CN109810517A - Resin combination, preliminary-dip piece used for printed circuit and metal-coated laminated board - Google Patents
Resin combination, preliminary-dip piece used for printed circuit and metal-coated laminated board Download PDFInfo
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Abstract
The disclosure provides resin combination, preliminary-dip piece used for printed circuit and metal-coated laminated board.The resin combination includes: silicon aryne resin；Cyanate esters；And maleimide compound.By using resin combination, metal-coated laminated board obtained can be at least with one in the characteristics such as low-dielectric loss factor, high-fire resistance, low thermal coefficient of expansion.
Description
Technical field
This disclosure relates to printed circuit board technology field.Specifically, this disclosure relates to a kind of resin combination, printed circuit
With preliminary-dip piece and metal-coated laminated board.
Background technique
Metal-coated laminated board be by electron glass fiber cloth or other reinforcing materials leaching with resin liquid, on one side or it is two-sided coated with
Metal foil and a kind of manufactured board-like material, referred to as metal-clad laminate through hot pressing, referred to as metal-coated laminated board or
Cover metal plate, such as copper clad laminate or copper-clad plate (Copper Clad Laminate, CCL).Metal-coated laminated board such as covers copper
Plate is the base veneer sheet material for manufacturing printed circuit board (Printed Circuit Board, abbreviation PCB), and PCB is electronics industry
One of important component.Almost every kind of electronic equipment, it is small to arrive electronic watch, calculator, computer, communication electronic device, army are arrived greatly
, for the electric interconnection between them, printed board will be used as long as there are the electronic components such as integrated circuit with weapon system.
Metal-coated laminated board is mainly responsible for the function of three aspects of conductive, insulation and support on entire printed circuit board.
With rapid development of the electronic equipment in terms of miniaturization, multifunction, high performance and high reliability, it is desirable that print
The development of circuit board processed towards high-precision, high density, high-performance, microporous and slimming direction is getting faster.And CCL is very big
The performance of PCB is determined in degree.
Printed circuit plate high precision, high density, high-performance, microporous, slimming and the development trend requirement of multiple stratification are covered
Metal plate such as copper-clad plate has higher hot property and mechanical property.As being more and more applied to multi-layer board in electronic product,
To guarantee that multilayer circuit board is stable and reliable for performance, this just needs to be laminated with swollen with low-dielectric loss factor, high-fire resistance, low-heat
The characteristics such as swollen coefficient.
Summary of the invention
One of the disclosure is designed to provide a kind of resin combination, by with (the letter of reinforcing material such as glass fabric
Claim glass-fiber-fabric) the obtained preliminary-dip piece used for printed circuit of the infiltration resin combination and and comprising the preimpregnation used for printed circuit
The metal-coated laminated board of piece, so that metal-coated laminated board at least has low-dielectric loss factor, high-fire resistance, low thermal coefficient of expansion
Etc. one in characteristics.
Another object of the present disclosure be to provide a kind of insulation board comprising the preliminary-dip piece used for printed circuit and comprising
The printed circuit board of the preliminary-dip piece used for printed circuit, the insulation board or the metal-coated laminated board, wherein the insulation board
Or metal-coated laminated board has one in the characteristics such as low-dielectric loss factor, high-fire resistance, low thermal coefficient of expansion.
Therefore, in one aspect, the disclosure provides a kind of resin combination, and the resin combination includes:
Silicon aryne resin；
Cyanate esters；With
Maleimide compound,
Wherein the silicon aryne resin, the cyanate esters and the maleimide compound weight ratio be
(5-95)∶(5-70)∶(5-70)。
According to the disclosure embodiment, the silicon aryne resin is expressed from the next:
Wherein
N is the integer between 1 to 5；And
R1It is the group in the group being made of the following terms: hydrogen, C each independently with R21-6Alkyl or C3-6Cycloalkanes
Base.
According to another embodiment of the disclosure, the number-average molecular weight of the silicon aryne resin is 250 to 10000.
According to another embodiment of the disclosure, the cyanate esters are selected from bis- (the 4- cyanic acid phenyl) third of 2,2-
Alkane, bis- (3,5- dimethyl -4- cyanic acid phenyl) methane, bis- (the 4- cyanic acid phenyl) ethane of 2,2- performed polymer or any in monomer
It is a kind of or at least two combination.
According to another embodiment of the disclosure, the cyanate esters are selected from: 2,2- bis- (4- cyanic acid phenyl) third
The combination of alkane and bis- (3,5- dimethyl -4- cyanic acid phenyl) methane or bis- (3,5- dimethyl -4- cyanic acid phenyl) methane and 2,2-
The combination of bis- (4- cyanic acid phenyl) ethane.
