CN110527037A - A kind of Halogen polyphenyl ether resin composition and prepreg and laminate using its production - Google Patents
A kind of Halogen polyphenyl ether resin composition and prepreg and laminate using its production Download PDFInfo
- Publication number
- CN110527037A CN110527037A CN201910921153.2A CN201910921153A CN110527037A CN 110527037 A CN110527037 A CN 110527037A CN 201910921153 A CN201910921153 A CN 201910921153A CN 110527037 A CN110527037 A CN 110527037A
- Authority
- CN
- China
- Prior art keywords
- resin
- parts
- carbon bond
- unsaturated carbon
- polyphenylene oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin 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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/285—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/08—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to polyphenylene oxides
- C08F283/085—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to polyphenylene oxides on to unsaturated polyphenylene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
Abstract
The invention discloses a kind of Halogen polyphenyl ether resin compositions, including following component: (a) containing the polyphenylene oxide resin of unsaturated carbon carbon bond: 100 parts；(b) containing the phosphorus-containing compound of unsaturated carbon carbon bond: 5 ~ 60 parts；(c) initiator: 0 ~ 10 part.The present invention plays the role of crosslinking agent in polyphenylene oxide and compound containing unsaturated carbon carbon bond using the phosphorus-containing compound containing unsaturated carbon carbon bond, can be good at by polyphenylene oxide and compound containing unsaturated carbon carbon bond uniformly it is compatible together, obtaining lower dielectric constant and low dielectric loss value, experimental data proves: resin combination of the invention and the laminate thus prepared can satisfy current 5G product.
Description
Technical field
The present invention relates to a kind of Halogen polyphenyl ether resin composition and using the prepreg and laminate of its production, belong to
Technical field of electronic materials.
Background technique
With the upgrading of technology, the consumer electronics such as automobile market, smart phone market proposes new demand to PCB,
And to after the listing of 5G commercialization in 2018, to the upper one layer of step of requirement in terms of the dielectric properties of PCB substrate, high-frequency high-speed
Copper-clad plate is 5G epoch indispensable one of electronic substrate.In simple terms, i.e., PCB substrate material needs to have lower dielectric
Constant and dielectric loss tangent, interference when reducing high-speed transfer between the delay, distortion and loss and signal of signal.
Accordingly, it is desired to provide a kind of compositions of thermosetting resin, the printed circuit plate made using this compositions of thermosetting resin
Expect high speed, high frequency signals transmission in can show substantially low dielectric constant and dielectric loss tangent and (be situated between
The lower electric constant and dielectric loss tangent the better).
In order to meet high dielectric properties requirement, the hydrocarbon resin system that the prior art can generally be selected, but can bring
The problems such as poor flame retardant properties, glass transition temperature be low, rigidity is insufficient, therefore when preparing high-frequency high-speed high-performance substrate, it is
The problems such as solution anti-flammability, rigidity, also add bimaleimide resin, benzoxazine resin or general in resin combination
The other components such as logical DOPO structure phosphonium flame retardant, still, the dielectric constant of the baseplate material finally obtained is also the failure to very well
Ground meets high-frequency high-speed substrate requirement.
Japan Patent JP2019023263 and JP2019044031 are disclosed unsaturated containing polyphenylene oxide resin and carbon carbon
The phosphonium flame retardant (such as phosphonitrile class) immiscible with polyphenylene oxide and bridging property, the technical side are added in the resin combination of crosslinking agent
Case can obtain halogen-free flame-retardance, and reduce the dielectric constant and dielectric loss of solidfied material to a certain extent, still, immiscible
Phosphorus atoms in phosphonium flame retardant cannot be introduced into polymer mesh structure well, affect the humidity resistance of solidfied material, together
When entirety crosslink density decline, affect the heat resistance of solidfied material.Further more, immiscible phosphonium flame retardant also will affect polyphenylene oxide
The compatibility of resin and crosslinking agent.
In view of this, developing a kind of with high glass transition temperature, high tenacity, lower dielectric constant and dielectric damage
The high frequency resin composition of consumption tangent value, more excellent anti-flammability, to meet the high performance printing such as high-frequency high-speed and high density interconnection
The requirement of wiring board, it is clear that there is positive realistic meaning.
Summary of the invention
Goal of the invention of the invention, which is to provide one kind, can satisfy the high performance track such as high-frequency high-speed and high density interconnection
The high frequency resin composition of the requirement of road plate.
