 60~89
Reaction 1~r for 24 hours at DEG C；
The mass ratio of the bimaleimide resin and the diamines of the structure containing benzoxazine is 100:30~30:100；
The chemical formula of the diamine compound of the structure containing benzoxazine is as follows:
Wherein, R is selected from-C (CH3)2-、-SO2Or-CH2, n=2~4.
The mass ratio of the bimaleimide resin and the diamines of the structure containing benzoxazine is 100:30~30:100, example
Such as, the mass ratio of bimaleimide resin and the diamines of the structure containing benzoxazine 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 solid content of the diamines modified bismaleimide resin of the structure containing benzoxazine be 30~
90%.It is preferred that 50~80%.The solid content is typical but non-limiting to can be 40%, 60%, 70%, 85% etc..
Preferably, the mass ratio of the bimaleimide resin and the diamines of the structure containing benzoxazine is 60:30~30:
60。
Preferably, in terms of 100 parts of solid weight, comprising:
(a) the diamines modified bismaleimide resin of the structure containing benzoxazine: 40~70 parts；
(b) epoxy resin: 10~30 parts；
(c) active ester: 20~30 parts.
It is furthermore preferred that component (a), component (b) and component (c) add up to 100 parts with solid weight meter, comprising:
(a) the diamines modified bismaleimide resin of the structure containing benzoxazine: 40~70 parts；
(b) epoxy resin: 10~30 parts；
(c) active ester: 20~30 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 common for brominated flame-retardant or the copper-clad plates such as phosphonium flame retardant or nitrogenous flame ratardant
The mixture of one of fire retardant or two kinds or more.
The brominated flame-retardant is selected from deca-BDE, decabromodiphenylethane, octa-BDE, pentabromotoluene, hexabromo ring
Dodecane, ethylene double tetrabromo phthalimide, brominated polycarbonate, brominated Polystyrene, bromination triazine, two pentabromo-s of ethylene
The double tetrabromo acid imides of benzene, ethylene, ten tetrabromos, two phenoxy group benzene, bis- (tribromophenoxy) ethane, tetrabromobisphenol A, brominated asphalt mixtures modified by epoxy resin
At least one of rouge；The phosphonium flame retardant is selected from three (2,6- 3,5-dimethylphenyl) phosphines, 10- (2,5- dihydroxy phenyl) -9,10-
Miscellaneous -10- phosphine phenanthrene -10- the oxide of dihydro-9-oxy, (2,6- 3,5-dimethylphenyl) the phosphino- benzene of 2,6- bis- or 10- phenyl -910- dihydro -
9- oxa- -10- phosphine phenanthrene -10- oxide, 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, ammonium polyphosphate, phosphonitrile compound, idol
Phosphorus-nitrogen compound, bisphenol-A bis- (diphenyl phosphoesters), three (2,6- 3,5-dimethylphenyl) phosphines, bis- [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 object, phenthazine, 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),
Aluminium oxide, magnesia, magnesium hydroxide, calcium carbonate, aluminium nitride, boron nitride, aluminium hydroxide, aluminum silicon carbide, silicon carbide, sodium carbonate,
Titanium dioxide, zinc oxide, zirconium oxide, quartz, diamond dust, class diamond dust, glass powder, graphite, magnesium carbonate, potassium titanate, ceramics are fine
Dimension, mica, boehmite, zinc molybdate, ammonium molybdate, zinc borate, 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 content is preferably 10~80
Part.
The shape of above-mentioned inorganic filler is not particularly limited, can for spherical, plate, needle-shaped, horn shape or unformed shape or
It mixes shape.Above-mentioned inorganic filler can be used silane coupling agent and is surface-treated, and improve the dispersion in resin combination
Property.When in use above-mentioned inorganic filler can direct plunge into previously prepared filler dispersion liquid or be made lotion investment resin combination
In object.
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- phenylimidazole, 2- 11
Alkyl imidazole, 1- cyanoethyl substituted imidazole；The pyridines are selected from triethylamine, benzyl dimethylamine or dimethylamino naphthyridine；It is described
Carboxylic acid metal's salt is that acetylacetone,2,4-pentanedione acid metal salt, sad metal salt, isooctyl acid or metal naphthenate, the metal are 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 amide based compound, acid anhydrides system chemical combination
The epoxy curing agents such as object, phenol system compound, but do not contain amine curing agent.The amide 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 resin etc., content are 100 parts of epoxy resin meters, contain 1~80 part.