According to another embodiment of the disclosure, the maleimide compound is in its molecular structure containing at least
One structure shown in following formula:
According to another embodiment of the disclosure, the maleimide compound is in its molecular structure containing at least
Two structures shown in following formula:
According to another embodiment of the disclosure, the maleimide compound is selected from: 4,4 '-diphenyl-methane spans
Come acid imide, phenylmethane maleimide low polymer, meta-phenylene bismaleimide, bisphenol-A diphenyl ether bismaleimide
Amine, 3,3 '-dimethyl -5,5 '-diethyl -4,4 '-diphenyl methane bismaleimide, 4- methyl-1,3- phenylene span
Come acid imide and 1, in 6- bismaleimide-(2,2,4- trimethyl) hexane any one or at least two combination.
According to another embodiment of the disclosure, the resin combination also includes promotor, wherein the promotor
Content in the resin combination is 0.01-5 weight %.
According to another embodiment of the disclosure, the promotor is selected from: peroxide, acetylacetone,2,4-pentanedione metal salt,
Metal salt, vanadium pentoxide, amine, quaternary ammonium salt, imidazoles, triphenylphosphine, boron trifluoride complex, caprylic acid or the isooctyl acid of aphthenic acids
Metal salt, acetylacetone,2,4-pentanedione, aphthenic acids, in stearic metal salt and salicylic acid any one or at least two mixing
Object.
According to another embodiment of the disclosure, the resin combination also includes filler.
According to another embodiment of the disclosure, the filler is selected from: aluminium oxide, titanium oxide, mica, silica,
Beryllium oxide, barium titanate, potassium titanate, strontium titanates, calcium titanate, aluminium carbonate, magnesium hydroxide, aluminium hydroxide, alumina silicate, calcium carbonate, silicon
In the clays such as sour calcium, magnesium silicate, silicon nitride, boron nitride, calcined clay, talcum, aluminium borate and silicon carbide any one or extremely
Few two kinds of mixture.
According to another embodiment of the disclosure, the resin combination also includes fire retardant.
According to another embodiment of the disclosure, the resin combination also includes solvent.
On the other hand, the disclosure provides a kind of preliminary-dip piece used for printed circuit, and the preliminary-dip piece used for printed circuit includes
Reinforcing material and pass through infiltration resin combination attached thereto as described in any one of above after dry.
In another aspect, the disclosure provides a kind of insulation board, and the insulation board contains at least one as described above
Preliminary-dip piece used for printed circuit.
In yet another aspect, the disclosure provides a kind of metal-coated laminated board, and the metal-coated laminated board includes at least one
Preliminary-dip piece used for printed circuit as described above and metal foil.
In another aspect, the disclosure provides a kind of printed circuit board, and the printed circuit board includes: at least one as above
Preliminary-dip piece used for printed circuit described in face, or an at least insulation board as described above, or at least one as described above
Metal-coated laminated board.
According to the disclosure, a kind of resin combination can be provided, obtained by infiltrating the resin combination with reinforcing material
The preliminary-dip piece used for printed circuit arrived and metal-coated laminated board or insulation board comprising the preliminary-dip piece used for printed circuit, and comprising
The printed circuit board of the preliminary-dip piece used for printed circuit, the insulation board or the metal-coated laminated board, so that metal-coating lamination
Plate can be at least with one in the characteristics such as low-dielectric loss factor, high-fire resistance, low thermal coefficient of expansion.
Specific embodiment
Below in conjunction with the specific embodiment of the disclosure, the technical solution in the embodiment of the present disclosure is carried out clear, complete
Site preparation description, it is clear that described embodiment and/or embodiment are only a part of embodiment of the disclosure and/or implementation
Example, rather than whole embodiments and/or embodiment.Based on the embodiment and/or embodiment in the disclosure, this field is general
Logical technical staff every other embodiment obtained and/or every other implementation without making creative work
Example belongs to the range of disclosure protection.
In the following description, layer and film use in which can be interchanged.Resin combination is hereinafter sometimes referred to as gluing
Agent.
In the disclosure, all numerical characteristics all refer within the error range of measurement, such as the numerical value defined by ±
Within 10%, or within ± 5%, or within ± 1%.
"comprising" described in the disclosure, " comprising " or " containing ", it is intended that it especially, can also have other groups except described group
Part, these other components assign the preliminary-dip piece different characteristics.In addition to this, "comprising", " comprising " described in the disclosure or
" containing " can also include " substantially by ... form ", and could alternatively be " for " or " by ... form ".
In the disclosure, if do not particularly pointed out, what amount, ratio etc. were by weight.
In the disclosure, it wraps solvent-laden resin combination and is referred to as resin adhesive liquid.
As described above, the disclosure can provide a kind of resin combination, the resin combination includes:
Silicon aryne resin；
Cyanate esters；With
Maleimide compound,
Wherein the silicon aryne resin, the cyanate esters and the maleimide compound weight ratio be
(5-95)∶(5-70)∶(5-70)。
Silicon aryne resin
Silicon aryne resin can be the resin that molecular backbone contains element silicon, phenyl ring and alkynes structure.