To achieve the above object of the invention, the technical solution adopted by the present invention is that: a kind of Halogen polyphenyl ether resin composition, with
Solid weight meter, including following component:
(a) containing the polyphenylene oxide resin of unsaturated carbon carbon bond: 100 parts；
(b) containing the phosphorus-containing compound of unsaturated carbon carbon bond: 5~60 parts；
(c) initiator: 0~10 part；
The phosphorus-containing compound containing unsaturated carbon carbon bond is selected from such as at least one of flowering structure compound:
Above, the phosphorus-containing compound containing unsaturated carbon carbon bond gives 13 chemical structural formulas altogether, wherein containing
There are 6 to contain sulphur structure, the i.e. phosphorus-containing compound containing unsaturated carbon carbon bond of sulfur-bearing.
Preferably, the phosphorus-containing compound containing unsaturated carbon carbon bond is the phosphorous chemical combination containing unsaturated carbon carbon bond of sulfur-bearing
The phosphorus-containing compound containing unsaturated carbon carbon bond of object or the sulfur-bearing and other phosphorus-containing compounds containing unsaturated carbon carbon bond
Composition.That is: in the described phosphorus-containing compound containing unsaturated carbon carbon bond preferably above-mentioned 6 chemical structural formulas containing sulphur structure
It is one or several, alternatively, being also possible to this 6 chemical structural formulas (can choose one of those or several) containing sulphur structure
With the combination of other chemical structural formulas without containing sulphur structure.
More preferably, the phosphorus-containing compound containing unsaturated carbon carbon bond contains phosphatization containing unsaturated carbon carbon bond for sulfur-bearing
The composition of object and other phosphorus-containing compounds containing unsaturated carbon carbon bond is closed, mass ratio is 100:0~100:100, preferably
100:10~100:60.
The initiator is the prior art, and azo-initiator, peroxide initiator, redox class can be selected to cause
Agent, one or more of preferably following initiator: cumyl peroxide, di-t-butyl peroxide, perbenzoic acid uncle
Butyl ester, di-cyclohexylperoxy di-carbonate, isopropyl benzene hydroperoxide, azodiisobutyronitrile.
Above, in terms of 100 parts by weight of polyphenylene oxide resin by component (a) containing unsaturated carbon carbon bond, the component (b) is carbon containing
The content of the phosphorus-containing compound of carbon unsaturated bond is 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, and 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15
Part, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, 30
Part, 31 parts, 32 parts, 33 parts, 34 parts, 35 parts, 36 parts, 37 parts, 38 parts, 39 parts, 40 parts, 41 parts, 42 parts, 43 parts, 44 parts, 45
Part, 46 parts, 47 parts, 48 parts, 49 parts, 50 parts, 51 parts, 52 parts, 53 parts, 54 parts, 55 parts, 56 parts, 57 parts, 58 parts, 59 parts, 60
Part, preferably 10-40 parts.
Preferably, the polyphenylene oxide resin containing unsaturated carbon carbon bond is selected from vinyl modified polyphenylene oxide resin, acrylic acid
At least one of ester modified polyphenylene oxide resin, allyl modified polyphenylene ether resin, dimaleoyl imino modified polyphenylene ether resin,
The number-average molecular weight of the vinyl modified polyphenylene oxide resin and acrylate modified polyphenylene oxide resin is respectively less than 6000.More preferably
It is 1000~3000.
Preferably, the vinyl modified polyphenylene oxide resin is selected from one in compound shown in following structural formula (1), (2)
Kind is several:
Wherein: X2Selected from having structure:
Wherein R1、R3、R6、R8、R9、R11、R14、R16、R17、R19、R22、R24It is identical or
Person is different, respectively halogen atom, alkyl or phenyl；Wherein R2、R4、R5、R7、R10、R12、R15、R18、R20、R21、R23It is identical
Perhaps difference is hydrogen atom, halogen atom, alkyl or phenyl respectively；
-Y2- O- structure are as follows:Wherein R26、R28It is same or different, it is halogen original respectively
Son, alkyl or phenyl, R25、R27It is respectively selected from hydrogen atom, halogen atom, alkyl or phenyl；
M, n respectively represents 0~30 integer, and cannot simultaneously be 0；
Wherein n is greater than 5 integer；
The acrylate modified polyphenylene oxide resin is selected from one of compound shown in following structural formula (3) or several
Kind:
Wherein: Y3For Wherein m, n
It is greater than the integer equal to 1 respectively.