Preferably, the chemical formula of the bimaleimide resin is as follows:
Wherein,
R1 is selected from:
R2 and R3 are identical or different, are respectively selected from H-, H3C- or C2H5-。
In above-mentioned technical proposal, preferably bimaleimide resin is 4,4 '-diphenyl methane dimaleimides, 4,4 '-
Diphenyl Ether Bismaleimide, 4,4 '-diphenyl sulphone (DPS) bismaleimide and bis- (3- ethyl -5- methyl -4- dimaleoyl iminos
Benzene) one of methane or more than one mixture.
Preferably, the epoxy resin is selected from isocyanate-modified bisphenol A epoxide resin, isocyanate-modified Bisphenol F ring
Oxygen resin, 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
Rouge, brominated epoxy resin, paraxylene epoxy resin, naphthalene type epoxy resin, benzo croak are muttered type epoxy resin, biphenyl epoxy novolac
One or more of resin, phenolic group benzene alkyl novolac epoxy resin.
In above-mentioned technical proposal, the active ester is selected from such as one or more of flowering structure:
, in formula, X is phenyl ring or naphthalene nucleus, and j is 0 or 1, and k is 0 or 1, and n is 0.05~2.5；
In formula, k
It is 0 or 1, n is 0.05~2.5；
In formula, k
It is 0 or 1, n is 0.05~2.5；
In formula, k
It is 0 or 1, n is 0.05~2.5；
In formula, k
It is 0 or 1, n is 0.05~2.5；
In formula, k
It is 0 or 1, n is 0.05~2.5；
In formula, k
It is 0 or 1, n is 0.05~2.5；
In formula, k
It is 0 or 1, n is 0.05~2.5；
In formula, k is 0 or 1, and n is 0.05~2.5；
In formula, k is 0 or 1, and n is 0.05~2.5；
,
In formula, k is 0 or 1, and n is 0.05~2.5.
Preferably, active ester is as shown in flowering structure:
, in formula, X is phenyl ring or naphthalene nucleus, and j is 0 or 1, and k is 0 or 1, and n is 0.05~2.5.
Preferably, in organic solvent by bimaleimide resin and the dissolution of the diamines of the structure containing benzoxazine, 60
Reaction 1~r for 24 hours at a temperature of~89 DEG C.Wherein, reaction temperature it is typical but non-limiting can be 61 DEG C, 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..Preferred 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, in organic solvent by bimaleimide resin and the dissolution of the diamines of the structure containing benzoxazine, 70
2~10hr is reacted at a temperature of~80 DEG C.
The organic solvent is selected from acetone, butanone, toluene, dimethylbenzene, methanol, ethyl alcohol, 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 of acid esters, ethoxyethyl acetate, Among acetic acid esters, ethyl acetate.
The principle of the present invention are as follows: by the diamines containing benzoxazine structure and bimaleimide resin 90 in solvent
It is preferentially reacted under the conditions of DEG C temperature (not including 90 DEG C) below, prepolymer is formed, when reaction temperature is at 90 DEG C or less
(not including 90 DEG C), mainly reacting between Amino End Group and bismaleimide, benzoxazine are not almost opened in resin
Ring；In addition, consuming a part of reactive group by pre-reaction in the present invention, the prepolymer with certain molecular weight is formed, is increased
The steric hindrance of benzoxazine ring-opening reaction, slowed down benzoxazine structure in resin structure reaction rate so that pressing
Rheology window in the process broadens, and thus greatly reduces the risk of copper-clad plate substrate 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 dissolution, and then reinforcing material is immersed in above-mentioned glue；After impregnating after reinforcing material heat drying
Obtain the prepreg.
The solvent is selected from acetone, butanone, toluene, dimethylbenzene, methanol, ethyl alcohol, 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 the laminate for producing 0.01~0.02mm of thickness, one
As use fibrillation cloth, flat fabric.In addition, glass fabric is generally all in order to improve the interface cohesion of resin and glass fabric
It is 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 comprising at least one such as above-mentioned prepreg.