Silicon aryne resin can be expressed from the next:
Wherein
N is the integer between 1 to 5；
R ' and R " is the group in the group being made of the following terms each independently: hydrogen, C1-6Alkyl or C3-6Cycloalkanes
Base.
Preferably, silicon aryne resin can be expressed from the next
Wherein
N is the integer between 1 to 5；And
R1And R2It is the group in the group being made of the following terms each independently: hydrogen, C1-6Alkyl or C3-6Cycloalkanes
Base.
In above-mentioned formula, two alkynyls on phenyl ring may be at ortho position, meta or para position.Silicon aryne resin can be with two
Acetylenylbenzene polymerize to obtain with dichlorosilane.For example, can be polymerize with dichlorosilane by grignard reaction by diacetylenic benzene
It obtains.
The example of diacetylenic benzene may include 1,2- diacetylenic benzene, 1,3- diacetylenic benzene and Isosorbide-5-Nitrae-diacetylene
Benzene.
The example of dichlorosilane may include R ' R " SiCl2Or R1R2SiCl2, wherein R ', R ", R1And R2Each independently
It is the group in the group being made of the following terms: hydrogen, C1-6Alkyl or C3-6Naphthenic base.
The specific example of dichlorosilane may include dimethyl dichlorosilane (DMCS) and dichlorodimethylsilane.
C1-6The example of alkyl may include methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, tert-butyl, each
Kind amyl and various hexyls.C3-6The example of naphthenic base may include cyclopropyl, cyclobutyl, cyclopenta and cyclohexyl.
The number-average molecular weight of silicon aryne resin can be about 250 to 10000, preferably from about 500 to 2000.The silicon of low molecular weight
Aryne resin is more soluble in a solvent, and more preferable with the compatibility of polyphenylene oxide resin, can reduce resin and split-phase is precipitated
Risk is conducive to preferably form inierpeneirating network structure.But the reaction time for crossing the silicon aryne resin of low molecular weight is too long,
It is unfavorable for the solidification processing of resin system.
Weight ratio of the silicon aryne resin in resin combination has apparent influence to the flame retardant property of resin combination.
When silicon aryne resin is greater than relative to the weight ratio of the sum of silicon aryne resin, cyanate esters and maleimide compound
When 70%, it is fire-retardant which can reach V-0 under conditions of not using fire retardant.
Cyanate esters
There is no limit to cyanate esters used for the disclosure.
The example of cyanate esters can be selected from bis- (the 4- cyanic acid phenyl) propane of 2,2-, bis- (3,5- dimethyl -4- cyanic acid
Phenyl) cyanates such as methane, bis- (the 4- cyanic acid phenyl) ethane of 2,2- performed polymer or any one in monomer or at least two
Combination.
The number-average molecular weight of the performed polymer of cyanate can be 200 to 10000.The viscosity of resin is too when too low molecular weight
It is low, and more long curing time is needed, it is unfavorable for hot pressing processing.When excessive molecular weight, the viscosity of resin is too big, is unfavorable for pair
The infiltration of reinforcing material, and the poor fluidity in hot pressing, are also easy to produce hole etc..In order to preferably adapt to cover metal plate such as copper-clad plate
The technique requirement of production, preferably 400 to 6000.
Typical but non-limiting combined example can be with are as follows: 2,2- bis- (4- cyanic acid phenyl) propane and bis- (3,5- diformazans
Base -4- cyanic acid phenyl) methane combination or bis- (3,5- dimethyl -4- cyanic acid phenyl) methane and 2,2- bis- (4- cyanic acid phenyl)
The combination of ethane.
For cyanate esters in these three resin Compositions, heat resistance is relatively weak, and dielectric properties are better than maleimide
Amine compounds, but it is inferior to silicon aryne resin.Cyanate esters cover metal plate such as copper-clad plate processing in craftsmanship it is best, have
The crystallinity for helping reduce silicon aryne resin and maleimide compound, improves the mobility of resin combination, but excessive
The toughness and heat resistance of cyanate esters are poor.
Maleimide compound
There is no limit to maleimide compound used for the disclosure.
Maleimide compound contains at least one structure shown in following formula in its molecular structure, preferably in its molecule
Contain at least two structures shown in following formula in structure:
The example of maleimide compound can be selected from 4,4 '-diphenyl methane dimaleimides, phenylmethane Malaysia acyl
Imines oligomer, meta-phenylene bismaleimide, bisphenol-A diphenyl ether bismaleimide, 3,3 '-dimethyl -5,5 '-two
4,4 '-diphenyl methane bismaleimide of ethyl-, 4- methyl-1,3- phenylene bismaleimide and 1,6- span carry out acyl
In imines-(2,2,4- trimethyl) hexane any one or at least two combination.