Still more preferably, the vinyl modified polyphenylene oxide resin is selected from such as flowering structure:
In above-mentioned technical proposal, there are also cross-linking aid, the cross-linking aid choosings in the Halogen polyphenyl ether resin composition
From maleimide compound, hydrocarbon resin, the benzoxazine containing unsaturated carbon carbon bond, the phenolic aldehyde tree containing unsaturated carbon carbon bond
One or more of rouge, the cyanate containing unsaturated carbon carbon bond, polyimides containing unsaturated carbon carbon bond.Preferably, described
Cross-linking aid is selected from hydrocarbon resin.
100 poidometer of polyphenylene oxide resin with component (a) containing unsaturated carbon carbon bond, the content of the cross-linking aid are 1-80
Parts by weight, preferably 10-50 parts by weight.
A kind of preferred resin combination, with solid weight meter, including following component:
(a) containing the polyphenylene oxide resin of unsaturated carbon carbon bond: 100 parts；
(b) containing the phosphorus-containing compound of unsaturated carbon carbon bond: 10~40 parts；
(c) initiator: 0.1~3 part；
(d) hydrocarbon resin: 15-40 parts.
In above-mentioned technical proposal, the hydrocarbon resin is selected from polybutadiene, polyprene, polystyrene, polybutadiene-benzene
Ethylene copolymer, styrene-butadiene-styrene, polyprene-styrol copolymer, styrene-pentadiene-benzene
Ethylene copolymer, talan ethane, talan methane, talan hexane, triallyl isocyanate and its prepolymer
One or more of.
Preferably, the hydrocarbon resin is selected from styrene-butadiene-styrene (SBS), talan ethane
(BVPE), one of talan methane (BVPM), talan hexane (BVPH), triallyl isocyanate (TAIC) or
It is several.
In above-mentioned technical proposal, the resin combination still further comprises filler, it is to be understood that the resin group
The filler can be contained by closing in object, can also not contain the filler.
When containing filler in the resin combination, by resin combination based on 100 parts by weight, including filler 0-200
Parts by weight, for example, 10 parts by weight, 20 parts by weight, 30 parts by weight, 40 parts by weight, 50 parts by weight, 60 parts by weight, 70 parts by weight,
80 parts by weight, 90 parts by weight, 100 parts by weight, 110 parts by weight, 120 parts by weight, 130 parts by weight, 140 parts by weight, 150 weight
Part, 160 parts by weight, 170 parts by weight, 180 parts by weight, 190 parts by weight or 200 parts by weight；Preferably, the filer content is
10-100 parts by weight, it is highly preferred that being 30-70 parts by weight.
Specifically, the filler is organic filler or inorganic filler, wherein inorganic filler is selected from nonmetal oxide, gold
Belong to one of nitride, non-metal nitride, inorganic hydrate, inorganic salts, metal hydrate or Phos or at least appoints
The mixture of two kinds of meaning；The organic filler in polytetrafluorethylepowder powder, polyphenylene sulfide, polyether sulfone powder at least one
Kind.
It is furthermore preferred that the inorganic filler is selected from fused silica, crystalline sillica, spherical silica, sky
Heart silica, aluminium hydroxide, aluminium oxide, talcum powder, aluminium nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanates,
At least one of calcium carbonate, calcium silicates, mica, glass fiber powder.Preferably, the filler is silica, it is highly preferred that
For surface treated preparing spherical SiO 2.Specifically, the surface treating agent is silane coupling agent, such as epoxy silane coupling agent
Or amino silicane coupling agent.
Preferably, angle value is 1-15 microns in the partial size of the filler, such as 1 micron, 2 microns, 5 microns, 8 microns, 10
Micron, 11 microns, 12 microns, 13 microns, 14 microns or 15 microns.It is highly preferred that angle value is 1-10 in the partial size of the filler
Micron.
As a further improvement of the present invention, elastomer is also contained in the resin combination, the elastomer is low mould
Component is measured, polybutadiene, phenylethylene, olefines, polyurethanes, polyesters, polyimides class, esters of acrylic acid or silicon are selected from
At least one of ketone, the preferably low modulus component containing reactive group, reactive group can be epoxy group, hydroxyl, amino, acid anhydrides
Base, carboxyl or vinyl etc., more preferably epoxy-modified polybutadiene, anhydride modified polybutadiene, styrenebutadiene copolymer
Object, styrene-acrylonitrile copolymer copolymer or styrene acrylic copolymer.In terms of 100 parts of resin solids weight, the content of elastomer is
5-20 parts.