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
Forming, can be obtained 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, be also possible to aluminium foil, their thickness is not particularly limited.
A kind of printed circuit board is claimed simultaneously in the present invention, contains at least one such as above-mentioned prepreg；
Or contain at least one such as above-mentioned laminate；
Or contain at least one such as above-mentioned metal foil laminate.
The interlayer dielectric using the production of above-mentioned resin combination is claimed in the present invention simultaneously, using above-mentioned resin combination
Object is added solvent dissolution and glue is made, and the glue will be coated in carrier film, by after the carrier film heat drying for coating glue, i.e.,
The interlayer dielectric can be obtained, the heat drying condition is to toast 1~10 minute at 50~170 DEG C.
In above-mentioned technical proposal, the solvent is selected from acetone, butanone, toluene, dimethylbenzene, methanol, ethyl alcohol, 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, release film, 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 layer another side covering protection film, the protective film
It can material identical as carrier film.
Due to the above technical solutions, the present invention has the following advantages over the prior art:
1. modified bismaleimide resin of the invention passes through bismaleimide and the diamines tree containing benzoxazine
Rouge (90 degree hereinafter, do not include 90 DEG C) preferential pre-reaction at low temperature, (90 degree hereinafter, do not include 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 increases the steric hindrance of benzoxazine ring-opening reaction, has slowed down the benzoxazine structure in resin structure in system
Reaction rate has adjusted the rheology Process window (rheology window broadens in rheological curve figure) of resin combination well, reduces
There is the risk of the defect of substrate dried flower or lineae ablicantes because reacting too fast during the pressing process in resin combination；Experiment shows
The present invention will not achieve significant effect in time apparent the phenomenon that forming dried flower and lineae ablicantes of copper-clad plate substrate；
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 advantageous to the application in copper-clad plate field, and high heat resistance and rigidity ensure that it
Application in aerospace and thin copper clad laminate field, low water absorption rate reduce the breathing ratio after substrate water suction, more
Inhibit the generation of bow warping；
3. the present invention is using the modification span with high glass transition temperature, good heat resistance, low water absorption rate
Bismaleimide resin, the resin are modified with the diamine resin modified bismaleimide resin containing benzoxazine structure
Resin has high glass transition temperature and low water absorption rate with the product after good dissolubility, solidification, solves existing
There is the problem that bimaleimide resin water absorption rate is high in technology, be greatly reduced the warpage of plate, is bismaleimide
Polyimide resin solves a great problem in the application of aerospace and electronic field；
4. diamines modified bismaleimide resin, epoxy resin and the active ester of the invention containing benzoxazine structure
Resin combination have good heat resistance, high glass transition temperature, low water absorption rate, low angularity and it is preferable just
Property, the requirement of thin base rigidity and angularity in impedance design and printed circuit process can be met well.
Detailed description of the invention
Fig. 1 is the rheological curve figure of the prepreg in the embodiment of the present invention and comparative example.
Specific embodiment
The present invention will be further described below with reference to examples:
The following are the preparations of the diamines modified bismaleimide resin containing benzoxazine, obtain modified resin, specific real
Apply mode:
Synthesis example one
Be equipped with blender, reflux condensing tube and thermometer 500ml three-necked flask, be placed in oil bath pan, successively plus
Enter bisphenol-A: 91.2g, p-phenylenediamine: 94.4g, formaldehyde: 48.0g；Add 80ml ethyl alcohol and 20ml toluene as solvent, slowly
It is warming up to 75 DEG C and keeps 3hr, be persistently kept stirring state in the process, and be passed through nitrogen in three-necked flask and be bubbled protection.On
Stating reaction terminates, and after product is cooled to room temperature, maintains to stir and methanol solution is added dropwise into flask, until there is no sediment analysis
Out, stop stirring, stand r for 24 hours at room temperature, filter off supernatant liquor, collect sediment, sediment is placed into 50 DEG C of vacuum drying and is dried
In case, 5hr is dried, the diamines of the structure containing benzoxazine is obtained, is denoted as N (BOZ) -1.