Phenylmethane maleimide low polymer is the resin material of following molecular structure, and wherein n is 0,1,2,3,4 or 5, excellent
It is selected as the mixture of different polymerization degree material.
The heat resistance of maleimide compound is preferable, but dissolubility is poor.Phenomena such as precipitation is reunited is had when being excessively used,
The caking property for covering metal plate such as copper-clad plate is caused to reduce, degraded toughness.
Promotor
Optionally, resin combination also includes promotor, copes with the demand of different conditions of cure.
In the case where containing promotor, content of the promotor in above-mentioned resin combination can be about 0.01-5 weight
Measure %.
Promotor can be selected from: peroxide, the metal salt of acetylacetone,2,4-pentanedione, the metal salt of aphthenic acids, vanadium pentoxide, amine,
It is quaternary ammonium salt, imidazoles, triphenylphosphine, boron trifluoride complex, the metal salt of caprylic acid or isooctyl acid, acetylacetone,2,4-pentanedione, aphthenic acids, hard
In the metal salt and salicylic acid of resin acid any one or at least two mixture.
The example of peroxide may include: dicumyl peroxide, tert-butyl hydroperoxide cumyl, di-t-butyl peroxide,
Tert-butylperoxy isopropyl carbonate, 2,5- dimethyl -2,5- di-t-butyl cumyl peroxy hexin -3,2,5- dimethyl 2,5-
Di-t-butyl hexane peroxide, peroxidating to Meng's alkane, 1,1- bis- (t-amyl peroxy) hexamethylenes, hydrogen peroxide diisopropyl benzene,
Benzoyl peroxide or benzoyl peroxide derivative.The example of amine may include aniline.
The metal salt of caprylic acid or isooctyl acid, stearic metal salt, the metal salt of acetylacetone,2,4-pentanedione and the metal of aphthenic acids
Metal in salt can stand alone as alkali metal, alkaline-earth metal or transition metal, for example, potassium, calcium, sodium, magnesium, aluminium, zinc, iron, cobalt etc..
The example of the metal salt of isooctyl acid may include zinc Isoocatanoate.
In order to better adapt to impregnating processing technology, solvent can also be added in the resin combination, to reduce dipping
Resin viscosity in the process.
It as this solvent, is not particularly limited, more than one preferably containing aromatic hydrocarbon series solvent.As fragrance
The concrete example of race's hydrocarbon system solvent is, it is preferable to use toluene, dimethylbenzene, mesitylene etc..These aromatic hydrocarbon series solvents can be independent
Using one kind, can also be used in combination.
In addition, if containing aromatic hydrocarbon series solvent, can further and with other solvents, as solvent,
It is not particularly limited, as concrete example, can enumerate: the alcohols such as methanol, ethyl alcohol, butanol；Ethyl cellosolve, butyl cellosolve, second
The ethers such as glycol monomethyl ether, carbitol, butyl carbitol；The ketones such as acetone, methyl ethyl ketone, methylisobutylketone, cyclohexanone；First
The esters such as oxygroup ethyl acetate, ethoxyethyl group acetate, butoxyethyl group acetate, ethyl acetate；N, N- dimethyl methyl
The nitrogenous class equal solvent such as amide, n,N-dimethylacetamide, n-methyl-2-pyrrolidone, these solvents can be used alone one
Kind, it can also be used in combination.In addition, in aromatic hydrocarbon series solvent and when being made into mixed solvent with other solvents
Mixed proportion, optimization aromatic hydrocarbon system solvent are the 50 weight % or more in total solvent.
In the case where containing solvent, content of the solvent in resin combination can be 10-99.5 weight %, preferably from about
20-99 weight %.
In order to which the metal-coated laminated board as made from the resin combination has better modulus and heat resistance, the resin combination
Filler such as filler can be added in object.
Filler is not particularly limited, specifically, aluminium oxide, titanium oxide, mica, silica, beryllium oxide, titanium can be used
Sour barium, potassium titanate, strontium titanates, calcium titanate, aluminium carbonate, magnesium hydroxide, aluminium hydroxide, alumina silicate, calcium carbonate, calcium silicates, silicic acid
The clays such as magnesium, silicon nitride, boron nitride, calcined clay, talcum, aluminium borate, silicon carbide etc..These fillers can be used alone,
It two or more can be used in combination.The shape of filler is not particularly limited, but preferred ball-type.There is certain limit to the partial size of filler
System is preferably 0.01 to 30 μm, more preferably 0.1 to 15 μm of filler using partial size.