It is required according to the difference of final products, the resin combination further comprises 0~5 part of other auxiliary agent.It is described
Other auxiliary agents include coupling agent, dispersing agent, dyestuff.The coupling agent is silane coupling agent, such as epoxy silane coupling agent or amino
Silane coupling agent；The dispersing agent is γ aminopropyltriethoxy silane, N- β-(amino-ethyl)-gamma-amino propyl front three
Amino system silane compound, the 3- acryloxypropyl three with amino and with hydrolization group or hydroxyl such as oxysilane
Epoxy silane compound, the γ-methacryl with epoxy group and with hydrolization group or hydroxyl such as methoxy silane
Ethylene base system silane compound, the sun with vinyl and with hydrolization group or hydroxyl such as oxygroup propyl trimethoxy silicane
Ionization series silane coupling agent, dispersing agent can Disperbyk-110 with BYK, 111,118,180,161,2009, BYK-
W996, W9010, W903 (being ProductName)；The dyestuff is fluorescent dye and black dyes, and wherein fluorescent dye is pyrazoline
It is carbon black (liquid or powdered), pyridine complex, azo complex, nigrosine, black talc powder, cobalt Deng, the black dyes
Chromium metal oxide, azine, phthalocyanine etc..
A kind of prepreg made of above-mentioned resin combination is claimed in the present invention simultaneously, by the resin combination
Glue is made in the dissolution of object solvent, and then reinforcing material is immersed in above-mentioned glue, the reinforcing material after dipping is heated dry
After dry, the prepreg can be obtained.
Wherein, the reinforcing material is natural fiber, organic synthetic fibers, organic fabric or inorganic fabric；Preferably,
The reinforcing material uses glass fabric, and it is preferable to use fibrillation cloth or flat fabrics in glass fabric.In addition, in the enhancing
Material use glass fabric when, the glass fabric, which is typically necessary, to be chemically treated, with improve resin combination with
It is combined between the interface of glass fabric.The chemical treatment main method is coupling agent treatment.Coupling agent used preferably uses ring
Oxosilane or amino silane etc., to provide good water resistance and heat resistance.
The prepreg the preparation method comprises the following steps: reinforcing material is immersed in above-mentioned resin combination composition glue liquid, then
Reinforcing material after dipping is toasted into 1-10min under 50-170 DEG C of environment, the prepreg can be obtained after dry.
A kind of interlayer insulating film made of above-mentioned resin combination is claimed in the present invention simultaneously, by the resin
Glue is made in the dissolution of composition solvent, then coats the glue on a carrier film, will coat the carrier film heat drying of glue
Afterwards, the interlayer dielectric can be obtained.
The interlayer dielectric the preparation method comprises the following steps: above-mentioned resin combination is added in solvent, glue is made in dissolution,
The glue is coated in carrier film, by after the carrier film heat drying for coating glue, glue forms insulating resin layer
Obtain the interlayer dielectric.The solvent be selected from acetone, butanone, toluene, methylisobutylketone, N, dinethylformamide,
N, one or more of N- dimethyl acetamide, ethylene glycol monomethyl ether, propylene glycol monomethyl ether.The carrier film can be polyethylene to benzene
Dicarboxylic acid esters (PET) film, release film, copper foil, aluminium foil etc., the carrier film is preferably PET film.Above-mentioned heat drying condition is
It is toasted 1-10 minutes at 50-170 DEG C.
Further, the interlayer dielectric is covered with protective film away from the side of the carrier film, with protection insulation tree
Rouge layer.The material of the protective film is identical as the material of the carrier film, certainly, is not limited thereto.
A kind of laminate is claimed simultaneously in the present invention, is covered with metal in the single or double of an above-mentioned prepreg
Foil, or by after at least 2 above-mentioned prepreg superpositions, it is covered with metal foil in its single or double, hot forming can obtain
To the laminate.
The preparation step of the laminate is as follows: it is covered with metal foil in the single or double of an above-mentioned prepreg, or
Person will be covered with metal foil in its single or double, metal can be obtained in hot forming after at least 2 above-mentioned prepregs superpositions
Foil laminate.The pressing conditions of above-mentioned laminate are as follows: it is small that 2~4 are suppressed at a temperature of 0.2~2MPa pressure and 180~250 DEG C
When.
Specifically, the thickness for the laminate that the quantity of the prepreg can be as needed determines, can use one or more
.
The metal foil, can be copper foil, be also possible to aluminium foil, and material is unlimited；The thickness of the metal foil does not have yet
Especially limitation, such as 5 microns, 8 microns, 12 microns, 18 microns, 35 microns or 70 microns.
The present invention also provides a kind of printed wiring board, the printed wiring board include an at least above-mentioned prepreg,
An or at least above-mentioned insulation film.