Synthesis example two
Be equipped with blender, reflux condensing tube and thermometer 500ml three-necked flask, be placed in oil bath pan, successively plus
Enter Bisphenol F: 79.2g, p-phenylenediamine: 94.4g, formaldehyde: 48.0g；Add 80ml ethyl alcohol and 20ml toluene as solvent, slowly
It is warming up to 60 DEG C and keeps 5hr, be persistently kept stirring state in the process, and be passed through nitrogen in three-necked flask and be bubbled protection.On
Stating reaction terminates, and after product is cooled to room temperature, maintains to stir and methanol solution is added dropwise into flask, until there is no sediment analysis
Out, stop stirring, stand r for 24 hours at room temperature, filter off supernatant liquor, collect sediment, sediment is placed into 50 DEG C of vacuum drying and is dried
In case, 5hr is dried, the diamines of the structure containing benzoxazine is obtained, is denoted as N (BOZ) -2.
Modified resin example one
100g solvent n,N-Dimethylformamide is added in 500ml three-necked flask, 4,4 '-diphenyl-methane spans are carried out into acyl
The diamine resin N (BOZ) -1 of imines and the structure containing benzoxazine, according to mass parts 100:30 successively in investment three-necked flask in,
It is persistently stirred under the conditions of 75 DEG C of oil bath, starts timing after solid in flask is completely dissolved, it, will after persistently stirring 2.5hr
Products therefrom is distilled, and the modified bismaleimide resin solution 1 that solid content is 75% is obtained.
Modified resin example two
120g solvent n,N-dimethylacetamide is added in 500ml three-necked flask, 4,4 '-diphenyl-methane spans are carried out into acyl
The diamine resin N (BOZ) -2 of imines and the structure containing benzoxazine, according to mass parts 100g:50g successively in investment three-necked flask
In, it is persistently stirred under the conditions of 85 DEG C of oil bath, starts timing after solid in flask is completely dissolved, it, will after persistently stirring 1hr
Products therefrom is distilled, and the modified bismaleimide resin solution 2 that solid content is 60% is obtained.
Modified resin example three
In 500ml three-necked flask be added 150g solvent acetone, will be bis- (3- ethyl -5- methyl -4- dimaleoyl imino
Benzene) methane and the structure containing benzoxazine diamine resin N (BOZ) -1, according to mass parts 100g:100g successively in investment three mouthfuls burning
In bottle, is 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, the modified bismaleimide resin solution 3 that solid content is 60% is obtained.
Modified resin example four
100g solvent n,N-dimethylacetamide is added in 500ml three-necked flask, by 4,4 '-diphenyl ether bismaleimides
The diamine resin N (BOZ) -2 of amine and the structure containing benzoxazine, according to mass parts 30g:100g successively in investment three-necked flask in,
It is persistently stirred under the conditions of 80 DEG C of oil bath, starts timing after solid in flask is completely dissolved, after persistently stirring 4hr, by institute
It obtains product to be distilled, obtains the modified bismaleimide resin solution 4 that solid content is 65%.
Modified resin example five
100g solvent n,N-Dimethylformamide is added in 500ml three-necked flask, 4,4 '-diphenyl-methane spans are carried out into acyl
The diamine resin N (BOZ) -1 of imines and the structure containing benzoxazine, according to mass parts 100:30 successively in investment three-necked flask in,
It is persistently stirred under the conditions of 60 DEG C of oil bath, starts timing after solid in flask is completely dissolved, it, will after persistently stirring 2.5hr
Products therefrom is distilled, and the modified bismaleimide resin solution 5 that solid content is 75% is obtained.
Modified resin comparative example one
4,4 '-diphenyl methane dimaleimides and diallyl bisphenol resin are placed in burning according to mass ratio 100:60
In bottle, 100min is reacted under the conditions of 130 DEG C of oil bath, obtains the modified span 1 of allyl.
Modified resin comparative example two
4,4 '-diphenyl methane dimaleimide 100g are weighed, diaminodiphenylmethane 40g is dissolved in DMF solution,
5hr is reacted under the conditions of 100 DEG C, obtains the modified span 2 of amine.