When the partial size of filler is 0.01 μm or less, therefore the mobility decline of resin combination makes preliminary-dip piece and covers gold
Mouldability when belonging to laminate is deteriorated, and the surface area for being easy to produce gap etc. or filler becomes larger, therefore, metal and resin it is viscous
Junction product is reduced, and will lead to the peel strength decline of printed wiring board, therefore not preferably.On the other hand, when partial size is more than 30 μm,
It will lead to the insulating reliability decline of the wiring closet or insulating layer of printed wiring board, therefore not preferably.
In the case where containing filler, content of the filler in resin combination can be about 1 to 90 weight %, preferably
About 5 to 80 weight %.
In order to preferably meet fire-retardant equal requirement, fire retardant can also be added in the resin combination.
As fire retardant, it is preferable to use the fire retardants such as bromine class, Phosphorus, metal hydroxides.
The example of brominated flame retardant are as follows: brominated bisphenol a type epoxy resin and brominated phenol phenolic resin varnish type epoxy resin etc.
Brominated epoxy resin, hexabromobenzene, pentabromotoluene, ethylenebis (penta-bromophenyl), ethylenebis tetrabromo phthalimide, 1,
2- bis- bromo- 4- (1,2- dibromoethyl) hexamethylene, tetrabromo cyclooctane, hexabromocyclododecane, bis- (tribromophenoxy) ethane, bromination
Polyphenylene oxide, brominated Polystyrene and 2, the brominations additive flame retardant such as 4,6- tri- (tribromophenoxy) -1,3,5-triazines；Tribromo-benzene
Base maleimide, tribromophenyl acrylate, methacrylic acid tribromophenyl, tetrabromobisphenol A type dimethylacrylate, propylene
Bromination reaction type fire retardant of the group containing unsaturated double-bond such as sour pentabromo- benzyl ester and brominated styrene etc..
The example of phosphorus type flame retardant are as follows: triphenyl phosphate, tricresyl phosphate, tricresyl phosphate (dimethylbenzene) ester, phosphoric acid cresols
Diphenyl ester, phosphoric acid cresols two -2, the aromatics phosphate such as 6- diformazan phenyl ester and resorcinol bis- (diphenyl phosphoesters)；Phenyl
The phosphonate esters such as phosphonic acids diethyl enester, phenyl-phosphonic acid diallyl and bis- (1- cyclobutenyl) esters of phenyl-phosphonic acid；Diphenylphosphine acid phenenyl ester,
The phosphates such as diphenylphosphoric acid methyl esters, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative；Bis- (2- allyls
Phenoxy group) phosphazene compounds such as phosphonitrile, xylenol phosphonitrile；Melamine phosphate, melamine pyrophosphate, polyphosphoric acid melamine
The phosphorus type flame retardants such as amine, polyphosphoric acid melam, ammonium polyphosphate, phosphorous vinyl benzyl based compound and red phosphorus.
The example of metal hydroxide combustion inhibitor is magnesium hydroxide or aluminium hydroxide.
In addition, above-mentioned fire retardant can be used alone, can also be used in combination.
In the case where containing fire retardant, content of the fire retardant in resin combination can be about 1 to 40 weight %, excellent
It is selected as about 2 to 30 weight %.
In addition, resin combination can also also contain various auxiliary agents.As the concrete example of auxiliary agent, filler dispersion can be enumerated
Agent, defoaming agent, antioxidant, heat stabilizer, antistatic agent, ultraviolet absorbing agent, pigment, colorant, lubricant etc..These auxiliary agents
It can be used alone, it can also be with any two or more two kinds are used in mixed way.
The resin combination of the disclosure can pass through well known method such as cooperation, stirring, mixing silicon aryne resin, cyanate
Compound and maleimide compound and optional promotor, solvent, filler, fire retardant, dispersing agent, defoaming agent, antioxygen
Any one in agent, heat stabilizer, antistatic agent, ultraviolet absorbing agent, pigment, colorant and lubricant or at least two
It is prepared by mixture.
Dispersed by mechanical stirring, emulsification or ball milling, resin combination is configured to resin adhesive liquid, then uses the resin
Glue infiltrates reinforcing material, and drying obtains preliminary-dip piece.The preliminary-dip piece and metal foil such as copper foil or aluminium foil is warm in the vacuum press
Pressure can prepare metal-coated laminated board.
The example of reinforcing material may include: glass fabric, glass non-woven fabrics and organic non-woven fabric etc..
In order to reduce the viscosity of resin adhesive liquid, can be infiltrated under heating.Heated the temperature so that resin adhesive liquid
Degree is less than the boiling point of solvent for use, and the temperature of resin adhesive liquid is about 50-90 DEG C, further preferably about 55-85 DEG C when preferably infiltrating.
On the other hand, the disclosure can also provide a kind of preliminary-dip piece used for printed circuit, the preliminary-dip piece used for printed circuit
Including reinforcing material and by infiltration after dry it is any one of the upper surface of attached thereto described in resin combination.