Due to the above technical solutions, the present invention has the following advantages over the prior art:
1. the present invention is using the phosphorus-containing compound containing unsaturated carbon carbon bond in polyphenylene oxide and compound containing unsaturated carbon carbon bond
Play the role of crosslinking agent, can be good at by polyphenylene oxide and compound containing unsaturated carbon carbon bond uniformly it is compatible together, obtain
Lower dielectric constant and low dielectric loss value, experimental data proves: resin combination of the invention and thus making
Standby laminate can satisfy current 5G product；
2. the reactivity between three components with unsaturated carbon carbon bond of the invention is suitable, so system can be made
Reaction is consistent, forms homogeneous phase；Meanwhile the phosphorus-containing compound that the present invention selects has special structure: intermediate phosphorus nitrogen is in ring
Shape, the problem of avoiding the easy moisture absorption of phosphorous resin, and can produce electron conjugated, make final products that there is preferably dielectric
Performance and humidity resistance enable product to keep the stability of dielectric properties in high frequency；
3. the phosphorus-containing compound of the invention containing unsaturated carbon carbon bond forms crosslinking interpenetrating networks knot because it participates in reaction
Structure avoids addition type or other brought split-phase problems of phosphonium flame retardant and resistance that can not carry out Raolical polymerizable
The problems such as fuel efficiency rate is low；
4. the present invention uses the phosphorus-containing compound containing unsaturated carbon carbon bond of sulfur-bearing, not only with the effect of phosphorus sulphur cooperative flame retardant
Fruit, it is often more important that, the caking property of system can be improved, experiments have shown that: compared to other not sulfur-bearing contain unsaturated carbon carbon bond
Phosphorus-containing compound, the peel strength of the laminate as made from resin combination of the invention is much higher.
Specific embodiment
The present invention will be further described below with reference to examples:
Embodiment
A kind of Halogen polyphenyl ether resin composition is formulated referring to shown in the following table 1:
Table 1
The specific detail of said components is such as the following table 2:
Table 2
Above-mentioned phosphorus-containing compound A synthetic method: using hexachlorocyclotriph,sphazene, 3- chavicol and phenol as primary raw material,
A kind of novel three phosphonitrile chemical combination of ring containing allylic structure is synthesized through two step nucleophilic substitutions using the method that substep is added dropwise
Object.
Above-mentioned phosphorus-containing compound B synthetic method:
Above-mentioned resin combination is obtained using conventional preparation method, will contain polyphenylene oxide, triallyl isocyanate, phosphorous
Compound, initiator and suitable inorganic filler and solvent are added in mixed glue kettle, and solid content is 55~70%, and stirring is equal
It is even, and cure 4~8 hours, resin combination composition glue liquid is made, then, reinforcing material is immersed in above-mentioned resin combination composition glue liquid
In；Then the reinforcing material after dipping is formed after toasting 3~7min drying under 155~175 DEG C of environment and forms semi-solid preparation
Piece.
Using laminate made from above-mentioned prepreg, manufacturing method includes the following steps:
1) 8 prepregs are superimposed,
2) it is covered with copper foil in the two-sided of the prepreg,
3) hot forming, the lamination of copper-clad laminate need to meet claimed below: (1) heating rate being laminated: usually existing
Heating rate at 30~160 degrees Celsius of material temperature should be controlled in 0.8~5.0 DEG C/min；(2) the pressure setting being laminated: outer layer material
Temperature need to apply full pressure at 70~110 degrees Celsius, and full pressure pressure is 300psi or so；(3) when solidifying, material temperature is controlled at 195 DEG C
More than, and at least keep the temperature 90min.
Table 3 is the performance test carried out to embodiment one to five and comparative example one to three, as a result as follows:
Table 3
As seen from the above table, embodiment one and embodiment two be compared with comparative example two, glass transition temperature, humidity resistance,
In terms of dielectric properties and toughness it is excellent very much；Again from embodiment three, four, five compared with comparative example three: the present invention is made
Laminate not only humidity resistance it is preferable, excellent dielectric properties, high glass-transition temperature can also be obtained, especially existed
Reliability is very excellent in terms of humidity resistance.
Resin combination of the invention has high wet-hot aging performance, high glass-transition temperature, lower dielectric constant
With dielectric loss tangent value, the requirement of the high performance printed wiring board such as high-frequency high-speed and high density interconnection can satisfy.