Modified resin comparative example three
100g solvent n,N-dimethylacetamide is added in 500ml three-necked flask, by 4,4 '-diphenyl ether bismaleimides
The diamine resin N (BOZ) -2 of amine and the structure containing benzoxazine, according to mass parts 30g:100g successively in investment three-necked flask in,
It is persistently stirred under the conditions of 50 DEG C of oil bath, starts timing after solid in flask is completely dissolved, after persistently stirring 4hr, by institute
It obtains product to be distilled, obtains the modified bismaleimide resin solution 6 that solid content is 65%.
Modified resin comparative example four
100g solvent n,N-Dimethylformamide is added in 500ml three-necked flask, 4,4 '-diphenyl-methane spans are carried out into acyl
The diamine resin N (BOZ) -1 of imines and the structure containing benzoxazine, according to mass parts 100:30 successively in investment three-necked flask in,
It is persistently stirred under the conditions of 100 DEG C of oil bath, starts timing after solid in flask is completely dissolved, it, will after persistently stirring 2.5hr
Products therefrom is distilled, and the modified bismaleimide resin solution 7 that solid content is 75% is obtained.
The preparation of prepreg and copper-clad plate
According to solid masses meter, weighs 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 adds epoxy resin, inorganic filler, curing accelerator, and passes through solvent adjustment
When glue solid content is to 60%, glue is coated on glass fabric, infiltration a moment, until in 160 DEG C of air dry ovens, baking
Prepreg is made in 3~6min, and prepreg is cut to certain size, is respectively placing an electrolytic copper foil up and down, folded to be made into
Centainly 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.
1 resin composition content data of table
2 material trademark of table and producer
| Title | Producer |
| Bis- (3- ethyl -5- methyl -4- Mailed-phenyl) methane | Xi'an span new material |
| 4,4 '-diphenyl methane dimaleimides | Xi'an span new material |
| 4,4 '-hexichol isopropyl bismaleimide | Xi'an span new material |
| Epoxy resin 1 (bisphenol A type epoxy resin) | Dow |
| Epoxy resin 2 (naphthalene nucleus type epoxy resin) | Dic |
| Active ester (structural formula 1) | Dic |
| Active ester (structural formula 2) | 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' chemical conversion |
Active ester compound 1, structural formula (1) are as follows:
In formula, X is phenyl ring or naphthalene nucleus, and j is 0 or 1, and k is 0 or 1, and n is 0.25~2.5 (average value of number of repeat unit).
Active ester compound 2, structural formula are (2):
In formula, k is 0 or 1, and n is 0.25~2.5 (average value of number of repeat unit).
The prepreg and copper-clad plate that prepare in above-mentioned all embodiment and comparative examples are tested for the property.Test method
Are as follows:
Glass transition temperature (TMA): the Tg of the resistance to TMA instrument test plate speeded is used, heating rate: 10 DEG C/min,
Temperature range: 30-320 DEG C.
Glass transition temperature (DMA): using the Tg of the DMA Q800 instrument test plate of TA, heating rate: 3 DEG C/
Min, temperature range: 30-320 DEG C.
Peel strength (PS): according to " after thermal stress " experiment condition in IPC-TM-650 method, metallic cover layer is tested
Peel strength.
Wicking heat resistance: using the two sides band copper sample of 50 × 50mm, immerses in 288 DEG C of scolding tin, record sample layering
The time of blistering.
Wicking heat resistance after humidity processing: the pressurization by the substrate coupons of 3 pieces of 100 × 100mm in 121 DEG C, 105Kpa is steamed
It boils after keeping 3hr in processing unit, immerses 2min in 288 DEG C of solder bath, whether observation sample occurs phenomena such as layering is bubbled,
3 pieces do not occur layering be bubbled be denoted as 3/3,2 pieces do not occur layering be bubbled be denoted as 2/3,1 piece do not occur layering be bubbled be denoted as 1/3,
0 piece layering bubbling does not occur and is denoted as 0/3.
D23 DEG C/r water absorption rate for 24 hours: being measured according to standard method specified in IPC-TM-650
Harmomegathus after D23 DEG C/r water suction for 24 hours: using the harmomegathus situation after the test substrate water suction of triaxial coordinate method, substrate is swollen
Swollen to be indicated using "+numerical value ", substrate is shunk to be indicated using "-numerical value ", unit ppm, i.e. hundred a ten thousandths.