In another aspect, the disclosure can also provide a kind of insulation board or metal-coated laminated board, the insulation board or gold is covered
Belong to laminate and contains at least one preliminary-dip piece used for printed circuit as described above.
It yet still another aspect, the disclosure can also provide a kind of printed circuit board, the printed circuit board includes: at least one
Preliminary-dip piece used for printed circuit as described above, or an at least insulation board as described above, or at least one such as institute above
The metal-coated laminated board stated.
According to the disclosure, a kind of resin combination can be provided, obtained by infiltrating the resin combination with reinforcing material
The preliminary-dip piece used for printed circuit arrived and metal-coated laminated board or insulation board comprising the preliminary-dip piece used for printed circuit, and comprising
The printed circuit board of the preliminary-dip piece used for printed circuit, the insulation board or the metal-coated laminated board, so that metal-coating lamination
Plate can be at least with one in the characteristics such as low-dielectric loss factor, high-fire resistance, low thermal coefficient of expansion.
Embodiment
The technical solution of the disclosure is further illustrated below by specific embodiment.But these embodiments be for
The illustration disclosure, and it is not construed as the limitation disclosure.
Preparation example
Silicon aryne resin used in embodiment and comparative example is prepared as follows.
3.5 parts of magnesium powders (chemical pure, limited public affairs of Shanghai Chinese medicines group chemical reagent are added in the reaction kettle full of nitrogen
Department) and 40 parts of tetrahydrofuran (THF) solvents, it is stirred at room temperature and 13.5 parts of bromoethanes (chemical pure, Shanghai traditional Chinese medicines collection is added dropwise
Group chemical reagent Co., Ltd) and 40 parts of THF mixed solution, in 50 DEG C of heat preservation 1h after being added dropwise to complete.Then in ice water cryostat
Under the conditions of, the mixing of 7.5 parts of 1,3- diacetylenic benzenes (Shandong Jiaozhou Fine Chemicals Co., Ltd.) and 40 parts of THF solvents is added dropwise
Object, after being added dropwise, in 65 DEG C of heat preservation 1h.Then it cools down again, 5.5 parts of dichloro-dimethyl silicon is added dropwise under the conditions of ice water cryostat
The mixture of alkane (chemistry is pure, and Zhejiang new Anhua work Group Co., Ltd uses after distillation) and 40mlTHF, divides after being added dropwise
Not in 40 DEG C and 70 DEG C heat preservation 1h.After the reaction was completed, be evaporated off the THF in reactant, and with 7.2 parts are added dropwise under the conditions of ice water cryostat
140 part of 2.0% diluted hydrochloric acid aqueous solution is added dropwise again, is sufficiently stirred for the mixture of glacial acetic acid and 50 parts of toluene solvants after being sufficiently stirred
After isolate upper organic phase.Organic phase is sufficiently washed to neutrality, is then dried, filtered, and toluene is evaporated off, silicon benzyne is obtained
Resin is (that is, (number-average molecular weight 1200, the mobile phase that GPC is tested are silicon aryne resin used in embodiment and comparative example
THF), hereinafter referred to as PSA1200).
Embodiment 1-7 and comparative example 1-3
(parts by weight) are measured according to shown in table 1 or table 2, by silicon aryne resin, cyanate esters and maleimide
Compound and promotor sufficiently dissolve in a solvent, and are uniformly mixed, and filler and/or fire retardant is then added, and mixing is equal
It is even, obtain glue.E type glass fabric (spinning production in day east) the above-mentioned glue of homogeneous impregnation for taking model 1080, dries in air blast
Preliminary-dip piece is made in 155 DEG C of baking 3min in case.4 or 8 above-mentioned preliminary-dip pieces are overlapped respectively, cover 18 μm of reversion copper foils up and down
(production of Suzhou Co., Ltd, FUKUDA METAL) is suppressed 90min in vacuum hotpressing machine at a temperature of 3MPa pressure and 210 DEG C and is obtained
The laminate samples of two kinds of thickness (hereinafter, otherwise referred to as copper clad laminate or copper-clad plate).
The amount of component and the test result of resin combination are shown in the following table 1 and 2 in resin combination.
Table 1
Table 2
PSA1200: the resulting silicon aryne resin of preparation example；
CE01PS: bisphenol A cyanate ester performed polymer (number-average molecular weight: 3000), apocalypse chemical production；
CE01MO: bisphenol A cyanate ester monomer, apocalypse chemical production；
BMI-E:3,3 '-dimethyl -5,5 '-diethyl -4,4 '-diphenyl methane bismaleimide, circling in the air of Jiangsu
Work production；
BMI-1000:4,4 '-diphenyl methane dimaleimides, Japan is big and produces；
BMI-50P: phenylmethane maleimide low polymer, Japanese KI production；
Zinc Isoocatanoate: reagent, it is commercially available；
DQ1028L: spherical silica, about 3.0 μm of D50, Jiangsu joins auspicious production；
SC2050: spherical silica, about 0.5 μm of D50, Japanese Toyota Tsusho provides；
BT-93w: addition type bromide fire retardant, the refined precious production in the U.S.；
XP7866: add phosphorus containing flame retardant, the refined precious production in the U.S.；
Aluminium hydroxide: OL-104, the refined precious production in the U.S.；
DMF:N, dinethylformamide, industrial goods are commercially available；
Toluene: industrial goods, it is commercially available.