About caking property: referring to embodiment one, four and five, compared with other embodiments and comparative example, using containing for sulfur-bearing
After the phosphorus-containing compound of unsaturated carbon carbon bond, not only have the effect of phosphorus sulphur cooperative flame retardant, it is often more important that, it can mention
The caking property of high system, i.e. its peel strength are done sth. in advance significantly.Illustrate the stripping of the laminate as made from resin combination of the invention
It is much higher from intensity.
The test method of each performance is as follows in table 3:
(1) compatibility of glue each component: range estimation.
(2) glass transition temperature (Tg): according to differential scanning calorimetry, according to IPC-TM-650 2.4.25 defined
DSC method be measured.
(3) peel strength (PS): according to " after thermal stress " experiment condition in IPC-TM-650 2.4.8 method, test gold
Belong to the peel strength of cap rock.
(4) wicking heat resistance: using the two sides band copper sample of 50 × 50mm, immerses in 288 DEG C of scolding tin, record sample point
The time of layer bubble.
(5) wicking heat resistance after moist processing: by the substrate coupons of 25 pieces of 100 × 100mm 121 DEG C, 105Kpa's plus
After pressing boiling processing unit is interior to keep 3hr, 2min in 288 DEG C of solder bath is immersed, whether observation sample occurs layering bubbling etc.
Phenomenon.
(6) it thermal decomposition temperature Td: is measured according to IPC-TM-650 2.4.26 method.
(7) dielectric constant: flat band method is used according to IPC-TM-650 2.5.5.9, measures the dielectric constant under 1GHz.
(8) dielectric loss angle tangent: using flat band method according to IPC-TM-650 2.5.5.9, measures the dielectric damage under 1GHz
Consume the factor.
(9) it thermally stratified layer time T-300: is measured according to IPC-TM-650 2.4.24 method.
(10) it flame resistance (flame retardancy): is measured according to UL94 method.
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 Halogen polyphenyl ether resin composition, which is characterized in that with solid weight meter, including following component:
(a) containing the polyphenylene oxide resin of unsaturated carbon carbon bond: 100 parts；
(b) containing the phosphorus-containing compound of unsaturated carbon carbon bond: 5~60 parts；
(c) initiator: 0~10 part；
The phosphorus-containing compound containing unsaturated carbon carbon bond is selected from such as at least one of flowering structure compound:
2. resin combination according to claim 1, it is characterised in that: the phosphorus-containing compound containing unsaturated carbon carbon bond
Be the phosphorus-containing compound containing unsaturated carbon carbon bond of sulfur-bearing or the phosphorus-containing compound containing unsaturated carbon carbon bond of the sulfur-bearing and
The composition of other phosphorus-containing compounds containing unsaturated carbon carbon bond.
3. resin combination according to claim 1, it is characterised in that: the polyphenylene oxide resin containing unsaturated carbon carbon bond
Selected from vinyl modified polyphenylene oxide resin, acrylate modified polyphenylene oxide resin, allyl modified polyphenylene ether resin, maleimide
At least one of amino modified polyphenylene oxide resin,
The number-average molecular weight of the vinyl modified polyphenylene oxide resin and acrylate modified polyphenylene oxide resin is respectively less than 6000.
4. resin combination according to claim 3, it is characterised in that: the vinyl modified polyphenylene oxide resin is selected from such as
One of compound shown in flowering structure formula (1), (2) is several:
Wherein: X2Selected from having structure:
Wherein R1、R3、R6、R8、R9、R11、R14、R16、R17、R19、R22、R24It is identical or
Person is different, respectively halogen atom, alkyl or phenyl；Wherein R2、R4、R5、R7、R10、R12、R15、R18、R20、R21、R23It is identical
Perhaps difference is hydrogen atom, halogen atom, alkyl or phenyl respectively；
-Y2- O- structure are as follows:Wherein R26、R28It is same or different, it is halogen atom, alkane respectively
Base or phenyl, R25、R27It is respectively selected from hydrogen atom, halogen atom, alkyl or phenyl；
M, n respectively represents 0~30 integer, and cannot simultaneously be 0；
Wherein n is greater than 5 integer；
The acrylate modified polyphenylene oxide resin is selected from one of compound shown in following structural formula (3) or several:
Wherein:
Y3ForWherein m, n are respectively
Integer more than or equal to 1.
5. resin combination according to claim 1, it is characterised in that: in the Halogen polyphenyl ether resin composition also
Cross-linking aid, the cross-linking aid be selected from maleimide compound, hydrocarbon resin, the benzoxazine containing unsaturated carbon carbon bond,
Phenolic resin containing unsaturated carbon carbon bond, the cyanate containing unsaturated carbon carbon bond, in the polyimides containing unsaturated carbon carbon bond
It is one or more of.