Bow warping degree: using the test of standard method specified in IPC-TM-650, bow maximum percentage and torsion are obtained
Bent maximum percentage, the angularity of copper-clad plate substrate is judged with this.
Bending strength: the test of standard method specified in IPC-TM-650.
Substrate time is apparent: using the test of standard method specified in IPC-TM-650, by visual observation or dicing method judges
Whether there is or not the defects of dried flower, lineae ablicantes occur in substrate.
Prepreg powder rheometer test: Anton Paar MCR302 rheometer, the rheological curve of test sample, temperature model are used
It encloses: 80~160 DEG C, heating rate: 3 DEG C/min.
The copper-clad plate basic performance data of 3 embodiment and comparative example of table
By above-described embodiment and comparative example it is found that using the diamines modified bismaleimide resin containing benzoxazine,
Epoxy resin and active ester resin composition (embodiment 1) are relatively modified using allyl compound (comparative example 1) or common diamines
Bimaleimide resin (comparative example 2), epoxy resin and active ester composition are compared, and have lower water absorption rate and warpage
Degree, and high glass transition temperature and excellent humidity resistance are maintained, thin base can be met well and set in impedance
The requirement of meter and the angularity in printed circuit process；
Further, the diamines containing benzoxazine and bimaleimide resin are subjected to pre-polymerization, epoxy resin and work
Property ester resin formed composition (embodiment 3), with by conventional diamines modified bismaleimide resin, benzoxazine resin,
The composition (comparative example 5) that active ester is formed with epoxy resin is compared, and not only has lower water absorption rate, and have broader stream
Become window, the technology controlling and process being more advantageous in laminate lamination process reduces substrate time and the wind of dried flower and lineae ablicantes apparently occurs
Danger, is more advantageous to the manufacture of copper-clad plate.
Further, by the diamines containing benzoxazine and bimaleimide resin less than 90 DEG C at a temperature of carry out
Pre-polymerization (embodiment 1) be greater than 90 DEG C at a temperature of carry out pre-polymerization (comparative example 7) compared with, have broader rheology window (referring to
Rheology window broadens in the rheological curve figure of Fig. 1), while significantly improving substrate time apparent mass；Benzoxazine will be contained
Diamines and bimaleimide resin greater than 60 DEG C at a temperature of carry out pre-polymerization (embodiment 4) with less than 60 DEG C at a temperature of into
Row pre-polymerization (comparative example 6) is compared, obvious excellent in terms of water absorption rate and size harmomegathus.
In addition, with embodiment 5 (60 DEG C at a temperature of carry out pre-polymerization) compared with, embodiment 1 (75 DEG C at a temperature of carry out
Pre-polymerization) comprehensive performance it is more preferable.
The foregoing description of the disclosed embodiments enables those skilled in the art to implement or use the present invention.
Various modifications to these embodiments will be readily apparent to 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, of the invention
It is not intended to be limited to the embodiments shown herein, and is to fit to and the principles and novel features disclosed herein phase one
The widest scope of cause.
Claims (10)
1. a kind of resin combination, which is characterized in that in terms of 100 parts of solid weight, comprising:
(a) the diamines modified bismaleimide resin of the structure containing benzoxazine: 40~80 parts；
(b) epoxy resin: 10~50 parts；
(c) active ester: 10~40 parts；
Said components (a) the preparation method is as follows:
In organic solvent by bimaleimide resin and the dissolution of the diamines of the structure containing benzoxazine, at 60~89 DEG C of temperature
Reaction 1~r for 24 hours；
The mass ratio of the bimaleimide resin and the diamines of the structure containing benzoxazine is 100:30~30:100；
The chemical formula of the diamine compound of the structure containing benzoxazine is as follows:
Wherein, R is selected from-C (CH3)2-、-SO2Or-CH2, n=2~4.
2. resin combination according to claim 1, it is characterised in that: in terms of 100 parts of solid weight, comprising:
(a) the diamines modified bismaleimide resin of the structure containing benzoxazine: 40~70 parts；
(b) epoxy resin: 10~30 parts；
(c) active ester: 20~30 parts.