The method for testing performance described in table is as follows:
1) it glass transition temperature Tg: is tested using dynamic thermomechanical analysis (DMA), according to IPC-TM-6502.4.24 institute
Defined DMA test method；
2) it thermal decomposition temperature (Td): is tested using thermogravimetic analysis (TGA) (TGA), according to standard IPC-TM-6502.4.24.6；
3) peel strength (PS): refer to pulling force needed for every millimeter of copper foil is removed copper-clad plate at room temperature；
4) dielectric constant (Dk) and dielectric dissipation factor (Df): 10GHz is measured using Resonant-cavity Method (SPDR) method, according to mark
Quasi- IPC-TM-6502.5.5.5.
5) it anti-flammability: is tested according to UL94 " 50W (20mm) testing vertical flammability: V-0, V-1 and V-2 " test method.
6) thermal expansion coefficient (CTE) and 50-260 DEG C of thermal expansion ratio: test is tested using static thermal analyzer (TMA),
Test is according to standard IPC-TM-6502.4.24, and wherein Z axis indicates the thickness direction of laminate samples, and X-axis indicates laminate sample
The length direction of product, and Y-axis indicates the width direction of laminate samples.50-260 DEG C of thermal expansion ratio is in laminate samples
Z-direction measurement obtains.
7) copper clad laminate: being swum in the tin liquor surface of molten condition by thermal stress, and 288 DEG C of temperature, with layering or bubble
Time as test result.
8) it D50: indicates average grain diameter, refers to the total volume of particles is taken as 100% and find out the accumulation degree based on partial size
When number distribution curve, it is just equivalent to the partial size for the point that volume is 50%, is surveyed using the size distribution of laser diffraction scattering method
It is fixed.
There are above-described embodiment and comparative example test result it is found that the test result of the Tg and Td of the embodiment sample are all higher than
The Tg and Td of printed circuit board are commonly used in industry.The dielectric dissipation factor result of copper clad laminate illustrates that it is laminated in high-frequency high-speed
To have fine application performance, and its CTE, 50-260 in all directions DEG C thermal expansion ratio and thermal stress performance in plate
It is excellent.
As above, a kind of resin combination can be provided, by infiltrating the printing that the resin combination obtains with glass-fiber-fabric
Circuit preliminary-dip piece and metal-coated laminated board or insulation board comprising the preliminary-dip piece used for printed circuit, and include the printing
The printed circuit board of circuit preliminary-dip piece, the insulation board or the metal-coated laminated board, so that metal-coated laminated board can be down to
Less with one in the characteristics such as low-dielectric loss factor, high-fire resistance, low thermal coefficient of expansion, preferably there is low dielectric to damage simultaneously
Consume factor, high-fire resistance, low thermal coefficient of expansion.Meanwhile by addition fire retardant, it can achieve V-0 grades of flame retardant properties, so that its
It is suitable for needing in fire-retardant application.
Obviously, those skilled in the art can carry out various modification and variations without departing from this public affairs to the embodiment of the present disclosure
The spirit and scope opened.In this way, if these modifications and variations of the disclosure belong to disclosure claim and its equivalent technologies
Within the scope of, then the disclosure is also intended to include these modifications and variations.
Claims (18)
1. a kind of resin combination, the resin combination includes:
Silicon aryne resin；
Cyanate esters；With
Maleimide compound,
Wherein the weight ratio of the silicon aryne resin, the cyanate esters and the maleimide compound is (5-95)
∶(5-70)∶(5-70)。
2. resin combination according to claim 1, wherein the silicon aryne resin is expressed from the next:
Wherein
N is the integer between 1 to 5；And
R1And R2It is the group in the group being made of the following terms each independently: hydrogen, C1-6Alkyl or C3-6Naphthenic base.
3. resin combination according to claim 1, wherein the number-average molecular weight of the silicon aryne resin be 250 to
10000。
4. resin combination according to claim 1, wherein the cyanate esters are selected from bis- (the 4- cyanic acid benzene of 2,2-
Base) propane, bis- (3,5- dimethyl -4- cyanic acid phenyl) methane or 2, in the performed polymer or monomer of bis- (the 4- cyanic acid phenyl) ethane of 2-
Any one or at least two combination.
5. resin combination according to claim 1, wherein the cyanate esters are selected from: 2,2- bis- (4- cyanic acid benzene
Base) combination or bis- (3,5- dimethyl -4- cyanic acid phenyl) methane of the propane with bis- (3,5- dimethyl -4- cyanic acid phenyl) methane
With the combination of bis- (the 4- cyanic acid phenyl) ethane of 2,2-.
6. resin combination according to claim 1, wherein the maleimide compound contains in its molecular structure
There is at least one structure shown in following formula:
7. resin combination according to claim 1, wherein the maleimide compound contains in its molecular structure
There are at least two structures shown in following formula:
8. resin combination according to claim 1, wherein the maleimide compound is selected from: 4,4 '-hexichol first
Alkane bismaleimide, phenylmethane maleimide low polymer, meta-phenylene bismaleimide, bisphenol-A diphenyl ether span
Come acid imide, 3,3 '-dimethyl -5,5 '-diethyl -4,4 '-diphenyl methane bismaleimide, 4- methyl-1, the Asia 3- benzene
Base bismaleimide and 1, in 6- bismaleimide-(2,2,4- trimethyl) hexane any one or at least two group
It closes.
9. resin combination according to claim 1, the resin combination also includes promotor, wherein the promotor
Content in the resin combination is 0.01-5 weight %.
10. resin combination according to claim 9, wherein the promotor is selected from: the gold of peroxide, acetylacetone,2,4-pentanedione
Belong to salt, the metal salt of aphthenic acids, vanadium pentoxide, amine, quaternary ammonium salt, imidazoles, triphenylphosphine, boron trifluoride complex, caprylic acid or
Any one in the metal salt of isooctyl acid, acetylacetone,2,4-pentanedione, aphthenic acids, stearic metal salt and salicylic acid or at least two
Mixture.
11. resin combination according to claim 1, the resin combination also includes filler.
12. resin combination according to claim 11, wherein the filler is selected from: aluminium oxide, titanium oxide, mica, two
Silica, beryllium oxide, barium titanate, potassium titanate, strontium titanates, calcium titanate, aluminium carbonate, magnesium hydroxide, aluminium hydroxide, alumina silicate, carbon
It is any one in the clays such as sour calcium, calcium silicates, magnesium silicate, silicon nitride, boron nitride, calcined clay, talcum, aluminium borate and silicon carbide
Kind or at least two mixture.
13. resin combination according to claim 1, the resin combination also includes fire retardant.
14. resin combination according to claim 1, the resin combination also includes solvent.
15. a kind of preliminary-dip piece used for printed circuit, after the preliminary-dip piece used for printed circuit includes reinforcing material and passes through infiltration drying
Resin combination as described in any one of claim 1 to 13 attached thereto.
16. a kind of insulation board, the insulation board contains at least one preliminary-dip piece used for printed circuit as claimed in claim 15.
17. a kind of metal-coated laminated board, the metal-coated laminated board includes at least one printing electricity as claimed in claim 15
Road preliminary-dip piece and metal foil.
18. a kind of printed circuit board, the printed circuit board includes: at least one as claimed in claim 15 used for printed circuit
Preliminary-dip piece, or an at least insulation board as claimed in claim 16, or at least one cover metal as claimed in claim 17
Laminate.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811596192.1A CN109810517B (en) | 2018-12-25 | 2018-12-25 | Resin composition, prepreg for printed circuit, and metal-clad laminate |
| TW108122363A TWI743501B (en) | 2018-12-25 | 2019-06-26 | Resin composition, prepreg for printed circuit and metal-clad laminate |
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|---|---|---|---|
| CN201811596192.1A CN109810517B (en) | 2018-12-25 | 2018-12-25 | Resin composition, prepreg for printed circuit, and metal-clad laminate |
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| TW (1) | TWI743501B (en) |
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| CN113352772A (en) * | 2020-06-24 | 2021-09-07 | 山东华菱电子股份有限公司 | Thermal print head and method of manufacturing the same |
| CN114634713A (en) * | 2020-12-16 | 2022-06-17 | 广东生益科技股份有限公司 | Resin composition, prepreg and metal-clad laminate |
| JP7252301B1 (en) | 2021-10-15 | 2023-04-04 | 日本化薬株式会社 | Curable resin composition, prepreg and cured product thereof |
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| JP7252301B1 (en) | 2021-10-15 | 2023-04-04 | 日本化薬株式会社 | Curable resin composition, prepreg and cured product thereof |
| JP2023059784A (en) * | 2021-10-15 | 2023-04-27 | 日本化薬株式会社 | Curable resin composition, prepreg and cured product of the same |
Also Published As
| Publication number | Publication date |
|---|---|
| TW202024235A (en) | 2020-07-01 |
| TWI743501B (en) | 2021-10-21 |
| CN109810517B (en) | 2021-08-27 |
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