6. resin combination according to claim 1, it is characterised in that: with solid weight meter, including following component:
(a) containing the polyphenylene oxide resin of unsaturated carbon carbon bond: 100 parts；
(b) containing the phosphorus-containing compound of unsaturated carbon carbon bond: 10~40 parts；
(c) initiator: 0.1~3 part；
(d) hydrocarbon resin: 15-40 parts.
7. resin combination according to claim 5 or 6, it is characterised in that: the hydrocarbon resin is selected from polybutadiene, gathers
Pentadiene, polystyrene, Polybutadiene-styrene copolymer, styrene-butadiene-styrene, polyprene-benzene
Ethylene copolymer, styrene-isoprene-styrene copolymer, talan ethane, talan methane, talan hexane,
One or more of triallyl isocyanate and its prepolymer.
8. a kind of prepreg using any resin combination production as described in claim 1-7, it is characterised in that: by institute
It states the dissolution of resin combination solvent and glue is made, then reinforcing material is immersed in above-mentioned glue, by the enhancing after dipping
After material heat drying, the prepreg can be obtained.
9. a kind of laminate, it is characterised in that: be covered with gold in a single or double by prepreg according to any one of claims 8
Belong to foil, or will at least 2 by prepreg according to any one of claims 8 superposition after, be covered with metal foil in its single or double, heat
The laminate can be obtained in pressing formation.
10. a kind of interlayer insulating film using any resin combination production as described in claim 1-7, feature exist
In, by the resin combination solvent dissolution glue is made, then coat the glue on a carrier film, the load of glue will be coated
After body film heat drying, the interlayer dielectric can be obtained.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910921153.2A CN110527037B (en) | 2019-09-27 | 2019-09-27 | Halogen-free polyphenyl ether resin composition and prepreg and laminated board manufactured by using same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910921153.2A CN110527037B (en) | 2019-09-27 | 2019-09-27 | Halogen-free polyphenyl ether resin composition and prepreg and laminated board manufactured by using same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110527037A true CN110527037A (en) | 2019-12-03 |
| CN110527037B CN110527037B (en) | 2022-03-25 |
Family
ID=68670527
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910921153.2A Active CN110527037B (en) | 2019-09-27 | 2019-09-27 | Halogen-free polyphenyl ether resin composition and prepreg and laminated board manufactured by using same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110527037B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111303484A (en) * | 2020-04-01 | 2020-06-19 | 吉林大学 | Irradiation-sensitized halogen-free flame retardant, preparation method and application in wires and cables |
| CN111635626A (en) * | 2020-06-30 | 2020-09-08 | 瑞声科技（南京）有限公司 | Resin composition, prepreg, laminated sheet, preparation method of prepreg, preparation method of laminated sheet and application of laminated sheet |
| CN113121999A (en) * | 2019-12-31 | 2021-07-16 | 广东生益科技股份有限公司 | Resin composition, and prepreg, laminated board and printed circuit board using same |
| CN114672167A (en) * | 2020-12-24 | 2022-06-28 | 广东生益科技股份有限公司 | Halogen-free flame-retardant resin composition, prepreg prepared from same and laminated board for printed circuit |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030194562A1 (en) * | 2002-01-28 | 2003-10-16 | Kenji Ishii | Polyphenylene ether oligomer compound, derivatives thereof and use thereof |
| CN102807658A (en) * | 2012-08-09 | 2012-12-05 | 广东生益科技股份有限公司 | Polyphenyl ether resin composite and prepreg and copper clad laminate made of polyphenyl ether resin composite |
| CN107868188A (en) * | 2016-09-23 | 2018-04-03 | 台光电子材料股份有限公司 | Phosphorus-containing ethylene polyphenylene ether, resin composition containing the same, and product thereof |
| CN109762115A (en) * | 2019-01-14 | 2019-05-17 | 上海安缔诺科技有限公司 | A kind of resin combination and its application |
-
2019
- 2019-09-27 CN CN201910921153.2A patent/CN110527037B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030194562A1 (en) * | 2002-01-28 | 2003-10-16 | Kenji Ishii | Polyphenylene ether oligomer compound, derivatives thereof and use thereof |
| CN102807658A (en) * | 2012-08-09 | 2012-12-05 | 广东生益科技股份有限公司 | Polyphenyl ether resin composite and prepreg and copper clad laminate made of polyphenyl ether resin composite |
| CN107868188A (en) * | 2016-09-23 | 2018-04-03 | 台光电子材料股份有限公司 | Phosphorus-containing ethylene polyphenylene ether, resin composition containing the same, and product thereof |