3. resin combination according to claim 1, it is characterised in that: with solid weight meter, component (a), component (b) and
Component (c) adds up to 100 parts, comprising:
(a) the diamines modified bismaleimide resin of the structure containing benzoxazine: 40~70 parts；
(b) epoxy resin: 10~30 parts；
(c) active ester: 20~30 parts；
(d) inorganic filler: 0~100 part；
(e) fire retardant: 5~30 parts；
(f) curing accelerator: 0.001~1 part.
4. 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,
R1It is selected from:R2And R3It is identical or not
Together, H-, H are respectively selected from3C- or C2H5-。
5. resin combination according to claim 1 or 2 or 3, it is characterised in that: the active ester is in such as flowering structure
One or more:
, in formula, X is phenyl ring or naphthalene nucleus, and j is 0 or 1, and k is 0 or 1, and n is 0.05~2.5；
Formula
In, k is 0 or 1, and n is 0.05~2.5；
Formula
In, k is 0 or 1, and n is 0.05~2.5；
Formula
In, k is 0 or 1, and n is 0.05~2.5；
Formula
In, k is 0 or 1, and n is 0.05~2.5；
Formula
In, k is 0 or 1, and n is 0.05~2.5；
Formula
In, k is 0 or 1, and n is 0.05~2.5；
Formula
In, k is 0 or 1, and n is 0.05~2.5；
In formula,
K is 0 or 1, and n is 0.05~2.5.
6. resin combination according to claim 1 or 2 or 3, it is characterised in that: by bimaleimide resin and contain benzene
And oxazines structure diamines dissolution in organic solvent, 70~80 DEG C at a temperature of react 2~10hr.
7. a kind of prepreg using the resin combination production as described in claims 1 or 2 or 3, it is characterised in that: will weigh
Benefit require 1 or 2 or 3 described in resin combination solvent dissolution glue is made, reinforcing material is then immersed in above-mentioned glue
In；After impregnating after reinforcing material heat drying, the prepreg can be obtained.
8. a kind of laminate, it is characterised in that: it includes an at least prepreg as claimed in claim 7.
9. a kind of metal foil laminate, it is characterised in that: in a single or double by prepreg as claimed in claim 7
Be covered with metal foil, or will at least 2 by prepreg as claimed in claim 7 superposition after, be covered with gold in its single or double
Belong to foil, the metal foil laminate can be obtained in hot forming.
10. a kind of interlayer dielectric, it is characterised in that: coat resin described in described claims 1 or 2 or 3 on a carrier film
After being coated with the carrier film heat drying of resin combination, the interlayer dielectric is can be obtained in composition.
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| CN112079722A (en) * | 2019-06-13 | 2020-12-15 | 苏州生益科技有限公司 | Active ester compound, resin composition, and prepreg, insulating film, metal-clad laminate, and printed wiring board having the same |
| CN111040163B (en) * | 2019-11-29 | 2022-09-16 | 航天特种材料及工艺技术研究所 | Bismaleimide resin, air bag for autoclave molding and preparation method thereof |
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| WO2015120653A1 (en) * | 2014-02-14 | 2015-08-20 | 广东生益科技股份有限公司 | Halogen-free resin composition and use for same |
| CN105348743A (en) * | 2015-12-07 | 2016-02-24 | 浙江华正新材料股份有限公司 | Halogen-free resin composition, prepreg and laminated board |
| CN106496936A (en) * | 2016-10-20 | 2017-03-15 | 蓝星（成都）新材料有限公司 | A kind of benzoxazine resins and preparation method thereof |
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|---|---|---|---|---|
| WO2015120653A1 (en) * | 2014-02-14 | 2015-08-20 | 广东生益科技股份有限公司 | Halogen-free resin composition and use for same |
| CN105348743A (en) * | 2015-12-07 | 2016-02-24 | 浙江华正新材料股份有限公司 | Halogen-free resin composition, prepreg and laminated board |
| CN106496936A (en) * | 2016-10-20 | 2017-03-15 | 蓝星（成都）新材料有限公司 | A kind of benzoxazine resins and preparation method thereof |
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