| CN109762115A (en) * | 2019-01-14 | 2019-05-17 | 上海安缔诺科技有限公司 | A kind of resin combination and its application |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113121999A (en) * | 2019-12-31 | 2021-07-16 | 广东生益科技股份有限公司 | Resin composition, and prepreg, laminated board and printed circuit board using same |
| CN113121999B (en) * | 2019-12-31 | 2023-04-07 | 广东生益科技股份有限公司 | Resin composition, and prepreg, laminated board and printed circuit board using same |
| CN111303484A (en) * | 2020-04-01 | 2020-06-19 | 吉林大学 | Irradiation-sensitized halogen-free flame retardant, preparation method and application in wires and cables |
| CN111303484B (en) * | 2020-04-01 | 2021-06-01 | 吉林大学 | Irradiation-sensitized halogen-free flame retardant, preparation method and application in wires and cables |
| CN111635626A (en) * | 2020-06-30 | 2020-09-08 | 瑞声科技（南京）有限公司 | Resin composition, prepreg, laminated sheet, preparation method of prepreg, preparation method of laminated sheet and application of laminated sheet |
| WO2022000629A1 (en) * | 2020-06-30 | 2022-01-06 | 瑞声声学科技(深圳)有限公司 | Resin composition, prepreg, laminated board, preparation method for prepreg, preparation method for laminated board and application thereof |
| CN114672167A (en) * | 2020-12-24 | 2022-06-28 | 广东生益科技股份有限公司 | Halogen-free flame-retardant resin composition, prepreg prepared from same and laminated board for printed circuit |
| CN114672167B (en) * | 2020-12-24 | 2023-11-07 | 广东生益科技股份有限公司 | Halogen-free flame-retardant resin composition and prepreg and printed circuit laminate prepared from same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110527037B (en) | 2022-03-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110527037A (en) | A kind of Halogen polyphenyl ether resin composition and prepreg and laminate using its production | |
| CN106832226B (en) | A kind of halogen-free epoxy resin composition and prepreg, laminate and printed circuit board containing it | |
| TWI548520B (en) | Low dielectric composite materials and laminated boards and circuit boards | |
| CN112250865B (en) | Modified maleimide resin prepolymer, preparation method thereof, resin composition, prepreg, laminated board and printed circuit board | |
| CN105936745A (en) | Resin composition | |
| CN101967264A (en) | Epoxy resin composition and high frequency circuit board made of same | |
| CN106832764A (en) | A kind of halogen-free epoxy resin composition and the prepreg containing it, laminate and printed circuit board | |
| CN111117154A (en) | Flame-retardant thermosetting resin composition, and prepreg, laminated board and printed circuit board manufactured from same | |
| TW202000683A (en) | Phosphorus-containing compound, phosphorus-containing flame retardant, preparation method thereof, and article made therefrom | |
| CN106349442B (en) | A kind of compositions of thermosetting resin and prepreg and laminate using its making | |
| CN102504201A (en) | Epoxy resin composition and high-frequency circuit board manufactured thereby | |
| CN101967265A (en) | High-frequency resin composition and high-frequency circuit substrate manufactured by using same | |
| CN108485182A (en) | A kind of high frequency resin composition and prepreg and laminate using its making | |
| CN111393594A (en) | Active ester resin and resin composition thereof | |
| TWI588204B (en) | An epoxy resin composition and a prepreg and a laminate using the same | |
| CN110669328A (en) | Resin composition containing phosphorus flame retardant BMI and application thereof | |
| CN110615876B (en) | Halogen-free polyphenyl ether resin composition and prepreg and laminated board manufactured by using same | |
| CN105131597B (en) | A kind of halogen-free resin composition and use its prepreg and laminate for printed circuits | |
| CN110922764B (en) | Silicon-containing resin composition and prepreg and laminated board manufactured by using same | |
| CN110950901B (en) | Silicone resin, method for producing the same, resin composition, prepreg, laminated board, insulating board, circuit board, and coverlay film | |
| CN111849122B (en) | Resin composition and application thereof | |
| WO2020248501A1 (en) | Active ester compound, resin composition, and prepreg, insulating film, metal foil coated laminate and printed circuit board having same | |
| CN114316264B (en) | Modified bismaleimide prepolymer, resin composition and application thereof | |
| CN114230794B (en) | Modified bismaleimide prepolymer, resin composition and application | |
| CN111961193B (en) | Resin composition, and prepreg, insulating film, metal-clad laminate and printed wiring board having same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |